Lecithin S

13
Lecithins
Bernard F. Szuhaj
Szuhaj & Associates LLC Fort Wayne, Indiana
1. INTRODUCTION Phospholipids are lipids containing a phosphoric acid residue; they are natures principal surface-active agents. They are found in all living cells, whether of animal or plant origin. In humans and in animals, the phospholipids are concentrated in the vital organs, such as the brain, liver, and kidney; in vegetables, they are highest in the seeds, nuts, and grains. As constituents of cell membranes, and active participants in metabolic processes, they are essential to life (18). The commercial term lecithin is very general, and it describes a composition of lipid constituents and surface-active compounds present in the product rather than in the chemical entity: phosphatidylcholine (PC). Thus, in general usage, lecithin refers to a complex, naturally occurring mixture of polar lipids obtained by water-degumming crude vegetable oils and separating and drying the hydrated gums (8). It is, however, the phospholipid portion of lecithin that is mainly responsible for giving form and function to commercial lecithin (6). Commercial lecithin is an important coproduct of edible oil processing because of its dietary signicance and multifaceted functionality in food systems and industrial applications. Unless indicated otherwise, the term lecithin will denote the commercial designation throughout the text in this chapter. Lecithin has a long history of use in foods, dating back more than 60 years (9). The 1930s brought widespread use of commercial solvent extraction techniques for
Baileys Industrial Oil and Fat Products, Sixth Edition, Six Volume Set. Edited by Fereidoon Shahidi. Copyright # 2005 John Wiley & Sons, Inc.
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LECITHINS
vegetable oil production, and because degumming of crude vegetable oil became necessary for shipping stability, a large supply of crude lecithin gums was produced. These gums were obtained in sufcient quantity to necessitate their becoming an item of commerce (9). In the ensuing years, there was extensive research into developing new lecithin applications, as well as product renements and modications. Lecithin ingredients are now recognized as valuable products that have both nutritional value and commercial, i.e., food/feed/industrial utility (2, 5). Two of the earliest edible applications of lecithin, viscosity reduction in chocolate and confectionery products, and emulsication/antispatter properties in margarine, still enjoy wide popularity and represent outlets for large volumes of lecithin products. In addition, other early uses such as in bakery goods, pasta, textiles, insecticides, and paints, among others, are still active today. 2. SOURCES OF PHOSPHOLIPIDS 2.1. Human/Animal Tissues Almost all body cells contain phospholipids. The common animal phospholipids are made of sphingomyelin, phosphatidylcholine (PC), phosphatidylethanolamine (PE), phosphatidylserine (PS), phosphatidylinositol (PI), and other glycerol phospholipids of complex fatty acid composition. PC, formerly referred to as lecithin, PE, formerly referred to as cephalin, and PS are by far the most predominant phospholipids from most animal sources. As constituents of cell walls and active participants in metabolic processes, they appear to be essential to life (8). The exact composition of human/animal phospholipids depends on the source and the method of extraction and purication. The central nervous system especially has a high phospholipid content. The liver is the site for their biosynthesis, and the lipids of the mitochondria, which are the regulators of cell metabolism and energy production in the body, consist of up to 90% phospholipids (10). A survey of improved fractionation and analytical methods for elucidating the molecular species of these complex animal phospholipids, and the phospholipids present in primary and processed foods, has been published by Kuksis (11). This survey also includes information on the quantitative analysis of phospholipids, peroxidation products of phospholipids, and the composition of selected animal phospholipids. Only egg yolk, milk, and brain have served as major animal sources of commercial lecithin. In some instances, isolated and puried lecithins have been developed for clinical nutritional uses. Weihrauch and Son (12) present a concise review of phospholipid composition in various foods. The following brief discussion covers phospholipids from animal sources that have some commercial signicance. Egg phospholipids. At one time, eggs, which possess a relatively high phospholipid content, served as a commercial source until soybean technology made it uneconomical to produce. The phospholipids in eggs are mainly in the yolk, where at least a portion of them are combined with protein and carbohydrates.
SOURCES OF PHOSPHOLIPIDS
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TABLE 1. Composition of Soy and Egg Lecithin (14). Polar Lipids Phosphatidylcholine Phosphatidylethanolamine Phosphatidylinositol Phosphatidic acid Sphingomyelin Other phospholipids Glycolipids Soy 2022 2123 1820 48 15 912 Egg 6872 1216 02 24 10
Compositional data on commercial egg products and various lipid extracts from egg yolk have been compiled by Gornall and Kuksis (13), Kuksis (11), Schneider (14), and Satirhos et al. (15). Tables 1 and 2 (14, 16) compare the composition of soy and egg lecithins and their fatty acids, and Table 3 (1621) shows the distribution of phospholipid classes in egg yolk. Besides phospholipid composition, the main difference between plant/legume lecithin (e.g., soy) and lecithin in egg yolk is that the former has a higher unsaturated fatty acid content and no cholesterol. Egg lecithin as a commercial ingredient, with the exception of some medical feeding programs, is too expensive for routine use in food (10). In some infant formulas, egg yolk lipids and egg lecithin are used (22). Milk phospholipids. Milk has a phospholipid content of about 0.035%, which is associated with the fat by virtue of being part of a colloidal membrane that surrounds the fat globule. Wittcoff (4), Morrison et al. (23), and Privett et al. (24) have reported the results of TLC analysis of the polar lipids of various milk fractions. Recently, Jensen (25) published extensive high performance liquid chromatography (HPLC) results of the phospholipid composition of cows milk during lactation, and typical data on phospholipid, sphingolipid, and glycosphingolipid classes in bovine milk. The feeding regime of fatty acids in the diet affects the fatty acid composition of the milk lipids to a certain extent. It might be expected that the fatty acid composition of the phospholipids will be affected as well.
TABLE 2. Fatty Acid Composition (%) (14). Type of Acid Saturated Palmitic Stearic Unsaturated Oleic Linoleic Linolenic Arachidonic Soy 1518 36 911 5660 69 0 Egg 2729 1417 3538 1518 01 35
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TABLE 3. Distribution of Phospholipid Classes in Egg Yolk (16). Analyses Phospholipid Classes % Total lipid (w/w) PC PE PS CL SPH LPC LPE Unidentied
a b
e,f
e,g
6676 1524 1 1 36 36
69.1 23.9 2.7 3.2 1.0
77.0 18.0
2.3 2.5
23 69 24 Trace Trace 3 3
82.6 9.1
87.1 7.8
1.8 6.5
2.5 2.5
Privett et al. (17). Noble and Moore (18). c Cook and Martin (19). d Gornall and Kuksis (20). e Connelly and Kuksis (21). f Commercial sample. g Intralipid.
Skim milk and milk serum have the highest portion of polar lipids as percent of the total lipids, and whole milk and cream have the least. Of the polar lipids, phosphatidylethanolamine constitutes the largest component, with phosphatidylcholine and sphingomyelin (being present in about equal proportions) at a signicantly lower level (Table 4) (16, 23, 24, 26). Brain phospholipids. The brain is a rich source of phospholipids, and together with the spinal cord, it probably possesses the highest phospholipid content of any of the organs. There are many different types of phospholipids in the central nervous system. As they bypass the blood-brain barrier, adequate nutrition (biosynthesis) of the nerve cells is assured with these substances. Special
TABLE 4. Distribution of Phospholipid Classes in Various Milk Fractions (weight %) (16, 24). Lipid Classes % Total lipid Ceramide monohexoside Ceramide dihexodide Phosphatidylethanolamine Plasmalogen Phosphatidylcholine Plasmalogen Sphingomyelin Phosphatidylserine Phosphatidylinositol Ganglioside (unknown)
a b
Whole Milk 2.0 Trace Trace 36.4 27.0 29.0 Trace Trace 7.6
Plastic Skim 19.0 19.5 10.1 27.5 7.3 18.2 1.9 Trace 15.54
Nonfat Skim 32.0 14.1 45.1 16.4 14.5 7.6 Trace 2.33
Serum 22.0 7.8 32.4 23.2 26.9 3.5 1.1 5.14
Cream 1.02.0 17.9 25.3 19.9 21.6 Trace Trace 15.34
Milka Serumb 3.0 3.0 30.0 1.0 28.0 3.0 19.0 8.0 5.0 0.0 26.9 29.3 31.3 5.0 5.9 1.0
Morrison et al. (23). Santha and Narayanan (26).
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TABLE 5. Distribution of Phospholipid Classes in Brain of Different Animal Species (weight %) (16). Animal Species Lipid Classes % Total lipid PC Plasmalogen PE Plasmalogen PS PI PA CL PG LPC (LPE) LbisPC SPH Unidentied
a b
Human 21.8 35.4 18.8 1.8 1.1 2.0 1.0 16.3
a,b
Bovine 18.4 36.1 18.0 1.8 1.7 0.2 0.4 15.0
a,b
Bovine 32.4 23.5 11.0 4.3 0.9 1.2 0.9 0.9 2.1 20.4
b,c
Humanc,d Bovinec,e Humanc,e Sheepf Ratg 33.2 25.2 10.7 4.8 0.3 1.0 NDh 1.0 0.2 17.0 48.2 24.2 6.7 7.1 1.3 NDh 0.4 1.0 0.7 4.9 47.6 17.8 9.3 5.0 1.2 0.3 0.6 2.5 0.2 10.7 37.3 0.9 7.7 16.5 9.2 2.1 2.6 2.0 12.9 36.8 36.4 11.8 3.1 1.2 2.2 5.7
Siakotos et al. (28). Myelin. c Siakotos et al. (27). d Edothelial cells. e Nuclei. f Scott et al. (29). g Wuthier (30). h ND not detected.
enzyme systems see to it that the most efcient functioning is accomplished at all times (4). The composition of brain phospholipids has been extensively investigated by adsorption column- and thin-layer chromatography (TLC). Table 5 lists the major classes of brain phospholipids from different animal species, as compiled by Kuksis (16, 2730). At the end of the 1990s, the fear of mad cow disease (BSE) may have addressed the purity criteria for the applications of brain phospholipids from cows. Phospholipids in liver, kidney, muscle, and other tissues. Organ meats such as liver, kidney, and muscles are a major source of dietary phospholipids. The reader is referred to Kuksis (16) for the distribution of various phospholipid classes in the liver, kidney, muscles (heart and skeletal), spleen, lung, blood cells, bile, and adipose tissue of different animal species. Compositional data of fatty acids for these tissues and uids are also given. In blood, phosphatidylcholine is quantitatively the most important phospholipid. Sphingomyelin is present in varying amounts in perhaps all of the animal organs, most of it in the soft organs, and to a lesser degree in skeletal muscles and eggs (4). Total blood contains about 0.2% to 0.3% phospholipids. In plasma and serum, phosphatidylcholine predominates, whereas in corpuscles, phosphatidylethanolamine and sphingomyelin constitute the bulk of phospholipids. Most workers have found
366
LECITHINS
that the phospholipid content is greater in red blood cells than in plasma, and it constitutes 60% to 65% of the total lipids in these cells (4). 2.2. Soybean Although the highest concentrations of phospholipids occur in animal products, i.e., meat, poultry, sh, eggs, and milk/cheese, the major commercial source is the soybean, which contains 0.3% to 0.6%. Nevertheless, phospholipids from other vegetable oilseeds, i.e., corn, cottonseed, linseed, peanut, rapeseed, safower, and sunower, and plants have also been studied and used (5). Standard-grade, commercial lecithin from the soybean is a complex mixture. It comprises phospholipids, triglycerides, and minor amounts of other constituents (i.e., phytoglycolipids, phytosterols, tocopherols, and fatty acids). The composition and molecular arrangement of this heterogeneous mixture of compounds denes a product that is low in apparent polarity and has a strong tendency to promote water-in-oil (w/o)-type emulsions (31). A wide range of data has been published showing the variability in the composition of phospholipids and fatty acids in soybean lecithin (Tables 6 and 7) (32). Older data were often determined by qualitative TLC, whereas today 31P-NMR, quantitative Li-Sc HPLC, and HPTLC methods have been developed. Soy lecithin is a coproduct of oil processing. As a result, purication steps used to produce quality oil may affect the lecithin components. Also, soybeans exposed to frost damage, or subjected to prolonged storage, have reduced lecithin yields (33). Phospholipases, which produce phosphatidic acid, are active during storage and may reduce the yield of lecithin (34). During the maturation process, the major phospholipids (PC, PE, and PI) increase, and others decrease or remain constant (32). A change in the relative concentration of any of these components, or an alteration of their chemical structures, may cause some change in the physical or chemical properties of commercial lecithins. Lecithins can exist as liquids, plastics,
TABLE 6. Components (%) of Soybean Lecithin (32). Range of Composition Component Phosphatidylcholine Phosphatidylethanolamine Phosphatidylinositol Phosphatidic acid Phosphatidylserine Lysophosphatidylcholine Lysophosphatidylinositol Lysophosphatidylserine Lysophosphatidic acid Phytoglycolipids Low 12.021.0 8.09.5 1.77.0 0.21.5 0.2 1.5 0.41.8 1.0 1.0 Intermediate 29.039.0 20.026.3 13.017.5 5.09.0 5.96.3 8.5 14.315.4 High 41.046.0 31.034.0 19.021.0 14.0 29.6
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TABLE 7. Fatty Acids (%) of Soybean Lecithin (32). Range of Composition Fatty Acid Myristic (C14:0) Palmitic (C16:0) Palmitoleic (C16:1) Stearic (C18:0) Oleic (C18:1) Linoleic (C18:2) Linolenic (C18:3) Arachidic (C20:0) Low 0.31.9 11.718.9 7.08.6 3.74.3 6.89.8 17.120.0 1.6 1.42.3 Intermediate 21.526.7 9.311.7 17.025.1 37.040.0 4.06.2 High 42.7 39.4 55.060.8 9.2
or free-owing solids. Their color, solvent solubility, surfactant properties, and chemical reactivity all can be modied. These modications, in turn, will alter the functional properties of the lecithin in a given application (31). The ensuing section is a brief review of phospholipid plant sources other than those from the soybean, which have current or potential commercial applications. Soybean lecithin then will be discussed in more detail later throughout the subsequent sections in this chapter. 2.3. Corn Weeks and Walters (35) have found that 2.5% to 4.5% of the phosphorus in corn is in the form of phospholipids, depending on the variety involved. The rst detailed analysis of commercial corn phospholipids was published by Scholeld et al. (36). Unlike the phenomenal growth in demand for corn sweeteners
TABLE 8. Distribution (%) of Polar Lipids in Corn and Soybean Lecithin (32). Polar Lipid Sterylglycoside ester Monogalactosyldiglyceride Digalactosyldiglyceride Other glycolipids N-Acyl phosphatidylethanolamine N-Acyl lysophosphatidylethanolamine Phosphatidylethanolamine Phosphatidylglycerol Phosphatidylcholine Phosphatidylinositol Phosphatidic acid Phosphatidylserine Lysophosphatidylethanolamine Lysophosphatidylcholine Corn 15.0 1.8 3.7 9.8 2.6 3.7 3.2 1.4 30.4 16.3 9.4 1.0 Trace 1.7 Soybean 4.3 0.8 3.0 6.4 2.2 10.4 14.1 1.0 33.0 16.8 6.4 0.4 0.2 0.9
368
LECITHINS
TABLE 9. Fatty Acid Composition (%) of Corn and Soybean Lecithin (32). Composition Fatty Acid Palmitic (C16:0) Stearic (C18:0) Oleic (C18:1) Linoleic (C18:2) Linolenic (C18:3) Corn 17.7 1.8 25.3 54.2 1.0 Soybean 17.4 4.0 17.7 54.0 6.8
and other products of the corn-rening industry, the commercial exploitation of the coproduct corn lecithin has not taken place in large quantities. Tables 8 and 9 illustrate the distribution of polar lipids and fatty acids in corn lecithin compared with those in soybean lecithin (32). Similar compositions were noted for corn and soy PC and PI. Phosphatidic acid and glycolipids represent a higher proportion of polar lipids in corn than in soybean lecithin. Cherry (37) and Cherry and Kramer (32) also stated that the percentage of minor components in corn, steryl-glycoside ester, and other glycolipids are more than twice that found in soybean. The physical properties, particularly the emulsifying properties of corn lecithin, differ from those of soybean lecithin because of the higher proportion of glycolipids in the corn lecithin. Both the glycolipids and the phospholipids of corn have lower percentages of linolenic acid (18:3) and are more saturated than those in the soybean. In general, crude corn and soybean lecithins are equal in linoleic acid (18:2) content, but linoleic acid in corn varies from 42% to 70% depending on the variety of corn. Phytic acid, 88% of which is in the corn germ, is extracted as part of the lecithin fraction (32, 37). Elimination of phytic acid in corn is desirable because it binds zinc, magnesium, and calcium. 2.4. Cottonseed The phospholipids in cottonseed are similar in many respects to those of soybeans, with the exception of their lower level of linolenic and higher level of saturated fatty acid content (38). Cherry and Kramer (32) compiled Table 10 to show the composition of cottonseed lecithin. Lecithin can be fractionated from cottonseed as phospholipids and glycolipids. Cottonseed lecithin shows avor and color deterioration when blended with other vegetable oils. The saturated/unsaturated fatty acid ratio of cottonseed phospholipids is approximately 1:2 (39). Palmitic acid constitutes 90% of the total saturated fatty acids (36%), and linoleic acid is approximately 80% of the total unsaturated fatty acids (64%). Gossypol binds to lecithin during oil extraction from glanded cottonseed (approximately 9% in crude phospholipids). This economically negates its
369
TABLE 10. Composition (%) of Cottonseed Lecithin (32).

Component Phospholipids Fatty acids Myristic (C14:0) Palmitic (C16:0) Palmitoleic (C16:1) Stearic (C18:0) Oleic (C18:1) Linoleic (C18:2) Total gossypol Free gossypol Extract 1.82.2 0.4 32.9 0.5 2.7 13.6 50.0 9.13 0.02 Phosphatidylcholine 34.935.9 0.3 31.1 0.3 2.8 11.5 54.0 2.34 2.24 Phosphatidylethanolamine 13.720.1 0.4 33.7 0.3 2.2 11.5 49.0 22.43 0.05 Phosphatidylserine 7.026.0 0.6 33.3 0.6 0.3 14.4 50.4 19.90 0.01
use as a commercial source. Cultivars of glandless or gossypol-free cottonseed may have some potential for providing commercial edible lecithins (37). The composition of cottonseed lecithin and the composition of the phospholipid fraction from hexane-defatted glandless cottonseed oil are summarized in Tables 10 and 11 (32, 37, 4042). As cottonseed lecithin contains only trace amounts of fatty acids with more than two double bonds (linolenic acid), it is more stable to oxidation and rancidity than soybean lecithin. Cottonseed phospholipids are relatively high in phosphatidylcholine, which could provide good emulsifying properties in foods (32, 37).
TABLE 11. Composition of Phospholipid Fraction from Glandless Cottonseed Oil (37, 40, 41). Phospholipida Origin Lysophosphatidylcholine Phosphatidylinositol Phosphatidylserine Phosphatidic acid Phosphatidylcholine Phosphatidylethanolamine Phosphatidylglycerol Lysophosphatidylserine Lysophosphatidylethanolamine Unknown (sum: 6 TLC spots) Composition (% of Total Phosphorus) 4.12 2.56 13.41 2.38 8.76 23.16 13.46 7.62 NDb ND 25.30
a Water (2 4%) was added to hexane-extracted glandless cottonseed oil, the resulting mixture stirred 30 minutes at 70 C, and centrifuged to separate the oil and phospholipid-containing fraction. The phospholipids were separated by twodimensional thin-layer chromatography (TLC) on Silica gel-60 plates. Dimension I chloroform: methanol:7N NH4OH (65:30:1); Dimension II chloroform: methanol:acetic acid:water (170:25:25:4). Quantitation of the phsopholipids was according to El-Sebaiy et al. (42). b ND not detected.
370
LECITHINS
2.5. Rapeseed Rewald (43) found approximately 20% phospholipids in rapeseed. Rapeseed lecithin has been reviewed, and an extensive bibliography has been compiled (44). Table 12 (44) shows the composition of rapeseed and soybean gums. The major phospholipids present in rapeseed lecithin are phosphatidylcholine, phosphatidylethanolamine, and phosphatidylinositol. The relative proportion of these components does not differ signicantly from that of soybean lecithin. In lecithin from high erucic oils, the long-chain fatty acids (C20C22) are present only in small amounts, and in low erucic oil lecithin (including canola), the fatty acid composition is not markedly different from that of the parent oil, except for a somewhat higher content of C16:0, leaving a slightly higher C18:1 and C18:3 fatty acid level in the degummed oil (44). Solvent-extracted rapeseed oil has been found to contain the highest level of phosphorus. For this reason, it is common practice to degum solvent-extracted oil or the mixed crude oil from pressing and subsequent solvent-extraction. As the double-zero rapeseed varieties such as canola became available, the applications of rapeseed lecithin have developed positively. Where at rst rapeseed lecithin was applied as an emulsier and energy component in animal feed, the recent concerns about GMO soybean varieties in some parts of the world have increased the market value of the softseed lecithins for food applications (45). The phospholipid composition is similar to soybean lecithin with variations due to crop and processing conditions. The rapeseed phospholipid compositions in Table 12 have been conrmed by recent data, whereas the soybean lecithin composition in
TABLE 12. Composition of Rapeseed and Soybean Gums (%) (44). Rapeseed Components Water Nonlipid Triglycerides or neutral lipids Phospholipids (total) Phosphatidylcholine Phosphatidylethanolamine Phosphatidylinositol Lysophosphatidylcholine Lysophosphatidylethanolamine Sterol glycosides or glycolipids Unidentied Unaccounted for
a b
Soybean (11)
b
(9)
(9)
(10)
(8)
(8)c 35 21 8 20 0 0 11 5
24 9 16 51
22 15 18 9e 36f
38.1 16.2 17.5 7.6 2.0 7.9 10.7
5.6 24.6 22.1 14.7d 19.4 13.6
29 20 16 8 1 11 15
Complete gum sample, including water. Acetone precipitate from gum sample. c Dried gum sample. d Tentatively identied. e Tentatively: phytoglycolipids. f Tentatively: 16% acidic phospholipids (plus 20% unidentied).
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the last column is not representative because of the low phosphatidylethanolamine content. Sosada (46) determined the optimum conditions for fractionation of rapeseed lecithin with alcohols to improve puried lecithin yield and phosphatidylcholine enrichment. 2.6. Sunower and Peanut Although sunower lecithin currently is not used to any great extent, as sunower oil production is increased, the availability of lecithin from this oil may be a possibility (47). Because of its high phosphatidylcholine content, sunower lecithin can be used in foods and feedstuffs. Its use in the manufacture of foods and cosmetics can be increased by rening and fractionation and/or modications (48). Sunower lecithin has a mild taste and similar emulsifying properties as soybean lecithin. The crude lecithin is pastier than soybean lecithin, because of waxes, but exact adjustment of the oil and acid content in rened sunower lecithin results in an effective emulsier with good handling properties. This makes sunower lecithin interesting for food manufacturers, particularly in Europe, the biggest sunower seed producing/processing continent. The percentage of phospholipids in sunower oil ranges from 0.02% to 1.5%, with an average of around 0.75%. The composition of the phospholipids is similar to soybean lecithin, with a tendency to higher phosphatidylcholine and lower phosphatidylethanolamine ratios, which might be caused by crop varieties and processing conditions. Hollo et al. (49) report positive results of physical and enzymatic modication of sunower lecithin for improving the emulsifying properties. Hilditch and Zaky (50) found that phospholipids in peanuts are considerably less unsaturated than those in soybean and cottonseed. Rewald (51) has shown 35.7% phosphatidylcholine and 64.3% phosphatidylethanolamine content in peanut phospholipids.
2.7. Other Plants and Micro-Organisms Table 13 shows the phospholipid composition of selected plant sources (32). Parsons and Price (52) have published compositional data on the phospholipids of barley grain based on thin-layer chromatography. Other than in animal tissues, egg, and oilseeds, quantitative data on the phospholipids in plants are meager because of the difculty involved in their isolation. The phospholipids in wheat are about 80% PC and 20% PE (4). Rye, barley, and other grains, vegetables, and fruits all contain small amounts of phospholipids. Microorganisms, especially those that are acid-fast, and lower plants, also contain large amounts of lipids, including phospholipids; these entities are of interest for clinical research (4). A survey of microbiological sources of phospholipids has been published by Ratledge (53).
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LECITHINS
TABLE 13. Phospholipids (%) of Selected Plant Sources (32). Phospholipids Source Rapeseed Sunower seed Peanut seed Cucurbit seed Rice bran Barley seed Olive fruit Avocado fruit Palash seed Jangli badam seed Papaya seed Coriander seed Carrot seed Phosphatidylcholine 16.2; 20.024.6 12.726.8; 42.264.2 49.0 55.874.9 20.423.1 44.344.4 47.358.9 37.044.9 44.6 30.0 28.1 44.0 29.1 Phosphatidylethanolamine 15.017.5; 22.1 9.929.4; 46.6 16.0 10.518.7 17.820.2 7.68.8 5.38.0 12.019.5 14.8 23.0 18.7 29.3 35.4 Phosphatidylinositol 7.68.0; 14.718.0 3.721.4; 24.036.6 22.0 13.717.2 5.86.6 1.11.3 18.023.9 12.118.0 27.0 40.6 34.0 23.1 23.1
3. NOMENCLATURE, CLASSIFICATION, STRUCTURE AND COMPOSITION, AND CHEMICAL/PHYSICAL PROPERTIES 3.1. Denition According to Wittcoff (4), three distinct polymeric alcohols provide the basic constituents for the various phospholipids. The rst of these is glycerol, and the phospholipids containing it are referred to as glycerophospholipids. Included herein, in addition to PC, PE, and PS, are the acetalphospholipids or plasmalogens (in body uids, muscles, and egg), the lysophospholipids, and the phosphatidic acids. The second polyhydric alcohol is the aminodihydroxy compound sphingosine, which is the basis for not only sphingomyelin (in the brain and spinal cord), but also for other glycolipids. All of these compounds based on sphingosine are also referred to as sphingolipids. The third polyhydric alcohol is inositol, which is included in PI. Phospholipids also form complexes with proteins (e.g., vitellin in egg yolk, animal and plant tissues, lipoproteins in blood serum, and milk), carbohydrates, glycosides, alkaloids, minerals, enzymes, cholesterol, and other substances. Lysophospholipids represent a special class of compounds resulting from the chemical or enzymatic hydrolysis of phospholipids. The role of phospholipases in normal and pathological conditions as well as in cell metabolism is of great biological signicance (4). For the elucidation, synthesis, chemical properties, physical chemistry, composition, and analytical determination of the various individual phospholipid structures in animal and plant sources, the reader is referred to Wittcoff (4). Schneider (14) discusses the nomenclature used for phospholipids in more detail and provides compositional data on commercial lecithins (Table 14). Because of the commercial signicance of soybean lecithin, this chapter will focus primarily on the structure, composition, analytical determination, properties, and applications of this product.
NOMENCLATURE, CLASSIFICATION, STRUCTURE AND COMPOSITION
373
TABLE 14. Composition of Commercial Lecithins (%) (on Oil-Free Basis) (14). Lecithin Phosphatidylcholine Phosphatidylethanolamine Phosphatidylinositol Phosphatidic acid Phosphatidylserine Sphingomyelin Glycolipids Soy 21 22 19 10 1 12 Corn 31 3 16 9 1 30 Sunower 14 24 13 7 Rapeseed 37 29 14 20 Egg 69 24 3 1 Bovine Brain 18 36 2 2 18 15
The U.S. Food Chemical Codex (54) denes lecithin as follows:

Food-grade lecithin is obtained from soybeans and other plant sources. It is a complex mixture of acetone-insoluble phosphatides that consist chiey of phosphatidylcholine, phosphatidylethanolamine, and phosphatidylinositol, combined with various amounts of other substances such as triglycerides, fatty acids and carbohydrates. Rened grades of lecithin may contain any of these components in varying proportions and combinations depending on the type of fractionation used. In its oil-free form, the preponderance of triglycerides and fatty acids is removed and the product contains 90% or more of phosphatides, representing all or certain fractions of the total phosphatide complex. The consistency of both natural grades and rened grades of lecithin may vary from plastic to uid, depending on the free fatty acid and oil content, and upon the presence or absence of other diluents. . .
3.2. Classication of Commercial Soybean Lecithin Products The simplest method for modifying natural (crude) lecithin is the addition of a nonreactive substance. Plastic lecithins are converted to uid forms by adding 2% to 5% fatty acids and/or carriers such as soybean oil. If the additives react with the lecithin to alter the chemical structure of one or more of the phospholipid components, the resulting product is referred to as a chemically modied lecithin. Modication can also be achieved by subjecting lecithin to partial controlled enzymatic hydrolysis. Finally, rened lecithin products can be obtained by fractionating the various phospholipid components. A method for classifying lecithin to include modied and rened forms has been proposed by Cowell et al. (55). This classication distinguishes between natural (crude) lecithins and those modied by either custom blending or chemical/enzymatic treatment, e.g., hydroxylation, hydrogenation, acetylation, or rening by acetone or alcohol fractionation. These latter products reect the state of the art regarding the availability of the various lecithin products on the market and have enhanced properties for specic uses. A listing of soybean lecithin classications follows (56).
374
LECITHINS
I. Crude commercial lecithin A. Plastic 1. Unbleached 2. Single bleached 3. Double bleached B. Fluid 1. Unbleached 2. Single bleached 3. Double bleached II. Compounded III. Chemically modied IV. Rened A. Deoiled 1. As is 2. Custom blended B. Fractionated 1. Alcohol soluble a. As is b. Custom blended 2. Alcohol insoluble a. As is b. Custom blended C. Puried phosphatides Natural (crude) lecithins. Specications as dened by the National Soybean Processors Association (19861987) for natural (crude) lecithins is presented in Table 15 (57). Specications have also been published by the Food Chemicals Codex (1996) (54). Phospholipid content is specied in terms of acetone-insolubles (AI); product clarity, and purity in terms of hexane-insolubles (HI). The lecithins are classied as plastic or uid in consistency, and they are further subdivided on the basis of manufacturing procedure as natural color, bleached, or double bleached. Acidity of phospholipids plus acidity of the carrier (i.e., the oil and fatty acids) is given by the acid value (AV), i.e., milligram of potassium hydroxide required to neutralize the acids in 1 g of the lecithin sample. Crude lecithin can be ltered for utmost purity and clarity. Filtration removes hexane-insoluble (HI) matter. Such products are in demand for encapsulated nutritional supplements, for pharmaceutical grades, and for advanced technology industrial uses requiring a high level of purity. Compounded lecithins. Compounded lecithins are blended products. Lecithin combined with selected additives can exhibit modied properties and functionalities. Lecithin may have a synergistic action with some additives or, simply, be
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TABLE 15. Soybean Lecithin Specications (57). Grade Fluid Fluid Unbleached Bleached Lecithin Lecithin 62% 1% 0.3% 32 18 15,000 62% 1% 0.3% 32 14 15,000 Fluid DoubleBleached Lecithin 62% 1% 0.3% 32 12 15,000 Plastic Plastic Natural Bleached Lecithin Lecithin 65% 1% 0.3% 30 18 22 mm 65% 1% 0.3% 30 14 22 mm Plastic DoubleBleached Lecithin 65% 1% 0.3% 30 12 22 mm
Analysis Acetone insoluble, min. Moisture, max.a Hexane insoluble, max. Acid value, (mg KOH/g), max. Color, Gardner, max.b Viscosity, centipoise, at 25 C, max.c Penetration, max.d
a b
By Karl-Fischer Titration (AOCS Method Tb 264). Undiluted basis. c By any appropriate conventional viscosimeter, or by AOCS Bubble Time Method Tq 1A-64, assuming density to be unity. Fluid lecithin having a viscosity less than 7,500 centipoises may be considered a premium grade. d Using Precision cone 73525, Penetrometer 73510; sample conditioned 24 hours at 25 C.
compounded with ingredients for making it more compatible in a particular system. Common additives include special oils, polysorbates, monoglycerides and modied monoglycerides, lanolin derivatives, solvents, plasticizers, or other surfactants. These are added either to the wet gums prior to drying or are blended with dry uid lecithin at elevated temperatures (7, 58). Modied lecithins. Lecithins may be modied chemically, e.g., hydrogenation, hydroxylation, acetylation, and by enzymatic hydrolysis, to produce products with improved heat resistance, emulsifying properties, and increased dispersibility in aqueous systems (7, 58, 59). One of the more important products is hydroxylated lecithin, which is easily and quickly dispersed in water and, in many instances, has fat-emulsifying properties superior to the natural product. Hydroxylated lecithin is approved for food applications under Title 21 of the Code of Federal Regulations 172.814 (1998) (60). Fractionated and oil-free lecithins. When crude lecithin is further rened by various fractionation methods to selectively separate its components, acetone and ethanol are the most common solvents used. Fractionation of crude lecithin yielding phosphatidylcholine of greater than 90% purity is done commercially. A commercial, nearly oil-free lecithin is prepared by acetone extraction of natural lecithin, which removes all but 24% oil and free fatty acids. Then an optional alcohol fractionation step can separate the oil-free lecithin into an alcohol-soluble lecithin enriched in phosphatidylcholine and an alcohol-insoluble fraction enriched in phosphatidylinositol. The choline fraction is an excellent emulsier for oil-in-water (o/w) emulsions and the inositol fraction for water-in-oil (w/o) emulsions.
376
LECITHINS
O CH2OCR1 O CHOCR2 O CH2O P O CH2CH2N(CH3)3 O Phosphatidylcholine O CH2OCR1 O CHOCR2 O CH2O P O O HO OH OH Phosphatidylinositol OH OH
O CH2OCR1 O CHOCR2 O CH2O P O CH2CH2NH3 O Phosphatidylethanolamine
R1 and R2 = C15C17 Hydrocarbon chains
Figure 1. Three principal components of soybean lecithin (7).
3.3. Structure of Phospholipids in Commercial Lecithins Chemical structures for the most commonly occurring phospholipids in commercial soybean lecithin are shown in Figure 1 (7). PC and PE are cationic and anionic at the same time; that is, they are zwitterions, and thus they can have some buffering action for both bases and acids. PI, however, is a relatively strong acid and, therefore, is anionic. The classes of compounds in commercial lecithin are as follows (31): Phospholipids Anionic Zwitterionic Glycolipids Steryl glucosides Esteried steryl glucosides Galactosyl glycerides
The reader is referred to Horrocks (61) for more specic discussion on the nomenclature and structure of phospholipids. 3.4. Composition Specication ranges, chemical and fatty acid compositions for commercial natural lecithins, along with approximate compositional data for commercially rened lecithin fractions are given in Tables 1619 (8, 6265), respectively.
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TABLE 16. Specications for Commercial Soybean Lecithin (62, 63). Grade Fluid Natural Color Lecithin 62 1 0.3 32 10 150 Fluid Plastic Plastic Fluid Double- Natural Plastic DoubleBleached Bleached Color Bleached Bleached Lecithin Lecithin Lecithin Lecithin Lecithin 62 1 0.3 32 7 150 62 1 0.3 32 4 150 65 1 0.3 30 10 22 65 1 0.3 30 7 22 65 1 0.3 30 4 22
Analysis Acetone insoluble, % min. Moisture, % max.a Benzene insolubles, % max. Acid value, max. Color, Gardner, max.b Viscosity, poises, at 25 C, max. Penetration, max., in mmc
a b
By toluene distillation for 2 hr or less. As a 5% solution in colorless mineral oil. c By specied cone penetrometer test.
Soybean oil contains 1.53.0% phospholipids (71). Crude soybean lecithin has an oil content of about 30%. PC is present at a level of about 16%., PE about 14%, and inositol phospholipids about 12% (7). As can be seen in Table 18 (8), the fatty acid compositions of soybean phospholipids are rich in polyunsaturated fatty acids. Miscellaneous low-level constituents include water, phosphatidic acid, pigments, galactosyl glycerides, various glycolipids, phosphatidylserine, carbohydrates, sterols, and tocopherols. Phosphorus content of crude soybean oil extracted from ours can vary depending on extraction temperature and our moisture (72). 3.5. Chemical/Physical Properties In practice, commercial lecithin products are not marketed by phospholipid content, but rather by a set of unique chemical and physical properties. These properties, as indicated by product specications, must be understood because they are used to characterize specic lecithin types.
TABLE 17. Approximate Chemical Composition of Natural Commercial Soybean Lecithin (64). Fraction Soybean oil Phosphatidylcholine Phosphatidylethanolamine Phosphatidylinositol Phytoglycolipids and other minor phosphatides and constituents Carbohydrates Moisture % 35 16 14 10 17 7 1
378
LECITHINS
TABLE 18. Composition Fatty Acids of Soybean Lecithin (%) (8).

Reference Hilditch and Zaky (50) Rzhekhin et al.a (66) Vijayalakshmi and Raob (67) Daga (68) Daga (69) Rydhag and Wiltonc (70) Rydhag and Wiltond (70)
a b
14:0 1.9 0.3
14:1 Trace 1.2
16:0 11.7 18.1 42.7 26.7 25.5 21.5 18.9
16:1 8.6 7.0
18:0 4.0 3.7 11.7 9.3 10.3 4.3 4.1
18:1 9.8 22.4 17.0 25.1 39.4 7.2 6.8
18:2 18:3 55.0 40.0 20.0 37.0 17.1 60.9 60.8 4.0 5.0 1.6 6.2 6.1 9.2
2022 20:0 Unsaturated 1.4 2.3 5.5 6.2
Also 2.3% unidentied. CHCl3/CH3OH extraction. c Acetone-precipitated. d Granulated.
Commercial soybean lecithin, being a complex mixture of polar lipids, performs as a wetting and emulsifying agent. Stanley (1) states that in heterogeneous systems such as oil and water, the phospholipid molecules arrange themselves in monomolecular layers with the fatty acid portion facing the oil surface and the phosphoric acid portion facing the water surface. The arrangement lowers the interfacial tension of the oilwater boundaries with resultant benets such as rapid wetting, lowering of viscosity, and better and more stable emulsions or dispersions. Soybean lecithin is soluble in aliphatic and aromatic hydrocarbon solvents, partially soluble in ethyl alcohol (principally the inositol fraction), and practically insoluble in acetone (less than 0.003% weight/volume at 5 C) and in water (73). When mixed with water, soybean lecithin hydrates to a thick emulsion that can be thinned with water to almost any desired dilution. Acetone does dissolve readily in lecithin and will form a thin, uniform imbibition as long as the quantity of acetone is insufcient to precipitate the phospholipids. Lecithin is soluble in
TABLE 19. Approximate Composition of Commercially Rened Lecithin Fractions (%) (65). Fraction Phosphatidylcholine Cephalin Inositol and other phosphatides, including glycolipids Soybean oil Other constituentsa Emulsion type favored
a
Oil-Free Lecithin 29 29 32
Alcohol-Soluble Lecithin 60 30 2
Alcohol-Insoluble Lecithin 4 29 55
3 7 Either oil-in-water or water-in-oil
4 4 Oil-in-water
4 8 Water-in-oil
Includes sucrose, rafnose, stachyose, and about 1% moisture.
379
mineral oils and fatty acids, and practically insoluble in cold vegetable and animal oils, but it will dissolve in hot oils. Soybean lecithin has a brown to light yellow color, depending on the conditions used in its manufacture and the degree of bleaching. Identication and characterization of phospholipids. For additional information on various techniques and methods used in the identication and characterization of phospholipids in general, the reader is referred to Kramer et al. (74). Fractionation and purication of lecithin. Because of space limitations, it is not possible to discuss fractionation and purication processes for all vegetable and animal lecithins in this chapter. The reader is referred to Schneider (14) who described the fractionation and purication of various vegetable lecithins and those from egg in considerable detail. Small-scale fractionation processes may include separation of neutral oil and polar lipids (deoiling) including the use of acetone; the adsorption of a hexane solution of lecithin on a silica column; separating neutral and polar lipids from a hexane solution with the aid of membranes; treatment of lipid mixtures with supercritical gases or gas mixtures, e.g., carbon dioxide or propane carbon dioxide; fractionation of neutral oil containing lecithins by solvent treatment, e.g., aqueous methanol, ethanol, and propanol; fractionation of de-oiled lecithins by solvent treatment, e.g., ethanol; solvent treatment after chemical modication, e.g., acylation prior to acetone de-oiling; precipitation methods, e.g., salt; ultraltration methods; and many chromatographic processes, mainly for polar lipid separation but also for separation focused on the degree of unsaturation. The commercial manufacture of fractionated soybean lecithins will be covered later in this chapter. Synthesis and modication of phospholipids. For an excellent review of the synthesis and modication of phospholipids, the reader is referred to Ghyczy (75). According to the review, depending on the starting material used, there are two ways to synthesize phospholipids. In the partial synthesis, phospholipids are isolated from natural sources and the individual constituents, fatty acids, and head groups are exchanged to obtain a certain phospholipid. In the total synthesis, phospholipids are produced from fully synthesized, available, basic molecules that were not obtained from phospholipids. Both methods are of importance today because each manufacturing process has certain advantages with regard to denite products and elds of application. The partial synthesis may involve several synthetic steps, depending on the basic phospholipid used, the enzyme, the nal product desired, and the type and position of the phospholipid constituents to be exchanged. For example, the partial synthesis may avail of the reacylation of 3-sn-glycerophosphorylcholine (GPC). Alternatively, by a deacylation step, GPC can be obtained from PC in soybean lecithin (75). Partial synthesis may include synthesizing PC with mixed fatty acids from GPC as the starting material. Other types of phospholipids yield compounds, after deacylation, which have certain functional groups, e.g., amino groups from PE. PI can be manufactured by using the enzyme PL-D, using phospholipids from soy lecithin (75).
380
LECITHINS
The most suitable starting materials, for the total synthesis of phospholipids, are optically active derivatives from glycerol, called chiral C3 building blocks. In addition to proper conguration, an early differentiation of the hydroxyl groups is also necessary to shorten the process of synthesis (75). Transesterication has also been investigated as a means for preparing polyunsaturated phospholipids from soy phospholipids (76). Specications for soybean lecithin. The following methods are routinely used for determining whether the specications for given products are met: AI. The amount of acetone-insoluble matter (%AI) is a measure of the polar material found in lecithin. In soybean lecithin, the acetone-insolubles typically contain 7075% phospholipids, with the remaining portion consisting of glycolipids, carbohydrates, and a small amount of residual triglyceride oil. The amount of acetone-insoluble matter is determined by the AOCS Ofcial Method Ja-4-46 (77). AV. The AV is the number of milligrams of potassium hydroxide necessary to neutralize the acids in 1 g of lecithin (62). A products AV is representative of the acidity contributed by both the phospholipids and any free fatty acids that are present. The AV is usually not indicative of pH, as the chemical nature of the phospholipid imparts buffering qualities to most systems. Lecithins typically exhibit a neutral pH value in aqueous media. An AV above 36 may indicate degradation of the lecithin because of improper processing or substandard quality soybeans. AV should not be confused with free fatty acid content, pH, or mineral acids. The correct method to assay for free fatty acids is to titrate only the acetone-soluble portion of the lecithin, whereby any contribution from the phospholipids in the acetone-insoluble portion is eliminated. AV is determined by the AOCS Ofcial Method Ja 6-55 (77). Moisture. The water content of lecithin products is usually less than 1.0%. As a consequence of lecithins essentially moisture-free state, lecithin products have very low water activity and do not adversely contribute to the microbiological prole of most food systems. Most lecithin products are preserved well in storage. Higher moisture levels usually indicate a greater potential for spoilage or chemical degradation. Moisture is determined by AOCS Ofcial Method Ja 2b-87 (77). A less accurate moisture level can also be determined by azeotropic toluene distillation (AOCS Ofcial Method Ja 2-46) (77). One cannot determine lecithin moisture by vacuum oven methods. These methods are known to degrade lecithin products and yield false moisture levels. HI. The level of HI matter is one measure of the purity of lecithin products. HI matter usually consists of residual ber, but also particulate contaminants that may be introduced during processing (e.g., lter aids). The level of HI matter in crude lecithin should never exceed 0.3% and rarely exceeds 0.1%. HI matter in lecithin is detrimental to clarity and use in specic applications. HI is measured by an ofcial Food Chemicals Codex (FCC) (1996) method (54) or by AOCS Ofcial Method Ja 3-87 (77).
381
Color. Commercial liquid lecithins vary in color from light honey to dark brown (62). De-oiled lecithins are typically a shade of yellow. Historically, lecithins have been color graded as unbleached, single-bleached, and double-bleached. The color of lecithin is commonly determined with the use of a GardnerHellige Varnish Comparator, or simply Gardner Liquid Color Standards. The color of various lecithin products is generally in the range of Gardner 918 in an undiluted form (AOCS Ofcial Method Ja 9-87) (77). Other physical/chemical properties and quality criteria. Consistency. Lecithins are available in both uid and plastic (solid) forms. Fluid lecithins generally follow Newtonian ow characteristics. The viscosity prole of lecithins is a complex function of acetone-insoluble content, moisture, mineral content, acid value, and the combined effects of assorted additives such as vegetable oils and surfactants. Generally, higher AI and/or moisture content yields higher viscosity, whereas an increased AV often decreases viscosity. Certain divalent minerals, such as calcium and others, can also adjust the viscosity level. Clarity. In some soy processing plants, high levels of HI may partition with the lecithin gums on separation from the oil. This lipid-insoluble material can cause haziness in uid lecithins. With modern miscella and oil ltration techniques, lecithins with very low HI contents can be produced. Consequently, modern lecithins are clear. Additionally, moisture can also contribute to lack of clarity. Generally, moisture levels over 1% can cause haziness. Besides being an aesthetic problem, if haziness is caused by HI material, it can result in sediment over time; solid particles may appear on the bottom of an otherwise clear liquid product containing lecithin. For a more detailed review of industrial methods of analysis, the reader is referred to Lantz (62). A review of traditional and novel approaches to the analysis of plant phospholipids has been prepared by Marmer (78). Ackman (79) has reviewed the early developments and practical applications of GLC analysis. Modern phospholipid analysis is typically accomplished by high-performance liquid chromatography (HPLC) methods (80) or by nuclear magnetic resonance (NMR) techniques (81). Chemistry and reactivity of phospholipids. The chemistry of the phospholipids is generally that of their ester linkages, unsaturated fatty acids, and other reactive groups. Most of the applicable reactions of organic chemistry have been employed in their study (82). Baer and Kates (83), Brockerhoff (84), Hanahan (85), Pryde (86), Scholeld (8, 82), Strickland (87), Verheij (88), and Wittcoff (4) provide major reviews of phospholipid chemistry and reactivity under various conditions. The latter covers hydrolysis, hydrogenolysis, acetolysis, hydroxylation, thermal decomposition, hydrogenation, autoxidation, browning reaction, and other reactions (e.g., bromination and complexing with various substances). Lecithin interaction with other food ingredients. Food systems are usually heterogeneous mixes of components, in which the interaction of ingredient classes
382
LECITHINS
TABLE 20. Alteration of Lecithin Form/Function (31). Action Decrease viscosity Increase hydrophilic properties Technique Add special diluents Solvent fractionation Chemical modication Enzyme modication Compounding Process controls Oxidative bleaching De-oil Mix with carrier Utility Sprayable Easier handling o/w emulsiers Wetting agents
Reduce color Convert to powder form
Light-colored foods Dry blendable
(e.g., proteins, starches, fats, surfactants) can be important to nished product quality, shelf life, and nutritional value. The most common modications of lecithin and the intended physical/functional alterations are shown in Table 20 (31). The range of physical/functional properties available in commercial lecithins is listed in Table 21 (31). These changes in lecithin allow for the basic lecithin obtained from soybean oil to be converted to various emulsier products having a wide variety of food, feed, and industrial applications. Reviews describing chemical reactions for phospholipid modications intended to obtain specic functionalities include those of Eichberg (89), Hawthorn and Kemp (90), Kuksis (91), Pryde (86), Snyder (92), Strickland (87), and Van Deenen and DeHaas (93). Model studies have given some insight into the mechanism of protein/phospholipid interactions. The interactions of soy globulins and phosphatidylcholine were reported by Kanamoto et al. (94). The results of these studies suggested that high-energy input is necessary to the formation of stable phospholipid/protein complexes. Interacting PC vesicles with 7S and 11S soy globulins, Beckwith (95) demonstrated that the extent of protein/phospholipid interaction was dependent on both the ratio of the reactants and the specic globulin.
TABLE 21. Physical/Functional Properties of Commercial Lecithin (31). Property Viscosity Color HLB pH Flavor/odor Solubility Nonpolar Lower alcohols Glycerine Water Commercial Range of Values 100 centipoise to plastic Light honey to dark amber 212 58 Slightly nutty to moderate bitter, pungent Soluble Partially soluble to soluble Partially soluble to soluble Insoluble to dispersible
383
Chen and Soucie (96) showed that treatment of soy protein isolate with hydroxylated lecithin lowered the isoelectric point, increased electrophoretic mobility, and signicantly increased protein dispersibility and suspension stability. Nielsen (97) investigated the interaction of peroxidized phospholipids with several proteins under N2. His ndings demonstrated a covalent attachment of phospholipids to proteins whose molecular size is increased. The interaction of lecithin with starch can also have great functional signicance in food systems. Not surprisingly, the structure of the lecithins involved determines their reactivity and hence functionality. Hydrolyzed lecithins have been shown to complex with starch, retarding starch crystallization, and thus slowing staling in yeast-raised baked goods (98, 99). The absorption isotherms of several emulsiers to fat and sugar crystals dispersed in oils have been examined (100). Unsaturated monoglycerides and phospholipids cause a decrease in adhesion for all concentrations examined. Phospholipids reduce the adhesion between sugar crystals, resulting in much denser sediments. The inuence of soybean lecithins on the spontaneous solidication of different model fats has been studied in the presence and absence of water (101). Lecithins added to dry fat do not affect crystallization, but in the presence of water, they clearly delay it. Lecithins as antioxidants. The literature is replete with references to the antioxidant properties of lecithins. For example, Pokorny (102) claimed that the addition of soybean phospholipids reduced the rate of autoxidation of sunower oil and prolonged the induction period. Hudson and Ghavani (103) published data showing that the addition of 0.3% dipalmitoyl phosphatidylethanolamine (DPE) to rened soybean oil increased the induction time during Rancimat analysis from 8.8 hours to 19.3 hours. Hildebrand et al. (104), and Jung et al. (105), also published data demonstrating the antioxidant properties of various phospholipids and commercial lecithins. Although lecithins may act as antioxidants in some systems, they also have a strong synergistic effect in combination with other antioxidants. Hudson and Mahgoub (106) found that although 98% PC and 98% PE acted as pro-oxidants in lard model systems, in combination with D-alpha-tocopherol and/or quercetin, they acted as powerful synergists for antioxidant activity. Hudson and Lewis (107) conrmed that PE and PC alone have negligible activity as antioxidants in lard, but they showed that PE is a very effective synergist when used in combination with polyhydroxy avonoids at levels of 0.1% or more. Hamilton et al. (108) stated that ascorbyl palmitate/lecithin and lecithin/tocopherol binary mixtures were strongly synergistic in delaying peroxidation in sh oils, with ternary blends of ascorbyl palmitate, lecithin, and tocopherols providing the greatest protection against autoxidation. Various mechanisms have been proposed for the mode of action of phospholipids as antioxidants or antioxidant synergists, including chelation of pro-oxidant metals (106, 108), the release of protons that bring about the rapid decomposition of hydroperoxides without generating free radicals (107), and the regeneration of
384
LECITHINS
the primary antioxidant (107, 108). Saito and Ishihara (109) provide evidence for the mechanism of action behind the antioxidant activity of PE and PC in puried sardine oil. They attributed the antioxidant activity to the basicity of the amino portion of these molecules. The base donates a pair of electrons to an oxygen of a hydroperoxide molecule, binds to this oxygen, and degrades the hydroperoxide to an alcohol. McLean et al. (110) have examined the role of lipid structure in the activation of phospholipase A2 by peroxidized phospholipids. Results showed that the increase in rate of hydrolysis of peroxidized phospholipid substrates catalyzed by phospholipase A2 is largely because of a preference for peroxidized phospholipid molecules as substrates, and that peroxidation of the host lipid does not signicantly increase the rate of hydrolysis of nonoxidized lipids. The reader is referred to Pryde (86) for a more thorough discussion on the kinetics of autoxidation of phospholipids; their forming metal ion, iodine, and other complexes; halogen addition; and their behavior during hydration, hydrogenation (with heterogeneous and homogeneous catalysts), hydrolysis and alcoholysis, hydroxylation, oxidation, radical, and other reactions. 4. MANUFACTURE, FRACTIONATION, AND PURIFICATION OF LECITHINS 4.1. Manufacture of Crude Lecithin Commercial soybean lecithin is obtained in the traditional manner by hexane extraction of the crude oil from the soybean ake and then water degumming the oil to yield a viscous uid product. The degumming of soybean oil is not an industry-wide practice. Brian (111) estimated that only about one-third of the soybean oil produced in the United States needs to be degummed to meet the U.S. needs for soybean lecithin production. Removal of all phospholipids and gums is a necessary part of the steam-rening process. However, this process has not yet been developed to the point where it can produce rened soybean oil that meets U.S. competitive requirements. Studies have been carried out to fulll this objective (112, 113). Based on a series of samples obtained from commercial processors, degumming of the oil from undamaged soybeans removed 79% to 98% of the phosphorus. Phosphorus content of the oil was lowered from 500 to 900 ppm in the crude to 12 to 170 ppm in the degummed oil (112). Water-degummed oil from damaged beans may have an abnormally high phosphorus level, and degumming these oils poses a difcult problem. Oil degumming. All stages of oilseed processing affect the quality of soy lecithin. Prior to degumming, the seed quality, cleaning of the beans, extraction of the oil, and the handling of the miscella and crude oil all have an important role in making a good quality lecithin. Hexane extraction removes about 50% of phospholipids from the meal (114). The presence of nes in the miscella is undesirable for making lecithin and should
MANUFACTURE, FRACTIONATION, AND PURIFICATION OF LECITHINS
385
be kept to a minimum (0.2% or less), and the crude miscella coming from the extractor should be ltered. Several miscella ltration methods are available. The crude oil also can be ltered to produce lecithin. The method of hexane removal from the miscella is also very important in that dark colors in lecithin are believed to be caused by an aldehydeamine reaction largely formed by heating the oil during the solvent stripping operation. Most U.S. processors employ a dual-stage evaporator followed by a low-pressure stripping system (115). Hydration causes most of the phospholipids and gums present in a crude oil to become insoluble in the oil. Such hydration can come about from water added to the oil in the degumming step or from moisture picked up from the air by the oil during storage (116). Current commercial practices. If the oil is recovered by solvent (hexane) extraction, some mills allow a portion of the steam blown through the oil for removal of last traces of solvent to condense and thus hydrate the gums. Sometimes operators nd it difcult to closely control the moisture addition with direct steam and prefer to add hot water in controlled amounts. Crude oil from which the lecithin is to be recovered is usually ltered prior to degumming to remove residual meal nes and seed fragments. Although more difcult to accomplish, dry lecithin can also be ltered. Careful ltration results in a highly claried lecithin with little or no residual hexane insoluble matter (33). Brian (111) describes two methods of miscella ltration, one with and one without lter aids, but both result in a lecithin that still remains somewhat cloudy. Highly claried lecithin products can be obtained only by ltering the crude oil, usually with the aid of vertical leaf or plate and frame lters, wherein the dry oil is heated to 82 C and 0.1% lter aid is added (33). Two principal degumming methods are employed: batch and continuous. The batch degumming process is shown in Figure 2 (115). A ow sheet for the continuous degumming of soybean oil and production of soybean lecithin is shown in
Figure 2. Batch degumming system for lecithin production (115).
386
LECITHINS
Figure 3. Flowsheet for degumming soybean oil and crude lecithin production (111).
Figure 3 (111). Recommended conditions for degumming of crude vegetable oils can vary greatly as shown in Table 22 (111, 117124). In a batch degumming system, crude soybean oil is typically heated to about 70 C in a large tank tted with an agitator. Water is added (about 2% by volume), and the hydrated oil is agitated for up to one hour. The hydration of soybean
TABLE 22. Degumming Conditions from the Literature (8, 118). Parameter Water Quantity 75% wt of gums 12.5% 23% 3% 1% 2% Equal to wt gums 25% 3249 C 5070 C 6575 C 70 C 95 C Vigorous Mechanical agitation 3060 min. 1015 min. Reference Crauer (119) Brian (111) Van Niewenhuyzen (59) Bernardini (121) Norris (122) Carr (123) Braae (117) Andersen (124) Norris (122) Van Niewenhuyzen (59) Bernardini (121) Carr (123) Andersen (124) Bernardini (121) Carr (123) Carr (123) Braae (117)
Temperature
Agitation Time
387
phospholipids proceeds rapidly, and for all practical purposes, 15 minutes is adequate for batch systems. The hydrated gums or lecithin emulsion are then removed by continuous centrifugation. This step is then followed by drying in a batch or lm dryer. The gums are usually dried to a moisture content of less than 1%, typically 0.30.75% (3, 33). In continuous systems, preheated crude oil (80 C) and water are metered into an in-dwell pipeline agitator, or a large agitated tank, and held only for a short period. In both systems, the oil is then pumped to a centrifuge for separation of the lecithin sludge from the oil (33, 118, 125126). Water with a low concentration of calcium and magnesium is preferred (115). In commercial processes, the amount of degumming water required (1.52.0%) is roughly equivalent to the phospholipid content of the crude oil (118). Too little water will result in a dark, viscous gums phase and hazy degummed oil that contains unhydrated phospholipids. Too much water will result in a three-phase system consisting of free water, a uid yellowish-brown gums phase, and a hazy degummed oil phase after centrifugal separation (33, 118, 119, 126). Flider (33) points out that the AI content of the gums is enhanced by raising the temperature of degumming. For example, degumming at 40 C yielded crude lecithin containing 6365% AI, whereas at 60 C, the yield increased to 6875%. Although above 60 C some darkening of the lecithin may occur, a higher temperature (e.g., 7080 C) produces a more consistent lecithin AI on a day-to-day basis. Agitation is an important factor in batch degumming. The AI content of the crude gums increases with agitation, presumably because at low agitation rates, more oil is entrained in the gums (118). Three types of centrifuges are in common use for oillecithin separations as described by Podbielniak et al. (127) and Sullivan (128): tubular bowl, disk bowl, and concentric plate. All of these centrifuges can be hermetically sealed, thereby protecting the process streams from the harmful effects of air (115). The newer disk-type centrifuges have a solid ejecting feature that allows the discharge of solid impurities on a regular basis. These centrifuges are also equipped with a discharge control valve that can be adjusted to vary the AI content of the gum or sludge phase. Because the hermetic centrifuges are capable of delivering sludge of lower oil content than the conventional open bowl-types, more neutral oil is available for rening, and lecithin with higher AI contents can be obtained (115). The efciency of commercial degumming operations is summarized in Table 23 (112). Removal of phospholipids in commercial operation ranges from 75% to 96%, with an average of 87% (112). For more specic information on the parameters of the degumming operation, the reader is referred to Brekke (129), Flider (33), List (115), List and Erickson (130), and List et al. (118). Novel degumming approaches. List et al. (131) reported on a hexane-extracted crude soybean oil that had been degummed in a reactor by countercurrently contacting the oil with supercritical CO2 at 10,000 psi at 60 C. The phosphorus content of the crude oil was reduced from 620 ppm to less than 2 ppm. Degummed feedstocks were fed, without further processing (i.e., bleaching),
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TABLE 23. Removal of Phosphorus by Commercial Degumming of Crude Soybean Oila (112). Phosphorus (ppm) Processor
A B C D E
Crude
733 683 867 684 711 588 615 713 623 580
Degummed
167 80 53 63 89 105 40 12 102 141
Phosphorus Removed (%)

77.2 88.3 93.8 90.7 87.5 82.1 93.4 98.4 83.6 75.8
Mean (%)
82.8 92.3 84.8 95.9 79.7
Plants located in Illinois, Iowa, Minnesota, Arkansas, and North Carolina. Two samples from each plant separated by at least 2 weeks.
directly to a batch physical rening step consisting of simultaneous deacidication deodorization (1 h at 260 C, 13 mm Hg) with and without 100 ppm citric acid. Flavor evaluation showed that the supercritical CO2- processed oil had the same avor scores, both initially and after 60 days of aging and light exposure tests, as the commercially renedbleached soybean oil control, deodorized under the same conditions. These results would indicate that bleaching with adsorbent clays may be eliminated by a supercritical CO2 countercurrent processing step. As a result of the considerable heat-bleaching that takes place during deacidication deodorization, colors of salad oils produced under the above conditions typically ran 3Y > 0.1R. A degumming process has been described by Dijkstra (132), wherein the washing water is recycled to the oil feed and used to dilute concentrated alkali. This process does not generate an aqueous efuent and can be used for both acid and alkali rening, thus allowing reners to change gradually from alkali rening to physical rening. A novel degumming process has been described by Jirjis et al. (133), wherein vegetable oil miscella is fed to a conditioned polymeric microltration membrane to produce a permeate stream containing decreased weight percentages of phospholipids, and a retentate stream containing increased weight percentages of phospholipids. The membrane is specically conditioned for the removal of phospholipids by treating with intermediate solvents, and it has an average pore size of about 0.1 to about 2 microns. Both product streams are then desolventized using traditional methods. The resulting vegetable oil stream is claimed to have a phosphorus level of less than 30 ppm. Bleaching. The color of soybean lecithin can be attributed to many factors: carotenoids, melanoids, and porphyrins (125, 134) in the product, age, quality of the source material, pretreatment prior to crushing of soybeans, thickness of akes and
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temperature during extraction, conditions during degumming, and lecithin processing conditions (33). Natural lecithin often has a brown color, although with advanced soybean processing technology, the color may approximate that of unbleached soybean oil (65). Traditionally, one referred to an unbleached product as one that has not been treated with bleach. A single-bleached product was treated with only one type of bleach (usually hydrogen peroxide), whereas a double-bleached product usually was treated with two types of bleach (i.e., hydrogen peroxide and benzoyl peroxide). Although these grades continue to exist by name, the bleaching methods used to manufacture them are no longer uniform. High-quality, relatively light-colored, unbleached lecithins are now available through modern manufacturing practices. Additionally, todays double-bleached product may have been treated with only a small quantity of one type of bleaching agent. Products are presently bleached to a color specication only, regardless of bleaching techniques or quantity (7, 33). Lecithin may also be bleached by replacing a portion of the degumming water with peroxide and carrying out the bleaching and degumming simultaneously. This method is less efcient, however, than bleaching the gums directly (33). Although the specications by the National Oilseed Processors Association (NOPA) Year Book and Trading Rules, 1998-1999 (135) recognizes color grades based on unbleached, bleached, and double-bleached lecithins, this nomenclature is technically incorrect as it is more descriptive of the process rather than of the product. From a regulatory point, bleached products are traditionally grouped with the unbleached forms of crude lecithin. No distinction is made between the bleached and unbleached forms as far as Generally Recognized as Safe (GRAS) status is concerned (136). Laboratory studies by List et al. (118) have shown that with 1% hydrogen peroxide, complete bleaching occurs in 30 minutes at 60 C; in commercial operations, where less efcient agitation occurs, up to 1 hour is required (33). Bleaching with peroxides involves oxidation of the carotenes and the other color bodies within the lecithin. There is no evidence that bleaching with either hydrogen peroxide or benzoyl peroxide functionally modies lecithins. Bleaching seems only to affect the pigments, which are not functional constituents. Scholeld and Dutton (134) reported that although hydrogen peroxide destroys all color bodies to some extent, its greatest effect is on lutein, the principle pigment (75%) found in soybean lecithin. The color of most lecithin products will darken on prolonged heating. Color stability can be achieved, however, by avoiding exposure of lecithin to temperatures over 60 C. There are now heat-resistant lecithins on the market that maintain their light color for extended periods even at elevated temperatures (7). Drying. After centrifugal separation and bleaching, the gums (containing 25 50% moisture) are dried (to 0.30.75%) as soon as possible to prevent microbial activity. The drying operation serves not only to remove moisture, but also to lower the peroxide value. Peroxide destruction is rapid at or near temperatures of 100 C.
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LECITHINS
Two types of dryers are commonly used throughout the industry. The sludge can be dried in batch dryers operating under vacuum (2060 mm Hg) and equipped with rotating, ball-shaped coils through which warm water is circulated to maintain the lecithin at 6070 C (140158 F). Although these dryers require longer residence times (35 hrs), they are popular among European processors because less charring is apt to occur (137). In domestic lecithin processing plants, continuous, agitated lm evaporators are the standard equipment. Evaporators operating on a vertical or horizontal axis are available. Film evaporators operate at temperatures ranging from 80 to 105 C, with vacuum of 25300 mm Hg. Residence times are very short, usually 1 to 2 minutes. Dry lecithin is highly viscous, and the viscosity increases drastically and then falls off as the moisture content increases. Comparative conditions used for drying lecithin in the two types of drying apparatus are given in Table 24 (59, 130). Because of the sensitivity of lecithin to heat, drying conditions are critical and the product should be cooled to 5560 C before additional processing, and/or to 3550 C before storage and packing (33). Shelf life of dried lecithin products in suitable containers is more than 1 year at 21 C (3). Fluidizing. Fluidizing additives such as soybean oil, fatty acids, or calcium chloride can be added to adjust the viscosity. The viscosity of dried crude lecithin can also be decreased by warming it to a maximum of 60 C. The dried crude lecithin product (unbleached or bleached) can also be used to prepare a variety of grades of lecithin by removing the oil to increase the phospholipid content, or by separating the oil-free lecithin into alcohol-soluble and alcohol-insoluble fractions. Besides calcium chloride, the viscosity of lecithin products may also be modied by the addition of other mono- and divalent ions, phosphoric acid, or acetic anhydride. Monovalent ions, such as sodium or potassium, are attracted to the negatively charged base groups, which tend to increase the crystalline order, thereby increasing viscosity. On the other hand, divalent calcium and magnesium reduce the crystalline order and thus reduce viscosity. These techniques are used to produce uid lecithins containing 6670% AI without the addition of fatty acids (33). In commercial practice, uidized lecithins usually are made by calcium chloride addition to the gums, by the inclusion of fatty acids or vegetable oil, or with the aid of special proprietary diluents.
TABLE 24. Average Process Conditions for Drying Lecithin Sludgea (59, 129). Process Variable Temperature C F Residence time, min. Absolute pressure, mm Hg
a b
Batch Dryer, Bollman Typeb 6080 140176 180240 2060
Continuous, Agitated-Film Evaporator 8095 176203 1 2 50300
Starting product: sludge with 50% moisture. End product: lecithin with less than 1% moisture. Vacuum dryer with rotating, ball-shaped coils heated with warm water.
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Fluidization with phosphoric acid is not recommended because darkening of the product and hydrolysis may occur. Degumming with acetic anhydride results in uidized lecithins possibly because PE is acetylated by the reagent. Nonedible lecithins may be uidized by the addition of acidulated and dried soapstock. Plastic lecithins are available in several forms and are typied by high AI, low AV, high moisture, or their content of certain minerals. One, or a combination of these, can produce a plastic lecithin. Oil-free lecithins are plastic, because of the removal of their nascent oil, i.e., residual soybean oil. They are generally powdered or granular in form. Nonhydratable phospholipids. According to Myers (138), about 90% of the phospholipids are removed from the oil by water degumming. Although most of the remaining phospholipids are removed by alkali neutralization, Braae et al. (139) report that soybean oil and several other types of vegetable oils often contain some phospholipids that are not removed by alkali neutralization and washing. The impact of enzyme activity on the nonhydratable phospholipid content of crude soybean oil was investigated by List et al. (140). Evaluation of akes subjected to live steam and whole beans treated by microwave heating to inactivate phospholipase D suggests that heat, moisture, and enzyme activity are important factors contributing to the formation of nonhydratable phospholipids in extracted crude oils. Approximately 810 minutes of microwave heating is required to completely destroy enzymatic activity. List et al. (141) later found that four interrelated factors promote nonhydratable phospholipids (NHP): (1) moisture content of beans or akes entering the extraction plant; (2) phospholipase D activity; (3) heat applied to beans or akes prior to and during extraction; and (4) disruption of the cellular structure by cracking and/or aking. Thus, NHP formation can be minimized by control of the moisture of beans and/or akes entering the extraction process, inactivation of the phospholipase D enzyme, and optimizing temperatures during the conditioning of the cracked beans or akes (141). In a subsequent study, List and Mounts (142) indicated that the adverse effects of storage conditions, excessive moisture levels, and elevated temperatures cannot be completely overcome by inactivation of phospholipase D prior to solvent extraction of the akes. Zhang et al. (143) reported the effects of an expander process on the phospholipids in soybean oil by comparing the differences in phospholipid compositions of the oils and the lecithins produced from expander and conventional processes by HPLC. The phosphorus content indicated that the expander-processed oil contained more phosphorus (985 ppm) than the conventionally processed oil (840 ppm). However, the phospholipids in the expander-processed oil were more hydratable than those in the conventionally processed oil. After degumming, the phosphorus content in the expander-processed oil and conventionally processed oil were reduced by 93.2% and 78.6%, respectively. The expander-processed lecithin contained 74.3% AI matter, and the conventionally processed lecithin contained 65.8%. There was also more phosphatidylcholine in the expander-processed lecithin (39.8%,
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LECITHINS
based on AI) than in the conventionally processed lecithin (34.2%), and the phosphatidylethanolamine was lower (12.4% vs. 18.1%) and the phosphatidylinositol contents were almost the same. Braae (144) believes that the nonhydratable phospholipids are present as calcium and magnesium salts. These phospholipids can have a deleterious effect on oil quality. They can be removed either by treatment of the oil (at 7090 C) with a small quantity of concentrated phosphoric acid (0.25%) ahead of the neutralization step (145) or by rening the oil with a mixture of lye and sodium carbonate. The phosphoric acid pretreatment apparently also aids in the removal of deleterious iron compounds in the subsequent processing of the oil, i.e., caustic rening, bleaching, and deodorizing of the oil (113). On the other hand, although such pretreatment aids in the lowering of renery losses and results in low phosphorus and iron content in the degummed oil, the resulting lecithin is dark and low in acetoneinsolubles (33). The use of acetic anhydride as a degumming adjunct has been described by Hayes and Wolff (146148) and Myers (138). In this process, 0.1 wt % of acetic anhydride is mixed for 15 minutes with crude soybean oil (phosphorus 750 ppm) that has been preheated to 60 C (140 F), followed by stirring the mixture for 30 minutes after the addition of 1.5% water. The reaction is completed within minutes. After centrifugation and water washing, the phosphorus content of the oil ranged from 2 to 5 ppm. The advantages claimed for this treatment are thought to be that the caustic rening step can be omitted, and thus the loss of neutral oil because of saponication is eliminated, and higher yields are obtained from both nished deodorized oil and lecithin. On the negative side, the disadvantages found were that equipment and piping must be constructed of type 316 stainless steel to handle the corrosive materials; more care is required in deodorization of the oil; and the process will not produce a satisfactory product from highly colored vegetable oil such as corn and cottonseed oils, nor from some lots of soybean oil (130). Also, according to Evans et al. (149), the process removes phosphorus but not iron, one of the metallic pro-oxidants that can give soybean oil a poor avor. Lecithin produced from this process, however, is claimed to be similar to that prepared in the conventional manner. Other degumming agents considered include acetic, oxalic, boric, and nitric acids (150) and surfactants (151). However, none of these are currently used in lecithin manufacture. Ringers (152) obtained good results in a two-step degumming process wherein an edible acid, presumably citric, was used. Soybean oil can also be degummed by heat, but this practice is conned to oils going into industrial uses. Lunde et al. (153) concluded that the sequestering action of fatty oil for metal ions depends at least in part on the oils phospholipid content and reaches a maximum at 0.12 ppm of phosphorus. As a point of information, hexane extracts only about one-half of the phospholipids present in soybeans (1, 114). For further information on the nonhydratable phospholipids, the reader is referred to Hvolby (154), Letan and Yaron (155), and Nielsen (114, 156).
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4.2. Manufacture of Rened-Grade Lecithins Producing high-clarity lecithins. Lecithin destined for certain applications may require more rigorous than usual initial rening conditions. Claried lecithins are carefully ltered in (1) the full miscella, (2) crude oil, and (3) directly as lecithin. As mentioned before, the ltration is carried out on plate and frame or vertical leaf lters with manual or automatic cleaning cycles. Filtration simply removes HI material, producing products of utmost purity and clarity. Such ingredients can be marketed as encapsulated nutritious supplements, as high-purity pharmaceutical adjuncts, and as additives for high-technology applications. Although the dry lecithin can be ltered, many processors prefer to lter the crude oil before degumming (111). Usually, the crude oil is ltered through large plate-and-frame lter presses. If the degumming operation is conducted at a solvent extraction oil mill, then either the miscella, i.e., oil-solvent mixture, or the oil can be ltered. If all of the nes and lter aid are not removed, the dry lecithin will appear cloudy. Brian (111) has made suggestions for the type of pumps, centrifuges, lters, heat exchangers, and drying equipment most suitable for lecithin production. He has also provided useful engineering design data on ltration ow rates for the crude oil, miscella, and dry lecithin, quality of lter aid needed, and the overall heat transfer coefcients for agitated-lm evaporators and shell-and-tube heat exchangers used for heating and cooling the oil. Producing compounded lecithins. Compounded lecithins are special purpose products made by the direct addition and/or blending of functional additives, emulsiers, diluents, surface active agents, and so on. Water-dispersible lecithins may be produced by adding a hydrophilic surfactant (520%) such as polysorbate or ethoxylated monoglycerides. A mixture of lecithin and nonionic surfactants (1020%) has utility in applications where water dispersibility is needed. Blending of partial glycerides and lecithin, followed by spray cooling, results in aked or powdered products (33). When lecithins are diluted with soybean oil or fatty acids, they have a tendency to separate. In such cases, substituting a portion or all of the soybean oil with other oils such as peanut, cottonseed, coconut, or partially hydrogenated soybean oil will increase stability (33). Lecithins may also exhibit synergistic actions with some compounds. Common additives include special oils, polysorbates, mono- or diglycerides, modied monoglycerides, lanolin and lanolin derivatives, solvents, plasticizers, and other surfactants. Producing de-oiled lecithins. De-oiled lecithin represents a special category where high phospholipid content (above 95% AI) is required. When contacted with acetone, phospholipids precipitate as a ne, free-owing powder. After removing the acetone, de-oiled lecithins are dry powders or granules (33). Depending on the type and efciency of the extraction equipment, the acetone/ crude lecithin ratio necessary to achieve a 95% phospholipid product is 1020:1 (v/v). In batch extraction, the tank is charged with acetone prior to crude lecithin
394
LECITHINS
addition. Crude lecithin is then introduced into a crystallizing vessel with agitation until an acetone/crude lecithin volume ratio of ca. 5:1 is achieved. Only the bestquality uid crude lecithin should be used for the preparation of de-oiled lecithins. The mixture is then agitated for 2030 min., after which time the phospholipids are allowed to settle. The triglycerideacetone miscella is then removed and the vessel charged again with fresh acetone for the second extraction. A single batch may be extracted 24 times to obtain the desired phospholipid concentration (95% minimum) (33). In a continuous extraction, crude lecithin and acetone are simultaneously metered into a vessel. Within limits, acetone consumption can be decreased by increasing residence time in the continuous extractor, increasing raw material efciency (33). After extraction, the de-oiled lecithin is recovered by ltration as a cake, containing 2550% acetone. According to Flider (33), the acetone concentration of the cake is critical for optimal granulation. Too little acetone will result in the formation of a high concentration of nes and powder. Too much acetone will result in a salt and pepper effect (i.e., a mixture of coarse and ne particles) caused by agglomeration of the nes and powder during granulation. The nes and powder output is 550% of the total de-oiled material, depending on production conditions (33). After granulation, the remainder of the acetone is removed by drying, preferably in a moving bed, forced-air dryer. Such dryers are preferred over uid-bed dryers because less destruction of the lecithin granules occurs. After drying, the acetone content of the product should be well below 50 ppm, preferably below 25 ppm (33). Flider (33) states that mesityl oxide, through an aldol condensation reaction, may be formed if excess acetone is present. When the lecithin is sufciently dry, however, this is not a problem. The dried de-oiled lecithin is sized by sieving through a series of screens (33). As the tocopherols are removed from the lecithin during the extraction process, the de-oiled lecithin has less oxidative stability than the crude product. Also, the surface/volume ratio of the de-oiled lecithin contributes to reduced stability. Mixed soy tocopherols are usually added back at a level of 500 ppm to prevent this. A small percent of an anticaking agent may also be added to ensure that the product remains free-owing. A free-owing de-oiled lecithin can be easily added to other products (33). When compared with crude lecithin, oil-free lecithin is more hydrophilic and seems to have better emulsifying activity than its AI alone would suggest. The removal of odor/avor components with the oil also produces blander lecithins (7). Rened de-oiled lecithin can also be blended with carriers such as cocoa butter, hard butters, medium-chain triglycerides, or other diluents to obtain products with more functionality and different physical characteristics. Up to 40% phospholipids may be incorporated in these carriers without the use of solvents. These products are usually stabilized against autoxidation by the addition of antioxidants (33). De-oiled lecithin should be packaged as soon as possible to prevent moisture
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absorption. For more specic details on various aspects of de-oiled lecithins, the reader is referred to Flider (33). Novel de-oiling approaches. A novel de-oiling process has been described by Hutton and Guymon (157) wherein a mixture of crude phospholipids and hexane is fed to a polyvinylidine membrane to produce a permeate stream containing triglycerides and hexane, and a retentate stream containing phospholipids (35 40%) and hexane (6065%). The membrane has a molecular weight cutoff of 10,000 50,000 daltons. The permeate stream is then desolventized using traditional methods. Bleaching earth is added to the retentate stream for color removal at a rate of 58% of the phospholipid mass portion of the stream. The bleaching earth is then ltered out of the mixture. Antioxidants in the form of mixed tocopherols are added to the phospholipid/ hexane mixture. The phospholipids are then desolventized through the use of a drum desolventizer followed by a uid bed dryer. Solvent residuals in the dried product are less than 5 ppm. The dried akes are placed in storage bins. From there, the akes are ground into powder and then agglomerated into granules. The acetoneinsoluble content of the nished product is claimed to be in the range of 9099.9%. Another novel de-oiling process has been described by Wendel (158) wherein supercritical gases are used to produce de-oiled lecithin. The crude lecithin is fed into a column where the supercritical gas mixture of propane and carbon dioxide ows at a pressure of 80 bar and temperature between 40% and 55 C. This uid then goes to a regeneration column where the temperature is increased to 75 C, and the lecithin component precipitates and falls to the bottom of the column. As the lecithin falls, it encounters pure supercritical extraction uid and the oil component is extracted. Oil-rich solvent leaves the top of the column. Through pressure and temperature changes, the lecithin and the oil are precipitated out of their respective streams and continuously removed from the process ow. The oil-free, lecithin-free solvent is returned to the column for reuse. Producing modied lecithins. The chemistry of lecithin has been reviewed by Pryde (86) and by Wittcoff (4). Schmidt and Orthoefer (58) have discussed the manufacture and use of modied lecithin products. The latter class is represented by chemically or enzymatically modied products that are commercially available in both uid and de-oiled forms. The traditional approach to the modication of phospholipid properties is by fractionation, isolation, and purication of a single component. Functions of phospholipid mixtures are also modied by partial chemical or enzymatic hydrolysis, acetylation, hydrogenation, and hydroxylation (5). Crude lecithin contains a number of functional groups that can be successfully hydrolyzed, hydrogenated, hydroxylated, ethoxylated, halogenated, sulfonated, acylated, succinylated, ozonized, and phosphorylated, to name just a few possibilities (1). The only chemically modied food-grade products produced in signicant commercial quantities at the present time are the ones obtained by hydroxylation, acetylation, and enzymatic hydrolysis (58). Hydroxylated or acylated lecithins represent chemical modications to improve the functionality in water-based systems.
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LECITHINS
Acetylated lecithin. Acetylation occurs primarily on the amino group of phosphatidylethanolamine (146148). The amino group of phosphatidylethanolamine, when acetylated, receives an acetyl group on the positively charged portion of the phosphatidylethanolamine, which converts it to a negatively charged lecithin with improved solubility and oil-in-water emulsifying properties (159). Lecithin can be acetylated using acetic anhydride either by adding the reagent prior to degumming or adding it to the wet gums. Acetylated lecithin products are made from natural soy lecithin hydrates by treating them with low levels of acetic anhydride (1.55.0%). Lecithin hydrates are obtained during the degumming of crude soybean oil. After the reaction with acetic anhydride, the resulting product is neutralized with a food-grade alkali to raise the pH to 6.5 to 8.0, depending on the intended application. The amount of acetic anhydride used in the process depends on the level of phospholipids in the gums, and the intended use of the nal product, requiring different degrees of acetylation for optimum functionality. The same is true for the choice of alkali (e.g., sodium hydroxide, calcium hydroxide, etc.) used. The product is then vacuum-dried (lm dryer in a commercial operation) to a nal moisture of less than 1.0% (160). The degree of reaction is measured by determining amine nitrogen content in the resulting product (usually by formol titration). Maximum (100%) acetylation would be indicated by a zero amine nitrogen value, whereas a minimally acetylated commercial product has approximately 1.7-mg amine nitrogen/g content. In a typical commercial operation, the amine nitrogen content is usually in the range of 0.7 to 1.7 mg/g. The total acetone insolubles content of commercial acetylated lecithin products can vary from about 52% to about 97%, the remainder being soybean oil (or another food-grade triglyceride or fatty acid as a natural constituent or added diluent), natural pigments, sterols, and other minor constituents present in crude lecithin from the soybean. The acetylated lecithin meets all the compositional requirements of the U.S. Food Chemicals Codex (54). Typical specications for a minimally and maximally acetylated, liquid product are given below.
Minimally Acetylated, Commercial, Liquid Lecithin Specication Acetone insolubles (%) Moisture (%) Acid value Viscosity (cP at 25 C) Color Peroxide value (meq/kg) Hexane insolubles (%) Amino nitrogen (mg/g) Divalent metals (%) pH
60.0 min.; 64.0 max. 0.75 max. 24 max. 10,000 max. 17 max. 10 max. 0.09 max. 1.65 max. 0.42 min.; 0.48 max. 6.5 min.; 8.0 max.
Maximally Acetylated, Commercial, Liquid, Lecithin Specication Acetone insolubles (%) 53.0 min.; 56.0 max. Moisture (%) 0.75 max.
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Acid value Viscosity (cP at 25 C) Color Peroxide value (meq/kg) HIM (Hexane insolubles 0.8 m-Millipore) Amino nitrogen (mg/g) pH Visual clarity Heat resistance test (Lovibond red) Appearance
36 max. 2,900 max. 12 14 100 max. 100 ppm max. 1.0 max. 7.0 min.; 7.5 max. pass 8.0 max. Clear and brilliant at 25 C
Acetylated lecithins have improved uid properties, improved water dispersibility, and are effective oil-in-water emulsiers for a wide variety of food formulations (56, 58). Moderately and highly acetylated lecithins are resistant to heat and can be repeatedly heated and cooled without darkening. The intended uses for minimally acetylated products are in infant foods, coffee whiteners, meat sauces, and gravies, and for oil-in-water cosmetic emulsions. Moderately and maximally acetylated products are used in cheese sauces, release agents in pumpable and aerosol formulations, and shortenings. The following patents have been issued on the topic of making and using acetylated lecithins: 1. 2. 3. 4. 5. 6. 7. U.S. Pat. 3,301,881 Process of Phosphatide Separation, 1967. U.S. Pat. 3,359,201 Lecithin Product and Method, 1967. U.S. Pat. 3,499,017 Alkaline-Hydrolyzed Phosphatides, 1970. U.S. Pat. 3,823,170 Phosphatides, 1974. U.S. Pat. 3,928,056 Pan Release Product and Process, 1975. U.S. Pat. 3,962,292 Phosphatide Preparation Process, 1976. U.S. Pat. 4,479,977 Method of Preparing Heat-Resistant Lecithin Release Agent, 1984.
Hydroxylated lecithin. Hydrogen peroxide, in addition to bleaching, can also hydroxylate lecithin. Hydroxylation imparts hydrophilic properties, improves moisture retention, and contributes to the formation of stable oil-in-water emulsions. Hydroxylated lecithin is a light-colored product with increased water dispersibility and enhanced oil-in-water emulsifying properties. Hydroxylated lecithin is useful in many applications in which a water-dispersible lecithin is desired. It is especially useful in baking applications where it can improve the dispersion of fats and retard staling. Hydroxylation of lecithin is carried out by the reaction of crude lecithin with hydrogen peroxide and lactic acid or acetic acid. Active sites for peroxidation appear to be double bonds as measured by IV drop and the isolation of dihydroxystearic acid from the reaction mixtures. Hydroxylation is allowed to proceed until
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a 10% reduction in iodine value occurs (115). The ethanolamine group is also modied during hydroxylation (58, 161). Hydrolyzed lecithin. Crude lecithin is readily hydrolyzed in the presence of strong acids or bases. Enzymes can be used for very selective hydrolysis. Prolonged treatment leads to fatty acids, glycerophosphoric acid, or their salts, with mixtures of amino compounds and carbohydrates (4, 115). In a commercial process, it is desirable to control the reaction so that just one of the fatty acids is cleaved from the phospholipid molecule. As acid or base hydrolysis is nonspecic and very difcult to control, enzymes are usually preferred for most applications (58). A number of phospholipase enzymes are available (i.e., phospholipase A1 or phospholipase A2). Haas et al. (162) have studied enzymatic phosphatidylcholine hydrolysis in organic solvents by examining selected commercially available lipases. Enzymatic hydrolysis of oat and soy lecithins, and its effect on the functional properties of lecithin, was investigated by Aura et al. (163). The phospholipase used was most effective at low enzyme and substrate concentrations. Partially hydrolyzed lecithins exhibit enhanced oil-in-water emulsifying properties, particularly in the presence of calcium and magnesium ions. They do not lose their emulsifying action in the presence of calcium and magnesium ions as rapidly as do the unmodied types. Enzymatically modied lecithins have been used in calf milk replacement formulations to improve the emulsication and digestibility of fats (56). Enzymatic hydrolysis of the polar head group of a phospholipid molecule can be carried out with phospholipase C and phospholipase D. Phospholipase D is used to exchange the amino head group of phosphatidylcholine with serine to form phosphatidylserine (164). Transesterication. Transesterication allows for the incorporation of free fatty acids into lecithin molecules. Unhydrolyzed lecithin contains two fatty acids, and the fatty acid moiety can be different at the two positions on the phospholipid molecule. The fatty acid composition can have an effect on the stability and functionality of the lecithin. Changes in the fatty acid composition can be done through transesterication (165). Transesterication using lipases can be used for the addition of polyunsaturated fatty acids to lecithin to enhance the essential fatty acid prole, or to improve functionality (166). Hydrogenated lecithin. Lecithin can be hydrogenated to a stearin-like solid that has greater oxidative stability and is less hygroscopic than unmodied lecithin, but it has reduced solubility in the usual solvents. Phospholipids are not hydrogenated as readily as soybean oil, which at lower hydrogenation pressures and temperatures, can be selectively hydrogenated (58). Hydrogenation of lecithin is usually done under conditions to reach iodine values of 1020 in the presence of a nickel or palladium catalyst and a suitable solvent (e.g., ethyl acetate) at 7585 C under 70 atmospheres pressure. Bromine or chlorine also readily adds across double bonds yielding products useful in lubricant formulations. Iodine can be added by warming granular lecithin dissolved in acetic acid in the presence of iodine and magnesium or aluminum catalyst (58).
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Producing fractionated lecithins. Finally, fractionating crude lecithin directly, or after de-oiling, is another way of creating a variety of products with tailor-made functionalities. Alcohol, or mixed solvent fractionation, combined with other techniques, can produce lecithin products that have been greatly enriched in particular phospholipids. Separating the acetone-solubles from crude lecithin increases the amount of phospholipids in the acetone-insoluble fraction by decreasing the amount of triglycerides. Further fractionation can separate the alcohol-soluble phosphatidylcholine from the alcohol-insoluble phosphatidylinositol. Commercial products that are alcoholsoluble contain concentrated phosphatidylcholine (4060%) and only low levels of phosphatidylinositol. The alcohol-insoluble products are enriched in phosphatidylinositol (4060%), whereas their phosphatidylcholine content is greatly reduced. The phosphatidylethanolamine component is approximately equally partitioned between the two fractions. The alcohol-soluble grades tend to be more oil-in-water emulsiers, whereas the alcohol-insoluble grades are more effective in water-in-oil systems (7). The PC/PE ratios of alcohol-fractionated lecithins are largely determined by processing variables such as alcohol polarity, concentration, lecithin/alcohol ratio, temperature, and extraction time (33). By extracting natural lecithin with a PC to PE ratio of 1.2:1 with 90% ethanol, an alcohol-soluble fraction with a PC/PE ratio of 8:1 can be obtained (33, 120). The fractions may be blended with other surfactants or carriers to obtain desired functionality. To obtain individual phospholipids of greater than 5060% purity, some form of selective adsorption process is usually required. Adsorption and distribution chromatography present these options. Treatment of the alcohol-soluble lecithin with alumina yields a fraction very rich in phosphatidylcholine and free of phosphatidylethanolamine and phosphatidylinositol (167). Although these products are available only in very limited quantities for highly specialized markets, products such as a lecithin containing up to 95% PC can be obtained commercially. Storage and handling. Liquid lecithin can be kept for years provided closed containers are used and the temperature does not exceed 2025 C. Bleached products require more careful storage and handling. Color reversion will occur rapidly in bleached products, particularly at elevated temperatures. Decomposition of peroxide is thought to contribute to color reversion in bleached products. In order to prevent this phenomenon, low storage temperatures are recommended (115). Very low temperatures should, however, be avoided when storing liquid lecithin products because physical separation of the phospholipids and oil may occur. Physical separation is more likely to occur in low AI products. When separation does occur, remixing at 4060 C will redisperse the oil and lecithin phases. In bulk handling of lecithin, storage temperatures of 3035 C are acceptable. However, prolonged storage at these temperatures may cause darkening (115). De-oiled granular lecithin can be stored up to 2 years at temperatures below 25 C. If desired, it may be stored in a frozen state at 0 C, but because of its hygroscopic nature, the product should be allowed to come to room temperature before it is exposed to the atmosphere (33).
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5. FOOD-GRADE LECITHIN PRODUCTS, USES 5.1. Functionality Commercial lecithins are multifunctional food ingredients. The combined hydrophilic and lipophilic properties of phospholipid molecules give them surface-active effects in many applications. As surfactants, they can exhibit a variety of functions common to other surfactants while they also have unique functionalities of their own. Commercial lecithin products that were sold many decades ago for applications such as chocolate and confectionery products, margarine, bakery goods, pasta products, textiles, insecticides, and paints are still active today because of their emulsifying, wetting, colloidal, antioxidant, and physiological properties. Lecithins multifunctional properties and its natural status make it an ideal food ingredient. The major applications and functional properties of lecithin products are shown in Table 25 (7).
TABLE 25. Functional Properties (7). Ingredient in Margarine Confections and snack foods Chocolate Caramels Coatings Instant foods Cocoa powders Instant drinks Instant cocoa Instant coffee Protein drinks Dietetic drinks Coffee whiteners Milk replacers Cake mixes Puddings Instant toppings Commercial bakery items Breads Rolls Donuts Cookies Cakes Pasta products Pies Cheese products Pasteurized processed Cheese and cheese food Imitation cheese Function(s) Emulsier, antispattering agent Crystallization control, viscosity control, anti-sticking
Wetting and dispersing agent, emulsier
Crystallization control, emulsier, wetting agent, release agent (internal and external)
Emulsier, release agent
FOOD-GRADE LECITHIN PRODUCTS, USES
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TABLE 25 (Continued ) Ingredient in Meat and poultry processing Meat and poultry glazes and basting compounds Pet foods Bacon Dairy and imitation dairy products Infant, milk formulas Milk and cream replacers Egg replacers Imitation eggs Whipped toppings Ice cream Flavored milks Flavored butters (garlic, etc.) Basting butters Miscellaneous products Peanut spreads Salad products Flavor and color solubilization Packaging aid Polymer package, interior coating Can interior coating Sausage casing coating Stocking net Processing equipment Frying surfaces Extruders Conveyors Broilers Dryers Blenders Evaporators Function(s)
Browning agent, phosphate dispersant Dietary supplement, release agent, emulsier
Emulsier, wetting and dispersing agent, anti-spattering agent, release agent
Crystallization control, emulsier
Release agent, sealant
Internal (in product) and/or external release agent, lubricant
As a variety of methods are available for modifying the emulsifying properties of commercial lecithin, the potential for improved, tailor-made, functional products is unlimited. The main functional properties are emulsication, antispatter, instantizing/wetting/dispersing, release/parting, viscosity modication, and baking applications. These functional characteristics are primarily derived from the chemical structures of lecithins major phospholipids (Figure 1) (7). Phospholipid molecules contain two long-chain fatty acids esteried to glycerol, as well as a phosphodiester bonding a choline, inositol, or ethanolamine group. A phospholipids fatty acid end is nonpolar and thereby lipophilic (or fat loving). Conversely, the phosphodiester, with the above-mentioned constituents, is zwitterionic (or dipolar), which
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explains the hydrophilic (or water loving) properties of this portion of the molecule (65). Because of their charged nature, the phospholipids are susceptible to the ionic environment in which they function. Based on testing in the laboratory, Dashiell (31) suggests that salt concentrations greater than 2%, and pH less than 4, contribute to a detectable loss in lecithin functionality. Similar results have been reported elsewhere (73). The following commercial lecithin modications were described in a publication from Central Soya Co., Inc. (168). 1. The use of oil free lecithins as emulsiers, lubricity enhancing agents, and blending aids. 2. Producing low-viscosity, uid lecithins as wetting, dispersing, and release agents. 3. Hydroxylated lecithins with enhanced emulsication, dispersing, and wetting properties. 4. Highly ltered lecithins for use in health food applications. 5. Special heat-resistant lecithins for release applications. 6. Lecithin/distilled monoglyceride blend for bakery applications. 7. Enzyme-hydrolyzed lecithin for bakery, and emulsication applications. Weete et al. (169) have reported on the improvement of lecithin as an emulsier for water-in-oil emulsions by thermalization. Various forms of lecithins can be heated under certain conditions of time and temperature to greatly improve their properties as emulsiers for water-in-oil emulsions. Viscosity, discontinuous phase-holding capacity, stability, and water retention were greatly enhanced in emulsions containing thermalized lecithins as the emulsier compared with those prepared with corresponding amounts of nonthermalized lecithins. The improved emulsication properties of thermalized lecithins appeared to be, at least in part, because of an increase in diglycerides and free fatty acids resulting from the thermal degradation of phospholipids. Emulsifying properties. One of the major functions of commercial lecithins is to emulsify fats. In an oil:water system, the phospholipid components concentrate at the oil:water interface. The polar, hydrophilic parts of the molecules are directed toward the aqueous phase, and the nonpolar, hydrophobic (or lipophilic) parts are directed toward the oil phase. The concentration of phospholipids at the oil:water interface lowers the surface tension and makes it possible for emulsions to form. Once the emulsion is formed, the phospholipid molecules at the surface of the oil or water droplets act as barriers that prevent the droplets from coalescing, thus stabilizing the emulsion (159). Commercial lecithins are used in both water-in-oil (w/o) and oil-in-water (o/w) emulsions. For w/o emulsions, like margarine or ready-to-use frostings, oil-loving, lipophilic lecithins are typically used. For o/w emulsions, like sauces or infant formulas, water-dispersible, hydrophilic lecithins are typically used (7, 31). The use of
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lecithin in oil-in-water emulsions requires the modication of lecithin to increase its apparent hydrophilicity. The techniques available are somewhat limited for food-grade lecithins. The commonly employed methods for producing waterdispersible lecithins include acetylation, hydroxylation, enzyme-hydrolysis, fractionation, de-oiling, or blending with other hydrophilic emulsiers. The manner in which lecithin is modied to achieve increased hydrophilicity will greatly affect its emulsication properties. Different modications will create lecithin products with different apparent HLB (hydrophile-lipophile balance) values, a term used to convey the approximate degree of water dispersibility (hydrophilicity) of lecithin products (31). The higher its HLB value, the more water dispersible the lecithin product. In o/w emulsions, the type of fat to be emulsied may require a specic type of hydrophilic lecithin for optimum emulsion stability. Dashiell (31) provides a short listing of fat types, and the corresponding class of lecithin found to give the most stable emulsion in model systems of water/fat/ emulsier. Standard-grade (crude) lecithins are excellent water-in-oil emulsiers. However, modied lecithins can function to emulsify either water-in-oil or oil-in-water emulsions, depending on the type of lecithin modication and the specic parameters of the system. These system parameters can include pH, types of components, component ratios, solids content, and others. Unlike crude lecithins, hydroxylated lecithins are stable in acid systems (pH 3.5). Fractionated lecithins can be manufactured for specic emulsion types. As lecithins emulsifying activity is partially dependent on its phospholipid ratio, changing the ratio can alter its emulsifying capabilities (7). Emulsier/stabilizer systems are normally used to make stable food emulsions. Thus, lecithin is generally not called on to handle the entire emulsication, but it works in combination with other emulsiers and stabilizing polymers such as proteins, starches, and gums (31). Lecithin will break up (emulsify) the particles, and a stabilizer (water-soluble polymer, etc.) will hold the particles in a dispersed orientation when a stable emulsion is formed. Marrs et al. (170), showed that a combination of lecithin and carrageenan produced more stable o/w emulsions with corn oil than either the lecithin or carrageenan alone. The emulsifying properties of the lecithin/carrageenan combination was thought to be caused by interactions in the aqueous phase between the negatively charged sulfate ester groups on the carrageenan with the positively charged amino head groups on the PC and PE of the lecithin. This stabilization occurs when the carrageenan component is of the kappa or iota type, both of which form macromolecular networks in the presence of cations. The rate of creaming of an emulsion is governed by Stokes Law (171). Consequently, in an o/w emulsion, fat separation can be delayed by reducing the fat droplet size, by matching the densities of the dispersed and continuous phases, and/or by increasing the viscosity of the continuous phase. The amount of energy applied to the system when the emulsion is created (for example, with a high-pressure homogenizer) determines the initial fat droplet size of the emulsion, and the presence of an emulsier on the surface of the droplets, prevents the dispersed oil
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droplets from coming together and creaming out. The viscosity of the continuous phase can be increased by the addition of gums, starches, or other stabilizers. Dashiell (31) reported that with high levels of good-quality protein present, the selection of a system-specic lecithin (one giving the best emulsion in an oil/emulsier/water system) becomes less important. In fat creaming tests, in fat/water/protein/lecithin emulsions, results showed that with limited protein in a wheystabilized (low-protein) system, more functional lecithins gave a clear advantage. In a casein-stabilized system (containing abundant protein), differences between lecithin products were less dramatic. Agboola et al. (172), showed that the presence of 0.25% of a de-oiled, hydroxylated lecithin, stabilized o/w emulsions formed with whey protein hydrolysate after retorting. Solubilization. Most lecithins can aid in the production of microemulsions, an example being oil-soluble avors in aqueous systems. Although standard-grade lecithins do not disperse in water, many modied or fractionated lecithins are water-dispersible, and they can be used to produce microemulsions. Standard-grade lecithin can be blended with other surfactants (e.g., ethoxylated monoglycerides) to produce synergistic emulsier blends that are also effective in producing microemulsions. Solid particle dispersions (Sols). Many lecithin products are still the best and most effective surfactants for dispersing sols. This seems to be because of lecithins afnity for solidsliquid surface interfaces. Phospholipids seem particularly attracted to particles containing metals and metal salts. Examples of food sols include some liquid chocolates, instant drinks, frosting mixes, pigmented foods, and others. The nonfood applications include paints, inks, and other pigmented coatings. Foams. Rened lecithins have been employed as effective foam control agents. Examples include whipped toppings, ice creams, and many types of candies. Rened lecithin products have also been employed as effective defoaming agents in foams caused by powdered proteins in water. This is an excellent example of the system specicity of lecithin products (7). Wetting/instantizing properties. Lecithin products are effective wetting agents for a wide variety of powdered or granular products. Lecithination of powders for improved wetting, and control of dusting problems, is widely practiced. Instantizing effects can be obtained by including the proper lecithin product in a food formulation. Specic lecithin products that are compatible with the various manufacturing techniques used for instantizing are commercially available. Lecithin products have been formulated to instantize many types of food powders to achieve rapid wetting and dissolution. As powder compositions can vary greatly (from hydrophilic to lipophilic), proper lecithin selection is done on something of an empirical basis (31). Certain general principles apply, however. If a powder is hydrophobic, or contains a signicant amount of surface fat, typically a water-dispersible, hydrophilic lecithin is used to reduce the surface tension between the powder and the water so that the powder wets and disperses easily. If a powder is hydrophilic, like protein concentrates or isolates, typically a lipophilic lecithin is used to control the rate of hydration of the powder so that it wets and disperses without skinning or forming large lumps.
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Manufacturing techniques employed in producing instant products include spray-coating dry powders with uid lecithin products, cospray drying powders with more hydrophilic lecithins such as the oil-free forms, or hydroxylated lecithin, and agglomeration of the powder with an aqueous dispersion of a hydrophilic lecithin. Some types of powders, for example, starches, gums, and chocolate drink mixes, require agglomeration with an aqueous dispersion of lecithin to achieve optimum wettability and dispersibility. Examples of foods that can be instantized with lecithins include cocoa powders, instant drink mixes, powdered coffee whiteners, milk replacers, cake mixes, powdered instant puddings, and instant soups and sauce mixes. Release/parting properties. Lecithin functions as the active ingredient in a wide variety of food-grade release formulations. Products for institutional and retail use are available in aerosol and nonaerosol forms containing from 0.5% to about 15% lecithin (31). Common ingredients in release formulations are as follows (31) (from a Central Soya Co. market survey, 1986). Vegetable oil (all major vegetable oil classes are used) Hydrogenated vegetable oil Mineral oil Lecithin Flour Amorphous silica Articial avor Articial color Beta-carotene Preservatives Antioxidants Antifoams Water Lecithin usage levels in commercial release formulas are limited by a tendency of the lecithin to separate from some oils. The tendency of ordinary lecithins to darken, polymerize, and foul on heated metal baking surfaces also limits their use level in commercial release formulas. Moderately and highly acetylated lecithins, however, are resistant to heat and can be repeatedly heated and cooled without darkening (173). Lecithins can be dissolved in oil, dispersed in water, or used as is, in release applications. Oil-free lecithins can be dry blended into breading, coatings, and spice or seasoning mixes for release of the coated food product from the food-contact surface. In food products that have a high surface area-to-volume ratio, like pancakes or fortune cookies, lecithin can be added directly to the product formulation to achieve release from the cooking/baking surface. Effective release depends on
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LECITHINS
the presence of lecithin between the food and the food contact surface. If this is achieved, the food product should not stick to the food contact surface. Crystallization control. Lecithin can control crystallization in various food systems. In foods containing sugars or fats, the presence of as little as 0.5% lecithin can produce altered crystal sizes and structures that can have positive effects on product texture and viscosity. This is important in cookie llings, butter-containing maple syrups, ice cream toppings, and similar products (7). 5.2. Specic Food Applications As mentioned previously, soybean lecithin is used in food because of its emulsifying, wetting, release, and other surfactant qualities. Relatively small amounts of the lecithin are needed, often only 0.1% to 2% in foods. These use levels are more or less consistent with those of chemical surfactants (7). At these low levels of usage, the color, avor, and odor of the lecithin normally are not noticeable. When lecithin is used in conjunction with synthetic emulsiers, it sometimes has a synergistic effect, and thus lesser amounts of the synthetic emulsiers need be used. General food applications of lecithin include margarine, confections, snack foods, soups, instant foods, bakery products, simulated dairy products, processed meat/poultry/seafood products, and dietary applications. The most widespread uses of crude lecithin products are in confections and margarine (7, 174). Margarine/shortenings. Standard-grade (crude) lecithin is the classic emulsier in margarine and is added at the 0.1 0.5% level to the fat phase. It is commonly used in conjunction with mono- and diglycerides. The lecithin prevents weeping or bleeding of the moisture present, reduces spattering, promotes browning during frying, increases the shortening effect when margarine is used in baking, and helps to protect the Vitamin A in fortied margarine from oxidation (174). More complete and uniform blending of shortening occurs when 0.5% to 1.0% lecithin is added (160). Confections. There are three major specic properties for lecithin in confections: emulsication (e.g., caramels), anti-stick/release properties, and viscosity modication (e.g., chocolate) (175). None of these properties stand alone. For example, emulsication in caramels will inuence shelf life and texture. In chocolate, viscosity modication will alter production costs and texture of the nished product. Addition of 0.250.35% standard-grade lecithin to the chocolate used in candymaking reduces its viscosity markedly, enables the manufacturer to apply a uniform coating and thus use lesser amounts of expensive cocoa butter, decreases the time for grinding and mixing the various ingredients, and produces a more stable chocolate. Stabilized lecithin-containing chocolate has improved handling characteristics and is more resistant to fat-and-sugar bloom or graying. Use of lecithin in other fat-containing candies also prevents graining, streaking, and greasiness. Studies by Sinram and Schmitt (176) have shown signicant improvements in dark and milk chocolates using a fractionated, phosphatidylcholine-enriched soy lecithin as compared with a standard soy lecithin or no lecithin at all. The effect
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of reduced viscosity and improved yield value in chocolate depended on the type and dosage of lecithin as well as the fat content of the chocolate. Addition of 1% to 2% of lecithin to peanut butter gives a smoother, creamier spread. The peanut butter does not separate under wide temperature variations. Bakery products. Lecithin is a useful emulsier in baked goods such as bread, cakes, sweet goods, biscuits, and crackers. Standard uid lecithin is not readily dispersible in water, giving it limited functionality in a dough or batter where water is a key component. Modied lecithins, which are water dispersible, provide many benets to baked goods including improved shelf life, a stronger gluten complex in yeast-leavened dough, reduced dough stickiness, improved tenderness, better release, and reduced checking in products such as crackers and thin bread sticks. Occasionally lecithin is incorporated into shortenings (solid or uid) that are used in baking, but it is more frequently added as a separate ingredient. It can also be added as part of a dough improver. Gaubert et al. (177) patented a baking improver composition that contained 20% to 30% (by weight) lecithin. It is an easy-to-handle dough improver where the lecithin acts as a binding agent and an emulsier. In yeast-leavened dough, the addition of 0.10.3% commercial lecithin improves water absorption, ease of handling, fermentation tolerance, shortening value of fat, volume and uniformity, and shelf life (89). If enzyme modied lecithin is used, it extends shelf life by retarding staling or starch retrogradation (99, 178). Lecithin is employed in cake formulations, such as box mixes, so that they will wet rapidly when mixed with water. In biscuits, crackers, pies, and cakes, 1% to 3% lecithin (on shortening basis) promotes fat distribution and shortening action, facilitates mixing, and acts as a release agent (179). Bread and rolls. There is a general consensus about the benecial effects of lecithin on dough-handling properties [Aberham (180), Kuntze (181), Pomeranz (179), Puchkova et al. (182), Pyler (183), and Zapryagaeva et al. (184)]. Lecithin also has a benecial effect on baking performance. It is commonly believed that surfactants, such as water-dispersible lecithin, form lamellar-type, ordered structures in the water phase of the dough. Those ordered structures improve the stability of the lm surrounding entrapped carbon dioxide (185, 186), resulting in increased volume and improved crumb structure (178). Over 50 years ago, it was conrmed that the addition of lecithin also improved the extensibility, dryness, and machinability of dough, producing bread that has improved symmetry, grain, and texture (187). Researchers have shown that the native phospholipids in wheat play an important role in the baking quality of our (188), and the addition of enzyme modied soy lecithin can make further improvements (99). Chung and Pomeranz (189) reported that fractionated lipids, especially phospholipids at 0.2%, provided a signicant increase in loaf volume when shortening was added. Johnson et al. (190) reported that adding soy lecithin (PC) to chlorinated, petroleum ether-extracted our, at 0.2% our weight, improved volume and grain beyond that obtained with the unextracted our. Chung et al. (191) found that petroleum-extracted polar lipids were required at a level of 180 mg per 100 g of our (H.R.W. 12% protein) to
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produce bread of desirable volume. Polar lipids were 50 times more functional than protein in improving loaf volume. Cole et al. (192) studied the effect of phosphoruscontaining lipids (polar lipids) and soy (PC) lecithin on the quality of cookies baked from defatted our. They found that although those fractions containing lecithin completely restored cookie quality, a phosphorus-free lipid fraction did not. Enzyme-modied lecithin has the ability to form a complex with the amylose portion of starch, and the straight portions of amylopectin (193195). By forming a complex with starch, enzyme-modied lecithin effectively slows starch retrogradation and staling. In a study, two water-dispersible lecithins were evaluated against hydrated monoglycerides as starch complexing agents to prevent staling in white pan bread (196). The staling indices demonstrated that water-dispersible, de-oiled soy lecithin gave no improvement in softening versus the control to which no emulsier was added. An enzyme-modied lecithin, however, gave a signicant softening response. This behavior was attributed to starch complexation by the lysophospholipids. Many workers have demonstrated the synergistic effects in bread making of lecithin in combination with mono- or diglycerides and other surface-acting agents. According to Hampl and Tvrznik (197), the use of lecithin in combination with monoglycerides (1) improves quality characteristics of the raw materials, (2) optimizes technical processing, (3) reduces shortening requirements, and (4) improves overall quality of the nal product, including freshness retention and nutritive value. Haarasilta et al. (198) patented an enzyme product containing de-oiled lecithin, or lecithin spray dried with a carrier, for use as a dough improver for bread. Pomeranz et al. (199) have also studied the effect of 0.5% commercially available lecithins on the quality of bread made from untreated and petroleum etherextracted our, at three different shortening levels (0.0%, 0.5%, and 3.0%). The best results were obtained with alcohol-soluble soy phospholipids containing a 2:1 mixture of PC and PE in both untreated and petroleum ether-extracted ours. When added to petroleum ether-extracted ours, 0.5% alcohol-soluble phospholipids replaced 0.8% extracted free our lipids and 3.0% shortening. Excellent results were also obtained with hydroxylated lecithin, but only with shortening present. In a separate study, Glabe and Anderson (200) tested carrageenan and hydroxylated lecithin in continuous mix bread. Their results indicated that hydroxylated lecithin increased dough stability and loaf volume when carrageenan was present. Pyler (183) reports that hydroxylated lecithin improves dough extensibility. It has been suggested (179) that hydroxylated lecithins are particularly valuable in bakery products because of their apparent synergy with mono- and diglycerides in addition to their high dispersibility in water systems in contrast to the oil solubility of most lecithins. Adler and Pomeranz (201) have shown that the addition of lecithin to soy ourenriched bread can improve its consumer acceptability in the absence of shortening. Even in the presence of shortening, an improvement was observed with the use of lecithin (202). Mizrahi et al. (203) described the improving effect of soy lecithin on bread containing soy protein isolate. The use of soy lecithin in conjunction with sucrose
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esters exerted an improving effect on bread quality in high-protein breads made with soy our (204). There is a patent on the synergistic effect of hydrophilic lecithins (HLB-8 or higher) on lipophilic surfactants such as glycerol monostearate (GMS), used primarily in bread and other bakery foods to retard staling (205). Not only does the use of a hydrophilic lecithin result in improved shelf life, but also in improved dough conditioning as exemplied by increased loaf volume, improved symmetry, grain, and texture. Larsson and Eliasson (186) tested the effect of added lecithin on the dough rheology of our milling streams. They used liposomes formed with a high phosphatidylcholine lecithin, and they concluded that ours containing less polar lipid would be most improved by lecithin addition. Shogren et al. (206) have found that lecithin, and other dough-conditioning surfactants, counteracted the deleterious effect of up to 15% wheat bran that was added as a source of ber in bread. Cookies, crackers, wafes. In the processing of cookies and other baked goods containing signicant quantities of fat, lecithin promotes even dispersion of the fat throughout the dough (1). Lecithin aids in the dispersion of fat in semisweet dough, and it improves the emulsication during the creaming stage of short dough (207). It also extends the fat. Lecithin is easily mixed into cracker and cookie dough to modify the consistency, and to make machining easier by reducing stickiness in the nished product. Greasiness of cookies with high shortening content is often reduced by adding small amounts of lecithin to the dough. Matz (208) also has reported on the improvements obtained with the use of lecithin in the production of cookies. Cookie dough is drier and more machinable with the use of lecithin. Lecithin improves the dispersion of fat so that it more readily mixes with sugar, our, and other ingredients. Improved emulsication also reduces mixing times. Overdevelopment of the dough can result in lack of tenderness in the cookie. The release quality of lecithin improves the extrudability and release from the die, improving denition of impression. Kissel and Yamazaki (209) studied the effects of lipid extracts from wheat our and soy and safower lecithins on improving cookie spread when the cookies were made from protein-fortied wheat our. Soy lecithin was most effective, and it also improved the quality of cookies made from weak ours such as sorghum and millet (210). Wafes made from dough that contains lecithin show better iron-grid release and easier handling. The wafes are stronger, crisper, do not become soggy, and retain freshness better (211). Pomeranz (179) reported that the use of lecithin in wafe formulations improves release from the grill, provides strength and crispiness, and reduces sogginess. He also cited the use of lecithin as a mold release agent (i.e., 0.3%) in low-fat formulations such as ice cream cones. Cakes, cake mixes, pancakes, doughnuts, sweet rolls, llings, etc. Incorporating lecithin in cake formulations substantially improves the quality of cakes (212). Hydroxylated products that have an intermediate degree of saturation were found to be best. Lecithins have been recommended as emulsifying agents for cake mixes
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to assure easy pan-release and to prevent the cakes from falling or dipping in the center (213, 214). They also improve volume, crumb structure, tenderness, and shelf life. When lecithin was incorporated at a rate of 1% to 3% into a powdery foaming agent for cake and fry batters, it homogenized the monoglycerides and provided the foaming property (215). Enzyme-modied lecithin could be used effectively. Wolf and Sessa (216) have advocated the use of lecithin in cake doughnut formulations at 0.5% to 1.0% (based on mix weight) to accelerate mixing of the batter. Prolonged batter mixing results in less tender crumb in the nished product. Lecithin is also benecial in white cakes, and others that contain only egg whites, by acting to replace the phospholipids normally coming from egg yolk in the formula. According to Wolf and Cowan (71), the emulsifying properties of phospholipids nd extensive use in cake mixes and instant foods. Adding 0.5% to 1.0% lecithin promotes wetting, thereby speeding up mixing of cake-doughnut mixes. Adding lecithin improved keeping qualities, grain, and texture in sweet-dough products (coffee cakes, sweet rolls, etc.), and produced shorter dough in these items. Incorporating lecithin into pie crusts reduced mixing time, produced akier dough, enhanced release, contributed to uniform browning, and aided as a moisture barrier to protect the crust (179). Lecithin acts as an aid for the blending of unlike ingredients. An excellent example is the formulation of cream llings for sandwich cookies. The use of low levels of lecithin signicantly improves the ease of blending and mouthfeel of these products, which consist mostly of low-polarity shortening and high-polarity sugar. The lecithin serves as an intermediary to signicantly reduce the stiffness and mixing time of the lling (31). Reduced fat baked goods and extrusion. Lecithin is well known for its lubricating effects. In 1947, Pratt (217) concluded that lecithin increased the effect of shortening in bread. Since then, it has become widely recognized that lecithin imparts a lubricating effect to dough and nished baked goods. Lecithin also has a positive effect on lubricity in extruded products. It contributes to increased throughput and decreased clean-out time. Lecithin improves product ow, and it does not have a negative effect on density. In the production of extruded, fat-free pretzels, down time for cleaning the cutting knives can be signicantly reduced with the use of 0.50.75% (our basis) de-oiled lecithin. De-oiled lecithin can also be used to replace monoglycerides in some extruded breakfast cereals and special pastas (218). De-oiled lecithin is also recommended to increase the lubricating properties of reduced fat dough. It helps reduce stickiness for improved production yields and reduce stress on pumps, belts, and motors. Lecithin is included in several patents for reduced fat bakery products. In a patent for a low-fat cereal-grain, food composition, lecithin is preferably included when an egg-like substance is used. The lecithin, along with other emulsier components and gums, presumably functions to incorporate air, which would otherwise be incorporated by fat (219). Another patent describes the production of reducedfat, low-fat, and no-fat baked goods, in which a substantial portion of the shortening
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or fat is replaced with an emulsier composition (220). The emulsier composition preferably contains 10% to 25% by weight of at least one type of lecithin. Specic reduced-fat products that can be made with the emulsier composition include fermented crackers, unfermented crackers, cookies, and brownies. In a patent obtained by Gautchier and Dyer (221), a fat-sparing composition is described that may be used to extend vegetable fat in cookie ller cremes and other cremes. The patent states that lecithin may be advantageously used in that composition. In a similar patent, Abboud (222) used lecithin in a fat replacement composition for ready-to-spread frosting. Instant foods. Lecithin has been used as a wetting agent and emulsier in instant foods. Foods including cocoa powder, instant drinks, instant cocoa and avored coffee, powdered protein drinks, coffee whiteners, instant puddings, cake mixes, and instant toppings are widely employed applications for specic lecithins. The most common method to incorporate lecithin is as an external coating on the powder particles. The particular lecithin to be employed largely depends on the hydrophilicity or lipophilicity of the powder system (7). In recent years, instant food manufacturers have become interested in oil-free lecithins. These products are granular, but they can be uidized by the addition of water or fats. Additionally, uid products are now available that are based on oil-free lecithin and have obvious advantages, because of their blandness and handling properties, for instant food manufacturers (223). Pan and food release agents. Lecithin-based release agents are employed in many applications such as frozen wafe manufacture, bakery products, pizza baking, and pasta products. Most industrial griddle frying fats are formulated with lecithin, solely for its release functionalities (7). The products may be spray- or brush-applied to achieve a thin lm capable of promoting easy release of baked items from pans and belts. Bakery release agents may contain 26% lecithin in a variety of oil bases, and they may also be formulated with particulate matter to provide an additional mechanical release. The simplest of all food release agents are found in the category of pan oils or griddle greases. These products contain low levels of lecithin (0.51.0%). Most of the release action is provided by the mechanical barrier established by liberally coating the cooking surface. Retail release agents for home use are marketed as aerosols and occasionally as pump sprays. In this setting, the release agent will be used for everything from simple release tasks like pancakes and fried eggs to more challenging systems like cakes or mufns. Consequently, retail products are formulated with relatively high levels of lecithin to provide extra release for difcult applications. As stated previously, moderately and highly acetylated lecithins exhibit heatresistant properties that are very desirable to have in many release agent applications (173). A natural crude lecithin is subject to thermally induced reactions that are responsible for the darkening and formation of insolubles that occur after prolonged heating. There are several viscosity grades of heat-resistant lecithins available, and lecithin viscosity varies with temperature. Low-viscosity lecithins can be easily sprayed without dilution, or prepared as part of a spray release system.
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Typical formulas for lecithin-based release systems are pan bread: oil 98%, lecithin 2%; aerosol spray: oil 70%, lecithin 8%, propellant 22%. Release formulas for cakes, cookies, and other difcult specialty products often include 515% lecithin, 110% particulates (our, silica, etc.), and various types of oils (mineral, vegetable, etc.). Lecithins can be directly applied to the surfaces of griddles, continuous oven conveyers, ame broiling equipment, and other cooking surfaces for better release and ease of cleaning. The thinnest layer possible should be used for surface release. Lecithin prepared according to U.S. Pat. 4,479,977 (173) is a very effective release agent when applied to a surface in a very thin lm, or used in spray pan release systems. For use on a grill, grinders, extruders, pans, or skewers, spray coverage should be applied with lower misting rather than with an air sprayer. Continuous, multipurpose ovens that are used to precook foods may use waterlled dip tanks for cleaning and rinsing the conveyor belt. An aqueous release system, containing a water-dispersible lecithin, is added to the dip tank to facilitate release of the food from the oven belt, as well as promote better rinsing and cleaning during cooking. A 10% aqueous dispersion of lecithin is commonly used for this application (224). An alternative to the use of dip tanks for continuous band ovens is to blend 2 10% heat-resistant lecithin in liquid oil or melted shortening, and spray-apply the blend to the conveyor belt with an air spray system (224). Rened uid lecithins are also used to prevent the sticking of high-moisture sliced and shredded products like cheese. Specialty uid lecithin products are sprayed or wiped onto sheets of processed cheese prior to slicing and stacking. Effective separation of the cheese product requires an even, very thin distribution of a low-viscosity lecithin applied as a ne mist to the moving sheet of processed cheese. Lecithin also works well in separating the slices of certain natural cheeses where the manufacturing process allows the lecithin to be applied as the cheese is sliced. For separating cheese slices and shredded cheese products, 1 kg for approximately 500 m2 (equivalent to 45,000 slices) of a low-viscosity, sprayable lecithin is used (224). Dairy-type foods. Another major application for lecithin products is in dairy and imitation dairy products. Bily (225) has shown that the addition of de-oiled lecithin to milk during cheese manufacture resulted in an increase of mozzarella cheese yield by 3.58%, and an increase in cottage cheese yield by 8.90%, primarily by increasing the moisture content of the nished cheeses. Turcot et al. (226), conrmed that as the phospholipid content of buttermilk increased, the moisture content of low-fat cheese increased in spite of cheese manufacturing modications. Drake et al. (227) showed that de-oiled lecithin improved process cheese texture without negatively affecting avor or acceptance. Trained sensory panelists determined that reduced-fat cheeses containing lecithin were more similar in texture attributes to full-fat control cheeses than reduced-fat cheeses without lecithin. Sipahioglu et al. (228) demonstrated that yield loss and the increase in hardness of feta cheese associated with fat reduction, was overcome by the water absorption capacity of starch and lecithin. The presence of lecithin in low-fat and reduced-fat
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cheeses improved the yield, primarily by increasing moisture, and reduced the hardness, while improving the avor and texture. Lecithin is used to improve the wettability and dispersibility of various milk powders including whole milk powder (229, 230) and caseinates (231). Oldeld et al. (232) demonstrated that lecithinated whole milk powder had increased coffee stability, with decreased coffee sediment levels over a water hardness range of 0308 mg/L. Enzyme-hydrolyzed lecithin has been shown to improve the heat stability of recombined milk products (233, 234), and almost all infant formulas contain either hydrophilic or de-oiled lecithins as fat emulsiers (235). Other dairy applications in which lecithins are used include frozen desserts, whipped toppings, and yogurt. Processed meats. De-oiled lecithin is used as a key ingredient for the emulsication of fat in canned or frozen meat-containing products. When properly formulated, the lecithin can dramatically reduce or eliminate fat-capping in products such as canned chili, sloppy joes, gravies, Mexican meat llings, and other meat products containing a sauce or gravy (236). A combination of lecithin, textured soy concentrate, and a starch has been recommended for reducing fat separation in canned meat products that are cooked in the can (237). Oil-free lecithins, or lecithin/distilled monoglyceride combinations, have been recommended for reducing water purge in frankfurter formulations that contain high levels of water (238, 239). Although the lecithin is functional in low-fat or high water frankfurter formulations, it has failed to function in some full fatcontaining emulsion meats (240). It was concluded that the presence of de-oiled lecithin in comminuted pork emulsions contributed to the destabilization of the emulsions. This destabilization of meat emulsions by higher-HLB surfactants was also seen by Cheong and Fischer (241). U.S. Patent 4,434,187 (242) covers a meat curing composition that contains deoiled, powdered lecithin. The purpose of lecithin is this application is to prevent separation of the brine solution. Lecithin is also used in release agents for meat casings and nets. Hammer, et al. (243) recommended that an aqueous-based release agent for cellulose sausage casings, which contained 512% lecithin, be applied at a rate of 450800 mg/m2, based on the lecithin weight. Egg replacers. Lecithins are used in conjunction with dairy and vegetable proteins in an attempt to functionally mimic the lipoprotein complex of egg yolks. A coagulable egg replacer based on whey protein, polyunsaturated fat, and lecithin has been described (31). Another formulation included soy and wheat our blended with oil, lecithin, carrageenan, and polysorbate 60 to replace up to 75% dry or liquid eggs in a variety of mixes and prepared foods (31). Dashiell (31) also reported on a lipoprotein complex formed from soy isolate, oil, carbohydrate, and various emulsiers, which is claimed to be useful for whole or partial replacement of egg yolks in baked goods. Nutritional and health-related applications. Lecithin has long been known in the worldwide nutritional community. Dietary supplement lecithin is generally derived from soybean lecithin. Because of its composition of various phospholipids, vitamins, and fatty acids, lecithin is involved in numerous physiological actions that
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TABLE 26. Basic Physiological Functions of Lecithin/Choline. Function Cell membranes Fat transport Methyl metabolism Description PC provides structural stability for cell membranes, provides a reserve supply of choline, and acts as a second messenger. PC is a main constituent of the membrane surrounding the fat transporting molecules called lipoproteins. Choline is one of a few B Vitamins that participate in methyl group metabolism. Methyl groups (CH3) are components of numerous important biological compounds. Choline is a principal component in the synthesis of acetylcholine.
Cholinergic neurotransmission
range from the molecular to the organ level. Among the phospholipid composition of lecithin, PC is considered the most nutritionally signicant. Indeed, choline phospholipids are involved in a myriad of essential metabolic reactions, are important structural components of cell membranes, and are important mediators and modulators of transmembrane signaling. Table 26 provides an overview of the physiological functions of lecithin/choline. Lecithin is the main dietary source of choline. The U.S. National Academy of Sciences (NAS) Food and Nutrition Board recently underscored the importance of lecithin in human nutrition by assigning choline (the vitamin component of PC) a dietary reference intake (DRI) in 1998 (244). Although it is true that lecithin and choline are present in a variety of foods, the specic amount of lecithin and choline in foods is currently unknown. At this time, no comprehensive analysis of choline in the food supply exists. Such an analysis is, however, underway and it is estimated that the extensive USDA database of foods will be fully analyzed for choline content by 2005. The analysis will include all forms of choline found in food. It is known that the richest sources of lecithin/choline are high-fat/saturated fat/ cholesterol-containing foods such as egg yolks, organ meats (liver, kidney), and whole milk. Analyses from the 1970s estimated choline intake to be 7301040 mg/day in adults consuming a typical western diet (244). However, since the 1970s, dietary recommendations have strongly advocated reducing intake of foods high in fat, saturated fat, and cholesterol. Although this dietary guideline policy has resulted in lower fat intake for many Americans, it is likely that lecithin intake has also decreased considerably in recent years. Indeed, a number of sources have reported steep declines in consumption of eggs, red meat, and whole milk over the past 25 years (245). Choline has been shown to be essential to the body. In a landmark study in 1991, Zeisel et al. (246) showed that healthy men with normal folate and Vitamin B12 status fed a diet decient in choline have diminished plasma choline and PC concentrations and subsequently developed liver damage. In other words, when other nutrients are adequate, the body is not able to produce choline in quantities sufcient to prevent liver damage as assessed by elevated serum levels of alanine-aminotransferase (ALT), a critical liver enzyme. These data served as the supporting
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TABLE 27. DRI for Choline (244). Adequate Intake Level for Males (mg/day) 125 150 200 250 375 550 550 Adequate Intake Level for Females (mg/day) 125 150 200 250 375 400 425 450 550 Upper Limit (g/day) Not possible to establish Not possible to establish 1 1 2 3 3.5 3.5 3.5
Group Infants
Age 06 months 712 months
Children
Adults Pregnancy Lactation
13 years 48 years 913 years 1418 years 19 years
evidence for the establishment of the DRI levels for choline. The adequate intake level for choline was determined as the point at which ALT levels returned to the normal range. The adequate intake level was originally set for adult males and has been calculated/extrapolated for other populations. Tolerable upper limits for choline have been set for various age groups. High doses of choline, in the form of choline salts (choline chloride or choline bitartrate), have been associated with sweating, salivation, a shy body odor, and hypotension (low blood pressure). Table 27 shows the AI and UI values for various populations (244). Although healthy individuals eating an omnivorous diet are not likely to be at risk of choline deciency, some groups such as vegetarians, athletes, dieters, and pregnant and lactating mothers can deplete choline stores. Lowered serum choline concentrations have major consequences including hepatic, renal, vascular, neuronal, and infertility problems (5, 247). Further, there is evidence that supplemental choline (intake levels >DRI levels) may be benecial to the health of some individuals. The following sections discuss the role of lecithin and choline health and disease prevention. Liver health. As noted above, a biomarker of choline deciency is elevated serum ALT levels, which is an indication of liver damage. One of the many functions of the liver is its role in fat metabolism. Without PC, the liver is unable to synthesize lipoproteins. Of particular importance in liver is the synthesis of very lowdensity lipoproteins (VLDL). With diminished VLDL production, the liver is not able to export lipid. This results in an accumulation of fat in the liver. Lipid accumulation in the liver leads to various stages of liver disease such as liver cell death, brosis, cirrhosis, and liver cancer (248250). The role of choline in liver disease was underscored in the early 1990s when it was determined that patients on extended total parental nutrition (TPN) treatment developed fatty livers (251). At that time, TPN formulas did not include choline. Adding choline (in the form of lecithin) to TPN formulas reversed fatty buildup in these patients, and a
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long-term study strongly suggests choline is an essential nutrient during long-term TPN (252). This nding led to the series of experiments that eventually determined the essentiality of choline, and to the choline DRI values. Because of the link between lecithin/choline and liver health, these substances are being studied for their therapeutic potential. In humans, the primary cause of fatty liver is overconsumption of alcoholic beverages. Results from several studies indicate that the phospholipids found in lecithin, particularly PC, may signicantly reduce liver damage caused by alcohol consumption (253, 254), and this effect was not seen when choline was supplemented in the form of choline salts. Interestingly, an editorial on diet and liver disease stated that the most exciting nding regarding diet and liver health is that supplementation with PC protects the liver from the damage associated with long-term alcohol consumption (255). Other studies in animal models show that a choline-decient diet promotes liver carcinogenesis (256261). In fact, choline is the only known nutrient for which deciency is directly linked to liver cancer in the absence of any known carcinogen (262, 263). Choline deciency is therefore considered to have both cancer initiating and cancer promoting activities. Effects on blood cholesterol. Many studies conducted from the 1960s through the 1980s investigated the relationship between lecithin administration and serum cholesterol concentrations. In 1989, Knuiman et al. reviewed 24 of these studies (264) and concluded that most of lecithins cholesterol-lowering benets were caused by its content of polyunsaturated fatty acids, primarily linoleic acid. They stated that soy lecithin, therefore, was no better than soybean oil in lowering total serum cholesterol. However, this research group failed to consider the effects in subclasses of lipoproteins, basing their conclusions only on total cholesterol. The analysis did not include the positive effects of lecithin on HDL cholesterol, the lipoprotein fraction that lowers cardiovascular disease (CVD) risk by reverse cholesterol transport in which cholesterol is removed from arteries and other tissues and returned to the liver for resynthesis. In a comprehensive review of risk factors for atherosclerosis, Ridker et al. considered 11 biomarkers thought to be associated with increased or decreased risk of CVD (265). They determined that the strongest predictor of cardiovascular disease is an unfavorable ratio of total cholesterol to HDL cholesterol, meaning that those most likely to develop heart and vascular disease are those with low HDL cholesterol and high total cholesterol. Thus, simply considering effects of lecithin on total serum cholesterol tells only part of the story regarding risk factors for CVD. OBrien and Andrews (266) found that, in men, soy lecithin increased HDL levels signicantly more than egg lecithin or fatty acids. Wojcicki et al. also showed that lecithin can reduce LDL cholesterol, although this study lacked proper control (267). The ability of soy lecithin to alter blood cholesterol has led to some provocative research in adding lecithin to certain cholesterol-lowering drugs. One of the problems with drugs like clobrate is that, although it can lower levels of VLDLs, thus lowering CVD risk, it can raise LDL levels, increasing CVD risk. One study found that, when administered with clobrate, lecithin prevented the increase in LDLs seen with clobrate alone (268).
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The primary mechanism by which lecithin lowers cholesterol is by decreasing the absorption of dietary cholesterol from the intestine to the blood stream (269, 270). There is also evidence that lecithin intake lowers cholesterol by increasing the amount of cholesterol used in the production of bile salts (271). As more cholesterol is used for bile salt synthesis, less is available to reach the blood stream and damage blood vessels. Lecithin also contributes polyunsaturated fatty acids to the diet, which may help control blood cholesterol levels. Direct effects on atheroclerosis and artery health. Data from the 1960s suggest that phospholipids may play a dual anti-atherosclerosis role by mobilizing cholesterol from arteries and by preventing the atherosclerogenic actions of cholesterol (272). Phospholipids administered intravenously have been observed to have an anti-atherosclerotic effect in several experimental animal species (273279). There are a number of theories on the mechanisms of lecithins anti-atherosclerotic actions. Older theories attributed these effects to detergent effects and simply the lowering of serum cholesterol (278). More recently though, Hsia et al. (279) suggested that PC is taken up by HDL to form PC-rich vesicles that have a greater capacity than native HDL for promoting cholesterol efux, leading to depletion of cellular cholesterol and increased LDL receptor activity and reduced arterial damage. However, exact mechanisms on endothelial repair and growth factors are yet to be determined. Finally, lecithin may also affect cardiovascular health by interactions with certain drugs. One such interaction is lecithin and nonsteroidal anti-inammatory drugs (NSAIDs). NSAIDs (aspirin, ibuprofen, and naproxen) are currently being studied in a number of trials for their potential effect on the reduction of arterial disease by decreasing the production of certain prostaglandins that cause inammation. However, because prostaglandins also act to protect the stomach lining, these drugs can also cause upset stomach, gastrointestinal bleeding, and ulcers. The addition of lecithin to NSAIDs not only prevents the stomach irritation associated with these drugs (282), but also may potentiate their effects (283). A study in rats showed that free and lecithin associated-aspirin appear to be equally absorbed, but the latter form has greater antipyretic, anti-inammatory, and analgesic efcacy. The improved efcacy may be caused by increased uptake by target cells, increased binding to cyclooxygenase (the rate limiting enzyme in the synthesis of proinammatory and other prostaglandins), or prolonged half-life (283). Effects on brain development. In the developing fetus, choline plays a critical role in the development of the hippocampus and septum, brain areas thought to be heavily involved in the formation and retrieval of memories (284, 285). Given the role of choline in the developing brain, it was speculated that choline supplementation may improve cognitive ability. In a series of experiments, Meck and Williams gave pregnant rats supplemental choline at various times during pregnancy (286289). After the pups were born and weaned, they were tested in a series of maze memory tests. In these maze tests, the rats need to remember which arms contain food. Rats with a greater ability to form memory cues make fewer mistakes when recovering the food. It was determined that rats whose mothers were given the supplemental choline in their drinking water during days 1217
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of pregnancy (corresponding to weeks 2025 in a human pregnancy) had signicantly better memories than the control animals and animals provided supplemental choline during other periods of gestation. Interestingly, this critical period for choline supplementation and cognitive enhancement corresponds with progenitor cell differentiation and migration during development of the hippocampus. Additional experiments indicate that numerous aspects of cognitive function are enhanced by supplying additional choline during this gestational period (286288, 290, 291). There may also be an additional critical period for choline supplementation soon after birth. Feeding choline to the rat pups, from day 16 to 30 of life, also resulted in better memories, but not as dramatically as did supplementation during the prenatal period (289). Importantly, the cognitive enhancements observed are not simply transient effects in young animals. Rats whose mothers were given supplemental choline during pregnancy consistently performed better in the maze and other tests throughout their lives (292). Further, when tested at a very elderly stage of life, these rats continued to have better memories and less mental deterioration. Choline plays many critical roles in human fetal development, and pregnant or lactating women have increased needs for choline. Choline is transported across the placenta from the mother to the fetus by a 1:14 ratio (293, 294). This creates a large drain on maternal stores of choline making the mother more vulnerable to the effects of choline deciency during pregnancy. Similarly, the choline concentration in mothers milk is over 100 times the level in the maternal bloodstream (295). Because of this heightened requirement for choline, it is likely that both pregnant and lactating mothers have lower serum choline concentrations than nonpregnant women. Currently, research is underway to investigate the impact of choline supplementation during human pregnancy, and during the rst 6 weeks after birth, on the brain function of babies. Effects on cognitive performance and memory in young adults. Because lecithin supplies added choline and PC, the precursors to the formation of acetylcholine in the hippocampus, lecithin has been studied for its possible memory-enhancing effects (296). Interestingly, it was found that, although improvement in memory was seen in almost all participants, those who were the slowest learners initially showed the greatest improvement with administration of a 25-g dose of lecithin (supplying 3 g of choline). Using a similar memory test, a second group of researchers found that subjects ingesting 7.5 g of choline (as choline chloride) signicantly improved/learning performance (297). Again, the memory improvements were most effective in the slowest learners in the study. Effects on memory in older adults. Studies have also shown that choline supplementation improved both immediate memory and logical memory, or free recall, in older adults with memory deciencies (298, 299). These studies demonstrate that choline ingested in the form of lecithin or lecithin precursors [diacylglycerol choline phosphotransferase (CDP)-choline] can improve mild memory loss associated with the aging process. Choline chloride, however, appears to be less effective than lecithin for improving memory, likely because of its lower bioavailability (300).
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5.3. Flavor in Food Systems The avor of lecithin products, and the effect of lecithin on other avoring materials, has received some attention, but much remains to be done. Some factors affecting avor biogenesis in phospholipids have been reviewed by Sessa (301). The avor prole of commercial lecithins can vary greatly. The typical odor/avor prole of commodity grade soybean lecithins is slightly green and beany. Certain additional notes may be present in chemically modied or fractionated lecithins. Much of the green, beany character can be eliminated by removal of the vegetable oil fraction, leaving a slightly nutty-avored, dry powder or granule. Through gas chromatography and mass spectroscopy, 79 volatile compounds were identied in soybean lecithin (302). Producing bland uid lecithins is possible by redispersing the de-oiled lecithin in clean oils that have been properly rened and deodorized. Lecithin avors are not typically a problem in food applications because lecithins are used in most foods at low levels. Laboratory tests have shown that in nished food formulations, lecithins can either accentuate or reduce the avor intensity of salt, acids, and some spices. However, lecithin avors can penetrate bland dairy-based systems. Studies have shown that 0.25% de-oiled lecithin could be detected in cottage cheese (31). Lecithin is used in some applications for its apparent ability to modify certain avors. Dashiell (31) has reported on the use of lecithin to modify avors in chewing gum products, claiming that the lecithin reduced certain bitter avor principles. In summary, phospholipids affect the sensory properties of appearance, color, avor, taste, and texture of foods, the key attributes that determine consumer acceptance. The avor of phospholipids, and their interaction with both desirable and undesirable avors, is extremely critical and contributes to the acceptability of foods containing these preparations. As various phospholipids have different physical and chemical properties, they can affect food quality to different degrees. This depends on the phospholipids nature and content in the oil, the presence of other compounds, and the oil system in which phospholipids exist (301). Although much progress has been made in reducing avor, some residual avors always remain (303). In most foods, they are diluted and masked when the lecithins are incorporated at low levels. Flavor is a particular problem, however, in bland foods, such as dairy products. For more details on the role of lecithin in avor development in foods, the reader is referred to reviews by Min and Stasinopoulos (304), Sessa (301), and Sipos (305). 5.4. Liposomes Liposomes typically consist of bilayers of phospholipid molecules arranged in a spherical manner. Liposomes can be either unilamellar, consisting of a single bilayer, or multilamellar, consisting of concentrate spheres of bilayers with water separating each bilayer. Liposomes have generated great interest as carriers for various active ingredients, with water-soluble actives encapsulated in the liposome core, and oil-soluble actives encapsulated in the bilayer. Figure 4 depicts a model of a liposome (306).
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Figure 4. Model of a Liposome (306). (This gure is available in full color at http:// www.mrw.interscience.wiley.com/biofp.)
Liposomes have been used for years as components of drug delivery systems, and as transdermal carriers of active ingredients in the cosmetic industry (307, 308). More recently, liposomes have found use in the food and nutritional supplement industries. Keller (308) lists more than a dozen nutritional products on the market that have been formulated with novel liposome-based delivery systems. In the food area, liposomes have been studied for their ability to encapsulate and provide controlled release of enzymes (309, 310), and liposome-encapsulated enzymes have been used to accelerate the ripening of cheese (311). U.S. Patent 4,999,208 (312) covers the extrusion baking of cookies having liposome encapsulated ingredients.
6. ANIMAL FEEDS, USES 6.1. Animal Feeds Many companies sell crude lecithin gums to the feed industry with little or no further processing. However, the full nutritional and functional advantages of phospholipid use in animal feeds can be obtained through exploitation of the different types of lecithins available (313).
6.1.1. Functional Uses of Lecithin in Animal Feeds
Lecithins can be employed in animal feeds for their numerous functional properties. These applications result from lecithins emulsifying, wetting, colloidal, antioxidant, and physiological properties.
ANIMAL FEEDS, USES
421
Milk replacer fat emulsion. One important application of lecithin in animal feeds is as an emulsier (314). As an example, milk replacer fat is emulsied to improve product wetting and dispersion upon mixing, to help minimize fat separation (i.e., emulsion stability), and to signicantly reduce fat particle size, allowing improved fat digestibility. As an emulsier in milk replacers, lecithin is used at 312% of the added fat. The type of lecithin used is affected by factors such as fat type, protein type, and the presence of stabilizers. Canned food emulsion. Another emulsication application for lecithins is in canned pet foods. Lecithin can help maintain homogeneity within the ingredient mixture during pumping to the cans, can reduce fat capping and crystallizing within the can, and can keep gravies and sauces consistent and smooth, without separation while stored in the cans. Lecithin is used at 0.25% to 0.75% of the canned pet food formula to achieve these effects (315). Canned food lubricity. Lecithin provides lubricity in canned pet food applications. This lubricity reduces stickiness and eases the ow of the food through the processing equipment. In this regard, lecithins are superior to fats. For this reason, the use of lecithin can reduce the need for fat in ingredient blends, and a superior machinability is achieved. Lecithin has been used at rates of 0.251.0% of the ingredient mixture in canned pet foods for these benets (315). Lecithin also functions as a release agent. Spraying a thin lm of lecithin on the inside surface of cans prior to lling helps to provide cleaner and faster parting of the contents from the can (315). Extrusion. Lecithin is used during the extrusion of pet foods. Specically, the lubricity property of lecithin has been capitalized on for extrusion of companion animal foods (e.g., dogs, cats, horses). De-oiled lecithin (0.51.0%) and uid lecithin (0.751.5%) reduce extruder motor load, allowing an increase in production rate at the same energy cost. At the quoted lecithin usage, production rate increases of 10% to 25% have been observed. Another aspect of lecithin use during extrusion is production stability. Ingredient combinations of some companion animal formulas are resistant to passage through an extruder. This characteristic results in surging of production as pressure is built up and released during extrusion. Lower calorie, higher ber food production is prone to this difculty. Lecithin reduces this uctuation of rate through the extruder, which allows more rapid establishment and maintenance of production stability. The natural lubrication properties of lecithin also reduce mechanical wear. Less wearing of parts increases their functional life and reduces production costs. Maintaining particle size and shape during extrusion is a problem with some foods. In some formulas, lecithin smoothes the passage of the extrudate through the die, which leads to improved product uniformity. Additionally, lecithin reduces the amount of clumping that occurs in some products particles prior to reaching the dryer. Clumped product is screened away and must be discarded or reworked, which decreases production capacity. Lecithin use in extruded foods increases bulk density 020%. The level of change is related to the amount of lecithin and the ingredient composition of the food. In some cases, the difference in density is so slight that no change in
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packaging is indicated. When density is signicantly increased, existing packaging is too large without modication. However, changes can be made during production to maintain product density as a constant when lecithin is used. For example, increased steam addition, and/or decreased die area, increase expansion and decrease density. An increase in density is not always a negative, especially with new formulas and low-calorie or light foods. Higher density foods require smaller bags and lower storage and transportation volumes. Lecithin benets water distribution and retention in nished extruded foods. Lecithin reduces moisture migration into and out of products. This inuence provides a benet through a reduction in the development of staleness of the food (316, 317). Baked pet food. A variety of baked products (foods, biscuits, cookies, and crackers) are manufactured for dogs. Lecithin has the same functions and provides the same benets in these products, as described earlier in this chapter for baked goods produced for human consumption. A usage of 13% lecithin, on a fat basis, promotes fat distribution in these baked products. Lecithin is also used in reduced-fat baked items for pets, to replace the lubricity that is lost when the fat is removed. Lecithin is used at rates of 0.252.0% of the mixture for these benets. In reference to machinability, lecithins are superior lubricants to fats. For this reason, the use of lecithin can reduce the need for fat in pet product ingredient blends (318). Lecithin will function as a release agent, providing cleaner and faster pet food or biscuit parting from a stamp or mold. A reduction in the amount of pressure required to create an impression with a stamp is seen when lecithin is used in the mix. The ease of formation of intricate, stamped, surface appearance details, especially with low-fat products, is also improved with lecithins. When dough is being cut, lecithin improves release from the die, especially with rotary cutters. With superior release, foods and biscuits are formed with a better impression, and lower numbers of cripples (i.e., improperly formed product). Some pet biscuits are formed from a batter injected into a mold prior to cooking. Lecithin can improve owability of the batter so that it lls all the mold corners and cavities. After cooking, lecithin improves release from the mold. Lecithin is known for its ability to create a nonstick surface. Although fats and oils have been used for this purpose, they can add unnecessary calories and leave an oily residue on the product surface. Lecithin functions by modifying the boundary between a pet food or biscuit and the cooking or mold surface. In this manner, lecithin prevents the products from coming into contact with surfaces where sticking can occur. Low-viscosity lecithins can easily be sprayed without dilution. Other lecithins can be mixed with oils, fats, or water, and then sprayed. Still other lecithins are heat resistant and can be used in applications where exposure to prolonged heating would normally cause darkening. Development of checks or cracks, potentially leading to in-package breakage, can be a problem with baked products, particularly those that are brittle. A lowlevel lecithin addition (0.250.50%) helps to reduce this problem by increasing product cohesiveness. A reduction in nes development within the packaging has also been noted.
ANIMAL FEEDS, USES
423
Antioxidant. Lecithin is a natural complement to antioxidants for stabilizing animal fats and vegetable oils. Phospholipids thus help to reduce development of rancidity and to prolong product freshness (319). Lecithin functions particularly well as a synergist with antioxidants. Aquatic feeds. Lecithin has also been found to have functional application in foods for aquaculture. Extruded sh or crustacean diets, which are designed to sink, must possess particular characteristics to satisfy physical and nutritional requirements. These include a high density, which enables the food pellet to sink in extreme open sea conditions; hardness, which allows the pellet to withstand transfer and handling throughout the feed mill and during shipment to the aquaculture farms; and an open cell structure to facilitate high external fat uptake. The use of de-oiled lecithin (e.g., 0.5%) in the aquatic food addresses these needs (320). Lecithins also reduce leaching of water-soluble nutrients (321) and act as an effective binder (322) in sh foods. The latter authors indicate that de-oiled lecithin is more effective than uid lecithin in reducing dissolution time and leaching of water-soluble nutrients. Lecithin also has application in articial microparticulate diets for larval sh. Phospholipids can benet lipid emulsion and lipid-walled microcapsule formation.
6.1.2. Nutritional Uses of Lecithin in Animal Feeds
The functional aspects of lecithin use as an emulsier are referenced above. Emulsication of dietary lipid is also nutritionally important for digestion. Immature animals of all species (e.g., calves, dogs, sh, pigs, and poultry) have limited production of digestive emulsiers (i.e., bile) and enzymes. Providing lecithin as a dietary emulsier allows improved utilization of feed energy. Piglet digestion. Low feed intake capacity and poor digestive capabilities characterize the early weaned pig. A challenge is to formulate a palatable, nutrient dense, highly digestible diet. In order to increase dietary energy, supplemental fat is used. An approach to improving digestion and pig performance is to use various supplemental dietary lecithins with or without supplemental fats. Pig responses with dietary lecithin have been inconsistent (323). The successes and failures seen in past studies are difcult to compare and critique. Variables that could have inuenced the experiments outcomes include type and level of lecithin, type and level of fat, diet composition, dietary calorie:amino acid ratio, absolute dietary caloric density and amino acid content, age of pigs, and performance potential of the pigs. Overall, the trend is for dietary lecithin addition, at a rate of 510% of the fat, to improve piglet performance. Calf digestion. The digestive system of young calves changes dramatically during the rst three weeks of life. During this time, calves are severely restricted in the nutrients that they can digest. Milkfat is the most highly digestible lipid source; however, other fats (e.g., tallow, lard. white grease, palm oil, coconut oil) can be used if they are emulsied and homogenized properly. The major factor inuencing digestion and absorption of fats by preruminant calves is emulsication of the milk replacer fat to a particle size less than 10 microns (324). Addition of
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lecithin (e.g., 10%) to the fat prior to mixing the fat into the milk replacer can inuence the fat droplet size in the emulsion. In ruminants, lecithins have also been shown to control bloat, a digestive disorder typied by distension of the rumen. The distension is caused by the formation of a foam above the rumen liquor, which blocks the escape of gases (325). Crustacean digestion. Initially, lecithins were believed to be required as a surfactant for lipid emulsication and digestion by crustaceans. However, other evidence suggested that dietary phospholipid improved growth and survival by effects other than enhancement of emulsication and absorption of dietary lipid from the digestive tract. The current consensus is that dietary phospholipids inuence the mobilization of lipids (e.g., cholesterol and triglycerides) from the midgut gland to the hemolymph and other extra hepatic tissues rather than in the direct digestion and absorption of dietary lipids. A signicant dietary interaction between cholesterol and lecithin exists. Neither of these lipid materials can replace the other in the diet of crustaceans. The zwitterionic properties of phospholipids have been shown to enhance the absorption of various drugs, including the drugs lipid permeability. This fact becomes interesting in terms of the use of carotenoids in shrimp nutrition. Carotenoids play important roles in health, in reproduction (e.g., development of eggs), and during embryonic and postembryonic development stages. A synergy could exist between phospholipids and carotenoids in the nutrition of shrimp. Another possible role of dietary phospholipids could be improved palatability (chemoattraction) resulting in stimulated food consumption. The phospholipid requirement for larval shrimp is in the range of 3.0% to 9.0% from soy lecithin, in order to supply 13% phosphatidylcholine plus phosphatidylinositol. The phospholipid need for juvenile shrimp is within the range of 3.754.5% soy lecithin (1.21.5% phosphatidylcholine plus phosphatidylinositol). The phospholipid requirement for broodstock is at least 2% soy lecithin (0.65% phosphatidylcholine plus phosphatidylinositol) (326). Most larval sh (e.g., sea bass, salmon, trout, turbot, seabream, ounder, carp, and goldsh) have a requirement for dietary phospholipids. The phospholipid requirement generally decreases with age or developmental stage. The requirements also differ between species (321). Companion animal digestion. Some nutritionists use phospholipids in the foods of puppies and kittens to improve dietary fat digestion. Other reasons exist for improving the nutrient provision of canine and feline foods. A desire to produce nutritionally optimal versus adequate foods has resulted in changes in pet foods. Many of these changes are reective of alterations in the eating habits of pet owners. A realization is that not all canines and felines have the same nutritional needs throughout their lifetimes. Advantages to companion animal life cycle foods exist. Foods for senior dogs and cats are among these. Objectives of nutritional management for older dogs and cats include enhancing the quality of life, delaying the onset of aging, extending life expectancy, slowing or preventing progressions of disease, eliminating or relieving clinical signs of disease, and maintaining optimal body weight. Lecithin use at a rate of 1.05.0% in the diet of older pets can be a nutritionally advantageous source of essential fatty acids, choline, and energy (327).
ANIMAL FEEDS, USES
425
Skin and coat health. Further justication of optimizing the nutrient provision of companion animal foods is an enhanced owner awareness of, and interest in, nutrition. Owners are more understanding of the quality and longevity of their pets/companions lives and the role that nutrition plays. The skin is the largest organ in the body. Maintaining the integrity of the skin, its component cells, and the plasma membranes of the cells is critical not only to the appearance of the animal, but also to the animals health and well-being. Signicant scientic information has been reported concerning the role of phospholipids and essential fatty acids (omega 6, omega 3) in the health of skin and other epithelial tissues such as hair and hooves. Lecithin is an excellent source of phospholipids and essential fatty acids. Dietary fortication and/or daily supplementation with lecithin can be part of an optimal nutritional program for companion animals. Phospholipids and essential fatty acids are present in companion animals foods. However, specic dietary recommendations for use of lecithin are anecdotal. Lecithin use in dog and cat foods has been in the range of 13% (e.g., equivalent to 0.52.0% phospholipids). As a daily supplement approximately 10 to 20 g lecithin per 100 pounds body weight (45 kg) is a starting point. A teaspoon of granule de-oiled lecithin is about 2 g and a tablespoon is about 7.5 g. The amount of supplemental lecithin to achieve the desired nutritional effect is inuenced by breed and individual animal genetics as well as environmental variables such as humidity level, exposure to sun and wind, frequency of bathing, and others (e.g., allergies). Lecithin is also used in complete equine foods. The usage level has been 15% (e.g., 0.53.0% phospholipids), with a more common usage level in the 1.02.5% range. As a daily nutritional supplement, the amount of lecithin fed is related to state of nutrition, general health, weight, age, and others. Lecithin supplementation can range from 15 to 20 g up to 90 to 100 g per 1000 pounds body weight (450 kg). Note: An eight-ounce standard measuring cup holds approximately 100 g of de-oiled lecithin granules (328). Lecithin is also used in the diets of fur-bearing animals (e.g. foxes, mink) to promote healthy, full hair coats. The reason for lecithins use in this application is the same as for its nutritional use with companion animals (328). Equine health. The lining of the gastrointestinal tract of animals is composed of a specialized epithelial tissue. Equine physiology, in combination with the employment (e.g., racing, trial events) of this companion animal, creates a unique nutritional application of phospholipids. Stomach ulcers represent a signicant problem, and well-studied health condition, in foals and adult horses. The incidence of ulcers in young foals may be 5060%. In adult horses involved in routine training or racing, the incidence of stomach ulcers can be 8090%. The presence of ulcers in horses is associated with poor condition, irritability, and poor performance. A majority of equine ulcers occur in the nonglandular fundic region of the stomach. Signicant research has suggested that surface-active phospholipids can play a role in supporting the defenses of the squamous epithelium in this region of the stomach. In fact, a number of studies suggest that orally supplemented lecithin can help reduce formation of, and contribute to, healing of stomach ulcers. Reviewing the published information, an approximate daily consumption of 90155 g of lecithin for a treatment period of 24 weeks may be indicated. Routine feeding of lecithin at
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a lower rate may help maintain gastric tissue health and avoid ulcer formation. Direct study of lecithin in horses is needed to gain more exact information (329). Companion animal memory. As mentioned, the emotional relationship between people and their companion animals continues to grow. Other areas of companion animals health and quality of life that can be addressed through their food include brain development, learning ability, and memory. Brain development and maintenance is a life-long process beginning in utero and continuing until death. The importance of optimizing the ability of companion animals to learn and remember will add to the quality of life that they and their owners experience. To this end, choline deserves special attention when companion animal foods are formulated. The unique attributes of lecithin (e.g., phosphatidylcholine) as a highly bioavailable source of choline should be recognized. Optimizing choline consumption during pregnancy can stimulate brain and nervous system development and growth in the fetal young, can result in improved ability of young animals to learn and remember, and can benet memory into old age. Optimizing dietary choline/ lecithin for young adults can improve serial learning and selective remembering, as well as benet behavior (e.g., reduced excitability, anxiety, reactivity, and aggression). Although memory diminishes with age, optimal dietary supplementation with choline/lecithin can reduce brain cell shrinkage and improve short-term memory and learning in geriatric animals (329). Companion animal exercise. In addition to choline/lecithin involvement in neural functions related to learning and memory, they are also involved with muscle function. Cholinergic nerves carry signals to muscle bers. Research has shown that intense, sustained exercise lowers plasma choline levels. These declines are prevented by choline/lecithin supplements, which in many cases enhance physical performance (330). In humans (e.g., marathon runners, swimmers, skiers), supplementation is reported to decrease the feeling of fatigue, increase the feeling of vigor, and improve race times. Mechanistically, the supplementation can alter the synthesis and release of acetylcholine from nerve endings, enhancing skeletal muscle contraction. Choline supplementation is also associated with increased choline content of skeletal and cardiac muscle cell membranes. This storage benets acetylcholine formation and release. Further, the supplementation complements membrane growth and repair. Lecithin use can expand the unsaturated fatty acid content of membranes, increase membrane permeability and cell energy metabolism, and improve exercise capability. The observed result can be improved physical capabilities of exercising horses and dogs (331). Poultry. Lecithin has nutritional application in poultry feeds. The caloric value of lecithin (8900 kcal/kg) for broilers was reported to be greater than tallow (5000 7000 kcal/kg) or soybean oil (8800 kcal/kg) (332). This research was complementary to earlier observations that fat utilization and metabolizable energy value were improved when lecithin was also included in chick diets (333, 334). Phospholipids can increase pigment absorption contributing to egg yolk pigmentation (335). Nutrition also plays a key role in the value of meat. Brazilian research found that lecithin in the diets of broilers improved the sensory scores for breast meat (336).
NONFOOD AND INDUSTRIAL USES
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7. NONFOOD AND INDUSTRIAL USES Utilization of lecithins has expanded beyond traditional applications in oil-based paints, chocolate, margarine, and bakery goods. Lecithin is not only used as a release agent for the baking industry, but also in the adhesives and plastics industries, and is used as a dispersing agent in many industrial applications. Lecithin destined for certain industrial applications may require more rigorous rening conditions than conventional lecithin grades. Cross-reacting lecithin also expands the applicability of lecithin for specic applications. Lecithin serves as a dispersing agent in water-thinned paints, latex paints, and printing inks; as an antisludge additive in motor lubricants; and in combination with phenolic antioxidants, it serves as an antigumming agent in gasoline. It serves as an emulsier, penetrant, spreading agent, and antioxidant in the textile industry, and as an antioxidant and dispersant in the production of rubber compounds. Lecithin has found a place in pesticide and herbicide formulations, and it is being used in cosmetics and the pharmaceutical industry. It has also been used for many years as a surfactant in magnetic recording media. Miscellaneous functions of lecithins in industrial applications and a listing of their nonfood uses are given in Table 28 (56).
TABLE 28. Nonfood Applications for Lecithin, Levels of Use, and Functions (56). Application Adhesives Adsorbents Catalysts Ceramics and glass Cosmetics and soaps 15 Levels of Use (%)a Miscellaneous Functions Dispersing agent or mixing aid, plasticizer Adhesion aid, coupling agent, occulant Catalyst, emulsier or surfactant, modier, wetting agent Dispersing agent or mixing aid, release or nonstick agent, water repellant Antioxidant, dispersing agent or mixing aid, conditioning agent, emollient or softening agent, emulsier or surfactant, liposomal encapsulating agent, moisturizer, nutritional supplement or vitamin source, penetrating agent, stabilizer, wetting agent Anticorrosive, emulsier or surfactant Adhesion aid, antidusting agent Dispersing agent or mixing aid, coupling agent Antidusting agent, emulsier or surfactant, stabilizer Antidusting agent, conditioning agent, spreading aid Color intensier, dispersing agent or mixing aid, emulsier or surfactant, grinding aid, stabilizer, suspending agent, wetting agent Conditioning agent, emollient or softening agent, emulsier or surfactant, lubricant, penetrating agent
Detergents Dust control Dyes Explosives Fertilizers Inks
0.52
0.53
Leather
12 of oil
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TABLE 28 (Continued ) Application Magnetic tapes Levels of Use (%)a 0.51.5 Miscellaneous Functions Antioxidant, dispersing agent or mixing aid, emulsier or surfactant, lubricant, wetting agent Anticorrosive, dispersing agent or mixing aid, emulsier or surfactant, plasticizer, release or antistick agent, strengthening agent, wetting agent Anticorrosive, antispatter agent, occulant, lubricant, release or antistick agent Antioxidant, color intensier, dispersing agent or mixing aid, emulsier or surfactant, grinding aid, promoter, spreading aid, viscosity modier, stabilizer, suspending agent, wetting agent Dispersing agent or mixing aid, emollient or softening agent Adhesion aid, antioxidant, biodegradable additive, dispersing agent or mixing aid, emulsier or surfactant, penetrating agent, spreading aid, stabilizer, synergist, biologically active agent Adhesion aid, anticorrosive, antioxidant, dispersing agent or mixing aid, emulsier or surfactant, lubricant, stabilizer Antioxidant, emulsier or surfactant, liposomal encapsulating agent, machining aid, nutritional supplement or vitamin aid, stabilizer, wetting agent, biologically active agent Antibleed agent (as in fat bloom), antioxidant, emulsier or surfactant, dispersing agent or mixing aid, modier, plasticizer, release or antistick agent, stabilizer, strengthening agent Color intensier, dispersing agent or mixing aid, grinding aid, photosensitive agent, wetting agent Emulsier or surfactant, lubricant, release or antistick agent Antidusting agent, conditioning agent, dispersing agent or mixing aid, emollient or softening agent, emulsier or surfactant, lubricant, release or antistick agent, water repellant, wetting agent Adhesion aid, dispersing agent or mixing aid, occulant
Masonry and asphalt products
Metal processing Paints and other coatings 0.55 of pigment
Paper Pesticides 0.15
Petroleum and other fuel products Pharmaceuticals
0.0052
Polymers, including rubber
0.51.5
Printing, photocopying, and photography Release agents Textiles 210 0.20.5
Waste treatment
a
Usage level is 0.051.5% unless indicated.
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7.1. Catalyst Applications Lecithin has some catalytic or cocatalytic effects in multiphase systems because of its surface-active properties. Lecithin is reported to be useful as an emulsier in the curing of aqueous dispersions of unsaturated polyesters (337). The products are more easily removed from their molds and have improved mechanical properties when lecithin is used. In a fermentation application, 1.5% soybean lecithin acts as an inducer in the preparation of cholesterol esterase using a strain of Pseudomonas bacteria (338). Aside from its role as a catalyst, initiator, or modier, lecithin may have ancillary uses in catalyst systems as part of a protective coating (339). 7.2. Detergents A patent describes the use of soybean lecithin to improve the detergency of anionic detergent compounds in the cleaning of dishes containing dried or baked soils (340). The use of soybean lecithin also has been described to improve a shcleaning composition containing alkali metal salts and soaps (341). Fractionated lecithin improves the detergency of N-acylglutamate salts (342). The addition of lecithin to a detergent for cleaning hard surfaces can leave behind a protective lm that protects against further soil deposition (343). 7.3. Paper, Printing, and Ink Lecithin is reported to be useful as a dispersing and softening agent in paper manufacturing (344). Addition of lecithin to a softened cellulose product such as tissue imparts lubricity that is perceived as softness. It can also help achieve the properties of strength and absorbency that are necessary (345). Partially saponied lecithin has been recommended for this use (346). Lecithin has functionality in printing inks and toner formulations for photocopying (347). It also increases the intensity of colors and serves as a grinding and remixing aid. Some patented products containing lecithin include multidetectable ink compositions (348) and magnetic ink (349). Lecithin is also useful in formulations for removing offset and printing inks (350). Paper and paperboard are often coated to improve properties such as printability and appearance (351). A coating with superior uniformity, ow properties, stability, and brightness is obtained with a blend of fatty acids and lecithin (351). The increased production speed in paper manufacturing today requires improved lubrication and release. For these purposes, lecithin can be included in the papermaking slurry, or sprayed directly on to the drying drums (352). Lecithin signicantly improves the rheological properties of aqueous coatings for rapidly moving webs (353). Hydroxylated and acetylated lecithins can eliminate the need for other surfactants in paper coating and improve the printed surface (354). The use of lecithin can permit the use of high amounts of polymeric binders in conventional processes and equipment and improve the strength of the nal product (355). In recent years, there has been an increasing awareness of recycling and the reuse of cellulose products. Often, used paper is contaminated with coatings and
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adhesives. Lecithin is useful as a dispersant for removal of wax and similar contaminants in a recycling process (355). Using lecithin in a rewet process enables processing speeds of 50 m/min in continuous operation for more than 24 hours without lowering the quality of the cast paper (356). Oil-free phospholipids can be used as photosensitive agents for making positive and negative photographic images for lithographic prints, printed circuits, or similar uses (357, 358). An electrosensitive lm useful for duplicating designs uses lecithin (359). Incorporating lecithin in the formulation of nitrocellulose-coated polypropylene lms, for preparation of plastic printing plates, improves the clarity and integrity of the copy (360). Lecithin can be used as a dispersing aid for oil-soluble photographic additives (361). It can also be used for pressure-sensitive sheets for transferring colors (362364) or for correcting typewriter errors (365). 7.4. Agriculture Lecithin can effectively be used as an additive in agricultural formulations for a wide variety of purposes. According to the environmental hazards they may cause, conventional agrochemicals can be classied in two categories. One includes pesticides with high nonselective toxicity, and the other comprises those compounds that, because of their chemical persistence, are easily concentrated in the food chain (366). In addition to the usual functional properties of emulsication, dispersion, and improved suspension, lecithin can improve adhesion, penetration, and performance (367). Efcacy of agricultural pesticides can be enhanced by incorporating the active ingredient into liposomes (368). Liposomes can also reduce, or eliminate, the phytotoxicity of the active ingredient to the recipient plant, with longer duration because of the time release properties obtained with the liposome (368, 369). It has been reported that lecithin can combine with the fatty substances of vegetable leaves, and form a coating that aids in the rejection of plant viruses. Phospholipid vesicles have been successfully used as model membrane systems to study permeability, ion transport, uidity, and other properties of biological membranes (370). The interactions among active ingredients, adjuvants, and target pests are very specic (371, 372). Machine oil and phospholipid mixtures have been patented as fungicides (373). Misato et al. (366, 374) have found that soybean lecithin will arrest the development of powdery mildew on cucumbers, eggplants, green peppers, and strawberries. Sodium bicarbonate containing 0.1% lecithin inhibited citrus common green mold, cucumber powdery mildew, and rice blast better than the bicarbonate alone (375). Another environmentally friendly fungicide, containing lecithin and phosphate, is effective against powdery mildew (oidium), peronospora, botrytis, red re disease, and black spot (376). Lecithin-containing formulations are active against mites (377, 378) and against worm infestations on apples (379). Recent developmental work on pesticide formulations has focused on targeted biological agents that are disease specic. A suspension of lecithin and nuclear polyhedrosis virus (NPV) was much more effective at infecting and killing the corn earworm (Heliothis armigera) than was NPV by itself
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(380). The insecticidal activity of Bacillus thuringiensis and its toxin is considerably increased when combined with lecithin (381). Many concerns have been raised regarding the topical application of N,Ndiethyltoluamide (DEET), the primary active ingredient in most commercial insect repellants (382). Because of this concern, alternative ingredients are being sought. A recent patent (382) has been led on the insect repellant characteristics of a blend of lecithin with other plant extracts. Incorporation of lecithin in an insecticidal collar not only facilitates the migration of the insecticide onto the animals fur, but also provides a softener and protector on the animals skin where it is most needed (383). Lecithin is reported to be an active agent in mosquito control (384, 385). The exact mechanism of action is unknown, but the lecithin forms a stable lm on water surfaces, which may interfere with the breathing mechanism of the mosquito pupae. Phosphatidylcholine is increasingly being used in insecticide formulations to improve performance. In the presence of lecithin, the stability of photolabile insecticides can be signicantly improved (386). Phospholipids formulated with alcohols, glycols, and/or glycol ethers are reported to have antibacterial effects in agrichemical applications (387). Lecithin is a component of coating compositions recommended for postharvest treatment of a variety of fruits, vegetables (388), and fungi (389). Postharvest treatment of apples with aqueous emulsions containing lecithin and various fats and oils can reduce the incidence of soft scald that occurs during cold (1 C) storage (390). Fungicidal preparations containing organic acids and lecithin have been reported to be useful for oranges (391). As with the pesticide applications, efcacy of any treatment may be very specic, not only fruit or vegetable specic, but cultivar specic has been observed with apples (392). Lecithin may also nd a signicant home in applications of fertilizers or growth promoters. Lecithin that has been acidied with propionic acid can signicantly enhance the performance of some plant growth modiers (393). With continued emphasis on environmentally friendly agrochemicals, and concern about pesticide residues in the food supply, the potential for lecithin in agriculture appears poised for growth.
7.5. Cosmetics and Personal Care Items Lecithin, being a natural compound and having multifunctional properties, is a logical choice for cosmetic formulations. These preparations include skin creams and lotions, foundations and cleansing creams, sunscreens, soaps, bath oils, shampoos and hair conditioners, shaving creams, preshave and aftershave lotions, nail enamels, face powder, eye color creams, lipstick, and hair sprays. Lecithin can be used as an emulsier, spreading agent and/or wetting agent, or as a penetration aid, but one of the primary reasons lecithin is chosen for use in cosmetics is its role in providing skin feel. When lecithin is used in coatings containing pigments and other particulates (e.g., Kaolin) (394396), it produces coatings with smoother surfaces, improved
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adhesion to the skin, and better color stability (397). This translates to longerwearing blushers, eye shadow, and face powders. Lecithin can also reduce the undesirable oily feeling in cosmetics containing oils. In the latter, the product also wears longer and reduces the transfer of substances to clothing because of improved lm adhesion. Lecithin alters the emulsion break (rubout) during the application of day creams, while acting as a moisturizer (398). Another important reason for using lecithin in cosmetics is the potential for a reduction in skin irritation. Addition of lecithin to cosmetic powders it can reduce irritation of inorganic powders, and it can even form a barrier that prevents these powders from coming into contact with the skin and drying it out (399). The irritation caused to the skin by soap can be signicantly reduced, if not eliminated, by incorporation of lecithin (400, 401). In moisturizing cosmetics, lecithin forms highly viscous liquid crystals, the structure of which inhibits the evaporation/transpiration of water from the skin (402). This moisturizing property extends to keratinized appendages as well. Phospholipid incorporation in formulations to treat hair, hooves, horns, claws, and nger and toe nails has proven to be effective at moisturizing and strengthening these same structures (403, 404). The release properties of lecithin play a function in dental care as well. Lecithin can be used to loosen plaque on tooth surfaces. In saliva, up to 14% of the total lipid content is lecithin (405). Once bacteria are removed, lecithin can be used as a barrier agent to prevent bacteria from sticking to the teeth. The charged head group of lecithin adheres to the enamel surface, and the hydrophobic portion facilitates removal of plaque and bacteria upon brushing (405, 406). Replacement dentures can also benet from the unique properties of lecithin. At low levels, lecithin can reduce the viscosity of denture pastes and permit higher adhesive loading, which ultimately results in a stronger adhesive that holds longer, and resists deterioration by saliva and moisture (407). Lecithin, however, does have some disadvantages. It makes products more susceptible to microbial growth and, being multifunctional, its efciency and ability to accommodate varying HLBs does not allow it to compete with a host of customized synthetics in special situations (398). 7.6. Pharmaceutical and Medical A signicant pharmaceutical application for lecithin is the forming of a protective coating on a capsule or tablet. However, this application will be addressed in a subsequent section (see 7.7.2). This section will focus on the incorporation of phospholipids in pharmaceutical formulations. Phospholipids are components of biological membranes in all living systems. They play important roles in biological processes such as cell permeability, the regulation of membrane-bound enzymes, and lipid and cholesterol transport (89, 408). The neurological importance of phospholipids is emphasized by the phospholipid composition of dry brain tissue, which is about 25% (409). Because of this biological activity, there is a great variety of applications for lecithin in the pharmaceutical eld. Liposomes have long been known as potential carriers of pharmacologically active ingredients.
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The inherent compatibility of lecithin with living membranes can improve the acceptance of the body for medications and implantable devices by modication of their surface chemistry. The poor aqueous solubility of many biologics presents a problem for human administration. Indeed, the delivery of pharmacologically active agents that are inherently insoluble can be seriously impaired if oral delivery is not effective (410). Liposomes have proved a valuable tool as an in vivo delivery system for enhancing the efcacy of various pharmacologically active molecules. Animal studies have shown that liposomes can decrease the toxicity of several antitumor and antifungal drugs (411). Studies have shown diseases associated with above normal levels of certain lipoproteins. Intravenous administration of liposomes can reduce lipoprotein concentrations in subjects at risk for such diseases (412). Arterial atherosclerotic lesions and plaques have been shown to shrink when treated with liposome infusions (413). Although liposomes make use of native phospholipids, conjugation of many biologically active agents with phospholipids via a phospodiester bond will signicantly enhance the bioactivity or bioavailability of such agents (414416). Modifying the phospholipids with a characteristic antibody, a liposome can be created to target specic cells (414). The biocompatibility of materials used in medical devices, or other implantable materials, is improved by covalently attaching PC to the surface of the device (417). Incorporating PC into the lling solution for soft tissue implants improves the stability, biocompatibility, and appearance of the implant (418). Aside from being an active pharmaceutical agent, or a liposome-type transport agent, lecithin also has a more traditional function as an emulsier, wetting and dispersing aid, and stabilizing agent, in pharmaceutical applications. Representative formulations incorporating lecithin include b-lactam antibiotics (419), steroids, such as diethylstilbesterol (420), prostaglandins (421), vitamins (422), and antidiarrhea medicine (423). Lecithin has been used as an aid to facilitate microencapsulation of pharmaceuticals with ethyl cellulose (424). Lecithin can also improve the processing properties of medications formed by extrusion (425). Medical testing can also benet greatly by the use of phospholipids. The Venereal Disease Research Lab test for syphilis is based on the use of an antigen solution that includes cardiolipin, cholesterol, and lecithin (426). 7.7. Paints and Coatings
7.7.1. Paints Paints and other types of coatings make up a major portion of nonfood applications for lecithin products. The broad range of functional properties of lecithin makes it highly suitable for many different coating formulations. These include paints, waxes, polishes, and wood preservatives. Lecithin is also used as a release agent in coating-related manufacture, including applications in cosmetics and magnetic tape coatings. The literature is replete with information on special lecithin products in coating applications (56). Various formulations have been published, and special lecithin blends patented, for improved functionality in specic areas. Examples of these
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functions are antioxidant; color intensier agent; catalyst; conditioning aid modier; dispersing aid; emulsier/surfactant; grinding, mixing, or spreading aid; wetting agent; stabilizer; suspending agent; synergist; and viscosity regulator (427). Miscellaneous applications involving coating principles include cosmetics, mold release agents, magnetic tape coatings, printing and inks, toner formulations, photographic additives, and polyamide coatings (i.e., nylon leather substitutes) (56). As lecithin products can function as interfacial agents in paints, lacquers, and printing inks, they can serve as wetting, dispersing, suspending, and stabilizing agents in both oil-base and latex/resin emulsion paints. In paints, lacquers, and printing inks, the choice of wetting agents to use depends on the nature of the pigment, the vehicle, and the processing procedure. As a rule, natural grades of lecithin have been recommended up to 1% (on pigment weight basis), and in some formulas containing carbon black or iron blues, as much as 2% may be required. However, comparative tests have shown that in many coatings, rened-grade lecithins are among the best wetting and dispersing agents, and they can compete with other surfactants available on the market (1, 56, 428). Lecithin products can function in paints to facilitate pigment dispersion and redispersion (429, 430), and to regulate (generally reduce) viscosity. Lecithin serves as an emulsier and wetting, dispersing, and stabilizing agent in both oil- and latexbased paints. It shortens mixing time, aids brushing, and increases the covering power of the paint. In oil-based paints, lecithin has been traditionally used as a low-cost pigment grinding aid. Lecithin coats the particles of metal oxide pigments rendering them readily dispersible. If more than one pigment is used, lecithin coating helps maintain a uniform mixture (427). In water-based paint systems, water-dispersible lecithin products are recommended as low-cost emulsiers, stabilizers, thickening agents, and spreading aids. It has been demonstrated that in latex paints, pigments were dispersed more rapidly in the presence of lecithin. Paints based on rubber-type vehicles may also be formulated with lecithin to improve color uniformity. In addition, the advantages claimed for lecithin in oil-base paints (i.e., aiding pigment dispersion, shortening grinding time, preventing undesirable hard settling of pigments, and eliminating deocculation while contributing to the overall stability of the emulsion system) are also valid in water-based coatings (427). Water-dispersible lecithins are made by chemical modication, or by mixing ordinary lecithin with nonionic surfactants. Many of the products recommended in the literature and technical brochures for water-based compositions include such chemically modied, water-dispersible, lecithin compounds (e.g., hydroxylated, acylated, fractionated, and rened grades) (428, 431433). Usually 0.5% to 1% modied lecithin is recommended in polyvinyl acetate-based paints, acrylic emulsions, and in butadienestyrene emulsion paints. In mixed pigmentations, lecithin additives help to maintain a uniform mixture in both alkyd and latex paints, ensuring uniform settling in storage. Latex paint redispersion is also made more effective with a water-dispersible lecithin additive than with a synthetic surfactant. Paint specimens with lecithin additives, remixed after 28 months of storage, maintained a very high level of uniform color stability (434).
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Metal salts of lecithin have been patented as paint additives (435). These salts are reported to improve pigment dispersion, and act as drying promoters and inhibit yellowing of the product. The same patent also promotes the use of phosphorylated lecithin as a rust inhibitor in primer paints. Further, if metal oxides are chemically reacted with lecithin by heating, the dispersibility of metal oxides in both aqueous and organic solvents is improved (436). Not only is lecithin used as a compounding and formulation aid in paints, but it has demonstrated useful properties in the coating. Standard-grade lecithin, as well as certain derivatized and hydrolyzed lecithins, was found to be useful in coatings to inhibit the rusting of steel in salt spray tests (437, 438). These ndings are expected, because lecithin functions as an antioxidant in a number of applications. Lecithin is particularly well suited for coatings used on food-grade containers. One example is its use on cardboard to help form a food-grade barrier (439). Lecithin is also used for its release and sealant properties in polymer coatings for interior coatings (440). Coating organic polymer lms with lecithin can improve the release properties of the lm from the crimp jaws of the automated packaging machine (441). In analytical equipment, lecithin is used to improve the wettability of the contact surface, which enables the solvent to be presented uniformly for analysis (442). Incorporation of lecithin in a masking application can reduce bubble formation and improve the uniformity of the application (443). And nally, lecithin can be used as a protective coating for a painted surface such as found on automobiles. Once applied, it facilitates the removal of insects and debris. The coating is resistant to rain and washing away (444).
7.7.2. Coatings Lecithin is also used in the production of a protective surface in
the manufacture of pharmaceuticals. Many medical substances undergo degradation during storage because of contact with moisture absorbed from the atmosphere (445). Frequently, lecithin is used as a detackier in coatings for tablets, pharmaceuticals, food, confectionary, and seeds. Often it is used in conjunction with maltodextrin, gelatin, and cellulosic polymers (446-448). Lecithin is also used in coating formulations to produce a coating that imparts sheen to the pharmaceutical, thereby improving its visual appeal (449). Some solid drugs are scarcely soluble in water. Because of low solubility, these drugs have a low degree of bioavailability. The coatings on pharmaceuticals also play a vital role of improving the dispersibility, and hence bioavailability, of pharmaceuticals (448, 450). On a larger scale, lecithin is used in many applications to reduce the viscosity of the coating material. When used with a casting resin, the integrity of the cast is improved by the viscosity reduction (451). When lecithin is incorporated into a rubberized asphalt coating (i.e., roong composition or oor coating), it reduces the viscosity and acts as a wetting agent, enabling the coating to be sprayed more easily (452, 453).
7.7.3. Magnetic Recording Media
Much of the magnetic recording media incorporates lecithin as a processing aid. This includes audio and video tapes, as
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well as magnetic media for digital applications. Lecithin functions as a dispersing agent, lubricant, wetting agent, and antioxidant in these formulations. De-oiled lecithins used for magnetic tape should be derived from standard-grade lecithin with very low peroxide and hexane-insoluble values. A typical coating contains iron oxides (sometimes doped with cobalt or chromium), a polymer system that acts as a binder, various additives (including up to 1.5% lecithin on a dry solids basis), and solvents such as methyl ethyl ketone and cyclohexanone (454458). This material is milled into a dispersion and deposited onto the tape and dried. Lecithin can also be used in a tape coating containing abrasive cleaning compounds for cleaning tape recorder heads (459). A magneto-optical imaging lm can be made by coating a support with a photosensitive resin-containing magnetic material (460). The coating is prepared using lecithin, and the lm is especially useful for Chinese character pattern memory. Chagnon and Ferris (461) reported a study on the effectiveness of soy lecithin as a surfactant in dispersing pigments for use in magnetic tapes (i.e., in recording media). These experiments indicated that oil-free soy lecithin is effective as a surfactant, and at dispersing a wide range of magnetic particle types in a wide range of solvents.
7.7.4. Adhesives Adhesives ll a special niche in the coating arena. They are
not to protect a surface, but rather perform the function of bonding two surfaces together. In this application, lecithin can demonstrate its diverse nature by functioning either as a release aid or to enhance the surface interactions. When it is applied to the backside of a pressure-sensitive adhesive, lecithin can prevent the lms from sticking to themselves (462). In the production of adhesives, and in processes involving the use of adhesives, invariably adhesive material needs to be removed from adjacent surfaces. Lecithin can be applied to these surfaces as a release aid to prevent adhesive from sticking to the equipment and facilities, and enabling easier cleanup (463). In processes with porous material, such as wood, lecithin can act as both a release aid, and a surface-active agent. Adhesive that gets on the clamp platen surface cures on a lecithin lm and can easily be removed. Because of the emulsifying action, the adhesive penetrates the substrate better to provide an improved bond (464). Lecithin can also improve the interaction between two materials, such as rubber belts and steel pulleys, to prevent slippage (465). 7.8. Lubrication With the excellent release properties of lecithin, lubrication would seem like a natural area for its use. Indeed, lecithin has been used as an emulsier to stabilize oil and water metal-cutting uids (466). Incorporation of lecithin in the lubricant for forming sheet metal products can improve the electrostatic application properties of the lubricant, especially for food contact applications (467). Soaking valve seals in a solution containing lecithin impregnates the rubber and imparts improved lubrication (468). As with other areas discussed, modication of the lecithin for the
437
specic application improves the desired properties. Hydrogenation of lecithin produces an effective friction modier for use in lubricating oils, transmission uids, hydraulic uids, and the like (469), whereas the pressure, thermal, and lubrication properties of grease can be improved by incorporation of a phospholipidboron composition (470). 7.9. Bioremediation There are many areas throughout the world where chemicals of varying persistency and toxicity have been disposed of by dumping onto the ground. In addition to presently existing dumps, there are numerous instances at industrial sites such as petroleum tank farms, chemical plants, and elsewhere, where crude or rened hydrocarbons, such as oil, gasoline, or the like, are spilled on the ground or into bodies of water. Such wastes not only spread out and soak through the surface of the ground, but also seep into the ground and disperse into the ground water (471). One method for cleaning up contaminants is by enhancing the degradation of them through the use of micro-organisms. Phospholipids facilitate the cleanup of contaminated soils by a combined effect of enhancing bacterial growth by supplying essential nutrients, while concomitantly modifying the physical state of oil or wastes, thereby making them accessible to interaction with, and biodegradation by, micro-organisms (471) Tests were conducted on soils articially contaminated with polychlorinated biphenyls (PCBs) using de-oiled lecithin as a natural surfactant. The degradation of PCBs was signicantly enhanced at lecithin concentrations in slight excess of the critical micelle concentration. Lecithin favors the degradation by both increasing the bioavailability of the contaminants and supporting the growth of the degradation bacteria (472). 7.10. Plastics and Polymers Lecithin functions as a pigment-dispersing agent and mold-release agent in the preparation of various polymer products. It facilitates dispersion of polymer resins in plasticizers to form plastisols (473). Polymerization of vinyl chloride in the presence of poly (vinyl alcohol) and lecithin gave a poly (vinyl chloride) that was more thermally stable than the polymer prepared without the lecithin (474). A curing agent for polyurethane contains lecithin as a dispersing agent (475). Inclusion of hydroxylated lecithin in the formulation of polyurethane elastomer functions effectively as an internal mold release agent (476). Hydroxylated lecithin and hydrolyzed lecithin are also suitable dispersants for aqueous polymer emulsions. Aqueous polymer emulsions form polymer lms on evaporation of the aqueous dispersing media. On this basis, they are widely used as binders in paper coating slips, textile inks, coating material, nishes, and adhesives. They are particularly useful in that they have a small tendency to promote foam formation, and they are biodegradable (477). More recent work on inclusion of lecithin in plastics has focused on applications in the medical eld. Phospholipids can be used as plasticizers or release agents in
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thermoplastics or elastomers for use in biomedical applications (478). Biomedical applications of polymers include use as implants, prostheses, blood or tissue contacting devices, and articial organs. There are many difculties because of the incompatibility of living tissues with foreign materials inserted into the body (478). The presence of appropriate phospholipids entrapped in the polymer matrix, at its interface with biological uids or tissue, can modify the interface and provide the appropriate biological effect (478).
7.11. Others An interesting coatings application for lecithin is in producing nonpyrophoric Raney nickel (339). The lecithin in this application creates a lipophilic surface on the metal, along with a wax, fat, or organic polymer. Polyamide coatings containing lecithin are recommended as a nish coat in nylon leather substitutes (479). Lecithin has been used in sizing for textiles to prevent the sizing from adhering to non-PTFE-coated equipment (480). In leather cleaning and conditioning compounds, lecithin can improve the wetting and penetration of the conditioning compounds into the leather (481). Lecithin is used as an emulsier, wetting and dispersing agent, plasticizer and/or release agent in concrete, asphalt and tar shingling, linoleum tiles and surface sealants, and caulking compounds (4, 440, 473, 482485). Lecithin is reported (at low levels, 0.050.1%) to improve the properties of water-glass-containing coatings for foundry cores and molds (486). Phospholipids are naturally occurring emulsiers in rubber latex. They can be used as a foam stabilizer in foam re extinguishing agents (487). Lecithin has also been used to improve the combustion of burner fuels. Burner fuels are typically sprayed into the combustion chamber of a boiler to heat water for steam or power generation. Emulsication of water into the burner fuel can improve the combustion efciency through a secondary atomization of the oil droplet as the emulsied water vaporizes to steam. These much smaller oil droplets burn more completely, resulting in signicant emissions reductions (488). Finally, lecithin-diamine compounds have been used as functional ingredients in multipurpose gasoline additives (489, 490). For additional lecithin uses, the reader is referred to List and Von Kleinsorgen (482), Meshandin et al. (491), Schmidt and Orthoefer (56, 58), and Wittcoff (4).
8. AVAILABILITY AND ECONOMICS Although lecithin may be obtained from other plant seeds and animal sources, soybeans provide the bulk of what is commercially available. Because they are multifunctional ingredients, lecithin products sell at a premium versus soybean oil. Current world demand is estimated to be 180,000 to 210,000 metric tons (150,000170,000 MT of standard products and 30,000 to 50,000 MT of value-added
REGULATORY ASPECTS
439
lecithins). Value-added products have been gaining market share because their specialized chemical and physical properties and the inherent limitations of the standard grades (160). There is no industry-wide reporting of lecithin sales in specic application areas, and so the exact percentage breakdown of uses is difcult to determine. This problem is also complicated by the fact that as much as 3040% of the domestic market involves hundreds of small volume users who are serviced by distributors (56). Additionally, some customers may have both food and nonfood applications for lecithin. For the most part, the greatest percentage of lecithin is used in foods. The second highest use is in animal feeds, followed by industrial applications. Paints and other coatings consume a major portion of the nonfood lecithin. Pharmaceuticals, including dietary supplements, and inks and cosmetics, however, also consume signicant portions.
9. REGULATORY ASPECTS In the United States, lecithin is afrmed by the FDA as GRAS and meets standards set by the Food Chemicals Codex (54). It is also an approved ingredient in many important foods having a standard of identity. Hydroxylated lecithin has special FDA approval with limitations for level and use (60). The U.S. Standards for Identity for Margarine and Bakery Products, and Food Additive Regulations, allow the use of lecithin; hydroxylated lecithin is allowed in breads without level limitations. Similarly, the use of lecithins is permitted in most countries. In Europe, lecithins are covered under E322 regulations (492). Advances in biotechnology in the 1990s has led to genetically modied organism (GMO) issues for phospholipids from soybean, corn, and canola. The European community has reacted to consumer pressure and the right to know by establishing GMO regulations (493) that clearly label the presence of GMO products. This has forced the ingredient supplier to validate non-GMO products by DNA quantication and identity preserved (IP) testing. No food regulations are anticipated, at this time, for GM in the United States. The European reaction to traces of GMO DNA in foods has markedly affected the uses of phospholipids in food and health applications. The consumers right to know, and ingredient users avoidance of GM products, has led to a decrease in soybean and corn lecithin usage, with a shift to the usage of soft-seed lecithins (rapeseed and sunower) that are non-GMO. The U.S. Food and Drug Administration has addressed the issue of labeling regarding genetically engineered foods in its policy position published in the May 29, 1992 Federal Register Notice (57 FR 22984). The U.S. policy reects the science-based consensus that there is nothing inherently unsafe about genetically engineered foods, and consequently, these foods do not warrant labeling
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considerations solely because of the application of genetic processes to maintain and improve characteristics.
10. FUTURE PROSPECTS Just as in some food uses, some of the nonfood applications of lecithin are in mature market areas such as paints and inks. Judging from patent activity, however, growth in some areas seems reasonably assured. In recent years, pharmaceutical patents accounted for almost 25% of the nonfood patent activity. Pharmaceutical applications, particularly those involving liposomes, should require increasing quantities of rened lecithins. An increased demand for lecithin as a dietary supplement is also anticipated, as the result of dietary reference intakes being established for choline. Besides being a multifunctional food ingredient, lecithin has the benet of being a widely recognized health food. The major process developments at the present time are in the fractionation of lecithin, and alternative extraction and de-oiling processes. Markets appear to be developing in the pharmaceutical and cosmetic industries, particularly for concentrated forms of PC. De-oiled, granular lecithins have rmly established markets, and new markets are developing that should ensure the growth of these products as emulsiers. Overall, the availability looks good for lecithin in both food and nonfood uses if good contact between commercial processors and patent developers can be maintained (7, 56).
ACKNOWLEDGMENTS Part of this chapter has been adapted from Lecithins, B.F. Szuhaj and G. List, eds., 1985, American Oil Chemists Society, and Lecithins: Sources, Manufacture, Uses, B.F. Szuhaj, ed., 1989, American Oil Chemists Society. Permission has been granted by the American Oil Chemists Society.
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13

69.1 23.9 2.7 3.2 1.0

Serum 22.0 7.8 32.4 23.2 26.9 3.5 1.1 5.14

Cream 1.02.0 17.9 25.3 19.9 21.6 Trace Trace 15.34

Morrison et al. (23). Santha and Narayanan (26).

Human 21.8 35.4 18.8 1.8 1.1 2.0 1.0 16.3

Bovine 18.4 36.1 18.0 1.8 1.7 0.2 0.4 15.0

TABLE 10. Composition (%) of Cottonseed Lecithin (32).

38.1 16.2 17.5 7.6 2.0 7.9 10.7

5.6 24.6 22.1 14.7d 19.4 13.6

NOMENCLATURE, CLASSIFICATION, STRUCTURE AND COMPOSITION

The U.S. Food Chemical Codex (54) denes lecithin as follows:

NOMENCLATURE, CLASSIFICATION, STRUCTURE AND COMPOSITION

O CH2OCR1 O CHOCR2 O CH2O P O CH2CH2N(CH3)3 O Phosphatidylcholine O CH2OCR1 O CHOCR2 O CH2O P O O HO OH OH Phosphatidylinositol OH OH

O CH2OCR1 O CHOCR2 O CH2O P O CH2CH2NH3 O Phosphatidylethanolamine

R1 and R2 = C15C17 Hydrocarbon chains

Figure 1. Three principal components of soybean lecithin (7).

NOMENCLATURE, CLASSIFICATION, STRUCTURE AND COMPOSITION

TABLE 18. Composition Fatty Acids of Soybean Lecithin (%) (8).

14:0 1.9 0.3

14:1 Trace 1.2

16:0 11.7 18.1 42.7 26.7 25.5 21.5 18.9

16:1 8.6 7.0

18:0 4.0 3.7 11.7 9.3 10.3 4.3 4.1

18:1 9.8 22.4 17.0 25.1 39.4 7.2 6.8

2022 20:0 Unsaturated 1.4 2.3 5.5 6.2

Also 2.3% unidentied. CHCl3/CH3OH extraction. c Acetone-precipitated. d Granulated.

3 7 Either oil-in-water or water-in-oil

Includes sucrose, rafnose, stachyose, and about 1% moisture.

NOMENCLATURE, CLASSIFICATION, STRUCTURE AND COMPOSITION

NOMENCLATURE, CLASSIFICATION, STRUCTURE AND COMPOSITION

Reduce color Convert to powder form

Light-colored foods Dry blendable

NOMENCLATURE, CLASSIFICATION, STRUCTURE AND COMPOSITION

MANUFACTURE, FRACTIONATION, AND PURIFICATION OF LECITHINS

Figure 2. Batch degumming system for lecithin production (115).

MANUFACTURE, FRACTIONATION, AND PURIFICATION OF LECITHINS

Phosphorus Removed (%)

MANUFACTURE, FRACTIONATION, AND PURIFICATION OF LECITHINS

Batch Dryer, Bollman Typeb 6080 140176 180240 2060

Continuous, Agitated-Film Evaporator 8095 176203 1 2 50300

MANUFACTURE, FRACTIONATION, AND PURIFICATION OF LECITHINS

MANUFACTURE, FRACTIONATION, AND PURIFICATION OF LECITHINS

MANUFACTURE, FRACTIONATION, AND PURIFICATION OF LECITHINS

MANUFACTURE, FRACTIONATION, AND PURIFICATION OF LECITHINS

MANUFACTURE, FRACTIONATION, AND PURIFICATION OF LECITHINS

Wetting and dispersing agent, emulsier

Emulsier, release agent

FOOD-GRADE LECITHIN PRODUCTS, USES

Browning agent, phosphate dispersant Dietary supplement, release agent, emulsier

Emulsier, wetting and dispersing agent, anti-spattering agent, release agent

Crystallization control, emulsier

Release agent, sealant

Internal (in product) and/or external release agent, lubricant

FOOD-GRADE LECITHIN PRODUCTS, USES

FOOD-GRADE LECITHIN PRODUCTS, USES

FOOD-GRADE LECITHIN PRODUCTS, USES

FOOD-GRADE LECITHIN PRODUCTS, USES

FOOD-GRADE LECITHIN PRODUCTS, USES

FOOD-GRADE LECITHIN PRODUCTS, USES

FOOD-GRADE LECITHIN PRODUCTS, USES

Age 06 months 712 months

Adults Pregnancy Lactation