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Volatile Constituents of Apricot (Prunus

armeniaca)

ARTICLE in JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · FEBRUARY 1990

Impact Factor: 2.91 · DOI: 10.1021/jf00092a031

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 J. Agric. Food Chem. 1990, 38, 471-477 47 1

duction of (Z)-abienol and a and (3 Cembratriene Diols. from the Green Leaf of Different Tobacco Types. J. Agric.
Ann. Tab.,Sect. 2 1983184, 123-130. Food Chem. 1984,32, 566-570.
Enzell, C. R. Terpenoid Components of Leaf and Their Rela- Severson, R. F.; Arrendale, R. F.; Chortyk, 0. T.; Green, C. F.;
tionship to Smoking Quality and Aroma. Rec. Adu. Tob. Thome, F. A.; Stewart, J. L.; Johnson, A. W. Isolation and
S C ~1976,
. 2, 32-60. Characterization of the Sucrose Ethers of the Cuticular Waxes
Gwynn, G. R.; Severson, R. F.; Jackson, D. M.; Stephenson, M. of Green Tobacco Leaf. J. Agric. Food Chem. 1985a, 33,870-
G. Inheritance of Sucrose Esters Containing P-methylvaleric 875.
Acid in Tobacco. Tob.Sci. 1985, 29, 79-81. Severson, R. F.; Johnson, A. W.; Jackson, D. M. Cuticular Con-
Johnson, J. C.; Nielsen, M. T.; Collins, G. B. Inheritanceof Glan- stituents of Tobacco: Factors Affecting their Production and
dular Trichomes in Tobacco. Crop Sci. 1988, 28, 241-244. their Role in Insect and Disease Resistance and Smoke Qual-
Kallianos, A. G. Phenolics and Acids in Leaf and Their Rela- ity. Rec. Adu. Tob.Sci. 1985b, 11, 105-174.
tionship to Smoking and Quality and Aroma. Rec. Adu. Severson, R. F.; Stephenson, M. G.; Johnson, A. W.; Jackson,
Tob.Sci. 1976, 2, 61-79. D. M.; Chortyk, 0. T. Isolation and Preparative Chromatog-
Kandra, L.; Wagner, G. P. Biosynthesis of Sucrose Esters and raphy of the Major Cuticular Diterpenes of Green Tobacco.
Diterpenes in Trichome Head Cells of Tobacco. Tobacco Tob.Sci. 1989, 32, 99-103.
Chemists Research Conference, Greensboro, NC, 1987.
Kasperbauer, M. J.; Collins, G. B. Reconstruction of Diploids Smeeton, B. W. Genetic Control of Tobacco Quality. Rec.
of Anther-derived Doubled Haploids in Tobacco. Crop Sci. Adu. Tob.Sci. 1987, 13, 3-26.
1972,12,98-101. Wagner, G. J. Personal Communication, University of Ken-
Keene, C. K.; Wagner, G. J. Direct Demonstration of Duva- tucky, Lexington, KY, 1988.
triendiol Biosynthesis in Glandular Heads of Tobacco Tri-
chomes. Plant Physiol. 1985, 79, 1026-1032.
Nielsen, M. T.; Jones, G. A.; Collins, G. B. Inheritance Pattern Received for review March 8, 1989. Accepted October 16,1989.
for Secreting and Nonsecreting Glandular Trichomes in Journal Article No. 89-3-24 is published with approval of the
Tobacco. Crop Sci. 1982,22, 1051-1053. Director of the Kentucky Agriculture Experiment Station.
Severson, R. F.; Arrendale, R. F.; Chortyk, 0. T.; Johnson, A.
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son, M. G. Quantitation of the Major Cuticular Components abienol, 17990-16-8.

Volatile Constituents of Apricot (Prunus armeniaca)

Gary R. Takeoka,*Vt Robert A. Flath,? Thomas R. Man,+ Roy Teranishi,+ and Matthias Guentert'
Western Regional Research Center, U S . Department of Agriculture-Agricultural Research Service,
800 Buchanan Street, Albany, California 94710, and Haarmann & Reimer GmbH, Postfach 1253,
D-3450 Holzminden, West Germany

Volatile constituents of fresh apricots (Prunus armeniaca) of the Blenheim variety were analyzed by
capillary gas chromatography and gas chromatography-mass spectrometry. The fruit was sampled
by simultaneous vacuum steam distillation-extraction. A total of 49 components were identified in
the extract, including 25 constituents reported for the first time in apricot. Linalool, lactones, and
c6 lipid peroxidation products were the major constituents in the extract. Odor unit values, calcu-
lated from concentration and odor threshold data, indicate that the following compounds are major
contributors to blended apricot aroma: @-ionone,linalool, y-decalactone, hexanal, (E)-2-hexenal, @,E)-
2,4-decadienal, (E)-2-nonenal, and y-dodecalactone. Headspace analyses of the intact fruit led to the
identification of 83 components, 60 of which had not been previously reported in apricot. Esters were
the dominant constituents in the headspace samples.

The first significant studies on apricot flavor were per- nerol for the first time in apricot. Later studies on the
formed by Tang and Jennings (1967, 1968) who utilized same variety led to the identification of damascenone,
direct extraction, vacuum steam distillation, and char- 0-ionone, dihydroactinidiolide, rose oxide, and nerol oxide
coal adsorption to isolate the volatiles from the Blen- (Chairote et al., 1981). These authors felt that the apri-
heim variety. A number of terpene hydrocarbons, ter- cot aroma was dependent on several constituents such
pene alcohols, and lactones were identified by gas chro- as lactones, terpene alcohols, and benzaldehyde. Gui-
matographic retentions and infrared spectroscopy. chard and Souty (1988) compared the relative concen-
Rodriguez et al. (1980) studied the variety Rouge du Rous- trations of various volatiles present in six different apri-
sillon and identified constituents such as camphene, y- cot varieties (Precoce de Tyrinthe, Palsteyn, Moniqui,
terpinene, hexanol, benzaldehyde, y-butyrolactone, and Rouge du Roussillon, Polonais, Bergeron) grown in the
south of France. A total of 82 compounds were identi-
fied, 58 of which had not been previously reported in
apricot. The most abundant constituents were c6 lipid
USDA-ARS. degradation products, lactones, terpene alcohols, and
* Haarmann & Reimer GmbH. ketones. Sharaf e t al. (1989) identified 31 components

002 1-856 1/90/1438-047 1$02.50/0 0 1990 American Chemical Society

472 J. Agric. Food Chem., Vol. 38, No. 2, 1990 Takeoka et al.

Table I. HeadsDace Constituents of Fresh ADricots (Ether Elution)

IDB-1 IDB-1
peak % T," peak % T,'
no.' constituent exptl ref areab ppb no.a constituent exptl ref areab ppb
440 54 linaloolf 1088 1085 0.106 d
2,3-butanedione'sf 560 558 56 hexyl propanoatee-f 1091 1088 0.431 8
60 1 57 2-methylbutyl 2-methylb~tanoate~1091 1090 ns
ethyl acetatef 600 600 58 methyl octanoatef 1108 1107 0.010
2-methylpropanol'sf 607 608 60 pentyl 2-methylbutanoate'f 1126 1123 0.161
1 butanolf 654 654 0.147 500h 61 hexyl 2-methylpr~panoate~f 1138 1137 0.766 13
3 ethyl propanoatef 700 699 0.009 62 2-methylpropyl hexanoateef 1139 1138 0.413
4 methyl butanoate' 708 705 0.009 76 63 2-methylbutyl pentanoatee 1142 1142 0.014
5 Z-methylbutanolef 728 729 0.062 300 64 (E,Z)-1,3,5-~ndecatriene~ 1167 1165 0.029
6 ethyl 2-methylpropanoate'f 751 751 0.018 0.18 ethyl (E)-4-octenoateef 1169 1169
9 methyl 2-methylb~tanoate~ 767 768 0.005 65 (Z)-3-hexenyl butanoateerf 1173 1170 0.053
10 hexanal 778 778 0.010 5h 66 butyl hexanoateef 1187 1176 24.544 700
11 ethyl butanoatef 789 789 2.000 1' 67 hexyl butanoatee*f 1188 1178 11.784 250
12 propyl propanoate' 796 796 0.006 57' 68 ethyl octanoateef 1189 1182 0.014
13 butyl acetate' 799 796 0.417 66' 69 P-cyclocitral' 1196 1194 0.014 5
17 2-propyl butanoatee 834 834 0.006 dodecaneef 1200 1200
18 ethyl 2-methylbutanoatee,f 841 842 0.228 0.3 71 y -0ctalactone 1208 1210 0.061 7k
22 hexanolf 860 860 0.307 2500 72 (Z)-3-hexenyl 2-methylbutanoate'f 1218 1215 0.033
23 propyl butanoate'f 885 885 0.186 124 74 hexyl 2-methylbutanoate'f 1228 1222 3.503 22
24 ethyl pentanoatee.f 887 888 0.030 5' 76 3-methylbutyl hexanoateef 1236 1233 0.024
25 butyl propanoate'f 895 894 1.301 200 77 2-methylbutyl hexanoatee-f 1240 1236 0.351 32
26 pentyl acetate 898 895 0.015 78 pentyl hexanoate'.' 1274 1270 0.696
27 2-methylpropyl 902 901 0.020 30 80 propyl octanoateeJ 1277 1277 0.039
2-methy lpropanoateef
28 methyl hexanoatef 909 910 0.071 84 tridecanee,f 1300 1300
29 propyl 2-methylbutanoate'tf 936 936 0.023 83 2-methylpropyl octanoateef 1334 1334 0.027
30 butyl Z-methylpropanoate'*f 944 943 0.670 80 84 +?
ethyl (Z)-4-decenoatee*f 1363 1361 0.237
31 2-methylpropyl butanoate'vf 946 945 0.572 85 hexyl hexanoateef 1374 1369 4.115
32 2-methylbutyl propanoate'f 961 961 0.020 86 butyl octanoate'f 1374 1373 0.438
33 butyl butanoateef 990 982 29.657 100 87 ethyl decanoate'f 1381 1379 0.074
34 ethyl hexanoatef 992 986 4.700 1 90 dihydro-P-ionone'vf 1414 1414 0.110
36 2-methylpropyl 995 991 0.141 91 y-decalactone 1424 1422 1.825 1l k
2-methylbutanoate'"
37 hexyl acetate' 999 995 0.146 2g 95 &decalactone 1444 1447 0.071 1OOk
38 2-methylbutyl 1001 1002 0.041 97 dihydroactinidiolide 1473 1475 0.046
2-methylpropanoate'ff
40 limonenef 1020 1020 0.033 10 98 pentadecane'f 1501 1500 0.440
42 butyl 2-methylbutanoate'f 1033 1030 2.759 17 100 hexyl benzoatee 1551 1551 0.020
43 butyl 3-methylb~tanoate~ 1035 1035 0.016 101 hexyl octanoatee 1566 1565 0.024
44 pentyl 2-methylpropanoate'f 1040 1039 0.040 102 butyl decanoatee 1570 1571 0.016
45 (E)-P-ocimenee 1042 1037 0.058 103 ethyl dodecanoate 1579 1578 0.033
46 3-methylbutyl butanoatee 1044 1041 0.042 104 tetradecanal 1591 1592 0.015
47 2-methylbutyl butanoate' 1047 1047 0.363 106 y -dodecalactone 1631 1635 0.096 7k
51 pentyl butanoateef + ? 1081 1080 1.452 210 110 hexadecanal' 1795 1796 0.117
52 propyl hexanoate'f 1081 1081 0.199 111 (phthalate)d 1900 0.023
53 ethyl heptanoatee*' 1084 1080 0.111 2.2 112 ethyl hexadecanoate 1978 1978 0.045
a The peak numbers correspond to the numbers in Figure 1. Mass spectra were consistent with those of authentic reference standards.
Peak area percentage of total FID area excluding the solvent peaks (assuming all response factors of 1). ns = not separated from preced-
ing compound. Odor threshold in water. Tentative or partial identifications enclosed in parentheses. e Identified for the first time in
apricot. Detected and identified with headspace method employing thermal desorption. Buttery et al., 1982. Buttery et al., 1971. Flath
et al., 1967, I Buttery et al., 1969. Engel et al., 1988.

in overripe apricots of the Zibda variety. This study reports lected volatiles were eluted from the Tenax trap with 100 mL
on the volatile constituents present in fresh apricots of of freshly distilled diethyl ether containing ca. 0.001% Ethyl
the cv. Blenheim, an important California variety. antioxidant 330. The ether extract was then concentrated with
a Vigreux column (16 cm) to a final volume of ca. 100 pL.
EXPERIMENTAL SECTION B. Thermal Desorption. The sampling chamber, activated
charcoal, air purifier, sampling pump, and Tenax traps have
Materials. Fresh, tree-ripened apricots (Prunus armeniaca) been described previously (Flath and Ohinata, 1982; Takeoka
of the Blenheim variety were obtained from an orchard in Hol- et al., 1988). Intact fruit (669 g) were placed in the sampling
lister, CA (June 1988). Ethyl antioxidant 330 (1,3,5-trimethyl- chamber, and the system was purged overnight with a 25 mL/
2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene) was received min flow of purified air. A Tenax trap was attached to the exit
from Ethyl Corp. (Baton Rouge, LA). port of the sampling chamber, and the air stream was collected
Sample Preparation. 1. Dynamic Headspace Sampling. for 15 min at 50 mL/min. The trap was removed, and its con-
A. Solvent Elution. Intact fruit (total weight 3.38 kg) were tents were examined by capillary gas chromatography with flame
placed in a 9-L Pyrex glass container. A Pyrex head to allow ionization detection (GC/FID). A second trap was attached to
the passage of air into and out was fitted into a standard ground the chamber and the headspace vapor sampled for 30 min a t
glass joint in the upper part of the container. Purified air (passed 50 mL/min. The trap was removed and used for capillary gas
through activated carbon filters) entered the bottom of the cham- chromatography-mass spectrometry (GC-MS).
ber via a Teflon tube and exited out the top through a Tenax
trap. The traps consisted of glass tubes packed with 10 g of 2. Vacuum Steam Distillation. Extraction. The fruit were
Tenax (Alltech Associates, Deerfield, IL) and terminated in stan- cut in half, and the stones were removed and discarded. The
dard ball and socket joints. The air stream was sampled at skin and pulp (1.7-1.9 kg) were blended with 1 L of water for
room temperature (ca. 24 "C) for 22 h at 3 L/min. The col- 15 s in a Waring blender. Two batches were prepared from a
Volatile Constituents of Apricot J. Agric. Food Chem., Vol. 38,No. 2, 1990 473

1 1113 1822 2325 303 3334 3 1 4 2 4 1 51 58 6061 68 85 91 98

w - - 7 . . . . , . . . . , . . . . , . .
10 20 30 40 50 60 7E? 0L3 90 min
Figure 1. Capillary gas chromatogram of intact apricot headspace volatiles (ether elution). Temperature programmed from 30 "C
(4 min isothermal) to 210 OC a t 2 "C/min on a 60 m X 0.32 mm (i.d.) DB-1 column. The peak numbers correspond to the numbers
in Table I.

63 12 15 81 io3 mi 118

-r, . . . I . . . . I ' ' . , - - , . . I . . . . I "

10 20 30 40 50 60 70 80 min
Figure 2. Capillary gas chromatogram of apricot volatiles obtained by vacuum steam distillation-extraction. Temperature pro-
grammed from 30 "C (4 min isothermal) to 210 "C a t 2 "C/min on a 60 m x 0.32 mm (i.d.) DB-1 column. The peak numbers cor-
respond to the numbers in Table 11.

total of 3.59 kg of fruit pulp. The following compounds were analyses was used. For the ether extract (obtained by dynamic
added to the blended slurry as internal standards: 4-methylpent- headspace sampling) the following conditions were employed:
2-yl acetate, 4-nonanone, and eugenol (final concentrations 0.7 The column temperature was programmed from 50 to 250 "C
ppm each). The mixture was blended for another 15 s and then a t 4 "C/min; A split ratio of 1:25 was employed. For the hex-
added to a 12-L round-bottomed flask. An additional 1000 mL ane extract (obtained by simultaneous vacuum steam distilla-
of water was added to the flask. Fifty milliliters of antifoam tion-extraction) the following conditions were employed The
solution was added. The antifoam solution was prepared by column temperature was programmed from 30 "C (4 min iso-
adding 12 mL of Hartwick antifoam 50 emulsion to 900 mL of thermal) to 210 "C a t 2 "C/min. A split ratio of 1:23 was used.
water in a 1-L flask and boiling until the volume was reduced Helium carrier gas was used a t a rate of 3.9 mL/min.
to ca. 600 mL to remove volatiles. A modified Likens-Nicker- For thermal desorption headspace analyses, this unit was
son distillation-extraction head was used (Schultz et al., 1977). equipped with a headspace unit operationally identical with one
The fruit slurry was subjected to simultaneous vacuum distil- described previously (Takeoka et al., 1988). The column tem-
lation-extraction for 3 h with 125 mL of hexane (60 mmHg). perature was programmed from 0 to 230 "C a t 3 "C/min.
After freezing (-20 "C) to remove residual water, the hexane Reference Compounds. Esters were prepared by refluxing
extract was concentrated with a Vigreux column under reduced the corresponding alcohol (0.1 mol) and acid (0.05 mol) and p -
pressure (60 mmHg) to a final volume of 0.6-0.8 mL. toluenesulfonic acid (5-10 mg) in benzene overnight. Water
Gas Chromatography. A Hewlett-Packard 5890 gas chro- was removed with a Dean-Stark trap. Propyl octanoate had
matograph (Hewlett-Packard, Avondale, PA) equipped with a the following mass spectrum: 186 (l),157 (2), 146 (8), 145 (loo),
flame ionization detector (FID) was used. Separations were per- 128 (8), 127 (94), 115 (17), 102 (321, 101 (151, 87 (161, 83 (111,
formed on a 60 m X 0.32 mm (i.d.) DB-1 column (d, = 0.25 pm; 73 (32), 61 (70), 60 (44), 57 (45), 55 (23), 43 (42). 2-Methylpro-
J&W Scientific, Folsom, CA). The oven temperature was pro- pyl octanoate had the following mass spectrum: 200 (>l), 170
grammed from 30 "C (4 min isothermal) to 210 "C at 2 "C/ ( l ) , 145 (49), 144 (lo), 128 (9), 127 (loo), 116 (6), 101 (lo), 87
min. Helium carrier gas was used a t a flow rate of 1.64 mL/ (7), 73 (13), 60 (16), 57 (74), 56 (71), 55 (14), 43 (16). Butyl
min (30 "C; iL = 34 cm/s). The injector temperature was main- octanoate had the following mass spectrum: 200 (>l), 157 (2),
tained at 200 O C ; the detector temperature was held at 230 "C. 146 (8), 145 (loo), 144 (8), 128 (7), 127 (80), 116 (9), 101 (21),
Split injections (1:30) were employed. Data processing was per- 89 (9), 87 (lo), 83 (9), 73 (24), 60 (25), 57 (591, 56 (92), 55 (22),
formed with an H P 5895 GC ChemStation. 43 (20). Butyl decanoate had the following mass spectrum: 228
The conditions and instrumentation used for the thermal des- (2), 185 (4), 174 (9), 173 (go), 172 (8), 155 (60), 129 (28), 116
orption headspace analyses were described previously (Take- (12), 101 ( l l ) , 85 (lo), 73 (29), 71 (18), 60 (26), 57 (37), 56 (loo),
oka et al., 1988). 43 (27). Hexyl octanoate had the following mass spectrum: 228
Gas Chromatography-Mass Spectrometry. A Finnigan (>l), 157 (l),145 (loo), 127 (53), 115 (4), 101 (12), 85 (16), 84
MAT 4500 GC/MS/INCOS system (Finnigan MAT, San Jose, (86), 73 (16), 69 (22), 61 (26), 57 (41), 56 (42), 55 (28), 43 (52).
CA) equipped with the same type of column used in the GC Other reference standards were obtained commercially or
474 J. Agric. Food Chem., VOI. 38, No. 2, 1990 Takeoka et at.

Table 11. Volatile Constituents of Apricot: Vacuum Steam Table 111. Approximate Concentrations, Odor Thresholds
Distilled Blended Fruit in Water, a n d Odor Units of Some Apricot Constituents.
IDB-1 approx approx odor odor
peak concn,* concn,b threshold,' units
no." constituent exotl ref ua/kn Constituent" d k g PPb ( UJd
1 2-methylbutanolc 730 729 1 p-ionone 14 0.007' 2000
4 2- hexanone 771 770 2 linalool 296 d 49
8 hexanal 779 772 220 y-decalactone 492 118 45
9 3-hexanol' 784 784 1
hexanal 220 5e 44
10 2- hexanol 789 788 1 (E)-2-hexenal 730 17' 43
16 ( E )- 2-hexenal 831 827 730 (E,E)-2,4-decadienal 3 0.07' 43
18 (Zb3-hexenol 844 843 56 (E)-2-nonenal 2 O.Oae 25
19 (E) -2-hexenol 863 856 750 y-dodecalactone 56 78 8
20 hexanol 867 860 740 6-cyclocitral 10 5 2
22 butyl propanoateC 895 890 2 phenylacetaldehyde 6 4e 1.5
24 benzaldehyde 925 926 56 y-octalactone 9 7' 1.3
25 ( 2 7 2 -heptenal' 931 927 6 geraniol 40 40 1.0
26 butyl 2-methylpropanoate' 935 936 tr hexyl 2-methylbutanoate 17 22 0.8
31 6-methyl-5-hepten-2-one 967 966 4 (Z)-3-hexenol 56 7oe 0.8
36 butyl butanoate 982 982 23 hexyl propanoate 4 8 0.5
38 ethyl hexanoate 986 986 tr hexyl 2-methylpropanoate 5 13 0.4
42 (E)-2-hexenylacetate 997 994 16 butyl 2-methylbutanoate 7 17 0.4
45 phenylacetaldehyde 1002 1002 6 6-decalactone 40 low 0.4
46 2,2,6-trimethylcycl~hexanone~1008 1008 2 hexanol 740 2500 0.3
48 butyl 2-methylbutanoate' 1030 1026 7 butyl butanoate 23 100 0.23
51 (E)-@-ocimenec 1041 1037 3 benzaldehyde 56 350e 0.16
60 pentyl butanoate' 1079 1080 7 hexyl butanoate 41 250 0.16
63 linalool 1086 1083 296 a-terpineol 49 330 0.15
64 hexyl propanoate' 1086 1083 4 geranylacetone 6 60e 0.1
65 3-nonen-2-one 1114 1114 2 6-methyl-5-hepten-2-one 4 50' 0.08
67 (E)-2-nonenalc 1134 1133 2 pentyl butanoate 7 210 0.03
69 hexyl 2-methylpr~panoate~ 1137 1137 5 butyl hexanoate 23 700 0.03
72 n-terpineol 1169 1170 49 2,2,6-trimethylcyclohexanone 2 100 0.02
73 (ZL3-hexenyl butanoate' 1169 1170 tr epoxy-&ionone 2 100 0.02
74 butyl hexanoate' 1176 1176 23 butyl propanoate 2 200 0.01
75 hexyl butanoate' 1179 1178 41 3-nonen-2-one 2 800 0.003
79 p-cyclocitral' 1190 1194 10 2-methylbutanol 1 300 0.003
80 y-octalactone 1205 1210 9
81 nerol 1208 1209 14 a The constituents were isolated by vacuum steam distillation-
85 hexyl 2-methylb~tanoate~ 1224 1222 17 extraction and are listed in descending order of their odor units.
87 geraniol 1234 1234 40 Only approximate concentrations since percent recoveries and FID
88 2-methylbutyl hexanoatec 1236 1236 tr response factors were not determined for each compound (assume
91 pentyl hexanoate' 1272 1270 3 all response factors of 1).'Odor threshold in water. Uo
94 (E,E)-2,4-decadienalc 1286 1287 3 = compound concentration divided by its odor threshold. e But-
97 hexyl hexanoate' 1370 1369 11 tery et al., 1971. f Buttery et al., 1969. # Engel et al., 1988.
99 3,4-didehydro-P-ionolc 1392 1397 10
102 dihydro-@-ionone' 1413 1414 8
103 y-decalactone 1425 1422 492 min), short sampling periods (15-30 min), and thermal
105 geranylacetone' 1428 1428 6
107 &decalactone 1445 1447 40 desorption of trapped volatiles. This technique was use-
108 epoxy-p-ionone" 1456 1456 2 ful for detecting low-boiling constituents that were obscured
109 @-ionone 1459 1462 14 by solvent peaks. The second method involved large Tenax
110 dihydroactinidiolide 1473 1475 3 traps (10 g), fast sweep gas flow rates (3 L/min), long
118 7-dodecalactone 1632 1635 56 sampling times (22 h), and solvent elution (ether) of
a The peak numbers correspond to the numbers in Figure 2. Mass trapped constituents. This method was more suited to
spectra were consistent with those of authentic reference stan- the analysis of higher boiling compounds and was less
dards. * Only approximate concentrations since percent recoveries prone to artifact formation (all glass surfaces and mini-
and FID response factors were not determined for each compound mal exposure to heat). The high air flow during trap-
(assume all response factors of 1). tr represents concentration less ping kept the sampling container well aerated; the fruit
than 1 ppb. Identified for the first time in apricot.
was maintained in good condition with no condensation
received as gifts. observed in the interior of the vessel. The importance
O d o r Thresholds. Odor thresholds of GC purified stan- of high gas flows during fruit headspace sampling was
dards were determined according to the procedure described discussed by Ismail et al. (1980) who felt these condi-
by Guadagni and Buttery (1978) and Guadagni e t al. (1973). tions were less conducive to microbial growth (which would
contribute their own volatiles). Table I lists apricot head-
RESULTS AND DISCUSSION
space constituents isolated by ether elution. With the
The volatile constituents from fresh apricots were iso- exception of early-eluting components, more constitu-
lated by two headspace methods and by simultaneous ents could be detected and identified by this procedure
vacuum steam distillation-extraction. The volatiles were than by the thermal desorption method. A GC/FID chro-
analyzed by GC and GC-MS. Sample components were matogram of apricot headspace volatiles (ether elution)
identified by comparison of the compound's Kovats index, is shown in Figure 1. Though many peaks overlapped or
I (Kovats, 1958), and mass spectrum with that of an were incompletely separated at this concentration, dilu-
authentic reference standard. tion of the extract was effective in resolving most of the
The intact apricots were sampled by two different head- components. This procedure was used in determining
space methods. The first method utilized small Tenax the percent area values listed in Table I. These values
traps (0.7 g of Tenax), low sweep gas flow rates (50 mL/ should be considered as approximate since there were
Volatile Constituents of Apricot J. Agric. Food Chem., Vol. 30, No. 2, 1990 475

constituents coeluting with solvent peaks and also sam- bramble (Kallio, 1976),and black chokeberry (Hirvi and
ple breakthrough during trapping was not determined. Honkanen, 1985).
Many of the esters are reported for the first time as 3,4-Didehydro-P-ionol has been found in quince fruit
apricot constituents. Previous studies have generally essential oil prepared by steam distillation (Ishihara et
involved blending of the fruit prior to sampling. This al., 1986). This labile compound appears to be the pre-
disruption of the fruit tissues may have caused changes cursor of the bicyclic hydrocarbon 2,2,6,7-tetra-
in ester concentrations due to enzymic activity (Schreier methylbicyclo[4.3.0]nona-4,7,9(1)-triene as refluxing the
et al., 1985). Guichard and Souty (1988) sampled apri- ionol in acidic solution produced 80% conversion (Ishi-
cot volatiles under enzymic inhibition (ammonium sul- hara et al., 1986). The precursor of 3,Cdidehydro-P-
fate) and identified 19 esters, 18 of which had not been ionol has not yet been identified though Winterhalter
previously reported in apricot. It was hoped that head- and Schreier (1988) have discussed possible formation
space sampling of the intact fruit would help to identify pathways. They have identified glycosidically bound 3-
compounds responsible for the pleasant fruity apricot hydroxy-6-ionol as a likely precursor.
aroma, Le., esters. The variety of esters was notably absent The monoterpene alcohols linalool, a-terpineol, nerol,
in the vacuum steam distilled samples from blended apri- citronellol, and geraniol have been shown to exist in gly-
cots. cosidically bound forms in apricot (Salles et al., 1988).
The esters were clearly the dominant constituents in With the exception of citronellol the previously men-
the headspace sample. The major esters identified were tioned monoterpene alcohols were identified in this study.
butyl butanoate (29.66%),butyl hexanoate (24.54%), hexyl Geraniol and nerol must exist predominantly in their
butanoate (11.78%),ethyl hexanoate (4.70%), hexyl hex- bound forms as Guichard and Souty (1988) did not detect
anoate (4.12%), hexyl 2-methylbutanoate (3.50%), butyl these compounds in apricot samples prepared under enzy-
2-methylbutanoate (2.76%), ethyl butanoate (2.00%),pen- mic inhibition. Salles et al. (1988) have also found the
tyl butanoate ( I & % ) , and butyl propanoate (1.30%). glycosidically bound forms of the linalool oxides, benzyl
The hydrocarbon (E,Z)-1,3,5-undecatriene has been iden- alcohol and 2-phenylethanol, in apricot. These com-
tified as an impact compound of Galbanum essential oil pounds have been previously reported in apricot (Tang
(Chretien-Bessiere et al., 1967; Naves, 1967) and pineap- and Jennings 1967,1968; Rodriguez et al., 1980; Chairote
ple (Berger et al., 1985a). Though the threshold of this et al., 1981; Guichard and Souty, 1988; Sharaf et al., 1989)
hydrocarbon in water has not been reported, sniffing of though they were not identified in this study.
the gas chromatographic effluent permitted detection in The relative contribution of various constituents to the
the picogram (1-2) range (Berger et al., 1985a). This potent blended apricot aroma was determined by calculating the
odorant has been detected in various fruits and vegeta- number of odor units (U,). The odor unit was defined
bles (Berger et al., (1985b). by Guadagni et al. (1966) as the concentration of the com-
The odor thresholds of some of the headspace constit- pound divided by its odor threshold. This value gives
uents are also listed in Table I. Based on their odor thresh- some idea of the significance of the volatiles to the apri-
old and their amount present in the headspace, the fol- cot aroma. Table I11 lists the odor units of some apricot
lowing compounds probably contribute to the intact apri- constituents calculated from their concentrations and odor
cot odor: ethyl butanoate, ethyl 2-methylbutanoate, butyl thresholds. Compounds are listed in descending order
butanoate, ethyl hexanoate, butyl 2-methylbutanoate,hexyl of their odor unit values. Despite its low concentration,
2-methylbutanoate, and y-decalactone. 0-ionone (14 ppb) appears to be an important apricot
constituent due to its rather low odor threshold (0.007
It appears that longer trapping times are necessary to ppb). Other important contributors include linalool, y-
detect the higher boiling compounds; no compounds elut- decalactone, hexanal, (E)-2-hexenal, (E,E)-2,4-decadie-
ing beyond C,, were detected with the heat desorption nal, (E)-2-nonenal, y-decalactone, /3-cyclocitral, phen-
procedure though many of the compounds listed in Table ylacetaldehyde, and y-octalactone. 6-Octalactonewas pre-
I were additionally confirmed by this procedure.
viously identified in the Blenheim variety (Tang and
Table I1 lists the apricot compounds identified in sam- Jennings, 1968). It was not found in this study though
ples prepared by vacuum steam distillation-extraction. it would have coeluted with other constituents on the
The concentrations listed in the table should be consid- nonpolar DB-1 column employed. With its relatively high
ered as only approximate values since the percent recov- odor threshold of 400 ppb, it probably does not contrib-
eries and FID response factors were not determined for ute to the apricot aroma. P-Ionone and linalool may be
the individual compounds. Figure 2 shows a GC/FID responsible for the floral character of apricots while the
chromatogram of apricot volatiles obtained by vacuum lactones provide the fruity, peach, and coconut-like back-
steam distillation-extraction. ground odor (Spencer et al., 1978). The esters may also
There was no attempt to inhibit the enzyme systems play a role in the fruity odor. Though their concentra-
of the fruit. The enzymic formation of secondary vola- tions were below their odor thresholds, these values may
tiles caused by disruption of the fruit tissues (blending not reflect their actual levels in the intact fruit. Schreier
of the fruit) was reflected in the high level (>50% of the et al. (1985) have shown a decrease in the concentration
total volatiles) of C, lipid peroxidation products. of certain esters in papaya as the result of enzymic activ-
Benzaldehyde probably arises from the cyanogenic gly- ity. The esters were the dominant constituents in the
coside, amygdalin, a typical constituent of many Prunus headspace sample yet were relatively minor components
species such as apricot. in samples prepared by vacuum steam distillation-
Dihydroactinidiolide, p-cyclocitral, and dihydro-p- extraction. An additional experiment to check the effect
ionone can be regarded as carotenoid metabolism prod- of enzymic inhibition on the concentration of apricot vol-
ucts (Ohloff, 1978). Dihydro-P-ionone has been found atiles would help clarify the role of the esters to the total
as a major constituent (15.7%) in the essential oil of the apricot odor.
blossoms of Osmanthusfragrans Lour. (Sisido et al., 1967).
It has also been reported in cassie (Demole et al., 1969), ACKNOWLEDGMENT
raspberry (Winter and Enggist, 1971), passion fruit (Win- We thank Bill Coates, UC Cooperative Extention, for
ter and Kloti, 1972), tea (Yamanishi et al., 1973), arctic his assistance in obtaining the fresh apricots used in this
476 J. Agric. Food Chem., Vol. 38, No. 2, 1990 Takeoka et al.

s t u d y and Jean T u r n b a u g h for her help with odor thresh- Ohloff, G. Recent Developments in the Field of Naturally-Oc-
old determinations. We also t h a n k R o n Buttery for help- curring Aroma Components. In Progress in the Chemistry
ful discussions and advice during t h e course of t h i s work. of Organic Natural Products; Herz, W., Grisebach, H., Kirby,
G. W., Eds.; Springer-Verlag: New York, 1978; Vol. 35, pp
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J . Agric. Food Chem. 1969,17, 1322-1327. der Papaya-Frucht (Caricapapaya, L.): Hinweiseauf Vorstufen
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Buttery, R. G.; Seifert, R. M.; Ling, L. C.; Soderstrom, E. L.; ishi, R. Isolation of Volatile Components from a Model Sys-
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1981,46, 1898-1901, 1906. Constituents of Osmanthus fragrans. 11. Perfum. Essent.
Chretien-Bessiere, Y.; Garnero, J.; Benezet, L.; Peyron, L. Sur Oil Rec. 1967, 58, 212.
un Hydrocarbon h Squelette Non Terp6nique Is016 & Partir Spencer, M. D.; Pangborn, R. M.; Jennings, W. G. Gas Chro-
de 1’Essence de Galbanum. Bull. SOC.Chim. Fr. 1967, 97- matographic and Sensory Analysis of Volatiles from Cling
98. Peaches. J . Agric. Food Chem. 1978,26,725-732.
Demole, E.; Enggist, P.; Stoll, M. Sur les Constituants Odor- Takeoka, G. R.; Flath, R. A,; Guentert, M.; Jennings, W. Nec-
ants de 1’Essence Absolue de Cassie (Acaciafarnesiana Willd.). tarine Volatiles: Vacuum Steam Distillation versus Head-
Helu. Chim. Acta 1969, 52, 24-32. space Sampling. J . Agric. Food Chem. 1988,36, 553-560.
Engel, K.-H.; Flath, R. A.; Buttery, R. G.; Mon, T. R.; Ram- Tang, C. S.; Jennings, W. G. Volatile Components of Apricot.
ming, D. W.; Teranishi, R. Investigation of Volatile Constit- J . Agric. Food Chem. 1967, 15, 24-28.
uents in Nectarines. 1. Analytical and Sensory Character- Tang, C. S.; Jennings, W. G. Lactonic Compounds of Apricot.
ization of Aroma Components in Some Nectarine Cultivars. J . Agric. Food Chem. 1968,16, 252-254.
J . Agric. Food Chem. 1988, 36, 549-553. Winter, M.; Enggist, P. Recherches Sur les Aromes. 17. Comm.
Flath, R. A.; Ohinata, K. Volatile Components of the Orchid Sur l’Arome de Framboise. IV. Helo. Chim. Acta 1971,54,
Dendrobium Superbum Rchb.f. J . Agric. Food Chem. 1982, 1891-1898.
30, 841-842. Winter, M.; Kloti, R. Uber das Aroma der Gelben Passions-
Flath, R. A.; Black, D. R.; Guadagni, D. G.; McFadden, W. H.; frucht (Passiflora edulis f. flaoicarpa). Helv. Chim. Acta
Schultz, T. H. Identification and Organoleptic Evaluation of 1972,55, 1916-1921.
Compounds in Delicious Apple Essence. J . Agric. Food Chem. Winterhalter, P.; Schreier, P. Free and Bound C,, Noriso-
1967,15, 29-35. prenoids in Quince (Cydonia oblonga, Mill.). J . Agric. Food
Guadagni, D. G.; Buttery, R. G.; Harris, J. Odour Intensities of Chem. 1988,36, 1251-1256.
Hop Oil Constituents. J . Sci. Food Agric. 1966, 17, 142-144. Yamanishi, T.; Shimojo, S.; Ukita, M.; Kawashima, K.; Naka-
Guadagni, D. G.; Maier, V. P.; Turnbaugh, J. G. Effect of Some tani, Y. Aroma of Roasted Green Tea (Hoji-cha). Agric. Biol.
Citrus Juice Constituents on Taste Thresholds for Limonin Chem. 1973, 37, 2147-2153.
and Naringin Bitterness. J . Sci. Food Agric. 1973,24, 1277-
1288.
Guadagni, D. G.; Buttery, R. G. Odor Threshold of 2,3,6- Received for review April 28, 1989. Accepted September 12,
Trichloroanisole in Water. J . Food Sci. 1978,43,1346-1347. 1989.
Guichard, E.; Souty, M. Comparison of the Relative Quantities
of Aroma Compounds Found in Fresh Apricot (Prunus arme- Registry No. Ethanol, 64-17-5; 2,3-butanedione, 431-03-8;
niaca) fromSixDifferent Varieties. Z. Lebensm. Unters.For- trichloromethane, 67-66-3; ethyl acetate, 141-78-6; 2-
sch. 1988, 186,301-307. methylpropanol, 78-83-1; butanol, 35296-72-1; ethyl pro-
Hirvi, T.; Honkanen, E. Analysis of the Volatile Constituents panoate, 105-37-3; methyl butanoate, 623-42-7; 2-methylbu-
of Black Chokeberry (Aroniamelanocarpa Ell.). J . Sci. Food tanol, 137-32-6; ethyl 2-methylpropanoate, 97-62-1; methyl 2-
Agric. 1985, 36, 808-810. methylbutanoate, 868-57-5; hexanal, 66-25-1; ethyl butanoate,
Ishihara, M.; Tsuneya, T.; Shiota, H.; Shiga, M. Identification 105-54-4;propyl propanoate, 106-36-5; butyl acetate, 123-86-4;
of New Constituents of Quince Fruit Flavor (Cydonia oblon- 2-propyl butanoate, 638-11-9; ethyl 2-methylbutanoate, 7452-
ga Mill. = C. oulgaris Pers.). J . Org. Chem. 1986, 5 1 , 491- 79-1; hexanol, 111-27-3; propyl butanoate, 105-66-8; ethyl pen-
495. tanoate, 539-82-2; butyl propanoate, 590-01-2; pentyl acetate,
Ismail, H. H.; Tucknott, 0. G.; Williams, A. A. The Collection 628-63-7; 2-methylpropyl2-methylpropanoate,97-85-8; methyl
and Concentration of Aroma Components of Soft Fruit Using hexanoate, 106-70-7;propyl 2-methylbutanoate, 37064-20-3;butyl
Porapak &. J . Sci. Food Agric. 1980,31, 262-266. 2-methylpropanoate, 97-87-0; 2-methylpropyl butanoate, 539-
Kallio, H. Identification of Vacuum Steam-Distilled Aroma Com- 90-2; 2-methylbutyl propanoate, 2438-20-2; butyl butanoate, 109-
pounds in the Press Juice of Arctic Bramble, Rubus arcticus 21-7; ethyl hexanoate, 123-66-0; 2-methylpropyl 2-methylbu-
L. J . Food Sci. 1976,41, 555-562. tanoate, 2445-67-2; hexyl acetate, 142-92-7; 2-methylbutyl 2-
Kovats, E. sz. Gas-Chromatographische Charakterisierung Orga- methylpropanoate, 2445-69-4; limonene, 138-86-3; butyl 2-
nischer Verbindungen Teil 1: Retentionindices Aliphatis- methylbutanoate, 15706-73-7;butyl 3-methylbutanoate, 109-19-
cherHalogenide,Alkohole,AldehydeundKetone.Helu.Chim. 3; pentyl 2-methylpropanoate, 2445-72-9; (E)-0-ocimene, 3779-
Acta 1958, 41, 1915-1932. 61-1; 3-methylbutyl butanoate, 106-27-4;2-methylbutyl butanoate,
Naves, Y. R. Etudes Sur les Matikres V6gBtales Volatiles CCIII 51115-64-1; pentyl butanoate, 540-18-1; propyl hexanoate, 626-
(1). PrBsence de n-UndBcatriknes-1,3,5 dans 1’Huile Essen- 77-7; ethyl heptanoate, 106-30-9; linalool, 78-70-6; hexyl pro-
tielle de la Gomme-RBsine de Galbanum. Bull. SOC.Chim. panoate, 2445-76-3;2-methylbutyl2-methylbutanoate, 2445-78-
Fr. 1967, 3152-3154. 5; methyl octanoate, 111-11-5;pentyl 2-methylbutanoate, 68039-
 J. Agric. Food Chem. IQQQ,
38, 477-483 477

26-9; hexyl 2-methylpropanoate, 2349-07-7; 2-methylpropyl diolide, 17092-92-1;pentadecane, 629-62-9;hexyl benzoate, 6789-
hexanoate, 105-79-3; 2-methylbutyl pentanoate, 55590-83-5; 88-4; hexyl octanoate, 1117-55-1;butyl decanoate, 30673-36-0;
1(E,Z),3,5-undecatriene,19883-27-3;ethyl (E)-Coctenoate,78989- ethyl dodecanoate, 106-33-2;tetradecanal, 124-25-4;y-dodeca-
37-4; (Z)-3-hexenylbutanoate, 16491-36-4;butyl hexanoate, 626- lactone, 2305-05-7; hexadecanal, 629-80-1; ethyl hexade-
82-4; hexyl butanoate, 2639-63-6; ethyl octanoate, 106-32-1;0- canoate,628-97-7;2-hexanone, 591-78-6;3-hexanol, 623-37-0;2-
cyclocitral, 432-25-7;dodecane, 112-40-3;y-octalactone,104-50- hexanol, 626-93-7;(E)-2-hexenal,6728-26-3;(Z)-3-hexenol,928-
7; (Z)-3-hexenyl 2-methylbutanoate, 53398-85-9; hexyl 2- 96-1; (E)-2-hexenol,928-95-0; benzaldehyde, 100-52-7; (2)-2-
methylbutanoate, 10032-15-2;3-methylbutyl hexanoate, 2198- heptanal, 57266-86-1; 6-methyl-5-hepten-2-one, 110-93-0; (E)-
61-0; 2-methylbutyl hexanoate, 24551-95-9; pentyl hexanoate, 2-hexenyl acetate, 2497-18-9;phenylacetaldehyde, 122-78-1;2,2,6-
540-07-8; propyl octanoate, 624-13-5; tridecane, 629-50-5; 2- trimethylcyclohexanone, 2408-37-9;3-nonen-2-one,14309-57-0;
methylpropyl octanoate,5461-06-3;ethyl (Z)-4-decenoate,7367- (E)-2-nonenal,18829-56-6;a-terpineol, 10482-56-1;nerol, 106-
84-2;hexyl hexanoate, 6378-65-0;butyl octanoate, 589-75-3;ethyl 25-2; geraniol, 106-24-1; (E,E)-2,4-decadienal,25152-84-5; 3,4-
decanoate, 110-38-3; dihydro-0-ionone, 17283-81-7; y - didehydro-6-ionol,3293-47-8;geranylacetone, 3796-70-1;epoxy-
decalactone, 706-14-9; &decalactone, 705-86-2; dihydroactini- 0-ionone, 36340-49-5;@-ionone,79-77-6.

Determination of the Protein Activity of Corn Zeins in Alkaline

Solutions from 'H Nuclear Spin Relaxation Data as a Function of
Concentration and Heat Treatments
Patricia A. Myers-Betts and Ion C. Baianu*
Department of Food Science, University of Illinois at Urbana, Urbana, Illinois 61801

A marked nonlinear concentration dependence was observed for 10-MHz 'H NMR transverse relax-
ation rates of corn zeins in solution a t p H 11.5 for both unheated and heat-treated solutions that were
cooled to room temperature. Simplex and Gauss-Newton nonlinear regression analyses of the NMR
transverse relaxation data were employed to calculate the average virial expansion coefficients of
protein activity. Two different virial expansions were found to fit the entire concentration range of
the NMR data. The first model (A) contains three virial coefficients, Bo, B3,,, and B,, for the cp,
c:l2, and c; terms, respectively, where cp is corn protein concentration up to 80% (w/w). The sec-
ond model (B) included four virial coefficients, Bo, B,, B,, and B,, for the cp, cp2,cp3, and cp4 terms,
respectively, with slightly improved standard deviations over the first model. In the lower concen-
tration range, up to 30570,an improved fit was obtained with only one virial coefficient, Bo = 2.46 f
0.18 mL/g, which is significantly lower than the value of 6.9 mL/g obtained from the best fit over the
entire concentration range with model B. All three models yielded a decrease in the average protein
activities and the average transverse relaxation rate (1/T2)of bound water after heat treatments.
Since the heated samples were measured a t room temperature after cooking, the changes in the aver-
age virial coefficients reflect irreversible protein conformational changes induced by heating. The
alternating signs of the virial coefficients in both models indicate the presence of both repulsive and
attractive interactions among corn zeins. A plot of the ratio T,/T, as a function of corn protein con-
centration indicates that cross-relaxation is much less significant than chemical exchange for these
samples. The decreasing T,/ TI ratio with increasing protein concentration suggests the presence of
certain, relatively slow, water motions that are detected by the T, relaxation measurements and not
by T,. For this reason, the T, relaxation dependence on concentration is much steeper than the T,
relaxation dependence.

1. INTRODUCTION 1970). In order to exploit this bvproduct for its Dossible

With the current emphasis of corn wet-milling focused use in human foods,- zein's phisicochemical prbperties
on the production of high-fructose corn syrups and corn must be characterized so that technologists may predict
starch, there is an increasing need to find uses for the and control its behavior during food processing. Nonde-
corn gluten byproducts, particularly zein. This prola- structive, useful techniques for conformation, composi-
mine protein fraction of corn is currently used as a coat- tion, and hydration analyses of proteins are provided by
ing agent in pharmaceuticals and as animal feed due to nuclear magnetic resonance (NMR) relaxation and spec-
the low "quality" of the product (Shroder and Heiman, troscopy. High-resolution NMR and relaxation tech-
niques have already been used to study other food svs-
tems such as wheat (Baianu e t al., 1982),corn (August-
* Address for correspondence: 580 Bevier Hall, 905 ine and Baianu, 19871, and soy proteins (Kakalis and
South Goodwin Ave., Urbana, IL 61801. Baianu, 1989).

0021-8561/90/1438-0477$02.50/0 0 1990 American Chemical Society