Professional Documents
Culture Documents
Overview
Coffees Origin
Early Cultivation and Consumption
Ways Out of Arabia
Discovery of the Robusta Variety
Coffee as a Trade Commodity World Production
From Field to Physiology
Botany
Plant Characteristics, Habit, and Growth
Species and Classification
Modern Classifications
Chemistry Components and Processes
Nitrogenous Compounds I: Caffeine
Processes and Reactions
Postharvest processing: dry and wet methods
Roasting
Extraction for beverage preparation
Carbohydrates
Chlorogenic Acids
Nitrogenous Compounds II
Amino acids and proteins
Trigonelline
Lipids
Total lipids
Triacylglycerols
Diterpenes and diterpene esters
Sterols, tocopherols
Coffee wax
Volatiles
Volatiles in green coffee
Volatiles on roasting
Volatiles in the brew
HumanEnvironment Interactions Smell and Taste
Organic Acids
Melanoidins
Conclusions
References
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Overview
Coffees Origin
The coffee plant most probably originated in Africa and Madagascar. Early cultivation is reported in the Ethiopian Highlands and
also on the other side of the Red Sea, in Yemen no surprise, since climate and geography are similar. According to legends, coffee
stepped out of Africa most likely in the first millennium. Other narratives deal with the discovery of roasting, leading to the
consumption of coffee as a beverage.
Coffee grows best in areas lying between the tropics. Today, it is found in all continents belonging to this geographic belt,
Figure 1, even in Australia and very recently, not yet shown here, at the Northern tropic in the Yunnan highland of China. There are
two main species of coffee, Arabica and Robusta, each with its own ecology.
Change History: March 2013. S Oestreich-Janzen has updated the text throughout in this chapter.
http://dx.doi.org/10.1016/B978-0-12-409547-2.02786-4
Chemistry of Coffee
Figure 1 The coffee belt around the globe, coffee relevant countries and latitudes highlighted at a blank world map (the latter courtesy of Creative
Commons).
Chemistry of Coffee
From the Dutch colonies, single plants were sent to the botanical garden of Amsterdam in 1706; from there, living plants were
transported to the Dutch colony in Surinam for cultivation and a grown-up tree was gifted to King Louis XIV in Paris in 1714.14
Some plants of the next Parisian generation were transferred to French colonies in the Caribbean, for cultivation in an appropriate
climate. There is a well-known textbook story of a single plant surviving on a ship to Martinique, nourished by the drinking water of
its officer, in about 1720. This was reported by the officer himself 50 years later.15 The coffee variety originating from Amsterdam,
called Typica, made its way step by step into Latin America.
At the same time, there was another route of Arabica plants out of Yemen: 60 seedlings, an official present by the Yemenite
sultan16 to Louis XIV, were sent to the French Bourbon Island (La Reunion, today) in 1715; again, these were a limited number of
plants. From there, the Bourbon variety of coffee entered the French colonies in the Americas and in other places.
Coffee cultivation was also promoted by other colonial powers such as Portugal, Spain, and England (and, for a few decades, by
Germany, too) and expanded to their respective spheres of influence.
Bourbon and Typica are the prolific ancestors of most of todays Arabica crops a genetically narrow route that expanded from a
few single plants to millions of tons of Arabica per year, all within 300 years.
Other coffee types, which grew without international demand in the humid tropical areas of their origin, became objects of
scientific surveys and explorations from the eighteenth century.
Today, independent coffee producing countries cooperate with the consuming ones in a worldwide research for the conservation of the coffee plants genetic heritage and diversity. Numerous so-called wild or spontaneous varieties deserve genetic resource
management. Since they are imminently threatened by advanced deforestation, an effective preservation strategy is needed.
Chemistry of Coffee
7 000 000
6 000 000
5 000 000
Vietnam
Colombia
Brazil
Indonesia
Others
Total
25 years average
4 000 000
2 000 000
1 000 000
Colombia
Brazil
Indonesia
Haiti
Yemen
3 000 000
Selected origins
of early production
500 000
1 000 000
00
17
20
17
89
17
00
18
20
18
40
18
60
18
80
18
00
19
0
1789
1820
1880
1940
1955
1970
1985
2000
2008
Figure 2 World Coffee production compiled from several sources. A. 1620, 1700: Becker,34 p 11. B. 1670, 1955: Sohn,35 p 11, 98. C. 1720:
Eccardi; Sandalj,9 p 48. D. 1789, 1936: Dahlgren,10 p 22, 41. E. 18001920, 1940, 1950, 1960, 1975: Sivetz,36 p 13. F. 19801995: ICO,33 historical
data, total production of member plus non member countries (2009). G. 20002008: ICO,33 world supply, total production (accessed July 2009).
standardization in the countries concerned, regarding registration, food surveillance, customs, subsidaries, analytical methods, and
many other aspects. Coffees agriculture has an impact even on the global ecology.
Originally, coffees stimulating property, its oldest-known physiological effect, was the basis of its use; later on the focus shifted
to enjoying aromatic roast coffee beverage as a psychoactive stimulant. Today, due to sophisticated research on the effects and
mechanisms of action of coffee, a more balanced view has emerged on the effects of coffee on our well-being and health.
Botany
Plant Characteristics, Habit, and Growth
In nonrestricted growth, the coffee plant is a perennial tree or treelet with a single main trunk and horizontal branches, ramifying
into secondary and tertiary ones (plagiotropic); pruning can lead to multiple-stem plants.
Coffees original place is the forest understorey. Coffee plants bear clusters of flowers and cherry-like fruits. A short central
taproot fades into axillary and lateral roots and a manifold of feeder bearers and root hairs. The dark green elliptical leaves grow in
opposite pairs on the main stem and branches. The wood is dense; the fruits, nectar, and leaves are food resources.
Under tropical conditions, flowering and fruiting happen in parallel; the nearer coffee plants are to the equator, the more
pronounced is a bimodal cycle.
Multistem growth is trained by either capping the main stem, giving rise to suckers that develop into new vertical stems with
horizontal branching, or bending the principal stem to the horizontal (agobiado technique), with several suckers in a row.
Periodic pruning is done to optimize the plant shape for good fruiting, easy harvesting, and effective disease and pest control, as
well as to rejuvenate the plant.
Pests may attack the plants in the field and the beans in store by boring, biting, mining, and sucking, or living as parasites on the
root system; fungi, viruses, and bacteria may cause severe coffee diseases.
Further characteristics and figures are given in Table 1. For each characteristic, the properties common to all species are written
in the first line, followed by the differing ones beneath in separate columns for the species.
The development of flowers from the buds takes several weeks, that of the fruits several months after flowering, with periods of
growth and of dormancy. The sequence of steps is enzymatically controlled in-plant and is triggered externally by photoperiodism,
relief of water stress, and temperature drop.
In a days-after-flowering (DAF) scale,43 depicted in Figure 3, the tissues of the growing fruit show marked changes in volume
ranking of all pericarp, perisperm, and endosperm. Embedded in the start-up pericarp, the perisperm expands to equal the pericarp
mass; then, it gets absorbed by the developing endosperm, the final organ for all storage compounds in the fruit.
Propagation to the next generation starts with either seeds from the farmers own plants, sown directly in the fields, or seedlings
from seeds or cuttings delivered by a nursery in plastic bags for planting. Development time in soil from the naked seed to the first
Chemistry of Coffee
Table 1
Coffee characteristics and requirements for cultivation (The table is compiled from several sources.24,3842)
Species character
Coffea
Chromosome status
Amphidiploid (2n 4x 44
Diploid (2n 22 chromosomes)
chromosomes)
Humid, evergreen tropical forest (cultivation with and without shade trees; intercropping)
Tropical highlands (950),
Tropical lowlands (50) 2501500 m
12001950 m
Warm, 1836 C
Temperature: moderate, 1524 C
Rainfall 22003000 mm year1
Rainfall 12002200 mm year1
Exceptional cultivations at sea
Sometimes in seasonally dry humid forest, or in
level (Hawaii)
gallery forest
46 m (pruned 23 m)
812 m (pruned 23 m)
Ecology
Plant height
Canopy diameter
Root system
Leaves
Inflorescences
Flowers
Fruit
Coffea arabica
Coffea canephora
Others
C. liberica up to
18 m; also 2 m
dwarf species
1.22 m
1.22 m
Tap root 0.51 m; several axillary roots, vertical depth 1.53 m; many lateral roots parallel to the soil, distance 1.51.8 m
from the trunk; hair roots overall; 90% of the root system in the upper 30 cm of the lateral parts
Deeper roots
Shallower roots
Elliptical; margin entire; tip accuminate; dark green to bronze green
Length 1015, width 46 cm
Length 2035, width 815 cm
Development time 78 weeks to full expansion
and optimum photosynthesis (Arabica); life
span 710 months (Robusta)
Paired, axillary; best flowering at 1-year-old wood; development time 4 months with periods of dormancy
412 with 1648 flowers per node 30100 flowers per node
Hermaphrodite; corollas white or rarely light pink; corolla lobes overlapping; anthers exerted; style long, exerted
Autogamous (self-pollinating)
Allogamous (cross-pollinating)
Time for pollination 1 day
Receptive to 6 days after flowering
Berry containing two seeds (rarely one or three); each seed with a deep groove, an invagination, on the flat ventral side
(coffee bean)
Length 1218 mm
Length 816 mm
Fruit maturation 79 months after
Fruit maturation 911 months after flowering
C. racemosa: 2
flowering
months
Perisperm phase
Flowering
Endosperm development
Pericarp maturation
Arabica 79 months
Robusta 911 months
250 DAF
300 DAF
Figure 3 Fruit development in coffee, days-after-flowering scale, adapted from several sources. A. Flower: Linnaeus,46 p 1. B. Bean development:
De Castro; Marraccini,43 p 177.
leaves is 12 months at best. A third method for propagation in vitro is used in research: the cultivation of a fragment of tissue from
a plant in a suitable substrate, producing a new plant that is genetically identical to the plant from which it originated.44
Chemistry of Coffee
Figure 4 Caffe in Linnes herbar, marked arabica by his own hand, courtesy of the Linnean Society, London.
The official reference for C. arabica L. is the type specimen from Cliffords herbarium,51 which Linne had described in 1737.49,50
It is designated as a lectotype52 on the basis of the procedures of the International Botanical Code (the Vienna Code of 200553).
Lectotype means that the first publisher had described the specimen prior to the reference to it the requirement to explicitly
design a reference specimen came up later.
Linnes typification became a benchmark for the botany of that time, as underlined by the title Order out of Chaos for an
anniversary book of 2007.54 Although his classification was soon overtaken,55 the binomial principle of naming remained the
first part indicates the botanic genus; the second is an epithet given by the first author, who is indexed. The overall genus for the
coffee species is Coffea L., indexed as named by Linnaeus. The principal commercial species used for beverage preparation are
C. arabica L., and C. canephora Pierre ex A. Froehner,25 commonly called var. Robusta. Coffea liberica Bull ex Hiern and some other
species are much less important today; there are numerous varieties, including cultivated ones (cultivars).
Chemistry of Coffee
The botanical classification of coffee has reached a high degree of consensus, presented in international conferences56,57 and
with ongoing publication in the World Checklist of Rubiaceae58 coffee is positioned in this family since Jussieu 1789.55
Chevaliers system,59 with four subgenera of Coffea, was popular for some decades of the last century. However, it became
obsolete the more taxa of the different pools of coffee origin were described and classified.6062
In terms of the Botanical Code, the classification lineage of coffee, starting at the family rank with Rubiaceae, goes down via
subfamily Ixoriadeae, tribe Coffeae DC,63,64 to the genus Coffea L. Some 100 accepted species of the genus, belong to the subgenus
Coffea, including all beverage coffees; subgenus Baracoffea holds about 10 species.42 That is the actual status.
Nevertheless, there are follow-up refinements.65
Modern Classifications
The changes in classification since Linnes time came along with a change of characterizing properties and of observables,
morphological characters against molecular phylogenetics. Involved is a change in the philosophy of systematic biology, from
being considered a plan in the mind of the creator, . . . finally to a phylogenetic mapping of the tree of life.66 Recently, a
phylocode had been proposed, to substitute the Botanical Codes system with its taxa and their hierarchy, at least partially.67
Discussions are under way.
Modern analytical chemical measurements can now be used in combination with chemometric comparison of secondary plant
metabolite levels such as caffeine or chlorogenic acids to classify varieties in phylogenetic trees. Studies of the molecular genetic
variation help to identify the relationships of species, presented in dendrograms and resulting in genetic clusters of coffees, which
can be compared to the biogeographical grouping of coffee clades. Several lineages with geographical or ecological coherence are
now recognized,68 as shown in Figure 5.
The phylogenetic approach widens the principles of classification from the morphological similarity of existing plants toward
an evolutionary dimension, with genetic clades, where the taxa are traced back to ancestry.
With these instruments, the genetic origin of C. arabica could be investigated, with a strongly supported hypothesis: Arabica
seems to have been formed by interspecific crossing of diploid progenitors, one species close to C. eugenioides as the maternal and
another species close to the canephoroid group as the paternal progenitor. This might have taken place in EastCentral Africa, very
likely in the late Quaternary period.69 Several mechanisms were discussed how the new species moved from a tetraploid via
Figure 5 The tropical African origin of coffee, distribution map showing the location of groups of Coffea, adapted from Maurin,68 overlaying a physical
map of Africa, the latter courtesy of Creative Commons.
Chemistry of Coffee
progressive diploidization toward the amphidiploid, which it is considered to be now. With the adaptation to the tropical
mountain climate of Ethiopia, a low but continued natural selection may have occurred.70
In contrast, the high genetic diversity found in the canephora branch of coffee encourages an earlier dating of the origins, as
some 500 000 years ago.71 The clustering of natural C. canephora diversity groups, with some 40 species in continental Africa,
supports the link to climatic variations in that tropical zone. In the last glacial maximum, an arid period 18 000 years ago, the
environment became hostile and few forest refugia72 remained. There, the differentiation of disseminated subgroups could have
occurred,73 with rare migration of species along the rivers74 and with unpopulated gaps in-between due to adverse conditions.
From the East African group, a dispersal to Madagascar and the neighboring islands might have taken place. They show more than
50 species of the genus Coffea, distinct from the continentals: no naturally occurring species is shared between Africa, Madagascar,
and the Mascarenes.42
Not so far away in history emerged the question about the origin of Bourbon Pointu from Reunion, C. arabica Laurina
whether it is a mutation of the Arabica introduced from Yemen or a result of crossing between this Arabica and the indigenous Cafe
marron of the island. A combination of historical and modern analytical research revealed that it is a very young mutant of the
Yemenite Arabica that was introduced in Reunion.75
The genomic era facilitates the understanding of coffee seed development. Using current knowledge, the metabolic pathways of
the major seed storage compounds of coffee were elucidated.76
Table 2
Constituent
Arabica greena
(%DW)
Robusta greena
(%DW)
Arabica roastedb (%
DW)
Robusta roastedb
(%DW)
Arabica instanta
(%DW)
Robusta instanta
(%DW)
Caffeine
Trigonelline
Carbohydrates
Chlorogenic acids
Lipids
Amino acids
Organic acids
Melanoidins
Volatile aroma
Ash (minerals)
Others,
partly unknown
1.3
0.8
53.7
8.1
15.2
11.1
2.3
Traces
3.9
2.3
0.7
50.7
9.9
9.4
11.8
1.7
Traces
4.4
1.3
0.3c
38
2.5
17.0
7.5
2.4
25.4
0.1
4.5
summarized in
melanoidins
2.4
0.3c
42
3.8
11.0
7.5
2.6
25.9
0.1
4.7
summarized in
melanoidins
2.5
0.7
46.6
2.6
0.11
6.2
8.1
25.1
3.8
0.4
44.7
1.6
0.26
6.0
7.9
28.6
8.0
7.4
Leloup.79 p 84.
Illy and Viani.80 pp 9899.
c
Macrae,81 Fig. 2, p 130.
b
Chemistry of Coffee
The first compound covered here is caffeine, associated even by name to our subject, coffee. Caffeine is a nitrogenous compound
that is not affected by the central process in coffee chemistry, roasting.
N1
2
6
3
CH3
N
5
4
CH3
Caffeine
Caffeine biosynthesis takes place in the leaves and in the pericarp, the outer part of the fruit. In aged leaves the caffeine content is
lower.88 In the pericarp tissues, light strongly stimulates the methylation step of caffeine synthesis. When the seed inside the fruit
starts growing, caffeine is translocated through the membranes and accumulates in the endosperm. There, the final value is reached
8 months after flowering.89
The caffeine content of the coffee beans depends on species and variety, from 0.6% in Laurina up to 4% in some extreme
Robustas; averages are given in Table 3.90
Not included here are coffees from the Mascaracoffea group of Madagascar, which do not belong to the beverage coffees.91
They have very low caffeine contents at the limit of analytical detection (caffeine free)92 and may serve as genetic resources for
further work. These low caffeine species also show low caffeine in their leaves.93
The caffeine content in dry matter base is not affected by postharvest processing, neither by the roasting. Although the roasting
process occurs well above sublimation temperature, during it only a small percentage of caffeine vanishes, which is overbalanced by
the organic weight loss.91
Caffeine is a physiologically active compound, and the human exposure to it after a cup of coffee is of interest. Some general
calculations can be made: an aqueous extraction at regular brewing conditions transfers the caffeine almost completely into the
beverage. A cup of 100 ml with a brew of 55 g l1 of roast and ground coffee, with the world trade ratio of 60% Arabica and an
average caffeine content of Table 2, supplies about 100 mg caffeine.
Looking beyond the averages, Table 4 roughly gives the variability (both with choice of coffee and brewing strength),94,95
omitting extremes and exotics a range of plus/minus 100%.
But even the term cup or serving is in motion: the mug has become widespread, with a volume of about 250 ml, and jumbos
are on the market, of about 500 ml.
A cup of tea for comparison, has a slightly lower caffeine content: Prepared from a 1.75 g teabag with an average caffeine content
for tea of 3%, a cup of 100 ml contains 50 mg, with a natural variability similar to the case of coffee.
For unexpected caffeine in non-coffee and non-tea drinks, at amounts exceeding 150 mg l1, a special labeling is requested by
the European legislation (high caffeine content with an indication of the amount of caffeine).96
Table 3
Species
Variety
Leaf (%DW)
Bean (%DW)
C. arabica
Mundo Novo
Typica
Catuai
Laurina
Robusta
Kouilou/Conillon
Laurentii
0.98
0.88
0.93
0.72
0.46
0.95
1.17
1.11
1.05
1.34
0.62
>4
2.36
2.45
C. canephora
10
Chemistry of Coffee
Table 4
Estimated ranges of caffeine content per cup, standard brewing of different strengths
Arabica (0.91.6%)
Caffeine per cup (mg/100 ml)
Robusta (1.42.9%)
Caffeine per cup (mg/100 ml)
40a
55b
70c
3664
5088
63112
67
92
118
56116
77160
98203
The data of Table 4 reflect a standard beverage preparation others exist. In an espresso-style percolation, for a cup of 30 ml,
6.5 g roast and ground are taken; with the average blend mentioned above, about 87 mg caffeine can be expected. The very short
time available to extract caffeine from the cellular structure leads to 7585% extraction yield only.97
While enjoying his coffee, the consumer may benefit from the stimulating effect of caffeine.
The alerting effects are well known and the mechanisms investigated.98,99
After its consumption, caffeine is readily and completely absorbed from the gastrointestinal tract. Within 1 h it is evenly
distributed within the body, readily passing the bloodbrain barrier. Peak plasma levels occur 3060 min after ingestion.
Provoked by a cup of regular coffee of the previously-calculated concentration, a caffeine level of 2 mg l1 body fluid is reached
(total body fluid taken as 60% of a 70-kg man), just in the range of the stimulatory level of about 14 mg l1 body fluid.100 At
blood concentrations such as these, the main mechanism of action in the central nervous system is the antagonism of adenosine
receptors, which increases central nervous system activity, with effects on alertness and cognitive control.
During circulation, caffeine is metabolized in the liver via successive demethylation and oxidative degradation to uric acid. The
breakdown products are excreted through the kidneys. About 5% of caffeine is excreted unchanged. The half-life ranges from 2.5 to
4.5 h in healthy male adults. For children, women, pregnant women, and people under stress, longer times were reported.
The caffeine content of coffee can be reduced by decaffeination. The process starts with a steam treatment of the green coffee to
soften the tissues, followed by solvent extraction. The first patent dates back to 1905.101 Today, processes run with dichloromethane, ethyl acetate, supercritical or fluid carbon dioxide, or water each process with its own special technology.102 In the
United States, nondecaffeinated coffee is called regular coffee.
Legal requirements on the caffeine content apply to decaffeinated coffee for the final product for consumption, that is, roast and
soluble coffees. In the United States, decaf coffee is defined through the degree of decaffeination; common are 97%.103 The
European legislation sets a maximum residual caffeine content of 0.3% for soluble coffee104; roast coffee is covered by national
legislations, in general 0.1% on dry matter.
The standard analytical methods for caffeine determination employ chromatographic separation and spectrometric
detection.105
Although caffeine as pure chemical has a clearly bitter taste (it can be used as a bitter standard in basic sensory tests), it plays
only a minor role in giving a bitter tinge to the coffee beverage.
Roasting
Roasting the coffee beans is an essential transformation, performed at about 200 C.110 The coffee beans become dry, expand in
volume, become brown and brittle, and develop a characteristic flavor and aroma profile.
During roasting, volatile aromatic compounds and polymeric brown pigments are formed in the beans, while water and carbon
dioxide are released. The principal thermally reactive constituents of the raw bean are the monosaccharides and sucrose, free amino
acids, chlorogenic acids and trigonelline, and the newly formed precursors of degraded carbohydrates and denaturated proteins.
The chemical reactions are complex.
Prevalent is the Maillard reaction of amino acids and/or proteins with reducing sugars, with a cascade of condensations,
cleavages, rearrangements, and degradations and oxidative polymerization in parallel, as recently shown.111
Chemistry of Coffee
11
Another pathway of roasting is the Strecker degradation, leading to pyrazines and oxazoles.
Degradation of trigonelline leads to nicotinic acid, pyrroles, and pyrimidines. Chlorogenic acids form lactones; in Robusta, they
may also end up in phenols like guaiacoles.
Carbohydrates
Carbohydrates are products of photosynthesis in plants. During coffee fruit development, they are produced in both the leaves and
the pericarp, as reducing sugars (glucose, fructose) and sucrose. Transported to the perisperm and the endosperm in their respective
phases of growing,113 they contribute to sucrose accumulation in the coffee seed. Robusta accumulates about 30% less sucrose than
Arabica.114
By far, polysaccharides of differing molecular sizes form the largest part of the green coffee carbohydrates. Names like
galactomannan and arabinogalactan protein reflect the constitutive units,115 the backbone chains and the substituting branches;
an overview is given in Table 5.
Recently, linkage analysis of the moieties revealed a glycoprotein backbone for the arabinogalactan fraction of green coffee,
which is now called arabinogalactan protein.116 The central chain consists of proteins, which account for 0.52% of the polymer;
they contain between 7 and 12% hydroxyprolin.117 For arabinogalactan proteins in plant tissues in general, a structure was
proposed.118 The analytical determination of carbohydrates in these structural elements starts with the separation and isolation of
the different fractions with chemical and enzymatic reactions.119 The detailed analytical data in Table 6, of 2006, are achieved by
this procedure; they confirm and refine those of Table 5, of 1987.
Roasting favors the degradation/depolymerization of polysaccharides,120 and transforms the sugar composition substantially.
The resulting oligo- and mono-saccharides can be solubilized during extraction, yielding a characteristic carbohydrate profile.
After roasting, the extractability of mannans in high temperature extraction is enhanced, important for the instant coffee
production; a maximum of extraction yield is achieved with medium roast.121
Carbohydrates are precursors for flavor generation. They react with proteinaceous components in the well-studied Maillard
reaction. The process generates essential contributors to coffee flavor, as either volatile aroma compounds122 or nonvolatile taste
compounds,123 and, simultaneously, a heterogeneous class of dark brown polymers, the melanoidins with different ranges of
molecular-weight.124
At darker roasting, pyrolytic degradations take place.
Carbohydrates are major components of both roast and soluble coffees. In home brews prepared from roast and ground coffee,
they are present in low quantities.
Analysis of the individual carbohydrates is presented in an internationally accepted standard with high performance anion
exchange chromatography (HPAEC),125 providing profiles of free carbohydrates and of total carbohydrates (the overall carbohydrate composition).
Table 5
Main carbohydrate structures in Arabica and Robusta green coffee beans, compiled from different tables112
Fraction
Structure
Arabica
(wt%)
Robusta
(wt%)
Monosaccharides
Oligosaccharides
Mannan (galactomannan)
0.20.4
5.18.6
22
0.50.70
2.26.6
22
1415
1617
8
Traces
8
Traces
Arabinogalactane-protein
(formerly arabinogalactan)
Cellulose (homoglucan)
Hemicellulose
12
Chemistry of Coffee
Table 6
Carbohydate composition of Arabica and Robusta green coffees and of the corresponding soluble coffees obtained by industrial
manufacturing (roasting, extraction, drying)
Component
Arabica
green
(%DW)
Robusta
green
(%DW)
Arabica
instant
(%DW)
Robusta
instant
(%DW)
Free arabinose
Free galactose
Free glucose
Free fructose
Free mannose
0.00
0.08
0.00
0.09
0.00
0.00
0.03
0.00
0.13
0.00
0.67
1.37
0.34
0.66
2.46
0.80
1.40
0.35
0.67
2.35
Sum of mono
saccharides
Sucrose
Other
disaccharides
Disaccharides
0.17
0.16
5.50
5.57
3.63
1.68
0.00
3.96
0.00
4.03
3.63
1.68
3.96
4.03
Component
Arabica
green
(%DW)
Robusta
green
(%DW)
Arabica
instant
(%DW)
Robusta
instant
(%DW)
Mannitol
Total arabinose
Total galactose
Total glucose
0.43
3.92
10.37
9.35
0.35
4.82
12.76
8.93
0.43
3.07
12.97
1.06
0.28
3.57
14.13
1.05
Total mannose
Total xylose
Sum of total
carbohydrates
19.85
0.22
49.90*
18.96
0.27
48.86*
18.81
0.13
37.1
15.34
0.09
35.1
79
Green coffee and instant coffee as the starting and end points, respectively, of all processing steps are set in parallel in Table 6,
with the free and total carbohydrate profiles of soluble coffee from medium roast compared with the figures for the corresponding
Arabica and Robusta green coffees.
The sucrose of the green coffee disappears totally with roasting, while small amounts of monosaccharides and other disaccharides are released by roasting and extraction. A significant portion of the total carbohydrates is transformed into solubles.
Other investigations show that the mannose/galactose ratio changes during plant development.126 Several studies on carbohydrate composition give ratios different from the one cited here.
The standard method mentioned previously is also used, when the available carbohydrates and sugars are required for
nutritional evaluation the relevant European legislation127 says, any carbohydrate metabolized in man and all monosaccharides and disaccharides present in food, respectively. Using the ISO method, the carbohydrates are to be determined individually
and summed up the resulting energetic amounts are negligible for instant coffee,128 36 kCal/100 g and 0.7 per cup, respectively;
for the roast coffee beverage, probably even lesser.
A traditional procedure for nutritional carbohydrate evaluation, summing up all other components (water, fat, ash, proteins)
and taking the difference to 100% for carbohydrates, is not suitable for coffee.
The procedure for specific carbohydrate profiles of soluble coffee may indicate whether or not extraneous material was used for
extraction and serves as a criterion for judging soluble coffees authenticity.129
Chlorogenic Acids
Chlorogenic acids are widely distributed secondary metabolites in plants, and they are also present in the coffee bean in relatively
large quantities.
OH
OH
C
O
HOOC
OH
C
C
5
2
OH
OH
5-CQA
The parent structure is a conjugate of tetrahydroxy-cyclohexane carboxylic acid (quinic acid) and caffeic acid (3,4-dihydroxy
cinamicacid). Due to isomers and epimers in the cylohexane part and substitutions at the aromatic ring, a whole family of
chlorogenic acids exists.
Chemistry of Coffee
Table 7
13
Typical contents of chlorogenic acid (CGA) and CGA-like components in commercial green coffee beans
Component
Arabica (%d.b.)
Robusta (%d.b.)
CQA
pCoQA
FQA
diCQA
CFQA
5.26.5
0.030.07
0.30.5
0.71.0
n.d.
5.58.0
0.050.06
0.71.5
1.42.5
0.20.3
The most common chlorogenic acid is 5-O-caffeoyl-quinic acid (5-CQA); the formula shows the actual numbering at the caffeic
acid moiety.130 Isomers in the quinic acid part are 3- and 4-CQA, each at an amount of about 10% of 5-CQA. Widespread in the
chlorogenic acid family are also substitutions at the aromatic ring, naming the respective cinnamic moiety, with common
synonyms as feruloyl quinic acid (FQA, 4-hydroxy, 3-methoxy-) and p-coumaroylquinic acid (pCoQA, 4-hydroxy-). Their
concentration is orders of magnitude lower than for (caffeic) CQA, and again, the 3- and 4-isomers show 10% of the respective
5-O-isomer. Several isomeric di-esters of quinic acid exist (e.g. di-caffeoylquinic acid, diCQA), and even ester mixes, like caffeoylferuloylquinic acid (CFQA). Table 7 shows the typical contents of Arabica and Robusta green coffee for these chlorogenic acids,
values from Clifford.131 For analytical determination, HPLC is the method of choice.
Chlorogenic acid is biosynthesized in the perisperm and accumulated in the beans endosperm76; di-CQAs are converted into
mono-CQAs during the last phase of bean maturation. The latter is important for harvesting management,132 as di-CQAs would
negatively affect the sensory quality of coffee, and in case of nonuniform ripening and simultaneous harvesting, the immatures
might be included in the crop.
Roasting reduces progressively the amount of free chlorogenic acids in coffee, creating a series of transformation products that
may be unique to coffee.133 In the quinic part of CQA, a lactonisation occurs; the chlorogenic lactones (quinides) show a marked
bitterness and possible biological effects.134 Within the series of isomers, the 1,5 quinides are the most common. The general
structure is shown. A great portion of the CQAs of green coffee disappears via Maillard-type reactions into more complex
macromolecules, i.e. melanoidins,135 and partly decomposes into quinic acid and caffeic acid, to form quinides and to be
incorporated in the melanoidins. Another transformation leads via decarboxylation and cyclisation to phenylindanes, identified
as a strongly bitter component of coffee.131,149
O
O
OHO
OH
1,5-Quinide
Domestic brewing and commercial instantization substantially extract the CQAs from the melanoidines and hydrolyzes the
lactones.131 CQA contents in the brew are about 3% DW, in instant coffee about 57%.138
In human digestion, CQA is bioavailable; it reacts with the microflora of the gut, and reaches the plasma within one to four
hours.136 The metabolism is under investigation.
Plant-derived phenolics are reported to have wide ranging biological activities and a high potential as antioxidants. Coffee with
its chlorogenic acid is one of the richest dietary sources; many studies deal with the fate and effect of chlorogenic acid, in order to
elucidate on protective effects against degenerative diseases such as cardiovascular disease, cancers, and also diabetes II: Regular
Reviews137 over the years reveal the accumulating epidemiological evidence and support for the positive health impacts of coffee
consumption.
Nitrogenous Compounds II
This section deals with those nitrogenous compounds of coffee that are transformed during the processes of roasting and
extraction. Proteins, the classic nitrogenous compounds of food, constitute about 12% of green coffee, peptides and free amino
acids up to 1.5%, alkaloids 34%, of which trigonelline represents about 1%. Most of these compounds are transformed at
roasting.
The roast-stable caffeine was covered in the first section of nitrogenous compounds.
14
Chemistry of Coffee
Table 8
Free and total amino acid content of coffee, green, roasted, brew, from different sources
Amino acid
Alanine
Arginine
Aspartic acid
Cysteine
g-Amino
butyric acid
Glutamic acid
Glycine
Histidine
Ileucine
Leucine
Lysine
Methionine
Phenylalanine
Proline
Serine
Threonine
Tryptophan
Tyrosine
Valine
Sum
Mean
0.025
0.008
0.033
n.d.
0.028
0.034
0.018
0.033
n.d.
0.047
0.53
0.72
1.03
0.26
0.05
0.58
0.64
1.22
n.d.
0.61
0.00
1.15
n.d.
035
0.00
0.73
n.d.
0.102
0003
0.004
0.005
0.006
0.006
0.002
0.017
0.047
0.006
0.004
0.008
0.010
0.011
0.001
0.021
2.20
0.69
0.35
0.45
0.93
0.69
0.017
0.003
0.016
0.005
0.57
0.40
0.005
0.009
0.27
0.02
0.011
0.017
0.29
0.02
0.43
0.58
10.5
0.66
2.43
1.14
0.29
0.49
1.09
0.81
0.14
0.61
0.64
0.49
044
n.d.
0.34
0.65
12.0
0.75
2.47
103
0.24
0.50
1.11
0.11
0.11
0.63
0.62
0.24
0.27
n.d.
0.28
0.72
10.1
0.63
2.06
0.71
0.15
0.26
0.57
0.00
0.07
0.32
0.45
0.15
0.12
n.d.
0.18
0.28
6.4
0.40
0.60
Amino acids are constituents of peptides and proteins; their individual contribution can be analyzed as total amino acids after
appropriate analytical hydrolysis.135 The sum of total amino acids roughly accounts for the protein content.
Protein content is required for nutritional declarations of foods,127 which is, in fact, optional.
The traditional determination of protein in food via conversion of total nitrogen into protein content with the legal (!)
empirical factor of 6.25 (the Kjeldahl nitrogen method) does not give correct protein values for coffee unless several corrections
have been introduced for the nitrogen of caffeine and trigonelline, for other nonprotein nitrogen, and for those components that
in the case of roast coffee do not reach the consumers beverage. Table 8 lists the results of free and of total amino acid
determination of Arabica and Robusta green coffees, taken from two doctoral theses; data for totals of Arabica roast and brew
are added. Trautwein used samples of different origins; great variation was found in each dataset,139 which is not evident in the
overall mean. In total amino acids, the results of Arabica and Robusta overlap widely, as Table 8 shows.
The free amino acids of green coffees are largely transformed upon roasting. They take part in the Maillard reaction, resulting in
components that contribute to flavor and color of the coffee brew. In roasted coffee, only negligible amounts remain.140
Sulfur amino acids, cystine, cysteine, and methionine in green coffee mostly bound in proteins, degrade at roasting, and interact
with reducing sugars and Maillard intermediates to form intensely aromatic volatiles, for example, furfurylthiol, an aroma
impact compound with a very low aroma threshold value, and thiophenes and thiazoles.
Hydroxyl-amino acids serine and threonine react with sucrose to give volatile heterocyclic compounds, inter alia the
alkylpyrazines.
Proline and hydroxyproline react with Maillard intermediates to give pyrroles, pyrrolizines, and pyridines and also alkyl-, acyl-,
and furfurylpyrroles.
Tryptophan is transformed into serotonine in the last weeks of grain development.
The protein content of green coffee is about 1013%. The protein profile of coffee changes during roasting; the proteins are both
fragmented and polymerized, and integrated into melanoidins. Their concentration in the brew is at the end about 67%, a figure
relevant for nutritional value calculations.79
The principal protein of green coffee is a storage protein of 11S type. It is biosynthesized in the endosperm141 during maturation
and accounts for about half of the protein content.142 The 11S protein has an a- and a b-arm of different length, with a disulfide
bridge, and allows covalent bindings of chlorogenic acids at the higher reactive b-branch143 upon roasting. A 7S- and a 2S-type
protein were also reported. The 11S protein itself and the DNAs encoding its expression are subjects of European and US patents.144
Chemistry of Coffee
15
Trigonelline
Trigonelline, the N-methylpyridinium-3-carboxylate, is, after caffeine, the second most important alkaloid of coffee, with about 1%
of the green bean. During leaf development, it is synthesized in the leaves and in the fruits pericarp and accumulated in the seeds.
The direct precursors are nicotinic acid and nicotine amide, deriving from the pyridine nucleotide cycle.145
COO
N+
CH3
Trigonelline
Trigonelline is rapidly degraded during roasting, strongly depending on temperature and roasting time, with about 6090%
being lost.146 The products are nicotinic acid via demethylation and methyl-pyridines and pyridines via decarboxylation, with
reactive intermediates and further recombination products including pyrrols.
Trigonelline products have an impact on the overall aromatic perception of roast coffee and beverage. Niacin (nicotinic acid),
the degradation product of Trigonellin, serves for vitamin supply in human nutrition; it is an accepted vitamin in European
legislation.147
Physiologically important are the recently identified N-methylpyridinium (NMPY) ions148; they act in vivo, as identified
through an activity guided screening procedure in the coffee brew,149 as key components to turn on the endogeneous antioxidant
defense system through induction of the phase II biotransformation enzymes.149
+
N
CH3
N-Methylpyridinium
Lipids
Food lipids are substances that are soluble in organic solvents. The category includes structurally different compounds.150 In green
coffee, the biggest part of the lipids is the coffee oil in the beans endosperm; lipids outside the bean are found in the small amount
of coffee wax on the outer layers of the bean. The coffee oil consists of triglycerides (the fats), phospholipids, sterols, tocopherols,
the coffee characteristic diterpenes, and the respective esters with fatty acids. The coffee wax consists of 5-hydroxytryptamide esters
with fatty acids. The fatty acids are unbranched with a chain length of 1624 carbons.
The overall range of lipid content in green beans is 717%, with an average of about 15% for Arabica and 10% for Robusta.
Table 9 shows the relative content of the different components, as averages151 and ranges,152 respectively, from literature
compilations.
Lipids in coffee serve as carriers for flavors and for fat-soluble vitamins and contribute to texture and mouthfeel in the brew. The
diterpenes among them have received attention in recent years due to their different physiological effects.
Table 9
Compounds
Triacylglycerols
Esters of diterpene alcohols and fatty acids
Diterpene alcohols
Esters of sterols and fatty acids
Sterols
Tocopherols
Phosphatides
Tryptamine derivatives
a
Maier.151
Viani.152
Rangeb
75.2
18.5
0.4
3.2
2.2
0.040.06
0.10.5
0.61.0
7080
1518.5
011.2
1.43.2
1.32.2
0.30.7
0.1
0.31.0
16
Chemistry of Coffee
Total lipids
The total lipid content of coffee is most reliably determined via selective solvent extraction with tertiary butyl methyl ether.153 This
separation is the first step of the follow-up fractionating. It is validated as part of a German standard procedure.154
For further investigations, the total lipids can be fractionated via gel permeation chromatography into free fatty acids,
triglycerides, and diterpene fatty acid esters.155
Triacylglycerols
Triacylglycerols accumulate in the fruit endosperm from day 120 onward after flowering. The preceding steps of lipid synthesis76
are supposed to occur in both the perisperm and the endosperm: prolongation of fatty acids with 2-carbon units, desaturation steps
with different enzymes, second desaturation with phosphatidylcholine as the intermediate host of fatty acids, and sequential
acylation to end up with the triacylglycerol.
The final accumulation is visible in the bean by electron microscopy distinct oil bodies in the coffee material, forming droplets
of about 0.5 m diameter, positioned near the cell wall. Figure 6 shows this at day 187 after flowering.156
The fatty acid distribution of the coffee triglycerides is special in tropical plants, as the polyunsaturated fatty acids (common
acronym PUFAs) exceed the saturated ones: about 50% linoleic acid, C-18, twice doublebonded, versus 30% palmitic acid, C-16;
the third in line is oleic acid, C-18 monounsaturated, with about 10%. There are variations between Arabica and Robusta, but in
general they are similar.
During roasting, the triacylglyceroles remain unchanged, prone to become the carrier of the emerging flavor volatiles. With very
strong roasting, they gather at the outer bean surface, sweating.
At the beverage preparation, intended to extract the coffee ingredients for consumption, the lipids in most cases do not reach the
brew, as they stick to the spent grounds and are filtered off, in filter home brew as well as in soluble instant coffee production.
With this in mind, soluble coffee manufacturers often remove the aroma compounds with their carrier coffee oil before the
aqueous extraction, and reincorporate them at a final step before packaging many sophisticated solutions to this challenge exist.157
Other brewing methods, like preparation by boiling the roast and ground coffee without filtering separation, leave the lipids in
the cup for consumption an old-fashioned style, which had been used until the late 1970s in Scandinavia.
In the true espresso preparation,158 advancing since half a century, the coffee lipids in the cup play an outstanding role. Because
of the quick preparation under pressure, the lipids can reach the beverage to form a stable oil in water emulsion, with high content
of aromatic volatiles; the consumer is touched via the retronasal sensation and through enhanced mouthfeel Espresso, a festival
for all senses was the title of a German popular-scientific paper in 2003.159
21
Figure 6 Lipid bodies in the cells of the coffee grain, 187 days after flowering, scanning electron microscopy, adapted from Dentan, ASIC 1985.156
Chemistry of Coffee
17
17
CH2OH
CH3
16
OH
O
Cafestol
CH2OH
CH3
OH
O
Kahweol
CH2OH
CH3
OCH3
O
16-O-methylcafestol
Cafestol, kahweol, and their respective esters undergo decomposition and isomerisation at roasting, to form
dehydrocafestol/-kahweol by water elimination, cafestal/kahweal by ester cleavage and oxidation at C-17, and isomerisation
and elimination to isokahweol and dehydroisokahweol; paralled by a decrease in the ester contents, strongly depending on
roasting conditions.163
An adverse association between coffee consumption and serum cholesterol levels, reported in Norwegian study of 1983,164 was
identified as linked to the presence of cafestol (and kahweol) esters in the beverage.165 Like with the other lipids, their amount is
connected to the style of coffee making. Data are shown in Table 10, with small pictures of the brewing equipment, a description of
the procedures, and with estimates on cholesterol rises according to the literature.166
The ester content is high for boiled coffee, French press (Plunger pot), and Middle Eastern style preparations, where there is no
separation of grounds, is intermediate in espresso coffee, and negligible in instant and filtered coffees.
Meanwhile, most of the Scandinavians have changed their habit of coffee making from the traditional boiling style to the
filtering method; insofar, a cholesterol raising effect of coffee is no longer a problem there. Regarding the other preparation
techniques mentioned, the choice is up to the consumer.
Sterols, tocopherols
Coffee contains a number of sterols that are also typical of other seed oils. In addition to 4-desmethylsterols, various 4-methyl- and
4,4-dimethylsterols have been identified, both in free and in esterified form. The distribution of the main desmethylsterols in
Robusta and Arabica coffee differs markedly, and with a special statistical evaluation, their use for identification of Robusta in
Arabica coffees had been proposed.167
Tocopherols in coffee oil hold for about 120 mg kg1, in Robusta slightly more than in Arabica. They are also found in roast
coffee and in the brew and in soluble coffee.
Coffee wax
Coffee wax, a thin layer on the surface of green coffee beans, is composed of fatty acids of a chain length up to C-22, linked as an
amide to the amino-group of serotonine, 5-hydroxytryptophan (C-5-HT, carboxylic-acid-5-hydroxy-tryptamide).
HO
Insoluble in petroleum ether, it is defined and prepared by solubility in chlorinated organic solvents.
For some time, its reduction was taken to indicate a treatment of green coffee,168 executed to reduce possible irritating
compounds that might be formed on roasting and hence result in a more digestible coffee brew.
18
Chemistry of Coffee
Table 10
Preparation techniques of coffee brews, resulting levels of cafestol and kahweol in the brew, and predicted effects on serum cholesterol
with a habitual consumption of 5 cups per day
Type of coffee
Preparation techniquea
Kahweol (mg)
Filtered
0.1
0.1
<0.01
Percolated
0.1
0.1
<0.01
0.2
0.2
0.01
Chemistry of Coffee
Table 10
19
(Continued)
Type of coffee
Preparation techniquea
Instant
Espresso
Kahweol (mg)
1.5
1.8
0.10
(Continued)
Volatiles
The ingredients of this section do not share a common chemical characteristic, but the physical property of being volatile, and
contributing to the aroma of coffee.
The estimation of their individual contribution to the overall sensation of coffee smell can be performed with different
instruments.
The equipment of choice is the gas chromatograph, with a sniffing port at the detector side (GC-O) for the description and a
mass spectrometer (GCMS) for the identification of the separated components. Precise quantification of the odorants is achieved
using stable isotope dilution assays as internal standards.169
Based on the minimum identifiable odor concentration, an Odor Value or a Flavor Dilution Factor can be defined, thus ranking
the volatiles on the basis of their odor units determined by GC/O. A frequently used visualization is the FD chromatogram: FD
factor versus retention index on the chromatographic column used.170
The importance of the odor active components on the overall impression of coffee is proved by a recombination experiment.
With a synthetic blend of some 20 compounds on the basis of quantitative data, the sensation roast coffee was met. The impact of
individual compounds in interaction to the others is evaluated by omission experiments.
20
Chemistry of Coffee
The vast majority of coffee volatiles is connected to roast coffee and generated by green coffee roasting.
Volatiles on roasting
Roast coffee aroma is a complex mixture of more than 1000 volatile compounds. With the instruments mentioned above, their
quantity could be condensed to some 20 key aroma compounds.122
Of these, the roasty-sulfurous smelling 2-furfurylthiol (FFT) is by far the outstanding odorant. During roasting it is formed by
reactions of cysteine with arabinose which is released from the polysaccharides in coffee.171
Next in line as revealed by the omission-experiment, are the pyrazines, followed by furanones and further sulfur compounds.
The volatiles can be grouped according to their odor qualities.
The concentrations in solid roast (mg kg1) and in the brew, FD factors, sensory impressions are given together with the
numbering in the chromatographic analysis (Figure 7) for medium roasted Arabica coffee (compiled from different
sources.122,172,173 not all entities present). Not all volatiles were grouped.
Tables 1419 contain the positively grouped volatiles with their characteristics, when known not all compounds identified in
the FD-chromatogram are grouped, and not all are completely characterized.
Some of these roast coffee odorants differ markedly between Arabica and Robusta.
Table 11
Key odorants in green coffee and concentration in roast coffee, compiled from Grosch122
Odorant
FD
factor
Impression
3-Isobutyl-2-methoxypyrazine
2-Methoxy-3,5-dimethylpyrazine
2-Methoxy-3-isopropylpyrazine
4-Vinylguaiacol
4-Ethylguaiacol
3-Hydroxy-4,5-dimethyl-2-furanone
(Sotolon)
(E)-b-Damascenone
97
0.5
2.3
117
21
0.7
4096
512
128
Pea-like
Earthy
Pea-like
Spicy, phenolic
64
Spicy
97
1.1
2.4
39 000
4060
1870
Table 12
>0.3
Fruity, honeylike
255
Odorant
Robusta green
Arabica green
2-Methylisoborneol
2-Ethyl-3,5-dimethylpyrazine
2,3-Diethyl-5-methylpyrazine
0.74 mg kg1
824
233
0.42 mg kg1
492
112
Table 13
Odorant
Impression
Defect caused by
Geosmin
2,4,6-Trichloroanisol/-phenol
2-Isopropyl-3-methoxypyrazine
4-Heptenal
Ethyl-2-methylbutyrate
Ethyl-3methylbutyrate
Earthy
Rioy, corky
Peasy, potato-taste
Rotten fish
Moulds
Degradation of a fungicide
Bacterial infection after insect attack
Immature beans
Uncontrolled fermentation
2048
512
128
FDfactor
Chemistry of Coffee
21
32
16
36
4
38
1 2
700
900
1100
1300
(RI ; OV-1701)
1500
1700
Figure 7 FD-chromatogram of Arabica roast coffee powder. Reproduced from Blank, I.; Sen, A.; Grosch, W. Aroma Impact Compounds of Arabica and
Robusta Coffee. Qualitative and Quantitative Investigations. ASIC 14e Colloque, San Francisco, 1991, pp 117129.
Table 14
Sweetish/caramel odorants
120
49.4
36.2
23.4
16.7
28.2
17.8
4.1
7.2
3.1
1.6
0.9
0.8
0.8
0.6
0.2
Table 15
FD factor
Impression
N in Figure 7
24
1
5
128
Caramel-like
Buttery
Buttery
Malty, pungent, sweety
Caramel-like
Malty, pungent, fruity
Malty, pungent, sweety
Sweet (vanilla)
29
2
38
Earthy odorants
FD factor
Impression
N in Figure 7
2-Ethyl-3,5-dimethylpyrazine
2,3-Diethyl-5-methylpyrazine
2-Ethenyl-3-ethyl-5-methylpyrazine
3-Isobutyl-2-methoxypyrazine
2-Ethenyl-3,5-dimethylpyrazine
0.326
0.090
0.017
0.087
0.053
0.017
0.0036
0.002
0.0015
0.001
2048
2048
Earthy, roasty
Earthy, roasty
Roasty, earthy
Earthy, roasty
Roasty, earthy
17
21
26
25
19
Table 16
Sulfurous/roasty odorants
Methanethiol
2-Furfurylthiol
Methional
3-Mercapto-3-methyl-butyl formate
2-Methyl-3-furan-thiol
3-Methyl-2-buten-1-thiol
Dimethyl trisulfide
455
1.7
0.239
0.112
0.0064
0.0099
0.028
0.170
0.017
0.010
0.0057
0.0011
0.0006
FD factor
Impression
N in Figure 7
2048
Putrid, sulfury
Roasty (coffee)
Potato-like, sweet
Catty, roasty
Meaty
Sulfurous, amine-like
Vegetable (cooked)
6
8
14
15
4
22
Chemistry of Coffee
Table 17
Smoky/phenolic odorants
FD factor
Impression
N in Figure 7
4-Vinylguaiacol
Guaiacol
4-Ethylguaiacol
55
3.2
1.6
0.74
0.12
0.05
512
Spicy, clove-like
Phenolic, spicy
Spicy, clove-like
34
23
31
Table 18
Fruity odorants
Acetaldehyde
Propanal
b-Damascenone
130
17.4
0.226
4.7
Table 19
FD factor
Impression
N in Figure 7
Fruity, winey
0.0016
2048
Fruity, honey-like
35
Spicy odorants
FD factor
Impression
N in Figure 7
3-Hydroxy-4,5-dimethyl-2-furanone (Sotolone)
4-Ethyl-3-hydroxy-5-methyl-2(5H)-furanone
1.6
0.132
0.08
2048
1024
Spicy
Spicy
30
Chemistry of Coffee
23
Odor perception happens on sniffing at roast coffee or at the coffee brews headspace; volatile odorant molecules enter the nasal
cavity with the inhaled air stream, are absorbed in the mucous layer inside, arrive at the dendritic cilia at the olfactory epithelium,
and bind to the fitting odorant receptor sites. The receptors response pattern serves for identifying the specific odorants179; via the
glomeruli of the olfactory bulb, the signals reach the olfactory cortex, to be forwarded to other brain areas for recognition of odors
through memory and emotion. The human olfactory system has millions of olfactory cells with about 400 distinct receptor types;
they allow a sufficient number of combinations to discriminate the different odorants.180 For some of the analytically separated
volatile components of coffee, the perceived impressions were given in the last section.
In general, natural odors consist of mixes of odorants. When they are smelt the merging of receptor codes evokes novel
perceptions in the olfactory cortex,181 which need special characterizations. To communicate on the odor of coffee, the establishment of a consensual pool of linguistic descriptive attributes is necessary a challenge up to now.
The other route of olfaction is the retronasal; it happens on coffee drinking, when odorant molecules are released inside the
mouth, and reach the olfactory epithelium via the nasopharynx. For better distinction, coffee people like the term flavor, which is
used toward any product that has interaction with the oral system.182 The components can be analytically separated by techniques
like exhaled odorant measurement,183 or oral breathe sampler,184 identified, and described.185 The overall perception is different
from the orthonasal one on inhalation at the brews headspace, as the experience of flavor also incorporates gustatory information
and somatosensation.186
The gustatory system and the sense of taste are activated by the coffee drink, when its tastant substances get in contact to
epithelial taste receptor cells in the mouth. The gustatory sensation of coffee follows the general way of mammalian taste
perception,187 through detection by distinct receptors on specialized taste cells within taste buds, interacting via receptor proteins
(coffees bitterness) or ion channels (coffees acidity) to transmit the information to the respective gustatory nerves to further
processing in the brain. The perceived taste intensity corresponds to the level of the stimulus.
At the intensities found in coffee, bitter is taken as a positive attribute, adding richness to the beverage. The stimulus can show a
longer duration, an aftertaste or persistence.
Recently, a bio-response guided screening method was developed, to identify bitter tastants in coffee. Combining the human
bio-response and a detective work with chemical fractionating and instrumental analysis, this is leading to new insights188 on
chemically different classes of bitter tasting substances.
Acidity is the other big taste for coffee, with many positive epitheta like fine, mild, fruity, balanced, and distinct from the sour.
The perceptions of bitterness and of acidity are influencing each other, bitterness may mask acidity. These two taste qualities show
the strongest marked cross-cultural differences.176
The mouthfeel when tasting coffee is a somatosensory sensitivity, resulting from tactile or thermal stimulation by the texture
and viscosity of the liquid, as well as from activation of receptors on the perigemmal fibers outside the taste buds. The stimulations
are believed to be transmitted directly to the brain through trigeminal nerve endings in the mouth, to contribute to the somatogustatory sensation during food intake.
Astringency is a drying or rough mouthfeel suggested to result from decreased oral lubrication, following the binding of
salivary proteins by polyphenols.189 Most coffee consumers dislike it.
On search for a consensual linguistic communication on coffee, a set of a consumer oriented descriptors was proposed by the
International Coffee Organization ICO in 1991,190 with the main sections aroma, taste, and mouthfeel, and also including
off-flavors. In 1996, a consumer oriented case study on coffee followed; it was performed in parallel in several European
countries.191 Sensory evaluation of coffee and its verbal expression by different panels varies remarkably dependent on culture
and language, as recently pointed out in a Korean study,192 comparing consumer vocabularies with the advertisings of mass media
and the panelists analysis.
With a given set of terms and a trained panel, a quantitative descriptive sensory analysis may result in a sensory profile, often
presented as a spider graph.
The question of pleasantness of an odor, flavor, taste, or mouthfeel sensation on a hedonic scale opens another field of
sensorics.
Organic Acids
The Organic Acids of Table 2 in section Chemistry Components and Processes are discussed here, because of their impact on
coffee taste. They are totaling less than 3% of dry weight both in green or roast coffee.
An overview was given in 2001.193 Compiled from several sources, mass contents were reported for green, roast and soluble
coffee, thus covering the changes with roasting and extraction.
Apart from chlorogenic acids, the most prominent acid in green coffee is citric acid with 1.3%, followed by malic (0.30.4%)
and phosphoric acid (0.10.3%), the latter originating from phytic acid, inositol hexakis phosphate. At the stage of coffee roasting,
further acids are formed by carbohydrate degradation, predominantly acetic (0.30.5%), formic (0.2), glycolic (0.10.2), and lactic
acid (0.1%); a mechanism for the carbohydrate degradation was proposed.194 Citric and malic acid are reduced to contents of
0.60.8 and 0.2% respectively by degradation, with classical elimination reactions. Due to their volatility, acetic and formic acid are
at least partly lost at higher roasting temperatures. The expected increase in quinic acid on cleavage of chlorogenic acids is balanced
by the immediate reaction to the respective lactones,133 blocking the acid functions.
24
Chemistry of Coffee
After preparation of the beverage, any longer storage will cause an increase on acid content in the brew, presumably most
influenced by hydrolysis of the lactones, with a change from acid to sour taste.
A recent paper describes some model experiments in the extraction of roast and ground coffee during the production of instant
coffee, with, inter alia, special reference to changes in the acid profile.195 The contents of formic, quinic and acetic acid are relatively
more increasing than those of citric and malic acid; and this might be the reason for a qualitative and quantitative change of acidic
taste in the course of extraction.
The overall acidity perceived on tasting the coffee beverage correlates to the total titrable acidity unto an endpoint, which
mimics the pH setting of the saliva, varying from 6 to 7; a preferential value might be around 6.7. The correlation seems reasonable
and is repeatedly confirmed196; an analytical procedure for determination is established with a standardized methods.197,198
The sensory effect of the individual acids is due to their degrees of dissociation, indicated by the pKs-values. The contribution to
the total acidity (calculated including the some 100 minor acids) could be calculated to 25% for acetic acid, 20% for citric, for the
chlorogenic acids with 8%, followed by formic and malic acid with 6% each199 a marked difference in ranking in the first lines,
compared to the percentage by weight.
Melanoidins
During roasting, a marked browning of the coffee beans occurs, together with intrinsic transformation of coffee components, the
formation of aromatic volatiles and the formation of a new class of products, the melanoidins.
For a long time, the melanoidins were the dark end of the browning reactions, with unstructured, scarcely defined macromolecular material, which nevertheless enters the brew. The dissolved components of the brew are larger than the molecules of the
solvent water, in terms of physico-chemistry, we deal with suspensions.
Just these melanoidins were the topics of international scientific networking on Melanoidins in Food and Health,200 of 1999
and on Thermally processed foods: possible health implications201 of 2004.
The melanoidins are part of the coffee brew, with about 20% of the dry matter, and can be isolated from it. Recent investigations
revealed,135 that they consist of an about 80% fraction with low molecular weight compounds (up to 3 kDa),202 and of a residual
high molecular weight fraction (molecular weight up to 12 kDa).124
Conclusions
Coffee contains a wide spectrum of compounds. Many contribute to the flavor of coffee, and some compounds have an effect on
our health, such as caffeine with a stimulating effect, chlorogenic acids as antioxidants, nicotinic acid as vitamin and the diterpene
esters as cholesterol-increasing compounds. Despite the similar importance of coffee as beverage, the research on health promoting
effects has not yet developed to the same extent for coffee as for tea. At least it is clear that the whole processing of coffee beans and
the method of coffee brewing play a crucial role for the final melange of compounds that is consumed when drinking coffee.
References
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
Chemistry of Coffee
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
25
26
Chemistry of Coffee
85. Crozier, A.; Baumann, T. W.; Ashihara, H.; Suzuki, T., IV; Waller, G. R. Pathways Involved in the Biosynthesis and Catabolism of Caffeine in Coffea and Camellia. In ASIC 17e
Colloque, Nairobi, 1997; pp 106113.
86. Baumann, T. W. Biochemical Ecology. In Espresso Coffee: The Science of Quality; Illy, A., Viani, R., Eds.; Elsevier: Amsterdam, 2005, p 58, Table 2.8.
87. Guerreieo Filho, O.; Mazzafera, P. Caffeine Does Not Protect Coffee against the Leaf Miner Perileucoptera coffeella. In ASIC 18e Colloque, Helsinki, 1999; pp 520523.
88. Ashihara, H.; Monteiro, A. M.; Gilies, F. M.; Crozier, A. Biosynthetic Pathways of Caffeine in Coffea arabica Leaves. In ASIC 16e Colloque, Kyoto, 1995; pp 589598.
89. Baumann, T. W.; Wanner, H. Planta 1972, 108, 1120.
90. Illy, A.; Viani, R. Espresso Coffee, The Chemistry of Quality; Academic Press: London, 1995; Table 3.6, p 25.
91. Davis, A. P.; Govaerts, R.; Bridson, D. M.; Stoffelen, P. Bot. J. Linn. Soc. 2006, 152, 465.
92. Rakatomalala, J.-J. R.; Kumamoto, T.; Aburatani, T.; Rabemiafra, A.; Nagai, C.; Kawashima, Y.; Rabenatoandro, Y. N. Caffeine Content Distribution among Mascarocoffea Species
in Madagascar. In ASIC 20e Colloque, Bangalore, 2004; pp 154160.
93. Ashihara, H.; Cozier, A. Biosynthesis and Catabolism of Caffeine in Low Caffeine-containing Species of Coffea. In ASIC 19e Colloque, Trieste, 2001Article PB702.
94. Dutch Nutrient Database, De Nevo tabel van Stichting Nederlands Voedingsstoffenbestand, 5th ed.; 2001, Den Haag, p 644.
95. ISO 6668:2008, Green Coffee Preparation of Samples for Use in Sensory Analysis, 2nd ed.; ISO: Geneva, 2008.
96. Regulation (EU) No 1169/2011 on the provision of food information to consumers (OJ L304, 22. 11. 2011, pp 1863), Annex III, 4.1; insofar replacing directive 2002/67/EEC on
the labelling of foodstuffs containing quinine, and of foodstuffs containing caffeine (OJ L 191, 19.7.2002, p 2021), Article 2(1) and 2(2), and whereas (4).
97. Petracco, M. Physico-Chemical and Structural Characterisation of Espresso Coffee Brew. In ASIC 13e Colloque, Paipa, Colombia, 1989; pp 246261.
98. Snel, J. Coffee, Sleep and Wakefulness: Research Trends. In ASIC 20e Colloque, Bangalore, 2004; pp 6976.
99. Tieges, Z. Caffeine and Cognitive Control. Ph.D. Thesis, University of Amsterdam, 2007.
100. Daly, J. W.; Fredholm, B. B. Mechanism of Action of Caffein on the Nervous System. In Coffee, Tea, Chocolate, and the Brain; Nehlig, A., Ed.; CRC Press: Boca Raton, FL, 2004;
p 2.
101. Kaffee-Handels-Aktiengesellschaft, Bremen, Applicant (inventor not named). Verfahren zur Gewinnung kaffeinfreier Kaffeebohnen. Dt. Reichs-Patent 198, 279. October 28, 1905.
102. Holscher, W. Rohkaffeebehandlung im Verbraucherland. In Kaffee: Die Zukunft; Rothfos, J. B., Lange, H., Eds.; Behrs Verlag: Hamburg, 2005; pp 88109.
103. FDA opinion letter of 1981.
104. Directive 1999/4/EEC relating to coffee extracts and chicory extracts (OJ L66, 13.3.1999, p 26, Art. 2, (b).
105. ISO 20481:2008, Coffee and Coffee Products Determination of the Caffeine Content Using High Performance Liquid Chromatography (HPLC) Reference Method. 1st ed. ISO,
Geneva, 2008.
106. Illy, A.; Viani, R. Espresso Coffee, The Chemistry of Quality; Academic Press: London, 1995; p 40.
107. Bytof, G.; Knopp, S. E.; Schieberle, P.; Teutsch, I.; Selmar, D. Eur. Food Res. Technol. 2005, 220, 245250.
108. Bytof, G.; Knopp, S.-E.; Schieberle, P.; Teutsch, I.; Selmar, D. Ann. Bot. 2007, 100, 6166.
109. Mazzafera, P.; Purcino, R. P. Post Harvest Processing methods and Physiological Alterations in the Coffee Fruit. In ASIC 20e Colloque, Bangalore, 2004; pp 811819.
110. Eggers, R. Rostkaffee. In Kaffee: Die Zukunft; Rothfos, J. B., Lange, H., Eds.; Behrs Verlag: Hamburg, 2005; pp 112137.
111. Ledl, F.; Schleicher, E. Angew. Chem. 1990, 102, 597626.
112. Viani, R.; Petracco, M. Coffee, Ullmanns Encyclopedia of Industrial Chemistry, 7th ed., print ed. Vol. 9, pp 467498, Wiley-VCH, Weinheim; parallel electronic release
unchanged since 2007.
113. Geromel, C.; Ferreira, L. P.; Guerreiro, S. M. C.; Cavalari, A. A.; Pot, D.; Pereira, L. F. P.; Leroy, T.; Vieira, L. G. E.; Mazzafera, P.; Marraccini, P. J. Exp. Bot. 2006, 12(57),
32433258.
114. Privat, I.; Foucrier, S.; Prins, A.; Epallel, T.; Eychenne, M.; Kandalaft, L.; Caillet, V.; Lin, C.; Tanksley, S.; Foyer, C.; McCarthy, J. New Phytol. 2006, 178(4), 781797.
115. Viani, R.; Petracco, M. see Ref. [112], Table 8; citing V. Leloup; R. Liardon, Ref. [120].
116. Bradbury, A. G. W.; Hallyday, D. J. J. Agric. Food Chem. 1990, 38, 389392.
117. Redgwell, R. J.; Curti, D.; Fischer, M.; Fay, L. B. Carbohydr. Res. 2002, 337(3), 239253.
118. Showalter, A. M. Cell. Mol. Life Sci. 2001, 58, 13991417.
119. Bradbury, A. G. W.; Halliday, D. J. Polysaccharides in Green Coffee Beans. In ASIC 12e Colloque, Montreux, 1987; pp 265269.
120. Leloup, V.; Liardon, R. Analytical Characterisation of Coffee Carbohydrates. In ASIC 15e Colloque, Montpellier, 1993; pp 861863.
121. Leloup, V.; de Michieli, J. H.; Liardon, R. Characterisation of Oligosaccharides in Coffee Extracts. In ASIC 17e Colloque, Nairobi, 1997; pp 122127.
122. Grosch, W. Volatile Compounds. In Coffee: Recent Developments; Clarke, R. J., Vitzthum, O. G., Eds.; Blackwell Science: Oxford, 2001; pp 6889.
123. Homma, S. Non-Volatile Compounds Part II. In Coffee: Recent Developments; Clarke, R. J., Vitzthum, O. G., Eds.; Blackwell Science: Oxford, 2001; pp 5067.
124. Bekedam, E. K.; Schols, H. A.; Van Boekel, M. A. J. S.; Smit, G. J. Agric. Food Chem. 2006, 24, 76587666.
125. ISO 11292:1995, Instant Coffee Determination of Free and Total Carbohydrate Contents Method Using High-Performance Anion-Exchange Chromatography, 1st ed.;
ISO: Geneva, 1995.
126. Redgwell, R. J.; Curti, D.; Rogers, J.; Nicolas, P.; Fischer, M. Planta 2003, 217(2), 316326.
127. Regulation (EU) No 1169/2011 on the provison of food information to consumers (OJ L304, 22. 11. 2011, pp 1863), Annex I, definitions of nutrients; Annex V, exemption
from mandatory labeling for coffee, thus following the repealed directive 90/496/EEC on nutrition labelling for foodstuffs (OJ L 276, 6.10.1990, pp 4044, with subsequent
amendments); definitions of nutrients as of Art.1, (4), unchanged since 1990.
128. Leloup, V. Evaluation of Nutritive Value of Soluble Coffee. In ASIC 21e Colloque, Montpellier, 2006; pp 8087, Table 3.
129. Prodolliet, J.; Bruelhart, M.; Blanc, M.; Leloup, V.; Cherix, G.; Donnelly, C.; Viani, R. J. AOAC Int. 1995, 78(3), 761768.
130. IUPAC, Pure Appl. Chem. 1974, 37, 283297, rule (23).
131. Clifford, M. N. The Nature of Chlorogenic Acids Are They Advantageous Compounds in Coffee?In ASIC 17e Colloque, Nairobi, 1997; pp 7991.
132. de Menezes, H. C. Food Chem. 1994, 50(3), 293296.
133. Leloup, V.; Louvrier, A.; Liardon, R. Degradation Mechanisms of Chlorogenic Acids during Roasting. In ASIC 16e Colloque, Kyoto, 1995; pp 192198.
134. Ginz, M. Bittere Diketopiperazine und Chlorogensaurederivate in Rostkaffee. Ph.D. Thesis, University of Braunschweig, 2004.
135. Bekedam, E. K. Coffee Brew Melanoidins. Structural and Functional Properties of Brown-Colored Coffee Compounds. Ph.D. Thesis, University of Wageningen, 2008.
136. Monteiro, M.; Farah, A.; Perrone, D.; Trugo, L. C.; Donangelo, C. J. Nutr. 2007, 137, 21962201.
137. Clifford, M. N. Chlorogenic Acids Their Characterization, Transformation during Roasting, and Potential Dietary Significance. In ASIC 21e Colloque, Montpellier, 2006;
pp 3649.
138. Farah, A. Chlorogenic Acids: from Coffee Plant to Human Body. In ASIC 22e Colloque, Campinas, 2008; pp 71101.
139. Trautwein, E. Untersuchungen uber den Gehalt von freien und gebundenen Aminosauren in verschiedenen Kaffeesorten sowie uber deren Verhalten wahrend des Rostens. Ph.D.
Thesis, University of Kiel, 1987.
140. Homma, S. Non-Volatile Compounds Part II. In Coffee: Recent Developments; Clarke, R. J., Vitzthum, O. G., Eds.; Blackwell Science: Oxford, 2001; pp 5054.
141. Marraccini, P.; Allard, C.; Andre, M.-L.; Courjault, C.; Gaborit, C.; Lacoste, N.; Meunier, A.; Michaux, S.; Petit, V.; Priyono, P.; Rogers, J. W.; Deshayes, A. Update on Coffee
Biochemical Compounds, Protein and Gene Expression during Bean Maturation and in other Tissues. In ASIC 19e Colloque, Trieste, 2001 Article B214.
142. Rogers, W. J.; Bezard, G.; Deshayes, A.; Meyer, I.; Petiard, V.; Marraccini, P. An 11S-Type Storage Protein from Coffea arabica Endosperm: Biochemical Characterization,
Promoter Function and Expression during Grain Maturation. In ASIC 17e Colloque, Nairobi, 1997; pp 161167.
143. Rawel, H. M.; Rohn, S.; Kroll, J. Dtsch. Lebensm. Rundsch. 2005, 101, 148161.
Chemistry of Coffee
144.
145.
146.
147.
148.
149.
150.
151.
152.
153.
154.
155.
156.
157.
158.
159.
160.
161.
162.
163.
164.
165.
166.
167.
168.
169.
170.
171.
172.
173.
174.
175.
176.
177.
178.
179.
180.
181.
182.
183.
184.
185.
186.
187.
188.
189.
190.
191.
192.
193.
194.
195.
196.
197.
198.
199.
200.
201.
27
Marraccini, P.; Rogers, J. Coffee Storage Proteins. U.S. Patent 6,617,433, 9 September 2003.
Ashihara, H. Braz. J. Plant Physiol. 2006, 18, 18.
Macrae, R. Nitrogenous Components. In Coffee Chemistry; Clarke, R. J., Macrae, R., Eds.; Elsevier: Amsterdam, 1985; Vol. 1 Fig. 2, p 130.
Regulation (EU) No 1169/2011 on the provision of food information to consumers (OJ L304, 22. 11. 2011, pp 1863), Annex XII; ncotinic acid is mentioned as vitamin Niacin, which
may be declared; thus following Annex I of the repealed directive 90/496/EEC on nutrition labelling for foodstuffs (OJ L 276, 6.10.1990, pp 4044, with subsequent amendments).
Stadler, R. H.; Varga, N.; Milo, C.; Schilter, B.; Vera, F. A.; Welti, D. H. J. Agric. Food Chem. 2002, 50, 12001206.
Hofmann, T. W.; Somoza, V. Antioxidant Components in Roast Coffee. In ASIC 20e Colloque, Bangalore, 2004; pp 7787.
Speer, K.; Kolling-Speer, I. Braz. J. Plant Physiol. 2006, 18(1), 201216.
Maier, H. G. Kaffee; Parey: Hamburg, 1981; p 21.
Viani, R.; Petracco, M. see Ref. [112], table 19, originating from Ullmanns 5th edition, 1986.
Speer, K. Z. Lebensm. Unters. Forsch. 1989, 189, 326330.
DIN 10779:2011, Analysis of coffee and coffee products Determination of 16-O-methyl cafestol content of roasted coffee HPLC-method; Beuth: Berlin, 2011.
Speer, K.; Sehat, N.; Montag, A. Fatty Acids in Coffee. In ASIC 15e Colloque, Montpellier, 1993; pp 583592.
Dentan, E. Etude microscopique du developpement et de la maturation du grain de cafe. In ASIC 11e Colloque, Lome, Togo, 1985; pp 381396, Fig. 21, p 391.
Sivetz, M.; Desrosier, N. W. Coffee Technology; AVI: Westport, 1979; pp 434483.
Petracco, M. Espresso. In Kaffee: Die Zukunft; Rothfos, J. B., Lange, H., Eds.; Behrs Verlag: Hamburg, 2005; pp 140143.
Roth, K. Chem. unserer Zeit 2003, 37, 280282.
Folstar, K.; Pilnik, W.; de Heus, J. G.; van der Plas, H. C. Lebensm. Wiss. Technol. 1975, 8, 286288.
Speer, K. 16-O-Methylcafestol A New Diterpene in Coffee; the Fatty Acid Esters of 16-O-Methylcafestol. In Proceedings of the Euro Food Chemistry VI, Vol. 1, Hamburg,
Germany; Baltes, W., Eklund, T., Fenwick, R., Pfannhauser, W., Ruiter, A., Thier, H.-P., Eds.; Behrs: Hamburg, 1991; pp 338342.
Speer, K.; Kurzrock, T.; Kolling-Speer, I. 16-O-Methylcafestol in the Quality Control of Instant Coffees. In ASIC 20e Colloque, Bangalore, 2004; pp 880883.
Kurzrock, T.; Kolling-Speer, I.; Speer, K. Identification of Dehydrocafestol Fattyacid Esters in Coffee. In Proceedings of the 20th International Symposium on Capillary
Chromatography, Riva di Garda, Italy, 1998, CD-ROM, Sandra, P., Rackstraw, A. J., Eds.; Naxos: Schriesheim, Germany, No. 27.
Thelle, D. S.; Arnesen, E.; Frde, O. H. N. Engl. J. Med. 1983, 308(24), 14541457.
Urgert, R.; Katan, M. B. J. R. Soc. Med. 1996, 89(11), 618623.
Weusten-van der Wouw, M. P. M. E.; Katan, M. B.; Viani, R.; Huggett, A. C.; Liardon, R.; Lund-Larsen, P. G.; Thelle, D. S.; Ahola, I.; Aro, A.; Meyboom, S.; Beynen, A. C. J. Lipid
Res. 1994, 35, 721733, 729.
Duplatre, A.; Tisse, C.; Estienne, J. Ann. Fals. Exp. Chim. 1984, 828, 259270.
Culmsee, O. Dtsch. Lebensmitt. Rundsch. 1975, 71, 425427.
Grosch, W.; Semmelroch, P.; Masanetz, C. Quantification of Potent Odorants in Coffee. In ASIC 15e Colloque, Montpellier, 1993; pp 545549.
Blank, I.; Sen, A.; Grosch, W. Aroma Impact Compounds of Arabica and Robusta Coffee. Qualitative and Quantitative Investigations. In ASIC 14e Colloque, San Francisco, 1991;
pp 117129.
Grosch, W. Key Odorants of Roasted Coffee: Evaluation, Release, Formation. In ASIC 18e Colloque, Helsinke, 1999; pp 1721.
Steinhardt, H.; Hoelscher, W. Storage Related Changes of Low Boiling Volatiles in Whole Coffee Beans. In ASIC 14e Colloque, San Francisco, CA, 1991; pp 156164.
Cale, K.; Imura, N. Recovery of Beneficial Coffee Aromas from Thermal Hydrolyzates. In ASIC 15e Colloque, Kyoto, 1995; pp 685694.
Hofmann, T.; Czerny, M.; Schieberle, P. Instrumental Analysis and Sensory Studies on the Role of Melanoidins in the Aroma Staling of Coffee Brew. In ASIC 19e Colloque,
Trieste, 2001CD-ROM paper C308.
Breslin, P. A.; Spector, A. C. Curr. Biol. 2008, 18, R148R155.
Cappuccio, R. Physiology of Perception. In Espresso coffee: The Science of Quality; Illy, A., Viani, R., Eds.; Elsevier: Amsterdam, 2005; pp 310351.
Axel, R. Angew. Chem. Int. Ed. Engl. 2005, 44, 61106127.
Buck, L. B. Angew. Chem. Int. Ed. Engl. 2005, 44, 61286140.
Malnic, B.; Hirono, J.; Sato, T.; Buck, L. B. Cell 1999, 96, 713723.
Furudono, Y.; Sone, Y.; Takizawa, K.; Hirono, J.; Sato, T. Chem. Senses 2009, 34, 151158.
Zhou, Z.; Buck, L. B. Science 2006, 311, 14771481.
Ishikawa, M.; Warita, Y.; Takahisa, E.; Ohkubo, Y., HumanEnvironment Interactions (1): Flavor and Fragrance. In Natural Products II Chemistry and Biology; Mander, L.;
Lui, H.-W., Eds.; Elseviers: Oxford, 2010, Vol. 4, Chapter 15; pp 595629.
Buettner, A.; Schieberle, P. Lebensm.-Wiss. u. -Technolog. 2000, 33, 553559.
Legger, A.; Roozen, J. P. Gas Chromatography and Sensory Analysis of Chocolate Flavour: Intensity Changes in Time. In Trends in Flavour Research; Maarse, H., van der
Heij, D. G., Eds.; Elsevier Science: Amsterdam, 1994; pp 287291.
Denker, M. Retronasale Aromawahrnehmung von milchhaltigen Kaffeegetranken Einfluss der Milchtechnologie auf das Aroma. Ph.D. Thesis, University of Hamburg, 2006,
pp 1166.
Petracco, M. Beverage Preparation, Brewing Trends for the New Millenium. In Coffee: Recent Developments; Clarke, R. J., Vitzthum, O. G., Eds.; Blackwell Science: Oxford, 2001;
pp 157160.
Chandrashekar, J.; Hoon, M. A.; Ryba, N. J. P.; Zuker, C. S. Nature 2006, 444, 288294.
Frank, O.; Zehentbauer, G.; Hofmann, T. Eur. Food Res. Technol. 2006, 222, 492508.
Hofmann, T.; Ho, C.-T.; Pickenhagen, W. Challenges in Taste Research: Present Knowledge and Future Implications. In Challenges in Taste Chemistry and BiologyACS
Symposium Series 867; ; Hofmann, T., Ho, C.-T., Pickenhagen, W., Eds.; American Chemical Society: Washington, DC, 2004; pp 124.
ICO, Consumer-oriented vocabulary for brewed coffee. In Sensory Evaluation of Coffee. International Coffee Organization, Ed.; Technical Unit Quality Serie. Report no. 3; ICO:
London, 1991.
ESN, A European Sensory and Consumer Study A Case Study on Coffee. In European Sensory Network ESN; McEwan, J. A., Ed.; Campden & Chorleywood FRA: Campden
Hill, 1996.
Seo, H.-S.; Lee, S.-Y.; Hwang, I. J. Sensory Stud. 2009, 24, 111132.
Balzer, H. H. Acids in Coffee. In Coffee: Recent Developments; Clarke, R. J., Vitzthum, O. G., Eds.; Blackwell Science: Oxford, 2001; pp 1832.
Ginz, M.; Balzer, H. H.; Bradbury, A. G. W.; Maier, H. G. Eur. Food Res. Technol. 2000, 211, 404410.
Steinhauser, U.; Oestreich-Janzen, S.; Baltes, W. Dtsch. Lebensm. Rundsch. 1999, 95, 447453.
Brollo, G.; Cappuccio, R.; Navarini, L. Acidity in Coffee: Bridging the Gap Between Chemistry and Psychophysics. In ASIC 22eme Colloque, Campinas, Brazil, 2008;
pp 270280.
DIN 10776-1:1987, Analysis of Coffee and Coffee Products; Determination of pH and Acid Content; Method for Roasted Coffee; Beuth-Verlag: Berlin, 1987.
DIN 10776-2:1998, Analysis of Coffee and Coffee Products; Determination of pH and Acid Content; Method for Soluble Coffee, 2nd ed.; Beuth-Verlag: Berlin, 1998.
Maier, H. G. Dtsch. Lebensm. Rundsch. 1999, 95, 487495.
COST action 919 Melanoidins in Food and Health; 5th Framework Programme of the EU (19982002).
COST Action 927. Thermally Processed Foods: Possible Health Implications, within the 6th Framework Programme of the EU 20002006; the Wageningen University took part
in the program with the Melanoidin Research Group of the PhD thesis Bekedam, Ref. [135].
28
Chemistry of Coffee
202. Bekedam, E. K.; Ros, E.; Schols, H. A.; Boekels, M. A. J.; Smit, G. J. Agric. Food Chem. 2008, 56, 40604067.
203. Izawa, K.; Amino, Y., Kohmura, M.; Ueda, Y.; Kuroda, M., HumanEnvironment Interactions Taste. In Natural Products II Chemistry and Biology; Mander, L.; Lui, H.-W., Eds.;
Elseviers: Oxford, 2010, Vol. 4, Chapter 16; pp 631871.