Journal of Food Engineering 91 (2009) 287296

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Journal of Food Engineering

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Effect of maltodextrin and gum arabic on water sorption and glass transition temperature of spray dried chicken meat hydrolysate protein
Louise Emy Kurozawa a,*, Kil Jin Park b, Miriam Dupas Hubinger a
a b

Department of Food Engineering, Faculty of Food Engineering, State University of Campinas, Street Monteiro Lobato, 80, P.O. Box 6121, Campinas, SP, 13083-970, Brazil Faculty of Agricultural Engineering, State University of Campinas, P.O. Box 6011, 13084-971, Campinas, SP, Brazil

a r t i c l e

i n f o

a b s t r a c t
The water adsorption isotherm and glass transition temperatures (Tg) of chicken protein hydrolysate powder, with and without maltodextrin or gum Arabic, were studied in order to investigate their stability. The hydrolysate powder, pure and formulated with 10%, 20% and 30% (w/w) of additive, was obtained by spray drying. The sorption isotherm was determined by the gravimetric method. A differential scanning calorimeter was used to determine the Tg of samples equilibrated with several water activities. As results, the BET model tted the data for the sorption isotherm of the protein hydrolysate well. A strong plasticizing effect of water on the Tg was found, with a great reduction in this value with increase in water activity. The data for Tg versus solids content gave a satisfactory correlation with the Gordon-Taylor model. The addition of carrier agents increased the Tg of the hydrolysate, decreasing its hygroscopicity and, consequently, increasing its storage stability. 2008 Elsevier Ltd. All rights reserved.

Article history: Received 20 July 2008 Received in revised form 9 September 2008 Accepted 12 September 2008 Available online 20 September 2008 Keywords: Isotherms Calorimetry BET model GAB model Gordon-Taylor model Stability

1. Introduction Brazilian chicken meat production increased by 37% in the period from 2002 to 2006, reaching almost 9 million tons in 2006 (FAOSTAT, 2008) and becoming the third largest world producer. According to Barbut (2002), novel processed poultry products have been introduced onto the market in recent years, due to low raw material prices. In order to be competitive, the poultry industry must develop new products to satisfy emerging consumer demands and increase protability. Thus the protein hydrolysis of chicken meat could be an alternative solution to obtain valueadded products. Chicken breast meat has a higher protein content (22 g/100 g meat) and lower fat content (3 g/100 g meat) than other parts of the chicken, such as the drumsticks (18 g protein and 5 g fat/ 100 g meat) and wings (18 g protein and 18 g fat/100 g meat) (TACO, 2004). In addition, animal protein presents a perfect equilibrium of essential amino acids. Protein hydrolysates are mainly applied in the nutritional management of individuals who cannot digest whole/intact protein. Hydrolysates rich in low molecular weight peptides, especially di- and tri-peptides with as little as possible free amino acids, have been shown to have more dietary uses due to their high nutritional and therapeutic values (Bhaskar et al., 2007). Extensively hydroly* Corresponding author. Tel.: +55 19 3521 4088; fax: +55 19 3788 4027. E-mail address: louise@fea.unicamp.br (L.E. Kurozawa). 0260-8774/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.jfoodeng.2008.09.006

sed proteins also show reduced immunological reactivity, and can be used in formulas for hyper allergic infants (Mahmoud, 1994). Furthermore, peptides, being easily absorbed, may be an optimal nitrogen source in sports nutrition, and high biological value peptides are attractive as a general protein supplement in a wide vari yte et al., 2005). ety of diets (liz Protein hydrolysates are highly perishable due to their high moisture and protein content, and have therefore been processed to improve their shelf life. Of the various methods employed for preservation, drying is a process in which the food water activity is reduced by water removal through vaporization or sublimation, minimizing enzymatic and microbiological reactions. Spray drying involves both particle formation and drying, where the feed is transformed from the uid state into droplets and then into dried particles, by spraying it continuously into a hot drying medium. This technique is widely used in food manufacturing and presents low operating cost and a short contact time. Moisture sorption isotherms, important tools for predicting interactions between the water and the food components, describe the relationship between water activity and the equilibrium moisture content of a foodstuff. Knowledge of water sorption isotherms is important in various food processes, such as drying, storage and packaging, since they are used to estimate drying time, ingredient behavior on mixing, packaging selection and modeling moisture changes that occur during storage. Recently, the concepts related to water activity have been coupled with those of the glass transition temperature, Tg, providing

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Nomenclature aw CBET CGAB k KGAB n N Tg Tout VE Vp water activity constant of Eqs. (1) and (2) constant of Eq. (3) constant of Eq. (5) constant of Eq. (3) number of adsorbed layers population of experimental data glass transition temperature (C) outlet temperature (C) experimental value predicted value Xe Xm w equilibrium moisture content (g water/g dry matter) monolayer moisture content (g water/g dry matter) weight fractions (g/g total)

Subscripts c critical s solids w water

an integrated approach to the role of water in foods. The glass transition temperature is dened as the temperature at which an amorphous system changes from the glassy to the rubbery state. Molecular mobility in the glassy state is extremely slow, due to the high viscosity of the matrix (about 1012 Pa s). Thus the Tg can be taken as a reference parameter to characterize the properties, quality, stability and safety of food systems. Structural alterations, such as stickiness, agglomeration, caking and crystallization, occur in amorphous food powders when stored at temperatures above the Tg. Foodstuffs with low-moisture contents and Tg value above the storage temperature can be considered stable. However, a slight increase in moisture signicantly reduces the Tg. Therefore, the moisture sorption and Tg supply critical values for the water activity and moisture content at room temperature (Khallou et al., 2000; Roos, 1993, 1995; Roos and Karel, 1991a; Shrestha et al., 2007a). Protein hydrolysates contain low molecular weight peptides and present low Tg values and, consequently, high hygroscopicity and thermoplasticity. Since the Tg increases with molecular weight, the addition of carrier agents (like maltodextrins and gums) has been used in the production of powders, reducing the stickiness and wall deposition in spray drying (Bhandari et al., 1993; Roos and Karel, 1991a; Truong et al., 2005). Maltodextrins, products obtained by starch hydrolysis, consist of b-D-glucose units and are usually classied according to their dextrose equivalency, DE (Bemiller and Whistler, 1996). The addition of maltodextrin is mainly used in materials that are difcult to dry and has been used for mango, West Indian cherry, date palm and aai pulps (Jaya and Das, 2004; Righetto and Netto, 2005; Sablani et al., 2008; Tonon et al., 2008). Gum Arabic is a complex heteropolysaccharide with a highly ramied structure, with the main chain formed of D-galactopyranose units (Bemiller and Whistler, 1996). It has been used as an encapsulating agent in microencapsulation by spray drying, due to its good emulsifying capacity and low viscosity in aqueous solution. Its contribution to the stability of dehydrated foods was studied by Gabas et al. (2007) and Righetto and Netto (2005). The aim of the present work was to evaluate the inuence of maltodextrin or gum Arabic on the water sorption Tg and stability of spray dried chicken breast protein hydrolysate. Modeling of the sorption isotherms using selected models from the literature was studied (BET and GAB models), and also the Tg using the GordonTaylor model. 2. Material and methods 2.1. Material Frozen chicken breast meat was purchased from Doux Frangosul (Montenegro, Brazil). The meat was stored in a cold chamber at 18 C and thawed according to the quantity required to

produce the hydrolysate. The main characteristics of the meat, obtained according to AOAC (1995), are summarized in Table 1. For the enzymatic hydrolysis, the commercial protease Alcalase 2.4 L (Novozymes, Bagsvaerd, Denmark), which is a serine endopeptidase obtained from Bacillus licheniformis, with a declared activity of 2.4 AU/g, was used. The carrier agents used were maltodextrin Mor-rex 1910 (Corn Products, Mogi-Guau, Brazil), with 9.0 6 DE 6 12.0, and gum Arabic Instantgum (Colloides Naturels, So Paulo, Brazil). 2.2. Preparation of the protein hydrolysate The hydrolysis experiments were carried out in a 10 L thermostatically controlled stirred-batch reactor using the pH-stat procedure, as described by Adler-Nissen (1985). The samples were defrosted overnight. The tendons, nerves, skin and visible fat were removed from the meat, which was then fragmented, ground in a food processor and homogenized with distilled water (meat:water ratio 1:3 w/w). The mixture was heated to 52.5 C and the pH adjusted to 8.00 with 2 N NaOH. The enzyme was added (4.2 g enzyme/100 protein) to the mixture and the reaction pH maintained constant by the continuous addition of 2 N NaOH. After 6 h, the hydrolytic process was terminated by heating the mixture to 85 C for 20 min, assuring inactivation of the enzyme. The process conditions were established according to the results obtained by Kurozawa et al. (2008). The resulting slurry was centrifuged at 3500 rpm (Beckman Coulter, Allegra 25 R model) for 20 min, to separate the lipids. The protein hydrolysate was stored in a cold chamber at 18 C and thawed according to the quantity required for spray drying. The main characteristics of the chicken protein hydrolysate, obtained according to AOAC (1995), are summarized in Table 2. 2.3. Spray drying Before the spray drying process, carrier materials maltodextrin (MD) or gum Arabic (GA) were added directly to the protein hydrolysate with magnetic stirring, until complete dissolution. Table 3 shows the different formulations of the carrier materials

Table 1 Chemical composition of the chicken breast meat Analysis Moisture Proteins Fat Ash Content (%, wet basis) 74.10 0.14 19.36 0.94 1.55 0.12 1.10 0.01

Values represent means of three determinations standard deviations.

L.E. Kurozawa et al. / Journal of Food Engineering 91 (2009) 287296 Table 2 Chemical composition of the chicken breast meat protein hydrolysate Analysis Moisture Ash Protein Fat Content (%, wet basis) 91.32 0.06 0.68 0.03 7.05 0.06 0.08 0.01

289

Xe

X m C BET aw 1 n 1aw n naw n1 1 aw 1 C BET 1aw C BET aw n1

Due to lack of t for high water activities, the BET model (Eq. (1)) was not used in this work to t the experimental data. As a consequence, the isotherm models used were the modied BET (threeparameters) and GAB models (Van den Berg and Bruin, 1981) (Eqs. (2) and (3))

Table 3 Formulations of protein hydrolysate with maltodextrin (MD) or gum Arabic (GA) Formulation Concentration (%, w/w) Protein hydrolysate Without carrier agent 10%MD or 10%GA 20%MD or 20%GA 30%MD or 30%GA 100 90 80 70 Carrier agent 0 10 20 30

Xe

X m C GAB K GAB aw 1 K GAB aw 1 K GAB aw C GAB K GAB aw

In order to obtain the model parameters, a non-linear regression analysis was carried out using the Statistica 5.0 (Statsoft, Tulsa, USA) software package. The degree of tness of each model was evaluated by the determination coefcient and mean relative deviation modulus E

E
(10, 20 and 30% w/w, which correspond to 0.55, 0.73 and 0.83 g MD or GA/g total solids, respectively). The spray drying process was performed using a laboratory spray dryer (B191 model, Bchi, Flawil, Switzerland). The equipment was operated concurrently using a spray nozzle with an orice of 0.7 mm in diameter. The protein hydrolysate was fed into the drying chamber using a peristaltic pump. The inlet air temperature was 180 C and the outlet air temperature varied from 91 to 102 C for each sample. The feed mass ow rate and air compressed volumetric ow rate were 0.2 kg/h and 0.6 m3/h, respectively. 2.4. Sorption isotherms Sorption isotherms were determined by the gravimetric method. One gram of powder was placed into aluminum vials, weighed and equilibrated over saturated salt solutions (LiCl, CH3COOK, MgCl2, K2CO3, Mg(NO3)2, KI, NaCl and KCl, providing relative humidity values of 11.3%, 17.6%, 32.8%, 43.2%, 52.9%, 68.9%, 75.3% and 84.3%, respectively, according to Greenspan (1977)) in desiccators at 25 C until equilibrium. Once equilibrium was reached, the equilibrium moisture content of the sample was measured gravimetrically by drying in a vacuum oven at 70 C for at least 48 h, to determine the solid mass in the sample. The physical appearance of the samples was also observed to check whether the powder had suffered any transformation such as agglomeration, caking or collapse. Several models (empirical, semi-empirical and theoretical) with two or more parameters have been used in the literature to describe the sorption isotherms. Equations based on sorption theories, such as BET and GAB models, are usually preferred by most researchers, since some physical meaning may be attached to their parameters, aiding in the understanding of the water sorption phenomena. Derived by simple extension and generalization of Langmuirs theory of unimolecular adsorption, the classic BET (Eq. (1)) (Brunauer et al., 1938) is a two-parameter model assuming the condensation of an innite number n of layers from the vapor phase onto the adsorbent surface. Unfortunately, this model fails for higher water activities, aw > 0.5 (Jonquires and Fane, 1998).

N 100 X jV E V P j N i 1 VE

2.5. Glass transition temperature About 3 mg of protein hydrolysate powder were placed into differential scanning calorimetry (DSC) aluminum pans (20 ll) and equilibrated over saturated salt solutions in desiccators at 25 C until equilibrium was reached. The samples were then hermetically sealed with lids for analysis and weighed. The mass of each sample pan was matched in advance with the mass of an empty reference pan to within 0.1 mg. The DSC analyses were carried out in a TA-MDSC-2920 (Ta Instruments, New Castle, De, USA). For temperatures below 70 C, liquid nitrogen was used; otherwise a mechanical refrigeration system (RCS refrigerated cooling accessory) was applied. Equipment calibration was performed with indium (Tmelting = 156.6 C) and verication with azobenzol (Tmelting = 68.0 C). Dry helium, 25 ml/min, was used as the purge gas. After cooling the sample to 70 C, the glass transition temperature was determined on thermo-analytical curves obtained by heating the sample at 10 C/min up to 80 C (or other values for the initial and nal temperatures, according to the sample). The second scanning of each sample was performed to reduce the enthalpy relation of the amorphous powder, which appears in the rst scan. All analyses were done in triplicate and the data were treated by the software Universal Analysis 2.6 (Ta Instruments, New Castle, De, USA). To describe the plasticising effect of water on the protein hydrolysate, the glass transition temperature data were tted to the Gordon-Taylor model (Gordon and Taylor, 1952)

Tg

ws T gs kww T gw ws kww

The Tgw value was taken at 135 C (Johari et al., 1987). A non-linear regression analysis was carried out using the Statistica 5.0 (Statsoft, Tulsa, USA) software package to obtain the model parameters k and Tgs. 3. Results and discussion 3.1. Sorption isotherms Fig. 1 shows experimental sorption isotherms for the protein hydrolysates, pure and formulated with maltodextrin (MD) or gum Arabic (GA), at different concentrations, with their respective ttings to the BET model. The sorption isotherms showed an increase in equilibrium moisture content with increasing water activity, at constant

X m C BET aw Xe 1 aw 1 aw C BET aw

In their original publication, Brunauer et al. (1938) also derived a modied model, considering a limited number of adsorbed layers, allowing the modeling for water activities up to 0.9. As expected, the corresponding model yields a three-parameter (Eq. (2))

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Fig. 1. Water sorption isotherms of chicken meat protein hydrolysates, formulated with: (a) maltodextrin; (b) gum Arabic.

temperature, and it can be seen that the behaviors of all the curves were of type III, according to Brunauers classication (Rizvi, 1995). Similar isotherms were observed for protein hydrolysates from sh, pineapple, tomate pulp, West Indian cherry and lactose hydrolysed skim milk powders (Aguilera et al., 1993; Gabas et al., 2007; Goula et al., 2008; Righetto and Netto, 2005; Shrestha et al., 2007b). Analyzing Fig. 1, considerable differences could be observed between the isotherms of the pure protein hydrolysate powder and those formulated with additive. The equilibrium moisture contents of the samples with maltodextrin or gum Arabic were signicantly lower at a given water activity, than that of the pure hydrolysate. Similar results were observed by Gabas et al. (2007) and Righetto and Netto (2005). The presence of additives in the protein hydrolysate probably modied the balance of hydrophilic/hydrophobic sites, promoting a decreased amount of sorbed water (Prez-Alonso et al., 2006). The experimental equilibrium moisture content results were tted to the BET (three-parameters) and GAB models (Table 4) to describe the water sorption isotherms. Each model was tested for adequacy and goodness of t by determining the coefcient R2 and mean relative deviation modulus E. These values and the parameter models obtained by non-linear regression analysis are shown in Table 4. The results showed that for the different additive

concentrations, the BET model presented a better t than the GAB model, with mean relative deviations below 13% and determination coefcients close to unity.
Table 4 Estimated parameter values for the BET and GAB models for protein hydrolysate powders with and without maltodextrin (MD) or gum Arabic (GA) Model Sample (%) Constant Xm BET 0% 10%MD 20%MD 30%MD 10%GA 20%GA 30%GA 0.153 0.070 0.048 0.039 0.088 0.070 0.063 Xm GAB 0% 10%MD 20%MD 30%MD 10%GA 20%GA 30%GA 0.141 0.063 0.048 0.044 0.073 0.067 0.060 CBET 3.098 4.280 8.518 9.378 3.037 4.906 3.380 CGAB 5.766 6.553 6.706 6.996 6.734 6.850 7.285 n 19.080 26.381 26.163 25.934 21.703 21.518 21.382 KGAB 0.326 0.305 0.291 0.260 0.304 0.282 0.261 0.962 0.940 0.938 0.940 0.949 0.947 0.938 16.05 22.22 19.14 18.39 15.61 17.52 17.98 0.998 0.995 0.994 0.992 0.998 0.995 0.996 6.32 8.74 9.86 12.32 7.90 11.50 9.05 R2 E (%)

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Although the GAB model has been widely used for foodstuffs, it did not present a good t for the experimental data of the chicken meat protein hydrolysate (mean relative deviation above 15%). This fact can be explained due to the limiting values for the constants CGAB and KGAB as suggested by Lewicki (1997), based on the mathematical analysis of the model. For sigmoidal type curves, the author stated that the constants should assume values in the range 0.24 6 KGAB 6 1 and 5.6 6 CGAB 6 1, to guarantee a relatively good description of the isotherms and to fulll the requirements of the GAB model, as well as assuring that the calculated monolayer moisture content values differed by no more than 15.5% from the true monolayer capacity. In the present work the curve exhibited a non-sigmoidal type that explains the high mean relative deviation. The monolayer moisture content (Xm) is the amount of water that is strongly adsorbed to specic sites at the food surface and is considered an important value to assure food stability. For protein hydrolysates without additives, the Xm value was 0.153 g water/g dry matter. Aguilera et al. (1993) and Shrestha (2007b) found Xm values of 0.062 and 0.072 g water/g dry matter for protein hydrolysates from sh and lactose hydrolysed skim milk, respectively. These differences between the Xm values obtained for the chicken meat protein hydrolysates and those obtained in other studies could be attributed to compositional differences and to the degree of hydrolysis of the products. Adding maltodextrin or gum Arabic, the Xm values decreased from 0.067 to 0.038 g water/g dry matter and from 0.080 to 0.057 g water/g dry matter, respectively, with increasing carrier agent concentrations from 10% to 30%. This behavior can explain the encapsulation effect, which diminishes the surface exposed to water molecules. Gabas et al. (2007) veried the same behavior with pineapple pulp powder with (0.060 g water/g dry matter) and without maltodextrin (0.166 g water/g dry matter) or with gum Arabic (0.072 g water/g dry matter). Prez-Alonso et al. (2006) obtained Xm values between 0.0696 and 0.0735 for pure maltodextrin 10DE and 0.0811 and 0.1100 for gum Arabic, in the range of 2540 C, which are in agreement with the present work, since samples containing maltodextrin resulted in lower Xm than samples with gum Arabic. According to Prez-Alonso et al. (2006), these ndings can be attributed to a combination of factors, which include the conformation and topology of molecule and the hydrophilic/hydrophobic sites adsorbed at the interface. The physical appearance of the protein hydrolysate powder after reaching equilibrium at different relative moistures was observed. Samples without carrier materials, with water activity, aw, of 0.113, presented free-owing characteristics. However, liquefaction occurred for samples stored at aw above 0.176. For powders formulated with 10%, 20% and 30% of maltodextrin, caking only started at aw of 0.529, 0.689 and 0.753, respectively. Collapse and liquefaction were veried in samples (10, 20 and 30%MD) stored at relative moistures above 0.689, 0.753 and 0.843, respectively. The same behavior occurred for samples formulated with gum Arabic, with the exception of the sample with 30%GA, which collapsed at a water activity of 0.753. According to Aguilera et al. (1995), caking is an undesirable phenomenon in which a low-moisture and free-owing powder is initially transformed into lumps, then into an agglomerated solid and ultimately into a sticky material, resulting in loss of functionality and decrease in quality. The main cause of caking and agglomeration is water-induced plasticization of the particle surface. These physical changes can be explained by the glass transition concept on the basis of Tg. Below the Tg temperature, amorphous food material exists in a non-equilibrated, stable glassy state. As the product temperature exceeds the Tg, so the amorphous food enters the rubbery state, and some physical transformations, such as agglomeration, caking and collapse occur.

3.2. Glass transition temperature The thermograms of protein hydrolysates at various water activities are shown in Figs. 24. Generally the glass transition of the amorphous materials produces a stepwise change in the heat ow due to changes in the heat capacity, at the phase transition temperature. The glass transition temperatures (Tg) of the chicken meat protein hydrolysates are in good agreement with those reported for freeze-dried sh protein hydrolysate (Aguilera et al., 1993). The Tg is known to decrease with decreasing molecular weight (Roos, 1993). The low Tg value of the chicken meat protein hydrolysate was due to the presence of low molecular peptides as a result of the enzymatic hydrolysis. Hashimoto et al. (2004) observed higher Tg values for whole sh muscles. Shrestha et al. (2007b) veried that whole lactose presents higher Tg values than hydrolysed lactose. The effect of several water activities on the Tg of osmotically dehydrated tilapia llets using binary or ternary solutions was evaluated by Medina-Vivanco et al. (2007). The glass transition temperatures found by these authors were higher than those reported in the present study. The effect of water as a plasticizing can be seen in Figs. 24, in which the increase in moisture content caused a signicant decrease in Tg. Similar behavior was observed for several products such as osmotically dehydrated tomato, sh muscle and its protein fractions, abalone, hydrolysed lactose milk and freeze-dried pineapple (Baroni et al., 2003; Hashimoto et al., 2004; Sablani et al., 2004; Shrestha, 2007b; Telis and Sobral, 2001). In Fig. 5, the effect of adding maltodextrin or gum Arabic on the glass transition temperature of chicken meat protein hydrolysates can be observed. Since the Tg increases with the increase in molecular weight, the addition of materials such as maltodextrin or gum Arabic (in the solution to be dehydrated) contributes positively to powder stability. This behavior was also observed for mango pulp with maltodextrin; immature West Indian cherry with maltodextrin or gum Arabic; and date palm with maltodextrin (Jaya and Das, 2004; Righetto and Netto, 2005; Sablani et al., 2008). However, the increase the maltodextrin/gum Arabic concentration from 20% to 30% had no further inuence on the glass transition temperature. Grabowski et al. (2006), working with hydrolyzed sweet potato puree, also observed this same behavior. Using spray drying conditions of a temperature of 190 C and amylase level of 3.75 ml/kg puree, the pure sample and that with 10% of maltodextrin presented Tg values of 51.75 C and 60.21 C, respectively. However, when the maltodextrin concentration was increased to 20%, the Tg value was only 59.89 C. Shrestha et al. (2007a), studying the spray drying of orange juice with various levels of maltodextrin, reported that an increase on maltodextrin proportion from 60% to 75% in orange juice

Fig. 2. Thermogram of pure chicken meat protein hydrolysate powder equilibrated at different water activities.

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Fig. 3. Thermograms of chicken meat protein hydrolysate powders equilibrated at different water activities and formulated with maltodextrin: (a) 10%; (b) 20%MD; (c) 30%MD.

Fig. 4. Thermograms of chicken meat protein hydrolysate powders equilibrated at different water activities and formulated with gum Arabic: (a) 10%; (b) 20%; (c) 30%.

resulted in a relatively lesser increase in Tg value, compared to 50 60% increase in maltodextrin. For the authors, considering the very high Tg of anhydrous maltodextrin, higher Tg value was expected for maltodextrin:orange juice mixture (75:25). Based on the work of Roos and Karel (1991b), in which they predicted a Tg value of about 130 C for maltodextrin:sucrose mixture (75:25), Shrestha et al. (2007a) observed that DSC method gives better estimation of Tg values when the material has higher sugar concentration; however, Tg value of the mixture with high maltodextrin concentration might have been underestimated. Therefore, these authors studied the glass transition temperature behavior of this system using the thermal mechanical compression test (TMCT), showing that the method could measure the phase transition behavior of amorphous system that has high molecular weight component. According to Shrestha et al. (2007a), the ability of DSC to accurately

measure the Tg is diminished as less dened enthalpic change takes place in macromolecules. The experimental glass transition temperatures were tted to the Gordon and Taylor (1952) model. The parameters obtained by non-linear regression analysis are shown in Table 5, and Fig. 5 shows the curve predicted by the Gordon-Taylor model. According to Table 5, the Tgs value for the pure hydrolysate (44.4 C) was signicantly lower than that for samples with maltodextrin (91.9136.9 C) or gum Arabic (94.7125.12 C), showing that the addition of substances with high molecular weights increases the Tg of the product. In the Gordon-Taylor model, the adjustable parameter k, which controls the degree of curvature of the Tg composition dependence (in a binary system), can be related to the strength of the interaction between the system components (Gordon and Taylor, 1952). The addition of maltodextrin or gum Arabic increased the k value. Silva et al. (2006) found k values of

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293

Fig. 5. Effect of solids content on the glass transition temperature of chicken meat protein hydrolysates with: (a) maltodextrin; (b) gum Arabic as carrier agents.

Table 5 Estimated parameter values for the Gordon-Taylor models of the protein hydrolysate powders without (0%) and with maltodextrin (MD) or gum Arabic (GA) Powder 0% 10%MD 20%MD 30%MD 10%GA 20%GA 30%GA Tgs (C) 44.43 91.90 132.95 136.94 94.70 124.04 125.12 k 2.59 3.71 5.89 5.77 4.22 5.24 5.29 R2 0.9966 0.9907 0.9983 0.9925 0.9941 0.9990 0.9917 E (%) 41.35 17.67 8.63 16.47 8.69 4.46 17.48

5.52 and 3.92 for camucamu powder with and without maltodextin, respectively. 3.3. Storage under critical conditions The critical water content/water activity is the value when the glass transition temperature of the product is equal to the room temperature (which was assumed to be 25 C in this work) (Shrestha et al., 2007b). All amorphous products are metastable and are liable to caking, collapsing or crystallizing with time during

storage. The stability of these products is strongly associated with the Tg, which depends on the storage conditions such as water activity, humidity or temperature (Roos and Karel, 1991a). Roos (1993) suggested using sorption moisture data with glass transition temperature in order to evaluate food stability. Therefore the sorption moisture and Tg data were plotted in a single graph (Fig. 6). Analyzing this gure, it is possible to obtain the critical values for the water activity and moisture. The water content and Tg value were predicted by the BET and Gordon-Taylor models, respectively. The critical Tg and water activity for the powders are shown by the arrows. The critical water activity and moisture content for the protein hydrolysate were 0.1 and 0.04 g water/g solids, respectively at a storage temperature of 25 C. The lower critical water activity and moisture content clearly indicated the vulnerability of the chicken meat protein hydrolysate powder under the processing, handling and storage conditions. When the powder is stored at a water activity of 0.1 (or relative moisture of 10%), it will present a moisture content of 0.04 g water/g solids and its Tg will be 25 C. Therefore, when stored under conditions with a relative moisture of 10% and temperature above 25 C (or relative moisture above 10% and temperature of 25 C), the powder will suffer deteriorative changes such as structural collapse, stickiness and caking.

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Fig. 6. Relationship between the water activity at 25 C, water content and glass transition temperature of chicken meat protein hydrolysates: (a) without additive; (b) 10%MD; (c) 20%MD; (d) 30%MD; (e) 10%GA; (f) 20%GA; (g) 30%GA.

On the other hand, for the sample with 10% maltodextrin, the critical water activity and moisture content at 25 C were 0.5 and 0.11 g water/g solids, respectively. Therefore, the addition of

maltodextrin resulted in an increase in powder stability. The protein hydrolysate with 10% maltodextrin can be stored at 25 C and relative moisture of 50% or with a moisture content of 0.11 g

L.E. Kurozawa et al. / Journal of Food Engineering 91 (2009) 287296 Table 6 Critical values for the water activity (awc) and moisture content (Xc) of the protein hydrolysate pure (0%) and formulated with maltodextrin (MD) or gum Arabic (GA) Powder 0% 10%MD 20%MD 30%MD 10%GA 20%GA 30%GA awc 0.10 0.50 0.60 0.70 0.42 0.51 0.57 Xc (g water/g solids) 0.04 0.11 0.11 0.12 0.10 0.12 0.12

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Acknowledgments The authors gratefully acknowledge the nancial support from the Fundao de Amparo Pesquisa do Estado de So Paulo (FAPESP), the Coordenao de Aperfeioamento de Pessoal de Nvel Superior (Capes) and the Conselho Nacional de Desenvolvimento Cientco e Tecnologico (CNPq).

References
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water/g solids. These critical values are signicantly higher than the critical values found for the pure hydrolysate (10% and 0.04 g water/g solids). Similarly, analyzing the other samples formulated with maltodextrin or gum Arabic, one arrives at the critical values shown in Table 6 for these samples. Increasing the carrier agent concentration resulted in a rise in the critical water activity from 0.1 to 0.7 and 0.1 to 0.57, for maltodextrin and gum Arabic, respectively, in order to depress the Tg to ambient temperature (25 C). Shrestha et al. (2007b) evaluated the stability of whole and hydrolyzed lactose using sorption isotherms and the glass transition temperature. The critical water activity and moisture content for whole lactose were 0.39 and 0.08 g/g solids, respectively. The stability of hydrolyzed lactose was much lower than lactose with low critical values of aw and moisture content of 0.15 and 0.024 g/g solids, respectively. A low glass transition temperature of a product affects the drying process, since the conditions of the outlet air humidity and temperature of the spray dryer would be higher than the critical conditions. The higher the temperature difference (DT = ToutTg), the greater is the degree of stickiness. Visually, it could be seen that spray drying the pure protein hydrolysate resulted in a large amount of the powder being stuck in the dryer chamber and cyclone. This fact occurred because the outlet temperature of the dryer (Tout = 91 C) was higher than the Tg value of pure anhydrous protein hydrolysate (Tgs = 44.4 C), resulting in a higher DT value. Since the Tg of maltodextrin 10DE (160 C, anhydrous, according to Roos and Karel (1991b)) is high, then the addition of the carrier agent increased the Tg of the powder, reducing the DT, which in turn decreased the stickiness behavior. No data for the glass transition temperature of anhydrous gum Arabic was found in the literature. However, Righetto and Netto (2005) found some data for gum arabic at three different values for water activity, that were similar to the data for maltodextrin found by Roos and Karel (1991b). 4. Conclusions The BET isotherm was found to be adequate to describe the experimental data obtained for the chicken meat protein hydrolysate powder. The glass transition temperature was determined for different water activities and the effect of water as a plasticizing agent was observed, in which an increase in moisture content caused a signicant decrease in the glass transition temperature. The data for Tg tted the Gordon-Taylor model well. The chicken meat protein hydrolysate presented a low Tg and low critical values for moisture content and water activity, indicating its vulnerability during processing, handling and storage. The addition of maltodextrin or gum Arabic increased the Tg and, consequently, contributed to the stability of the powder. These data can be used to assist in choosing the proper spray drying operational conditions with respect to stickiness and the storage behavior of the chicken meat protein hydrolysate.

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