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Layten Davis
and Mark T. Nielson, Eds., Blackwell Science (Pub.), 1999
Chapter 8
leaf Chemistry
265
266 Tobacco: Production, Chemistry and Technology LeafCho
Table 8.1 Composition of cigarette tobaccos: representative analyses of cigarette tobaccos (leaf web after Table 8 ..
aging, moisture-free basis). tobacco
weight).
Component
(%)' Flue-cured, type 13 Burley, type 31 Maryland, type 32 Oriental 2 Constitue
Total volatile bases as ammonia 0.282 0.621 0.366 0.289 Starch
Nicotine 1.93 2.91 1.27 1.05 Free redu
Ammonia 0.019 0.159 0.130 0.105 Levulose
Glutamine as ammonia 0.033 0.035 0.041 0.020 Sucrose
Asparagine as ammonia 0.025 0.111 0.016 0.058 Crude fib
()(-Amino nitrogen as ammonia 0.065 0.203 0.075 0.118 Total nitre
Protein nitrogen as ammonia 0.91 1.77 1.61 1.19 Protein ni
Nitrate nitrogen as N03 trace 1.70 0.087 trace Nicotine
Total nitrogen as ammonia 1.97 3.96 2.80 2.65 Ash
pH 5.45 5.80 6.60 4.90 Calcium
Total volatile acids as acetic acid 0.153 0.103 0.090 0.194 Oxalic ac
Formic acid 0.059 0.027 0.022 0.079 Citric acic
Malic acid 2.83 6.75 2.43 3.87 Malic acio
Citric acid 0.78 8.22 2.98 1.03 Resins
Oxalic acid 0.81 3.04 2.79 3.16 Pectinic a
Volatile oils 0.148 0.141 0.140 0.248 pH of tob
Alcohol-soluble resins 9.08 9.27 8.94 11.28
Reducing sugars as dextrose 22.09 0.21 0.21 12.39 Source: Bao
Pectin as calcium pectate 6.91 9.91 12.41 6.77
Crude fiber 7.88 9.29 21.79 6.63
Ash
Calcium as CaO
10.81 24.53 21.98 14.78 I 20
2.22 8.01 4.79 4.22
Potassium as K2 0 2.47 5.22 4.40 2.33
Magnesium as MgO 0.36 1.29 1.03 0.69
Chlorine as Cl
Phosphorus as P2 0 5
0.84 0.71 0.26 0.69 f: 15
0.51 0.57 0.53 0.47
Sulfur as S0 4 1.23 1.98
"E
3.34 1.40 <ll
Alkalinity of water-soluble ash 3 15.9 36.2 36.9 22.5
0
cf 10
1
2
In %except for pH and alkalinity. .r:0
Blend of Macedonia, Smyrna, and Samsun types.
3
Milliliters of 1 N acid per 100 g tobacco. ~
(/)
Source: Harlan and Moseley (1955).
5
tobaccos possess significant amounts of reducing during flue-curing which causes enzyme inactivation.
sugars (which are virtually absent in the air-cured Nevertheless, considerable change has occurred (Table 0
tobaccos) and lesser amounts of protein and a-amino 8.2) in the leaf (during the period after priming and
nitrogen. Substantial changes in the chemical compo- early stages of curing) as starch loss occurs via enzy-
sition of tobacco leaf occur following harvest and matic hydrolysis with a concomitant increase in redu-
during subsequent processes. cing sugar (Bacon, et al., 1952). This is illustrated for Fig. 8.1 I
CARBOHYDRATES: STARCH, SUGARS, (Fig. 8.1) and the concurrent generation of reducing
sugars (Long & Weybrew, 1981) (Fig. 8.2). Starch
SUGAR ESTERS, CELLULOSE, AND
In burley tobacco the starch accumulation during saccharid
PECTIN growth is only about 25% the amount in Virginia has appr
(a) Starch and sugars tobacco (W eybrew & Hamann, 1977) and this is nearly pectin, v
depleted completely during the catabolic respiration of approx1m
In flue-cured tobacco, respiration in the primed leaf is the plant while air-curing leaving negligible sucrose, Gohnston
arrested by the controlled desiccative dehydration and reducing sugars in the cured leaf. estimated
nd Technology Leaf Chemistry: Basic Chemical Constituents & Differences among Tobacco Types 267
Table 8.3
~
:H 2 0R~ OH
more aromatic C 5 and C6 carboxylic acids (Severson, et
ar, 1985b).
Aglucone
OR H From a smoke aroma and flavor standpoint, it is
RO H
interesting that GTE and STE readily release free 3-MethylbL
H OR
carboxylic acids on thermolysis while totally esterified Benzyl alec
sucrose and glucose esters (such as glucose pentaiso- 2-Phenyletl
valerate and the sucrose octaesters) do not easily release 2-Methoxy-
GLUCOSE TETRAESTERS
their acid moieties on thermolysis. 4-Vinylphe-
3-Hydroxyl
4-Vinylsyri
(c) Glucosides 3-Keto-cx-io
~
CH 2 0R~ H
4-(4-Hydro-
H The suggestion that nonvolatile aroma precursors of
OR 3-Hydroxy-
tobacco existed in the form of glucosides was made by 4-(3-HydrOo
RO , ~CH,OH the observation that materials such as 3-hydro-
H OR OH H 3-(2-HydrOo
HOCH 2 H xydamascone and 3-keto-ionol were released from 6-Hydroxy-
H OH tobacco by hydrolysis (Green, eta!., 1980). Very little Vomifoliol
information on the hydrolytic release of aroma com-
Source: Hec
pounds from fruits and other plant materials by either
SUCROSE TETRAESTERS the acid or enzymatic hydrolysis of glycosidically
bound terpenoid and norterpenoid materials was
R = C 3 -C 8 Carboxylate known prior to the mid-1970s. Today, it is clear that Cellulo:
many plants, including tobacco, which have sugars (C 6H100s
R' =Acetate
(mono- and disaccharides) generate nonvolatile mate- units. Ac
Fig. 8.3 Sugar esters present in Oriental tobacco. rials with an inter-sugar link to aroma materials arising Japanese
from the oxidative and metabolic transformation of glucose fr
carotenoid pigments (Williams, 1993). Many tobacco another,
& Leffingwell, 1988) (Fig. 8.4) shows that accumula- arabinose
identical aroma compounds have now been found in
tion of STE for Oriental and burley is greater than for Normal
fruits, wines and other products, primarily bound as
Virginia tobacco, with the Oriental and burley maxima is a nega1
glucosides. Heckman, eta!. ( 1981) demonstrated that a
occurring at full maturity. impart as
series of tobacco aglucone isolates are significantly
It has been demonstrated that the tetraesters of odor to th
increased by enzymatic hydrolysis of glucosides from
Oriental STE tended to have higher amounts of the an import
Virginia tobacco (Table 8.3).
5000 r--------------------------------------, The commercial enzymatic hydrolysis of tobacco tobacco bo
The degr
scrap and dust has been used to generate tobacco aroma
materials from the glucosidically bound precursors in leaflamin:
4000 virginia liD Oriental stems (D.E
tobacco by one of the major flavor companies. The use
DBurley of glucosides for flavoring tobacco has been patented for leafm
E
(Anderson, et a!., 1976), and commercial use of the than that
"'
(5
3000 glucoside of ethyl vanillin (Herron, 1987) (an artificial addition, 1
.f flavor about three times more powerful than vanillin) than for a_
g for improving sidestream aroma was employed at one studies or:
8'"' 2000 time in the US in cigarettes. also suggt:
mean chai
~ As tob
(d) Cellulose modern
1000
It has been estimated (Green, 1977) that cigarette blends employed
contain approximately 10% of cellulose and hemi- cellulose
cellulose, which corresponds closely to the values that Virgi.
20 34 41 49 55 62 66 obtained for a series of flue-cured varieties (Collins & cured ster
Days After Transplant Legg, 1977). However, it must be noted that the tobacco to the difl
Fig. 8.4 Sucrose tetraesters in tobacco types (adapted from stalk, stem and mid-rib portion of the leaf are much other mal
Einolf & Chan, 1984). higher in cellulose than the lamina portion of the leaf. combustit
y and Technology Leaf Chemistry: Basic Chemical Constituents & Differences among Tobacco Types 269
acids (Severson, et Table 8.3 Aglucone increase from enzymatic hydrolysis of glucosides in Virginia tobacco (mg/1 00 g).
galactopranosyluronic acid interspersed with 2-linked lower fatty acids characteristic of Turkish smoke. In
1.-rhamnopyranosyl residues. Approximately 22% of addition, it has been noted that of the 14 7 pyrolysis
12.5
the galacturonic acid was methylated. The main pectic products reported from cellulose, starch, mono- and
chain was determined to be branched at carbon-4 of di-saccharides and pectic substances that 121 have been 10
rhamnose with the neutral side chains containing found in tobacco smoke (Heckman, eta!., 1981).
~
terminal and 4-linked ~-n-galactopyranosyl and ct-1.- X 7.5
arabinofuranosyl residues. ""'c:
Lauterbach and Moldoveanu (1991) determined the SENSORY ROLE OF CARBOHYDRATES, ~
"'0
degree of both methylation and amidation by pyrolysis AMMONIA AND NICOTINE- PH OF ~
<J>
<(
From a commercial aspect, pectins play an important tobacco alkaloids (Leffingwell, 1976 ). ""'c:
role in the manufacture of reconstituted tobacco. One In the section on nitrogenous constituents of ~
0
"' 7.5
of the two types of major commercial reconstituted tobacco, the interaction of amino acids and ammonia in .2
<(
Q;
tobacco processes involves the treatment of a tobacco the development of important compounds in both
Virginia and air-cured tobaccos (including amino-sugar
ti:
slurry with diammonium phosphate to solubilize the 2.5
tobacco pectin. When the tobacco slurry is then cast compounds) will be discussed.
onto a hot metal belt, a portion of the ammonia is However, at this point a brief discussion on the effect
volatilized, 'setting' the tobacco pectin to 'glue' the of the major acid forming constituents (carbohydrates)
reconstituted sheet together. Because the ammonia of tobacco smoke and the interaction with the major
generated plays an important role in natural tobacco basic substances of tobacco and smoke (nicotine and
Fig. 8.6 Tl
flavor formation, this reconstituted process not only ammonia) is in order.
Fenner, 19E
provides a means of extending tobacco utilization, it Fenner (1988) showed the striking differences in the
also provides a superior reconstituted tobacco from a generation of both formic acid (Fig. 8.5) and ammonia
smoking quality standpoint by increasing the flavorful (Fig. 8.6) from Virginia and burley tobaccos on ammo rna
pyrazines. The role of ammonia in tobacco will be pyrolysis over the temperature range encountered in a 350cC. tr~
discussed below. cigarette. transition i
In Fig. 8.5, we see the generation of formic acid in Acid for
Virginia tobacco to be far greater than for burley with constituen-
CARBOHYDRATES AND SMOKE the large transition at 190C being due to simple smoke pH
CHEMISTRY sugars, while the transition at 250C is due to pectin successive
plus hemicellulose and the transition at 310cC. is due to smoke has
Carbohydrates in the forms previously described can cellulose. cigarettes,
account for 40 to 50% of tobacco weight and contribute Conversely, Fig. 8.6 demonstrates that burley with low s
significantly to smoking quality. As mentioned, the tobacco generates significantly more ammonia than than those
sugar esters are a major contributor to the Oriental Virginia. The ammonia transition at 190"C. may sim- progreSS! VI
tobacco flavor, in that they thermally release the potent plistically be considered as a labile or exchangeable As nico
ry and Technology Leaf Chemistry: Basic Chemical Constituents & Differences among Tobacco Types 271
9.5
Turkish smoke. In
of the 147 pyrolysis 12.5 r-------------------- 8.5
starch, mono- and
9.5
s that 121 have been 10
... Rue-Cured Tobacco
I 7.5
a.
n, et a!., 1981 ). - Burley Tobacco
1! 8.5
X 7.5 g 6.5
""c (/)
7.5
Q) 5.5
BOHYDRATES, "'0
.0
.2:
Cil 6.5
NE- PH OF "'
~
.0
<( 4.5
g;
t
2.5
a 5.5 3.5
cco smoke has long 4.5
hange the sensory
3.5
baccos. Even before 100 200 300 400 500 600 700
60 50 40 30 20 10
were added to air- Terrperature, Celcius
Butt Length in Mllimeters
king to mitigate the
e. And, today, as 50 Fig. 8.5 Thermal generation of formic acid (adapted from
Fenner, 1988). D Virginia (15.5% Sugar) Ell Air-Cured (2% Sugar)
and blended based
r and nicotine con- lSI Blended (4.7% Sugar) agarillo (0.5% Sugar)
e criteria of appear-
on, it is a common Fig. 8.7 Cigarette smoke pH (cumulative puffs) (adapted
:rt sugar (Glucose + from Elson, eta/., 1972).
15
r which still contains
:igarettes. Sugars are 12.5 .... Rue-Cured Tobacco
Javor, primarily by 0
-Burley Tobacco cigarette smoke, the pH of smoke plays an exceedingly
~
nicotine and other X 10 important role on the sensory impression imparted.
'6). ""c The higher ammonia level of air-cured tobacco
us constituents of -e"' 7.5
containing low or negligible sugar content would pre-
i;l
.0
:ids and ammonia in <( sumably have two major effects. It has an effect on the
g;
ompounds in both ratio of nicotine/nicotine salts delivered on smoking
t
:luding amino-sugar 2.5 relative to high sugar and/or more acidic tobacco types
wherein the nicotine and other alkaloids are complexed
cussion on the effect (more) as salts in the smoke.
100 200 300 400 500 600 700
mts (carbohydrates) Terrperature, Celcius Acids ->
:ion with the major
moke (nicotine and :'-Jicotine Alkaloid <-+ Nicotine Alkaloid salt
Fig. 8.6 Thermal generation of ammonia (adapted from
Fenner, 1988). (Free base) +-- :\mmonia (Salt complex)
ag differences in the
:. 8.5) and ammonia Since the pH of smoke in air-cured tobacco is con-
urley tobaccos on ammonia source (e.g. ammonium salts), while the siderably more alkaline than flue-cured or Oriental,
~e encountered in a 350C. transition is amine derived and the 550 C the ratio of nicotine base to nicotine salts increases.
transition is amide-derived ammonia. This causes the sensory and physiological perception
1n of formic acid in Acid forming constituents (carbohydrates) and basic of increased nicotine strength (and harshness). It
~an for burley with constituents (ammonia) can have a significant effect on should also be noted that the pH of air-cured tobacco
.ng due to simple smoke pH. Figure 8.7 shows the cumulative effect of smoke increases with succeeding puff~ from such
1C is due to pectin successive puffs on the pH of water through which cigarettes. Accordingly, the increased alkalinity of
l at 310C. is due to smoke has been passed. In a study of over !50 brands of straight air-cured cigarettes renders them virtually
cigarettes, Elson, eta/. (1972), concluded that brands unacceptable to nearly all smokers as the high smoke
rrates that burley with low sugar content generated more alkaline smoke pH imparts an alkaloid harshness with a flavor distor-
~re ammonia than than those with high sugar content (which become tion which can be unpleasant. Conversely, many
1t 190C. may sim- progressively more acidic). American blend cigarette smokers find the 'acidic'
e or exchangeable As nicotine is a major volatile base present in smoke of straight Virginia cigarettes to be
ps
unbalanced. 'Nicotine alone does not determine proteinaceous aroma on smoking which is unpleasant.
smoking flavor' (Leffingwell, 1976 ). Even secondary fermentation of such poor tobaccos 600
often cannot provide sufficient improvement to make
them usable. By comparison to normal burley, in which 500
NITROGENOUS CONSTITUENTS approximately 50% of total protein undergoes hydro- E
~
lysis to amino acids, such poor tobaccos may exhibit
The data in Table 8.4 for air-cured cigar tobacco show less than 15% protein hydrolysis during air-curing "c..
Q;
400
the gross chemical changes in nitrogen compounds (Heinzer, 1986). Normal air-curing of fully mature
during air-curing (Frankenburg, 1946; Frankenburg, burley shows a rapid drop in protein (Fig. 8.8) "'
..92 300
0
1950). E
(Hamilton & Lowe, 1978; Long & Weybrew, 1981) l:
with a concomitant initial increase in free amino acids i .!.! 200
:::ii
for the first few days in cure (Fig. 8.9) (Burton, et al.,
Table 8.4 Changes of nitrogenous compounds in
1983). Then, there is a decrease and finally a leveling
!
100
air-cured cigar tobacco (percent of harvested dry
off in total free amino acid concentration. The decrease I
weight). i
in free amino acid content after the fifth day of air- 0
Primed leaf Stalk cured curing is due to both metabolic deamination and
decarboxylation as well as nitrogen translocation. Even
Before After Before After though a slight decrease from a maximum in total free
Type of nitrogen curing curing curing curing amino acids occurs during the cure, some individual Fig. 8.9 T
amino acids show a net decrease while others have a net curing (ada
Total 5.61 5.34 4.70 3.80
Protein (insoluble) 3.69 1.65 3.80 1.85
increase (Burton, et al., 1983). It should be noted that
Soluble 1.92 3.69 0.90 1.95 the ammonia level of air-cured tobacco rapidly
Amino 0.23 0.80 0.15 0.15 increases during this period (Fig. 8.10) (Burton, et al.,
Ammonia plus amide 0.15 1.07 0.05 0.80 1983). 150
Alkaloid 0.35 0.32 0.40 0.40 The role of ammonia on smoke pH and nicotine
Nitrate 0.63 0.77 0.20 0.25 perception has been discussed above, but ammonia also 125
Remainder 0.56 0.73 0.10 0.35 plays an important role in the formation of aroma and E
~
taste compounds.
Source: Frankenburg (1946).
It is important to remember that, before curing, air- " 100
ich is unpleasant. Table 8.5 Free amino acids in high quality smoking
ch poor tobaccos 600 grade blends (mg/g).
ovement to make
1! burley, in which Amino acid Flue-cured Burley
500
mdergoes hydro- E
Aspartic acid 0.13 7.84
lccos may exhibit (5"' 400 Threonine 0.04 0.43
luring air-curing ~
Q)
Serine 0.06 0.17
0..
of fully mature VI Asparagine 1.12 10.30
otein (Fig. 8.8) .92 300
0 Glutamic acid 0.10 1.78
Weybrew, 1981) E Glutamine 0.82 0.38
~
free amino acids <.J 200 Proline 4.11 0.45
~
9) (Burton, et a!., Glycine 0.02 0.14
finally a leveling Alanine 0.32 0.35
100
ion. The decrease Valine 0.06 Trace
Isoleucine 0.06
fifth day of air- 0 Leucine Trace 0.10
deamination and 0 5 10 15 20 25 Tyrosine 0.68 0.84
mslocation. Even Days From Harvest Phenylalanine 0.24 0.50
num in total free Lysine 0.03 0.33
some individual Fig. 8.9 Total free amino acid changes during burley air- Histidine 0.11 0.45
others have a net curing (adapted from Burton, eta/., 1983). Arginine 0.26
1ld be noted that Tryptophan 0.50
tobacco rapidly
Source: Leffingwell (1976).
)) (Burton, et a!.,
150
pH and nicotine smoking quality blends of flue-cured and burley
mt ammonia also 125 tobaccos with similar nicotine content illustrates this
ion of aroma and E
~
dramatically (Leffingwell, 1976). In burley, we find the
(!)
100 main free amino acids present to be aspartic acid,
efore curing, air- ~ asparagine and glutamic acid, while for flue-cured,
VI proline, asparagine and glutamine are dominant. In
.92 75
0 total, 43 amino acids have been found in tobacco leaf.
E
~ Cigarette tobaccos are almost never utilized in con-
<.J 50
~ sumer products unless they have undergone a period of
aging ranging from 12 to 60 months. Of course,
25 inventory control is an important factor requiring
eaf #17 maintenance of adequate stocks to allow periodic blend
0 changes to occur; but, freshly cured and redried leaf is
eaf #2 0 5 10 15 20 25
--
not used primarily because the smoke changes
Days From Harvest dramatically from a raw, somewhat irritating and dis-
agreeable taste to a smoother, more rounded flavor
Fig. 8.10 Ammonia increases during burley air-curing
during the aging process. Aging is ordinarily carried
(adapted from Burton, eta/., 1983).
out at ambient temperatures and about 12/o moisture.
In areas with relatively long-term high ambient tem-
cured burley or cigar tobaccos may contain 3 to 4% peratures the desired aging effects are produced in
protein nitrogen, while flue-cured tobacco contains shorter periods than in colder climates (Bates, et a!.,
only 15 to 20% of that amount. In addition, about 50% 1974), and it is common for companies located in cold
I
of the protein in burley may undergo hydrolysis during climate regions to store and age their tobaccos in
20 25 air-curing while only about 20% of the protein is southern locales. The role that nitrogen compounds
est hydrolyzed in curing flue-cured tobaccos. Thus, bur- play in the improvement of tobacco flavor quality with
ley tobacco possesses a relative abundance of free aging is important and the reasons for this will become
'ir-curing (adapted am~no acids compared to flue-cured tobacco. Repre- apparent.
sentative free amino acid analysis (Table 8.5) of high The role of certain amino acids in flue-cured tobacco
274 Tobacco: Production, Chemistry and Technology Leaf Chern
pyrroles and a number of simple pyrazines (including to the interaction of amino acids and/ or ammonia with
14
the major tobacco leaf pyrazines, 2,5- and 2,6- sugars or carbonyl constituents, suffice it to say, no
13
dimethylpyrazine, trimethylpyrazine and tetra- single pathway is involved and that this complex
12
~..
methylpyrazine) (Heckman, et a!., 1981). Although transformation is dependent on a variety of factors and
11 pyrazines as a class represent a very small percentage of chemical mechanisms (Leffingwell & Leffingwell,
10 tobacco weight, they are known to be very important to 1988). The generation of certain pyridines (e.g. methyl
" 9 the flavor and aroma of roasted foodstuffs and tobacco. nicotinate, 3-cyanopyridine and 3-acetylnicotine) can
~
Bright and co-workers demonstrated that the weight be derived from degradation of nicotine.
ose I 8
percentages of five amino acids were significantly
7
reduced by heat treatment, while the roasting of
........... ............ 6
5
tobacco caused dramatic increases in pyrazine levels
(especially those high in ammonia or ammonia pre-
TOBACCO ALKALOIDS
4 cursors) under conditions where percent of nicotine The major tobacco alkaloids are nicotine, cotmme,
3 remained constant (Tables 8.6 and 8.7) (Bright, eta/., nornicotine, myosmine, nicotyrine, anabasine and
2 1975). anatabine. This subject is covered in greater detail
3 4 elsewhere in this book (Chapter 8B) and will not be
Table 8.6 Change in amino acid levels of tobacco discussed here except to note that nicotine can range in
Grade Leaf (Kurashaki) after roasting (complete cigarette blend). concentration from 0.5 to 8% in the major cultivated
tobacco species, N. tabacum and N. rustica. The
Amino acid Before After D.% interaction of smoke pH and the sensory perception of
(%) (%) nicotine is discussed above.
pounds (prolino-
.obacco (adapted from Aspartic acid 1.39 0.82 -41
Proline 0.65 0.31 -52
Lysine 0.32 0.10 -69 PLASTID PIGMENTS
Histidine 0.24 0.16 -33
Arginine 0.16 0.06 -62 The major pigments of tobacco are the chlorophylls
and carotenoid pigments, plastid pigments found in a
Source: Bright, eta/. (1975). wide variety of plants. The chlorophyll and carotenoid
contents and changes during the latter stages of
-----.10 Table 8.7 Effects of roasting on dimethylpyrazine growing (and the curing processes) have been studied
concentration. in significant detail for both burley and Virginia
9 tobaccos.
Concn before Concn after
8 roasting roasting
(ppb) (ppb) (a) Chlorophylls
~7 Virginia
Turkish
0.1
0.1
0.3
0.8
As shown in Fig 8.13 for burley tobacco, the major
green pigments are chlorophyll-A and chlorophyll-B,
6
Burley 0.1 460
both of which decrease as the tobacco reaches maturity,
Reconstituted leaf 0.1 200 proceeds into senescence and continues to decrease
5 during barn curing (Burton & Kasperbauer, 1985).
Tobacco samples were shredded, without additives and roasted for 4 Studies on Virginia tobacco show similar trends as the
4 hours at 120 YC. tobacco reaches maturity (Court & Hendel, 1984).
Source: Bright, eta/. (1975).
Leaf color in the field as well as for cured leaf is
....L-.--..L..l3
3 4
considered to be important in judging the quality ofleaf
Wahlberg, et al. (1977) have examined the chemical and this has been extensively studied (Tso, 1972; Tso,
changes occurring during the flue-curing and aging of 1990).
~e Leaf (Kurashaki)
Virginia tobacco. One of the observations was that a
number of pyrazines, pyrroles and pyridines increased
(b) Carotenoid pigments
during the flue-curing and aging process (Enzell, eta!.,
1unds (alanino- 1977). As pyrroles, pyridines and pyrazines can arise in The major carotenoid pigments in tobacco are lutein,
acco (adapted from tobaccos by a number of chemical pathways ranging P-carotene, neoxanthin and violaxanthin. In addition to
from the heating or aging of proteins and amino acids being major color pigments (red-orange to yellow), the
276 Tobacco: Production, Chemistry and Technology LeafChem
7
More extensive degradation oflutein has been reported Table 8.8
6 for Virginia tobacco (Court & Hendel 1984 Court et products.
al., 1993). ' ' '
6 Compound
5
E
~ 5
(!) 4 TOBACCO ISOPRENOIDS
~ 4
3
~ Wahlberg and Enzell ( 1987) have comprehensively lsophorone
~ 3
reviewed the subject of tobacco isoprenoid con-
f 2
2
stituents, therefore only comments on some of the .ff
more important materials will be included in this 4-Ketoisopn
0
section.
Oc
Safranal
0 7 14 21
Days After Harvest
28 42 90 (a) Degraded carotenoids
A large number of carotenoid metabolites are
ep..
Dihydractin
fig. 8.13 Changes in chlorophyll content of burley tobacco encountered in tobacco. The degradation process of the
during air-curing (adapted from Burton & Kasperbauer,
1985).
carotenoid pigments in tobacco has been hypothesized
to be probably both enzymatic and autooxidative in .~
Oxoeudala1
nature. As indicated in Fig. 8.15 for carotene, the
carotenoids are the precursors to many of the volatile
aroma components of tobacco.
carotenoid chain may be cleaved in a number of loca-
tions resulting in a variety ofC9 to C 13 chemicals, many
.~
Figure 8.14 shows the decrease in carotenoids dur- of which possess important aroma properties. Table 8.8
(Wilson, et al., 1982; Leffingwell & Leffingwell, 1988)
D~
ing maturation, senescence and curing for burley
tobacco (Burton & Kasperbauer, 1985). Unlike the illustrates the quantitative amounts found for a number cx-lonone
~
chloroplastid pigments, the carotenoids do not undergo of important nor-carotenoids for various tobacco types.
as extensive degradation (metabolism). Lutein and The degradation of both lutein and ~-carotene by
carotene undergo about 65% degradation in burley. both photo-oxidation and high pressure oxidation (at ~-lonone
elevated temperature) has been shown to generate
.r
3-Keto-cx-io
~ 1000
~
Ol 800 ~
Damasceno
a, HO
e
~~
600 \IOL.\X.\:".Tfll:\
~ OH
400 3-Hydroxy-
200 ~
HO .~
LL'TEI!\1
(5 Isomers)
-28 -14 0 14 28 90
-21 -7 7 21 42
Days From Harvest
HO
4-Keto-~-ic
1 has been reported Table 8.8 Major tobacco carotenoid degradation many of the same nor-carotenoid components found in
lei, 1984; Court, et products. tobacco (Heij, et a!., 1992).
metabolites are
Hi on process of the
Cv
Dihydractinodiolide
150 26 73
5
r-----------------------------~ 5
139 25 34
been hypothesized
d autooxidative in .$
Oxoeudalane
0 Free Solanesol
4
~
ious tobacco types. + + +
md P-carotene by
;sure oxidation (at ~-Ion one
.~
aown to generate + NR NR
3-Keto-cr-ionone
3-Keto-cr-ionol
23 Fig. 8.16 Changes in solanesol levels of burley tobacco
.JX-L
3-Ketodihydroionone
51 31
during air-curing (adapted from Long & Weybrew, 1981 ).
~OH
~
168 42 39
It should be noted that solanesol is present as both
the free alcohol and in bound forms primarily as
Damascenone
acetate, palmitate and linolate esters. Solanesol nor-
~~
24 11 +
mally ranges from I to 2% in Virginia tobacco and from
1% to as much as 4% in burley tobacco.
~OH 3-Hydroxy-~-damascone
The concentration of solanesol in burley tobacco has
.~
1272 248 415
Megastigmatrienones been shown to be effected by genetic lines and, more
(5 Isomers) importantly, by production practices. Water stress,
+ NR through decreased soil moisture, leads to an increase in
~
NR
solanesol content as does the length of senescence from
0
time of topping (Burton, et a!., 1989).
4-Keto-~-ionone Neophytadiene (a C 20 isoprenoid polyene) IS a
tobacco diterpene whose concentration increases sig-
NR = not reported; + = present, but quantitation not available.
Table adapted from Wilson, eta/. (1982) and Leffingwell & nificantly upon curing and aging. Generally, low levels
rley tobacco. Leffingwell (1988). are present in green tobacco leaf, but neophytadiene
p
increases during the yellowing and curing phases. Fig. It has been assumed that neophytadiene is produced (d) Cern
8.17 shows the neophytadiene change in curing burley by dehydration of phytol. Phytol is a metabolite from products
tobacco (Burton & Kasperbauer, 1985) and Fig. 8.18 chlorophyll hydrolysis, but it has been concluded that
shows the change in flue-curing Virginia tobacco only 15 to 30% of neophytadiene generated during More thar1
(Long & Weybrew, 1981). flue-curing could be accounted for from this source in tobacco. T
the case of flue-cured tobacco (Amin, 1979). Neo- major cern-
phytadiene has been suggested to be a tobacco flavor example, h
1200 0.23% by.
enhancer in that it may act as a flavor carrier by
entrapping volatiles in the tobacco smoke aerosol
E 1100 (Leffingwell & Leffingwell, 1988).
~
C!) Among other major acyclic isoprenoids are linalool,
~ 1000 linalool oxide, geranylacetone and farnesylacetone.
Table 8.9 provides comparative data on some acyclic
"'
E isoprenoids, nor-derivatives and neophytadiene
"' 900
0, obtained by the steam distillation of various tobacco
e types (Wilson, et a!., 1982).
~ 800
700
Table 8.9 Some major acyclic isoprenoids and nor- CEMBR.
isoprenoid products isolated from the steam
distillation of tobacco types. Fig. 8.19 C
ytadiene is produced (d) Cembranoids and their degradation growth regulator. During air- and sun-curing, the
is a metabolite from products concentration of abienol decreases significantly while
been concluded that numerous other labdanoids and labdanoid degradation
1e generated during More than 50 cembranoids have been isolated from products are formed. In cured leaf about 20 labdanoids
r from this source in tobacco. The cembra-2, 7, 11-triene-4 ,6-diols are the and an additional 25 or more degradation products are
:Amin, 1979). Neo- major cembranoids of tobaccos (Fig. 8.19) which, for found. (Z)-Abienol has been shown to undergo various
1 be a tobacco flavor
example, have been found in Virginia to be present at oxidative processes to many of these products (Wahl-
a flavor carrier by 0.23% by weight (Court, eta!., 1993). berg & Enzell, 1987). Figure 8.20 shows some impor-
~ceo smoke aerosol tant labdanoid derived products in Oriental tobacco.
Oriental tobacco, but this material is a key component citric and oxalic acids (Kalianos, 1976), although this is Table 8.12
in ambergris derived from whales; the exotic aroma and probably just an indicator, and is not due to the abso- tobacco smc
fixative value of ambergris is largely due to this lute amounts of these acids present in leaf. tetraesters.
material. The volatile CrC 8 acids are known to be important
The combination of labdanoid-derived flavorants aroma compounds in many fruits, foodstuffs and Acid
and sucrose tetraesters present in Oriental tobacco tobacco. Table 8.11 shows the relative amounts of the
comprises the major flavor-forming components of this major volatile organic acids for various tobacco types Propionic acic
variety (Leffingwell & Leffingwell, 1988). Within the (Kalianos, 1976). Butyric acid
Oriental types, the Greek and Macedonian types tend Valerie acid
to be higher in labdanoid-derived compounds, while Table 8.11 Volatile organic acids in tobacco. 2-Methylbuty!
the Turkish Smyrna (lzmir) types are higher in sucrose Isovaleric acic
tetraesters containing the 3-methylvaleric acid com- Acid Virginia Burley Oriental Threshold 3-Methylvaler
ponent. (!lg/g) (!lg/g) (!lg/g) (ppb) Hexanoic acic
Octanoic acic
Formic acid 597 288 587 45000 Phenylacetic
Acetic acid 877 372 688 22000
CARBOXYLIC ACIDS Propionic acid 12 Source: Heckm
13 24 20000
Isobutyric acid 32 29 72 8100
The major carboxylic acids in tobacco are citric, malic, Butyric acid 2 0 0 240
oxalic and malonic which in total can comprise 14 to ing cigarett<;;
2-Methylbutyric 247 26 313 1 600
18% in burley and cigar tobacco, 7 to 10% in Mary- provides an i
acid
land, 6 to 8% in Oriental and 5 to 10% in Virginia leaf, Isovaleric acid 116 20 202 120
to thermolys
after curing. A substantial portion of such acids are 2-Butenoic acid 12 1 3 NA Leffingwell,
complexed as salts with nicotine, ammonia and inor- Valerie acid 0 4 3000 Withoutq
ganic anions of calcium, potassium and sodium. The 3-Methylvaleric 4 1 1372 300* of the most ir
bar diagram (Fig. 8.21) adapted from Kalianos (1976) acid the powerfu.
graphically shows the differing acidity profiles by Hexanoic 5 3 5 3000 additions to c
Heptanoic acid 5 5 6 3000 have a profo
tobacco type.
Octanoic acid 5 12 5 3000 The high
Considerable effort has been expended trying to Nonanoic acid 16 21 24 3000
relate such acids to tobacco quality. Several studies oleic, linolei
2-Furoic acid 32 36 125 NA
indicate that there is an inverse relationship to the 1.1% in Vir
Benzoic acid 22 14 25 85000
smoking quality of Virginia tobacco and the quantity of Phenylacetic acid with palmiti
36 0 65 10000
Table 8.13
*Author's estimate. found in a 2:
Delphi, Ont:
Mlliequivalents Per Gram It should be noted that the Oriental sample above is
o __or.2__orA__o,..s--;::=o::r.a=::::::!==1.c2==,!:.4=~,.s an Izmir type which should have a high 3-methylvaleric Table 8.13
1 acid content and that the reported values must include
the bound acids released by hydrolysis of sucrose tet- Acid
Malonic Acid
0 Virginia IZI Ogar raesters.
One of the ways to assess a compound's odor or Myristic acid
ll! Burley Oriental
Palmitic acid
Oxalic Acid Ill Maryland llll Latakia flavor potency is to evaluate its minimum detectable
Stearic acid
threshold level. In the table above are included the Oleic acid
detection thresholds (Leffingwell & Leffingwell, 1991) Linoleic acid
for many of the tobacco acids. If one divides the relative Linolenic acic
concentration of a material by the threshold one can
approximate the relative odor potency. For example,
for acetic acid, 688/2200 = 0.03, while for 3-
methylvaleric acid, 1372/300 = 4.57, indicating the
TOBACC
aroma contribution of the latter would be about 152 x
that of the acetic acid.
(a) Polypi
Fig. 8.21 Major organic acids in different tobacco types Table 8.12 shows the concentrations of free acids in The amoum
(adapted from Kalianos, 1976). an Oriental tobacco blend and that of the correspond- tobacco type
y and Technology l.eaf Chemistry: Basic Chemical Constituents & Differences among Tobacco Types 281
6), although this is Table 8.12 Increase in aromatic acids in Oriental Table 8.14 Polyphenols by tobacco type.
lt due to the abso- tobacco smoke due to thermolysis of sucrose
tetra esters. Tobacco 1980 1981
in leaf.
(%) (%)
vn to be important
Acid Tobacco Smoke Change
s, foodstuffs and Virginia 3.13 3.75
()lg/g) ()lg/g) (%)
ive amounts of the Burley 1.78 2.05
ious tobacco types Propionic acid 17.0 66.8 +293 Cigar wrapper 2.13 2.65
Butyric acid 2.5 9.7 +288 Cigar filler 2.03 3.40
Valerie acid 4.3 3.6 -16 Cigar binder 2.27 3.54
2-Methylbutyric acid 2.1 12.4 +490 Maryland 2.09 3.25
in tobacco. Dark fire-cured 2.78 3.64
Isovaleric acid 5.1 19.7 +286
3-Methylvaleric acid 12.0 62.0 +417 Oriental 1.83 2.09
Oriental Threshold
()lg/g) (ppb) Hexanoic acid 7.5 3.9 -48
Source: Smeeton (1987).
Octanoic acid 1.7 6.2 +265
587 45000 Phenylacetic acid 48.9 19.9 -59
688 22000 tural variability. In a 2-year study the average poly-
Source: Heckman, eta/. (1981 ).
24 20000 phenol amounts found were as listed in Table 8.14
72 8100 (Smeeton, 1987).
0 240 ing cigarette smoke (Heckman, et a!., 1981 ). This Major polyphenolics found in tobacco include
313 1600
provides an indication of the increase in free acids due chlorogenic acid, rutin, scopoletin and scopolen, along
to thermolysis of the sucrose tetraesters (Leffingwell & with materials such as quercetin and kaempferol. The
202 120
Leffingwell, 1988). biogenesis of plant phenolics with relationship to the
3 NA
4 3 000 Without question, the volatile tobacco acids are some pathways relevant to the major groups in tobacco for
1372 300* of the most important contributors to smoke quality and compounds formed via shikamic acid has been
the powerful contribution from Oriental means that reviewed by Enzell & Wahlberg (1980). The amounts
5 3 000 additions to cigarette blends at even low percentages can of polyphenols for Virginia NC 95 and Burley 21 have
6 3000 have a profound effect on product acceptability. been reported (Table 8.15) (Sheen, eta!., 1979).
5 3000 The higher fatty acids (myristic, palmitic, stearic,
24 3 000 oleic, linoleic and linolenic) comprise about 0.75 to
125 NA
Table 8.15 Typical polyphenols in tobacco.
1.1% in Virginia tobacco and about 0.5% in burley,
25 85000
with palmitic being about 25% of these total acids. Virginia Burley
65 10000
Table 8.13 lists the average amounts of fatty acids (mg/g) (mg/g)
found in a 2-year study on Virginia tobacco grown at
Chlorogenic acids 34.71 12.83
Delphi, Ontario, Canada (Court, eta!., 1993).
Rutin 7.95 4.00
ttal sample above is Scopoletin 0.13 0.06
igh 3-methylvaleric Table 8.13 Fatty acids in Virginia tobacco. Scopolin 0.94 0.35
ralues must include
Source: Sheen, eta/. (1979).
lysis of sucrose tet- Acid %
coniferyl alcohol, p-coumaryl- and synapyl alcohol. In distribution of sterols for both green and cured leaf has holding pro
many reviews on tobacco, lignin has been classified been studied and they can vary greatly within the chloride ten
with 'carbohydrates' due to its association with, and tobacco plant. The major sterols are cholesterol, cam- chloride lev
being bound to hemicellulose. In woody plants, lignin pesterol, stigmasterol and ~-sistosterol. Table 8.17 characterist:
acts as a cementing agent to help bind the matrix of provides the amounts of total individual sterols (after Tobacco\0
cellulose fibers (Goheen & Hoyt, 1985). hydrolysis) reported in a sample of Virginia tobacco the burnin
Lignin is known to produce high levels of phenolic (Ellington, et al., 1977) and in two lines of burley material. Ir:
constituents on thermolysis, such as 2-propylphenol, tobacco (Davis, 1976). accumulate
vanillin, eugenol, guaiacol, pryrogallol and cresols, major reasc
which are found in tobacco smoke. stems are i1
Table 8.17 Major sterols in tobacco.
major cigar
Burley lines stems to re
(c) Other phenolics purposes:
Many more phenolics are found in tobacco smoke than Virginia L-1 L-7 removed th.
(mglg) (mglg) (mglg) nitrosamine
in leaf, but the major isolated leaf phenols are shown in
Table 8.16 (Wilson, et al., 1982), albeit they are present The trac
Cholesterol 0.30 0.18 0.21
in low quantities in leaf. Campesterol 0.53 0.23 0.33
have a proi
Stigmasterol 0.75 0.72 0.82 pie, iron h:
Table 8.16 Major phenolics isolated from steam Sistosterol 0.88 0.38 0.94 that develo
distillation of tobacco types (parts per billion in leaf). Total sterols 2.46 1.51 2.30 of Virginia
een and cured leaf has holding properties of cigarettes. Phosphorous and Bright, M.N., Larsen, T.M. & Lewis, C.I. (1975) Analytical
y greatly within the chloride tend to slow the burning process. In fact, high method for the determination of pyrazines and alkylpyrazines
chloride levels provide both negative burning and taste in shredded tobacco. In: 29th Tob. Chem. Con[., College Park,
are cholesterol, cam-
MD, 8-10 October (abstract 27).
;tosterol. Table 8.17 characteristics.
Burton, H.R., Bush, L.P. & Hamilton, JL. (1983) Effect of
dividual sterols (after Tobaccos with high nitrate content are assisted in curing on the chemical composition of burley tobacco. Rec.
e of Virginia tobacco the burning process as nitrate is itself a combustible Adc'. Tob. Sci., 9, 91-153.
two lines of burley material. In air-cured tobaccos, the nitrate tends to Burton, H.R. & Kasperbauer, M.J. (1985) Changes in chemical
accumulate in the stem portion and is considered a composition of tobacco lamina during senescence and curing,
major reason why the smoking properties of burley I. Plastid pigments, J. Agric. Food Chem., 33, 879-83.
1acco. stems are inferior to Virginia stems. For many years, Burton, H.R., Leggett, E. & Philips, R.E. (1989) Factors influ-
major cigarette manufacturers 'washed' their burley encing the concentration of solanesol in burley tobacco. Beit. Z.
Burley lines stems to reduce the nitrate content. This served two Tabakforsch., 14(5), 313-20.
purposes: improved the smoking properties and Collins, G.B. & Legg, P.O. (1977) Genetic control of chemical
L-1 L-7 constituents in tobacco. In: Recent Advances in the Chemical
removed the nitrate oxidant which lowered the level of
(mg/g) (mg/g) Composition of' Tobacco and Tobacco Smoke, Proc. Am. Chem.
nitrosamines in smoke. Soc. Svmp., New Orleans. pp. 290-327.
0.18 0.21
The trace elements (such as iron) in tobacco can Court, \V.A. & Hendel, j.G. (1984) Changes in leaf pigments
0.23 0.33 have a profound effect on tobacco quality. For exam- during senescence and curing of flue-cured tobacco. Can. J.
0.72 0.82 ple, iron has been implicated in the speckling effects Plant Sci., 64, 229-32.
0.38 0.94 that develop in the so-called 'grey tobacco' deficiency Court, \V.A., Hendel, JG. & Pocs, R. (1993) Influence of
1.51 2.30 of Virginia tobacco (Tso, 1972; Tso, 1990). transplanting and harvesting date on the agronomic and
chemical characteristics of flue-cured tobacco. Tob. Sci., 37,
59-64.
SUMMARY Davis, D.L. (1976) Waxes and lipids in leaf and their relationship
to smoking quality and aroma. Rec. Adv. Tob. Sci., 2, 80-111.
yland tobaccos have
Dawson, R.F. (1952) Chemistry and biochemistry of green
sterol contents than Tobacco is a complex plant material from a chemical
tobacco. Ind. Eng Chem., 44, 266-70.
'tobaccos Oohnstone composition standpoint. No other plant material has Einolf, W.N. & Chan, W.G. (1984) Estimation of sucrose esters in
been studied more extensively in the history of man. tobacco by direct chemical ionization mass spectrometry. J.
red to be a potential Yet even today, the quality of tobacco is judged largely Agnc. Food Chem., 32, 785-9.
: polycyclic structure by empirical experience and subjective sensorial Ellington, ].]., Sclotzhauer, P.F. & Schepartz, A.I. (1977)
ms on pyrolysis (e.g. evaluation. It is not possible to replicate the smoking Quantitation of tobacco lipids: analysis of serial samples of flue-
1e at 7500C) Oohn- properties of the tobacco leaf synthetically. Yet, cured tobacco. In: Recent Adcances in the Chemical Composition
, 1968). through chemical knowledge and genetic advances, of Tobacco and Tobacco Smoke, Proc. Am. Chem. Soc. Svmp.,
there is now a much better understanding of tobacco 1'\ew Orleans. pp. 255-68.
Elson, L.A., Betts, T.E. & Passey, R.D. (1972) The sugar content
growth and important constituents that allows for
and the pH of the smoke of cigarette, cigar and pipe tobaccos in
improvements in quality using the best laboratory m
relation to lung cancer. Int. J. Cancer, 9(3), 666-75.
the world - through optimization of the biology of Enzell, C:.R. & Wahlberg, I. (1980) Leaf composition in relation to
potassium, magne- tobacco itself in the tobacco growing field. smoking quality and aroma. Rec. Adl'. Tob. Sci., 6, 64--122.
tlfur are found in the Enzell, C.R., Wahlberg, I. & Aasen, A.J. (1977) Isoprenoids and
), as shown in Table alkaloids of tobacco. Pro g. Chem. Org. Nat. Prod., 34, 1-79.
tplexed ammonia and REFERENCES Fenner, R.A. ( 1988) Thermoanalytical characterization of tobacco
topic of ammonia in constituents. Rec. Adv. Tob. Sci., 14, 82-113.
.ssed in this section. Amin, A.N.M. (1979) Dynamic transformations of' chemical con- Frankenburg, \'i.G. (1946) Chemical changes in the harYested
stituents during flue-curing of Nicotiana tabacum L. PhD thesis, tobacco leaf. I. Chemical and enzymatic conYersions during the
norganics is in large
l'iorth Carolina State University. curing process. Ad1:. Enzymol., 6, 309-87.
ices. Lower amounts Frankenburg, \V.G. (1950) II. Chemical and enzymic conversions
Anderson, R.C., Gunn, D.M. & Gibson JA. (1976) Glycoside
e.g. zinc, aluminum smoke flavorants for tobacco and tobacco substitutes, South during fermentation and aging. Adl'. Enzymol., 10, 325.
idium, nickel, man- African Patent 7 604 !56, 1976. British Patent I 508 616. Goheen, D.W. & Hoyt, C.H. (1985) Lignin. In: Klrk-Othmer
, chromium, cesium, Anonymous (1989) Hemicellulose. In: The Merck Index, lith ed, Concise Entydopedia of Chemical Technology, (ed. D. Eckroth).
een found in tobacco (ed. S. Budavari). p. 733. Merck & Co., Inc, Rahway, 1'\j. p. 699. John Wiley & Sons, New York.
edman, 1968). The Bacon, C.W., Wenger, R. &Bullock,JF. (1952) Chemical changes Green, C.R. (1977) Some relationships between tobacco leaf and
ms certainly impacts in tobacco during flue-curing. Ind. Eng. Chem., 44, 292. smoke composition. In: Rec. Advances in the Chemical Compo-
ssium accelerate) the Bates, W.W.,Jr, Mitchem, A.R. & Rogers, J.D. (1974) Influence of sition of' Tobacco and Tobacco Smoke, Proc. Am. Chem. Soc.
J leaf and the ash-
aging and processing. Reco. Adv. Tob. Sci. !nang. Vol., 79-86. Symp., 1'\ew Orleans. pp. 426-70.
284 Tobacco: Production, Chemistry and Technology
Green C.R., Colby, D.A., Cooper, P.J., eta/. (1980) Advances in Severson, R.F., Arrendale, R.F., Chortyk, O.T., eta!. (1985b)
analytical methodology of leaf and smoke. Rec. AdL. Tob. Sci., Isolation and characterization of the sucrose esters of the
6, 123-83. cuticular waxes of green tobacco leaf.]. Agric. Food Chem., 33
Hamilton, J.L. (1974) Changes during curing ofburley tobacco. PhD (No 5), 870-75.
dissertation, University of Kentucky, Xerox University Severson, R.F., Arrendale, R.F., Chortyk, O.T. &Johnson, A.W.
Microfilms, Ann Arbor, Michigan. (1981) In: Proceedings of32nd Southeastern Reg. Am. Chem. Soc.
Hamilton, J.L. & Lowe, R.H. (1978) Changes in the concentra- Meeting, Lexington, Kentucky.
tions of proteins, amino acids and ammonia in burley tobacco Severson, R.F., Johnson, A.W. & Jackson, D.M. (1985a) Cuti-
during air curing. Tob. Sci., 22, 89-93. cular constituents of tobacco: Factors affecting their produc-
Harlan, W.R. & Moseley, J.M. (1955) Tobacco. In Kirk-Othmer tion and their role in insect and disease resistance and smoke
Encyclopedia of Chemical Technology, Vol. 14. pp. 242-61. John quality. Rec. Ad1:. Tob. SCI., 11, 105-74.
Wiley & Sons, New York. Sheen, S.]., Dejong, D.W. & Chaplin, J.F. (1979) Polyphenol TOBACC
Heckman, R.A., Dube, M.F., Lynm, D. & Rivers, J.M. (1981) accumulation in chlorophyll mutants of tobacco under two
The role of tobacco leaf precursors in cigarette flavor. Rec. AdL'. cultural practices. Beitr. Z. Tabakforsch., 10(1), 57-64. Nicotine is
Tob. Sci., 7, 107-53. Shigematsu, H. & Kitami, H. (1978) Identification of poly- Of the rna-
Heij, H.T. de, van Dort, H.M., Renes, H., eta!. (1992) High hydroxypyrazines in tobacco leaves and tobacco flavor pre- nicotine as
pressure oxidation and photo-oxygenation of ~-carotene and pared by sugar-amine reaction. Ntppon Sembai Kosha Chuo
amounts ol
lutein. In: PROC. 12th Int. Congr. Flac-ours, Fragrances and Kenkyusho Kenkyu Hokoku, 7-14.
Essential Olls, Vienna. pp. 471-90. Smeeton, B.W. (1987) Genetic control of tobacco quality. Rec.
tine, nomic
Heinzer, F. (1986) Ueber die behandlung von tabakpflanzen mit Adv. Tob. Sci., 13, 3-26. alkaloids p1
methyljasmonaten. Paper presented at Tabakkolloquim In Stedman, R.L. (1968) The chemical composition of tobacco and in 30 to 40
Aarhus., 8-13 June. tobacco smoke. Chem. Rev., 68(2), 153-207. the princip
Herron, J.N. (1987) Glucosides of aromatic agents as tobacco Sun, H.H., Wooden, J.B., Ryan, W.S., eta!. (1987) Structural usually the
flavorants, US Pat. Appl. 55 599. characterization of a tobacco rhamnogalacturonan. Carbohydr. accumulate
Johnstone, R.A.W. & Plimmer, J.R. (1959) The chemical con- Polym., 7, 143-58. species. M
stituents of tobacco and tobacco smoke. Chem. Rev., 59, 885- Tso, T.C. ( 1972) Physiology and Biochemistry of Tobacco Plants. tives of no
936. Dowden, Hutchinson and Ross, Stroudsburg, Pa. reported tc
Kalianos, A.G. (1976) Phenolics and acids in leaf and their Tso, T.C. ( 1990) Production, Physiology and Biochemistry of
al., 1993).
relationship to smoking quality and aroma. Rec. Adv. Tob. Sci., Tobacco Plant. Ideals, Inc., Beltsville, Md.
2, 61-79. Wahlberg, I. & Enzell, C.R. (1987) Tobacco isoprenoids. Nat.
present in
Kaneko, H. (1971) The aroma of cigar tobacco, Part II. Isolation Prod. Rep., 4(3), 237-76. many othe
of norambreinolide from cigar tobacco. Agric. Bioi. Chem., 35, Wahlberg, I., Karlson, K., Austin, D.]., et a!, (1977) Effects of of these r
1461-2. flue-curing and aging on the volatile neutral and acidic con- aberrant rr
Lauterbach, J.H. & Moldoveanu, S.C. (1991) A pyrolysis-gas stituents of Virginia tobacco. Phytochem., 16, 1217-31. alkaloids.
chromatography-mass spectrometry investigation of pectin. In: Weybrew, J.A. & Hamann, H.K~(1977) Growth measurements Nicotin
45th Tob. Res. Conf, Asheville, :\JC (abstract 40). under field conditions. In: Recent Advances in the Chemical research ~
Leffingwell, J.C. (1976) Nitrogen components of leaf and their Composition of Tobacco and Tobacco Smoke, Proc. Am. Chem. tobacco q-
relationship to smoking quality and aroma. Rec. Adv. Tob. Sci., Soc. Symp., New Orleans. pp. 164-83.
important
2, 1-31. Weybrew,J.A., Woltz W.G. &Johnson, W.H. (1966) Changes in
nornicotin
Leffingwell, J.C. & Leffingwell, D. (1988) Chemical and sensory the free amino acids of tobacco during curing. In: Pro c. 4th Int.
aspects of tobacco flavor. Rec. Adv. Tob. Sci., 14, 169-218. Tob. Sci. Conf, Athens. pp. 766-72.
quality. C
Leffingwell, J.C. and Leffingwell, D. (1991) GRAS flavor Williams, P.S. (1993) Hydrolytic flavor release in fruit and wines these two
chemicals-detection thresholds. Perf Flav., 16(1), 1-19. through hydrolysis of nonvolatile precursors. In: Flavor nicotine a
Long, R.C. & Weybrew, J.A. (1981) Major chemical changes Science: Sensible Principals and Techniques, (eds T. Acree & R. levels of a.
during senescence and curing. Rec. Adv. Tob. Sci., 7, 40-74. Teranishi). Am. Chern. Soc., Washington DC. route of 1
:--loguchi, M., Satoh, Y., Nishidi, K., et a!. (1971) Studies on Wilson, R.A., Mookherjee, B.D. & Vinals, J.F. (1982) A com- thylation.
storage and aging ofleaftobacco. Agric. Bioi. Chem., 35, 65-70. parative analysis of the volatile components of Virginia, burley, are affect~:
Schumacher, J.N. (1959) Tobacco, US Pat. No 2 905 576. Turkish and black tobaccos. Paper presented at !84th Nat! cultural p
Schumacher, J.N. (1970) The isolation of 6-0-acetyl-2,3,4--tri-0- ACS Meeting, Kansas City. Many
(( +)-3-methylvaleryl)-beta-D-glucopyranose from tobacco,
effects of
Carboydr. Res., 13, 1-8.
accumula1
about the;
change in
these par
reviews a1
& Saund