C H A P T E R

14
Volatile Chemicals from Thermal Degradation
of Less Volatile Coffee Components
Takayuki Shibamoto
Department of Environmental Toxicology, University of California, Davis, CA, USA

List of Abbreviations more than 800.3 This number is proposed to increase

following the development of analytical techniques in
UV Ultraviolet
GC  Gas chromatography the future.
MS  Mass spectrometry Coffee volatile chemicals vary from very low molecu-
MRPs  Maillard reaction products lar weight compounds, such as methane4 and formalde-
hyde,5 to relatively less volatile compounds quinoxaline,
such as 2,3-dimethylqunoxaline.6 Among volatile chemi-
14.1 INTRODUCTION cals identified in coffee, relatively low molecular weight
heterocyclic compounds, including furans, pyrroles,
The history of coffee goes back to the ninth century. thiophenes, thiazoles, oxazoles, pyridines, and pyr-
A unique nature of coffee was noticed when a goat azines, contribute to the characteristic roasted coffee
became friskier after eating red berries of a local shrub; flavor. For example, 2-furylthiol possesses a strong
subsequently, a goat herder who saw this phenomenon coffee-like aroma.7 More than 400 heterocyclic volatile
tasted some of the berries and experienced a pleasant compounds have been reported in roasted brewed coffee
feeling. In the beginning of the twelfth century, the first today.3 These chemicals produce extremely complicated
roasted and boiled coffee was prepared and consumed coffee aromas.1
by Arabians. Later, a beverage coffee became to be There are numerous reports on the formation of aroma
known by people in Europe, and the first coffee house chemicals in roasted coffee. Generally, they are formed
was opened in England in the mid-seventeenth cen- from the following:
  
tury. Since then, coffee has been gradually introduced
1. D  egradation of lipids.
to the world and has become the most popular bever-
2. Degradation of carbohydrates and sugars.
age today.
3. Maillard reaction between nitrogen-containing
Many people prefer coffee because of its character-
compounds and carbonyl compounds.
istic pleasant flavor given by the chemical’s so-called
4. Degradation of proteins and amino acids.
aroma volatiles. Analysis of coffee volatiles began in the
5. Degradation of less volatile constituents,
mid-1950s using conventional techniques such as paper
including chlorogenic acids, quinic acid, and
chromatography, ultraviolet (UV), and infrared. Later,
caffeic acid.
the invention of gas chromatography (GC) advanced   
the analysis of volatile chemicals significantly. In partic- All these reactions occur upon heat treatment.
ular, the development of GC/mass spectrometry (MS) Therefore, the roasting process is an ideal condition
in the late 1960s progressed identification of volatile for formation of volatile compounds from green cof-
chemicals in foods and beverages remarkably.1 Even fee beans because they contain various chemical raw
before the invention of GC/MS, nearly 350 volatile materials of volatiles. When coffee beans are roasted,
chemicals in coffee were identified.2 After the advance- the compositions of the chemical raw materials,
ment of GC/MS, the number of volatile chemicals iden- including carbohydrates, proteins, and amino acids,
tified in coffee steadily increased, and now has reached change significantly. The reduction of these chemicals

Coffee in Health and Disease Prevention 129

http://dx.doi.org/10.1016/B978-0-12-409517-5.00014-0 © 2015 Elsevier Inc. All rights reserved.
130 14.  DEGRADATION PRODUCTS IN COFFEE

in green coffee beans upon roasting indicates that reactants to form heterocyclic flavor chemicals reacting
the Maillard reaction occurs during roasting to form with amines.13
various aroma chemicals. At first, polysaccharides or Formation of α-dicarbonyl compounds such as gly-
lipids degrade into low molecular weight carbonyl oxal, methyl glyoxal, diacetyl—one of the major car-
compounds and then react with ammonia, which bonyl compounds formed by lipid peroxidation—in
formed from proteins or amino acids, to form hetero- oxidized edible oils have already been demonstrated in
cyclic aroma compounds.8 the mid-1980s.14 Later, those α-dicarbonyl compounds
were reported in coffee.15 Moreover, these α-dicarbonyl
compounds are known to produce volatile heterocyclic
14.2  VOLATILE CHEMICALS FORMED flavor chemicals reacting with amines via the Maillard
FROM LIPIDS IN COFFEE reaction as mentioned above.
Also in the mid-1980s, 5-alkyl (C0–C8) furanones—
It is well known that many carbonyl compounds, such possessing a caramel-like odor with low aroma thresh-
as acetaldehyde, malonaldehyde, glyoxal, and diacetyl, old values16—were reported in a heated beef fat.17
are formed from lipids upon oxidation.9 Figure 14.1 Later, 2-methyl-3(2H)-furanone was found in coffee,18
shows typical volatile lipid peroxidation products and and then eight furanones were reported in coffee up to
their generally recognized proposed formation path- now.3 Furan is formed via reactive aldehydes, such as
ways, established in the early 1980s.10,11 Some carbonyl 2-alkenal, that are lipid degradation products.19 Furans
compounds are known to possess characteristic aromas. are the most abundant volatile chemicals found in cof-
For example, acetaldehyde possesses reminiscent of cof- fee, and more than 130 furans have been reported in
fee in high dilution and has been used to create vari- coffee.3
ous imitation flavors including coffee.7 The presence of There is another possible pathway in which a lipid
acetaldehyde in coffee was reported in the mid-1920s.12 produces various low molecular weight radicals, such
Since then, there have been many reports on analysis as %CH3, %C]O, %C]O(CH3), and these radicals sub-
of acetaldehyde in coffee.3 Moreover, aldehydes and sequently combine to yield various volatile chemicals.
ketones shown in Figure 14.1 are important carbonyl This pathway could be proposed when the reaction

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I.   INTRODUCTORY AND GENERAL TEXT

 14.3  Volatile Chemicals FormED from Carbohydrates and Sugars in Coffee 131
systems absorb high levels of energy from high tem- The carbonyl compounds are formed by cleavage at
perature, such as cooking, or photoirradiation.20 In a keto-enol bonding in a diketone to form various
fact, when lipid, squalene was irradiated with UV less molecular weight carbonyl compounds.20 Conse-
light, volatile reactive carbonyl compounds were quently, these carbonyl compounds react with amines
formed.21,22,23 to form Maillard reaction products (MRPs). Therefore,
these carbonyl compounds participate in the forma-
tion of characteristic coffee flavors as reactants.
14.3  VOLATILE CHEMICALS FORMED One Canadian research group has been investigating
FROM CARBOHYDRATES AND SUGARS intensively the formation pathways of low molecular
IN COFFEE weight volatile compounds from oxidative degra-
dation of sugars and amino acids using 13C-labeled
It has been also known since the 1960s that sugars compounds since the late 1990s. One of their studies
degrade into many low molecular weight carbonyl proposed that the major formation pathway of furan
compounds.24,25 Figure 14.2 shows typical volatile from hexose involves an intermediate 1-deoxyosoe.19
sugar degradation products and their generally rec- Also, they proposed that low molecular weight reac-
ognized proposed formation pathways. Figure 14.3 tive carbonyl compounds, such as acetaldehyde,
shows that furans and related compounds are also react to each other to produce different chemicals.27
found as sugar degradation products. In this path- In addition, acetol, pyruvaldehyde, and glyceral-
way, a polysaccharide is hydrolyzed to monosugars dehyde were proposed to form from glucose via an
that produce various monosugar isomers, includ- intermediate 1-deoxyglucosone or 3-deoxyglucosone
ing fructose and glucose via keto-enol tautomeriza- yielded from a glucose/l-methionine or l-alanine
tion. Subsequently, the key intermediates, diketones Amadori product.28,29 These reports suggest that
for carbonyl compounds formation, are produced by amino acids play an important role in oxidative deg-
a dehydration reaction. Once diketones are formed, radation of sugars or lipids and may act as a catalyst
further oxidative degradation occurs to form vari- for formation of reactive carbonyl compounds from
ous reactive carbonyl compounds, such as diacetyl.26 lipids and sugars.

FIGURE 14.2  Proposed formation pathways of volatile sugar degradation products.

I.   INTRODUCTORY AND GENERAL TEXT

132 14.  DEGRADATION PRODUCTS IN COFFEE

FIGURE 14.3  Furans and related

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14.4  VOLATILE CHEMICALS FORMED products, heterocyclic compounds are known to contrib-
IN COFFEE BY MAILLARD REACTION ute characteristic flavors to roasted coffee significantly.7

A French chemist, L.C. Maillard, advanced the

theory that the reaction of a carbonyl group of a 14.5  VOLATILE COMPOUNDS FORMED
sugar and an amine group of an amino acid produces FROM AMINO ACIDS AND PROTEINS
browning pigments and polymers in 1912. Since then,
many studies using so-called Maillard model systems It is generally proposed that nitrogen atoms in het-
consisting of a sugar and an amino acid have been erocyclic compounds come from NH3, formed from an
conducted to investigate the formation of various amino acid via Strecker degradation.38 Many volatile
chemicals in foods and beverages, including flavors, chemicals were identified in Maillard systems consist-
mutagens, carcinogens, antidiabetics, and antioxi- ing of a sugar and NH3,39,40 suggesting that amine com-
dants.30 It is obvious that the Maillard reaction occurs pounds play as a souse of ammonia in the Maillard
in coffee beans during roasting because composi- reaction system. Some compounds with no nitrogen
tions of carbohydrates and amino acids/proteins are atom, such as carbonyl compounds and furans, form in
reduced significantly by roasting.31 Maillard reaction systems, also suggesting that an amine
Since the first comprehensive review on Maillard reac- compound acts as a catalyst for sugar or lipid degrada-
tion was published in 1953,32 there have been numerous tion as mentioned above. For example, maltose degraded
articles, books, and book chapters on the formation of into diacetyl through an Amadori product intermediate
volatile chemicals via Maillard reactions.33,34,35,36,37 Most when it was incubated with l-lysine.34 Various degrada-
flavor chemicals formed by the Maillard reaction are tion products, in particular α-dicarbonyl compounds, of
not first degradation products from less volatile chemi- oligosaccharides were reported in the glycine-catalyzed
cals, such as lipids and carbohydrates, but secondary Maillard reaction system.41 In contrast, 13C-isotope study
products formed from those less volatile degradation demonstrated that an alkyl group from an amino acid
products via Maillard reaction. Therefore, a detailed dis- was incorporated into a side chain of pyrazines found in
cussion on Maillard reaction products formed in coffee an alanine/glucose model system.42
is not the main subject of this chapter, but rather a brief When an aqueous solution of l-cysteine alone was
discussion of the role in Maillard reaction in formation irradiated with UV light at 253.7 nm for 24 h, some vola-
of flavor chemicals in coffee is presented. Any mixtures tile heterocyclic compounds, including thiophene, pyr-
containing an amine group (amino acids, proteins, etc.) azine, thiazole, thiazoline, and pyrrole, were formed,43
and a carbonyl group (sugars, carbohydrates, etc.) pro- suggesting that various low molecular weight radicals
duce a large number of so-called MRPs. Currently, more form from a sugar and an amino acid, and then subse-
than 1200 MRPs are reported.33,34,35,36,37 Among these quently these radicals are combined to form heterocyclic

I.   INTRODUCTORY AND GENERAL TEXT

 14.6  Volatile Chemicals Formed from Quinic Acid, Caffeic Acid, and Chlorogenic Acids 133
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compounds as mentioned above. It is obvious that there 12 min), Medium (240 °C, 14 min), City (250 °C, 17 min),
are two possible pathways—thermal oxidative reac- and French (250 °C, 21 min), the total content of chloro-
tion28 and radical reaction20—involved in Maillard reac- genic acids in roasted beans was reduced to 32 mg/g by
tion systems. Light roast, 20 mg/g by Medium roast, 1.8 mg/g by City
roast, and 0.34 mg/g by French roast.44
It is obvious that the total amount of chlorogenic
14.6  VOLATILE CHEMICALS FORMED acids is reduced parallel to the intensity of heating
FROM QUINIC ACID, CAFFEIC ACID, conditions; the more intensive condition the more deg-
AND CHLOROGENIC ACIDS radation. Surprisingly, there is no report on the forma-
tion of volatile chemicals from chlorogenic acids except
Quinic acid, caffeic acid, and chlorogenic acids are the report by Moon et al. (2009).45 One study reported
present in green coffee beans. Among individual chemi- the isomerization products of chlorogenic acids but
cals found in green coffee beans, chlorogenic acids are not their degradation products in roasted coffee.46
one of the most unique chemicals present in coffee Figure 14.4 shows a proposed formation pathway of
beans. The chlorogenic acids content varies in different volatile chemicals from chlorogenic acids, prepared
green coffee beans. One study on a total content of chlo- based on the proposal advanced previously.45 Among
rogenic acids in green coffee beans was 61 mg/g in Nica- 52 volatile chemicals identified in thermal degradation
raguan, 64 mg/g in Sumatran, 69 mg/g in Ethiopian, of a chlorogenic acid, 15 major chemicals identified
and 86 mg/g in Panamanian.44 The composition of chlo- were shown in Figure 14.4.45 In this proposed pathway,
rogenic acids in green beans reduces from 6.5% to 2.5% a chlorogenic acid is hydrolyzed into quinic acid and
by roasting,31 suggesting that they degrade into volatile caffeic acid that subsequently degrade into various
chemicals by heat treatment. When Ethiopian green cof- volatile chemicals. Furans and cyclohexanones were
fee beans (total content of chlorogenic acids, 69 mg/g) formed mainly from a quinic acid moiety via dehy-
were roasted under different conditions—Light (230 °C, dration. Aromatic compounds are also formed from a

I.   INTRODUCTORY AND GENERAL TEXT

134 14.  DEGRADATION PRODUCTS IN COFFEE

quinic acid moiety, but they form mainly from caffeic 5.  Shibamoto T. Formaldehyde in coffee. In: Linskens HF, Jackson
acid moiety because a benzene ring exists already in JF, editors. Analysis of nonalcoholic beverages. New York: Springer-
Verlag; 1988. pp. 173–83.
caffeic acid moiety. Many different and complex reac- 6.  Vizthum OG, Werkhoff P. Neu entdeckte Stickstoff heterocyclen
tions are involved in the formation of these volatile im Kaffee-Aroma. Z Lebensm Unters Forsch 1974;156:300–7.
chemicals from chlorogenic acids. Reactions involved 7.  Arctander S. Perfume and flavor chemicals Published by the author,
are dehydration, decarboxylation, dehydration, defor- Montclair; 1969.
mic acid, keto-enol tautomerization, and homolytic 8.  Lee K-G, Shibamoto T. Toxicology and antioxidant activities of
non-enzymatic browning reaction products: review. Food Rev Inter
bond cleavage as well as free radicals.45 2002;18:151–75.
Catechol formed the greatest amount (58,960.8 μg/g), 9.  Schaich KM. Lipid oxidation: theoretical aspects. In: Shahidi F,
followed by 4-ethylcatechol (31,437.5  μg/g), phenol ­editor. Bailey’s industrial oil and fat products. New York: John Wiley
(6637.8 μg/g), benzoic acid (2445.8 μg/g), 2,5-dimethylfu- and Sons, Inc.; 2005. pp. 269–355.
ran (2231.0 μg/g), 2-methylcyclohexanone (411.6 μg/g), 10. Frankel EN. Lipid oxidation. Prog Lipid Res 1980;19:1–22.
11. Frankel EN. Volatile lipid oxidation products. Prog Lipid Res
1,2-cyclohexadione (260.5  μg/g), furfuryl alcohol 1982;22:1–13.
(259.9 μg/g), pyridine (251.9 μg/g), 2-cyclohexen-1-one 12. Reichstein T, Staudinger H. A new or improved method of producing
(107.4 μg/g), 3-ethylcatechol (103.4 μg/g), 2-hydroxycin- aromatic principle contained in roasted coffee. Br. Patent 246454; 1962.
namic acid (74.8 μg/g), cyclotene (70.6 μg/g), 1-hydroxy- 13. Fujimaki M, Namiki M, Kato H. Amino-carbonyl reactions in food and
2-propanone μg/g),
(35.5  and 2-methylpyrazine biological systems. New York: Elsevier; 1986.
14. Hirayama T, Yamada N, Nohara M, Fukui S. The existence of the
(22.6 μg/g) from a chlorogenic acid degradation under 1,2-dicarbonyl compounds glyoxal, methylglyoxal and diacetyl in
various roasting conditions.45 The presence of chemicals autooxidised edible oils. J Sci Food Agric 1984;35:1357–62.
that are obviously not directly formed from a chloro- 15. Daglia M, Patett A, Aceti C, Sordelli B, Spini V, Gazzani G. Isolation
genic acid, such as 1-hydroxy-2-propanone and 2-meth- and determination of α-dicarbonyl compounds by RP-HPLC-DAD
ylpyrazine, indicates the involvement of low molecular in green and roasted coffee. J Agric Food Chem 2007;55:8877–82.
16. Slaughter CJ. The naturally occurring furanones: formation
weight radicals formed by the heat treatment as men- and function from pheromone to food. Biol Rev Camb Philos Soc
tioned above. 1999;74:259–76.
17. Ohnishi S, Shibamoto T. Volatile compounds from heated beef fat
and beef fat with glycine. J Agric Food Chem 1984;32:987–92.
14.7  SUMMARY POINTS 18. Silwar R, Kamperschroer H, Tressl R. Gaschromatographisch-
massenspektrmetrische Untersuchungen dees Röstkaffeeaomas.
Qunatitative Bestimmung wasserdampffuchiger Aromastoffe.
• T remendous numbers of volatile chemicals are Chem Mikrobiol Technol Lebensm 1987;10:176–87.
formed in coffee by roasting. 19. Locas CP, Yaylayan VA. Origin and mechanistic pathways of for-
• Major components of green coffee beans, mation of the parent furan—a food toxicant. J Agric Food Chem
carbohydrates, proteins, and lipids degrade into 2004;52:6830–6.
20. Yasuhara A, Tanaka Y, Hengel M, Shibamoto T. Gas chromato-
low molecular weight volatile compounds via heat graphic investigation of acrylamide formation in browning model
treatment. systems. J Agric Food Chem 2003;51:3999–4003.
• Lipids and carbohydrates produce carbonyl 21. Dennis KJ, Shibamoto T. Gas chromatographic analysis of reactive
compounds that react with amines to form carbonyl compounds formed from lipids upon UV-irradiation.
heterocyclic flavor chemicals. ­Lipids 1990;25:460–4.
22. Niyati-Shirkhodaee F, Shibamoto T. Formation of toxic aldehydes
• Maillard reaction plays an important role in in cod liver oil after ultraviolet irradiation. J Am Oil Chem Soc
characteristic coffee flavors. 1992;69:1254–6.
• Chlorogenic acids, one of the major components 23. Niyati-Shirkhodaee F, Shibamoto T. Gas chromatographic analysis
of green coffee beans, produce many furans and of glyoxal and methylglyoxal formed from lipids and related com-
aromatic compounds by roasting. pounds upon ultraviolet irradiation. J Agric Food Chem 1993;41:227–30.
24. Hodge J. Origin of flavor in foods nonenzymatic browning
­reactions. In: Schultz HW, Day EA, Libbey LM, editors. C ­ hemistry
and physiology of flavors. Westport: AVI Publishing Co.; 1967.
References pp. 465–91.
1. 
Shibamoto T. An overview of coffee aroma and flavor chemistry. 25. Gobert J, Glomb MA. Degradation of glucose: reinvestigation of re-
In: “Quatorziéme Colloque Scientifique International sur le Café” Pro- active α-dicarbonyl compounds. J Agric Food Chem 2009;57:8591–7.
ceedings of the fourteenth international conference on coffee science. San 26. Jang H-W, Jiang Y, Hengel M, Shibamoto T. Formation of
Francisco, July, 1991. Paris: ASIC; 1992. pp. 107–16. 4(5)-­methylimidazole and its precursors, α-dicarbonyl compounds,
2. 
Stoll M, Winter M, Gautschi F, Flament I, Willhalm B. Recherches in Maillard model systems. J Agric Food Chem 2013;61:6865–72.
sur les aromes 13e communication [1] Sur 1’ arome de café. I. Helv 27. Huyghues-Despointes A, Yaylayan VA. Retro-aldol and redox
Chim Acta 1967;50:628–94. reactions of Amadori compounds: mechanistic studies with vari-
3. 
Flament I, Bessiere-Thomas Y. Coffee flavor chemistry. New York: ously labeled d-[13C] glucose. J Agric Food Chem 1996;44:672–81.
John Wiley and Sons, Ltd; 2002. 28. Yaylayan VA, Keyhani A, Wnorowski A. Formation of sugar-­
4. 
Reymond D. GC analysis of the highly volatile constituents of specific reactive intermediates from 13C-labeled l-Serine. J Agric
roasted coffee. Rec Adv Food Sci 1963;3:151–7. Food Chem 2000;48:636–41.

I.   INTRODUCTORY AND GENERAL TEXT

 References 135
29. Yaylayan VA, Keyhani A. Carbohydrate and amino acid degrada- 39. Shibamoto T, Bernhard RA. Investigation of pyrazine formation
tion pathways in l-methionine/D-[13C] glucose model systems. pathways in sugar-ammonia model systems. J Agric Food Chem
J Agric Food Chem 2001;49:800–3. 1977;25:609–14.
30. O’Brien J, Morrissey PA. Nutritional and toxicological aspects of 40. Shibamoto T, Russell GF. A study of the volatiles isolated from a
the Maillard browning reaction in foods. Crit Rev Food Sci Nutr d-glucose-hydrogen sulfide-ammonia model system. J Agric Food
1989;28:211–48. Chem 1977;25:109–13.
31. Illy A, Viani R. Espresso coffee: the chemistry of quality. London: Aca- 41. Hollnagel A, Kroh LW. Degradation of oligosaccharides in nonen-
demic Press; 1998. zymatic browning by formation of alpha-dicarbonyl compounds
32. Hodge JE. Chemistry of browning reactions in model systems. via “peeling off” mechanisms. J Agric Food Chem 2000;48:6219–26.
J Agric Food Chem 1953;1:928–43. 42. Chu FL, Yaylayan VA. Isotope labeling studies on the origin of
33. Shibamoto T. Heterocyclic compounds in browning and brown- 3,4-hexanedione and 1,2-butanedione in an alanine/glucose model
ing/nitrite model systems: occurrence, formation mechanisms, system. J Agric Food Chem 2009;57:9740–6.
flavor characteristics and mutagenic activity. In: Charalambous G, 43. Sheldon SA, Shibamoto T. Isolation and identification of volatile
Inglett G, editors. Instrumental analysis of foods, vol. I. New York: chemicals formed in aqueous l-cysteine solution with a UV light.
Academic Press; 1983. pp. 229–78. Agric Biol Chem 1987;51:2473–7.
34. Whitfield FB. Volatiles from interactions of Maillard reactions and 44. Moon J-K, Yoo HS, Shibamoto T. Role of roasting conditions in the
lipids. Crit Rev Food Sci Nutr 1992;31:1–58. level of chlorogenic acid content in coffee beans: correlation with
35. Martins S, Jongen WMF, van Boekel MA. Review of Maillard reac- coffee acidity. J Agric Food Chem 2009;57:5365–9.
tion in food and implications to kinetic modeling. Trends Food Sci 45. Moon J-K, Shibamoto T. Formation of volatile chemicals from
Technol 2000;vii:364–73. thermal degradation of less volatile coffee components: quinic
36. van Boekel MAJS. Formation of flavour compounds in the Mail- acid, caffeic acid, and chlorogenic acid. J Agric Food Chem 2010;58:
lard reaction. Biotechnol Adv 2006;24:230–3. 5465–70.
37. Newton AE, Fairbanks AJ, Golding M, Andrewes P, Gerrard JA. 46. Jaiswal R, Matei MF, Golon A, Witt M, Kuhnert N. Understanding
The role of the Maillard reaction in the formation of flavour com- the fate of chlorogenic acids in coffee roasting using mass spec-
pounds in dairy products—not only a deleterious reaction but also trometry based targeted and non-targeted analytical strategies.
a rich source of flavour compounds. Food Funct 2012;3:1231–41. Food Funct 2012;3:976–84.
38. Strecker A. Notiz über eine Eigenthumliche Oxydation durch Al-
loxan. Ann Chem 1862;123:363–5.

I.   INTRODUCTORY AND GENERAL TEXT