Research Article

Received: 10 April 2013 Revised: 10 October 2013 Accepted article published: 12 December 2013 Published online in Wiley Online Library: 22 January 2014

(wileyonlinelibrary.com) DOI 10.1002/jsfa.6532

Chlorogenic acid in raw materials for the

production of chicory coffee
Renata Zawirska-Wojtasiak,a∗ Elżbieta Wojtowicz,b Krzysztof Przygońskib
and Mariola Olkowiczc
Abstract
BACKGROUND: Chicory coffee is produced from traditional raw materials. Other materials are added to improve its aroma. The
aim of this study was to test new raw materials with a high content of chlorogenic acid (CGA) as the criterion for their selection.
This acid is degraded in the course of roasting and is a source of phenolic compounds affecting coffee aroma. For this reason,
contents of CGAs were analyzed in traditional and new materials before and after roasting and compared with the chemicals
formed in the roasted pure standard of chlorogenic acid (5-CQA).

RESULTS: It was shown that the novel raw materials contained considerable amounts of 5-CQA, frequently higher than in
traditional chicory. The roasting process caused significant losses of 5-CQA in the tested raw materials, amounting to 55–91%.
In turn, the analysis of volatile compounds in roasted materials showed the presence of certain phenolic and heterocyclic
compounds that were also formed as degradation products of the pure 5-CQA chemical standard.

CONCLUSION: Novel raw materials, mainly chokeberry, artichoke and lovage, are rich sources of CGAs, particularly 5-CQA. Their
application in the production of chicory coffee may result in an increased content of primarily phenolic compounds in its aroma.

c 2013 Society of Chemical Industry

Keywords: chlorogenic acid; chicory coffee; raw materials; aroma; roasting

INTRODUCTION fruit, lovage, blueberry and chokeberry. Independently of the

Chicory coffee is a beverage obtained from chicory, barley, rye and
sugar beet. Its sensory attributes are similar to those of natural
coffee, making it a beverage of choice for people who because
of health concerns should not consume natural coffee (e.g. owing
to its caffeine content). Chicory coffee is becoming increasingly
popular as a wellness product.
Coffee drinkers value first of all its unique aroma. For gourmets
the aroma of coffee released in the course of brewing is associated
with one of the most pleasant moments in their everyday routine.
Components found in raw materials used to produce chicory
coffee and substances formed during the roasting process provide
it with unique sensory attributes. For the aroma of chicory coffee
to resemble that of natural coffee, apart from traditional raw
materials in its production, we may also use novel materials rich
in chlorogenic acid (CGA),1 – 3 which is one of the precursors of
aroma compounds in natural coffee and results in the formation
of coffee pigments and taste.4 – 9
Coffee is a very rich aroma product studied by many
authors.4,8,10 – 13 Over 1200 compounds have been reported,
among them the main important furans, pyrazines, pyrroles and
thiols. The formation of most of these compounds has been
characterized by pathways derived via the Maillard reaction.
However, the formation of some compounds such as phenols,
benzoic acid and catechols in roasted coffee is difficult to explain by
the Maillard reaction alone.7 According to some authors, CGAs are
precursors of the important coffee volatiles mentioned above.4 – 8
A high content of CGA was the criterion for selection of the novel
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typical aromas of these novel raw materials, during the roasting
process they changed dramatically to develop a roasted-like aroma
together with the scent of coffee.
Since CGA is found in the form of various isomers, we may
refer to CGAs. CGAs are a family of esters formed between
quinic acid and certain trans-cinnamic acids, most commonly
caffeic, p-coumaric and ferulic acids. Using a more general
definition, all esters of quinic acids and their diastereomers can
be considered as CGAs.14 The following CGAs are most commonly
found in nature: 5-O-caffeoylquinic acid, conventionally called
chlorogenic acid (5-CQA), 4-O-caffeoylquinic acid, also referred to
as cryptochlorogenic acid (4-CQA), and 3-O-caffeoylquinic acid,
also called neochlorogenic acid (3-CQA).
Green coffee beans are a rich source of 5-CQA, which is
transformed during the roasting process. Many literature sources
indicate considerable losses of 5-CQA, which is degraded or
∗
Correspondence to: Renata Zawirska-Wojtasiak, Department of Food Science
and Nutrition, Poznań University of Life Sciences, PL-60-637, Poznań, Poland.
E-mail: renazaw@up.poznan.pl
a Department of Food Science and Nutrition, Poznań University of Life Sciences,
PL-60-637, Poznań, Poland
b Department of Food Concentrates and Starch Products, Institute of Agricultural
and Food Biotechnology, Poznań, Poland
c Department of Biotechnology and Food Microbiology, Poznań University of

raw materials used in this study, namely artichoke, hawthorn Life Sciences, Poznań, Poland

J Sci Food Agric 2014; 94: 2118–2123 www.soci.org

c 2013 Society of Chemical Industry
Chlorogenic acid in raw materials for chicory coffee
isomerized as a result of roasting.4,15 With very dark roasting,
these losses may be as high as 90%. Farah and Donangelo8
found that after a short roasting time (∼7% weight loss) the
level of 5-CQA decreased considerably while those of 4-CQA and
3-CQA increased twofold as a result of isomerization occurring
at the beginning of the roasting process. A longer roasting
time led to the complete loss of 5-CQA. Clifford16,17 stated
that during the early roasting stages the isomerization process
is accompanied by partial hydrolysis of quinic acid and cinnamic
acids (including caffeic acid). Released cinnamic acids may undergo
decarboxylation, degradation to simple phenolic acids and further
transformations. The remaining quinic acid is dehydrated and
a lactone ring is formed. Lactones are formed only with those
acids in which position 5 of quinic acid is free, i.e. 4-CQA and
3-CQA.8,17 Literature sources report that thermal degradation of
5-CQA causes the formation of phenolic derivatives, resulting in
marked differences between the aroma of natural coffee and those
of its substitutes.2,5,16 The major volatile phenolic compounds in
natural coffee are guaiacol, 4-ethylguaiacol and 4-vinylguaiacol,
while di- and triphenolic compounds primarily include catechol,
4-ethylcatechol and pirogalol. Model studies have shown that
guaiacol comes from the degradation of ferulic acid arising from
feruloylquinic acid (FQA). In turn, catechol and pirogalol come
from transformations of quinic acid and 5-CQA. Certain catechols
may also come from derivatives of caffeic acid.6
According to a recent study, 1,4-diketones such as 1,4-
cyclohexanedione are among the degradation products obtained
in model roasting of 5-CQA. However, their share in the aroma
of roasted coffee has not been explained. It was only stated that
5-CQA and its lactones are also responsible for the bitter and tart
taste of coffee.7
5-CQA is a secondary metabolite produced by plants in response
to environmental stress conditions such as infections caused by
pathogenic microorganisms, mechanical damage and excessive
UV radiation.5,8,18 – 20 In relation to its protective function in plants,
considerable amounts of 5-CQA are found during plant growth
and fruit ripening. This compound is contained in many fruits and
vegetables, e.g. potatoes, cacao beans, plums, apples, artichokes,
hawthorn fruits, blueberries and lovage.15,20,21 The main CGAs
found in artichoke (Cynara scolymus L.) include 5-CQA and 1,5-
O-dicaffeoylquinic acid (cynarine), with 5-CQA present at 0.2–2.1
g kg−1 dry matter (DM) depending on the plant genotype and
plant part analyzed.22 – 24 In hawthorn (Crataegus spp.) the 5-CQA
level ranges from 0.2 to 1.6 g kg−1 DM, with its content varying
depending on the species and variety.24,25
Traditional chicory coffee is produced primarily from roasted
chicory roots, a mixture of roasted cereal grains and sugar beet.
In order to improve or add variety to the aroma of chicory coffee,
small amounts of additives characterized by attractive aromas are
also used. This study evaluated five novel raw materials for the
production of chicory coffee, with a high content of 5-CQA being
the selection criterion.
EXPERIMENTAL
Samples
Traditional raw materials for the production of chicory coffee were
obtained from a production plant of CYKORIA SA (Wierzchosławice,
Poland). They included chicory (Cichorium intybus), rye (Secale L.),
barley (Hordeum L.) and sugar beet (Beta vulgaris L.) before and
after roasting. Novel raw materials, i.e. artichoke (C. scolymus L.),
hawthorn fruit (Rosaceae), lovage (Levisticum officinale), blueberry
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c 2013 Society of Chemical Industry
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(Vaccinium myrtillus L.) and chokeberry (Aronia melanocarpa), were
purchased from retail outlets. Artichokes were reprocessed to
isolate their hearts, which were dried then in a laboratory drier at
60 ◦ C. Novel raw materials were roasted. All raw materials before
and after roasting were ground using a WŻ 1 laboratory mill (ZBPP,
Bydgoszcz, Poland).
Roasting treatment
All raw materials were roasted in a BRZ 2/4/6 sample roaster
battery (PROBAT, Emmerich am Rhein, Germany). Raw materials
(100 g) were roasted under various conditions – 180 ◦ C/10 min for
chicory, 170 ◦ C/12 min for rye, barley and sugar beet, 160 ◦ C/8 min
for artichoke, hawthorn fruit, blueberry and chokeberry and 160
◦
C/18 min for lovage – to obtain dark roasts.
Samples of 2 g of standard 5-CQA were roasted in sealed 10 mL
vials at 160 ◦ C for 20 min.
Assay of chlorogenic acid
Extraction
CGAs contained in plant origin raw materials were extracted using
AOAC method 957.04.26 In order to ensure greater efficiency
and to adapt the method for assays of the tested materials, the
procedure was modified by increasing the amount of sample and
repeating the extraction four times. Samples of approximately 0.5
g of raw material were weighed into 10 mL test tubes. Then 3 mL of
deionized water was added and the test tube contents were mixed
thoroughly to prevent caking. Next, 7 mL of 960 mL L−1 99.9%
ethanol was added and the test tube contents were shaken. Finally,
the samples were centrifuged and the eluates were transferred to
50 mL volumetric flasks and supplemented with deionized water.
The whole procedure was repeated three times.
Analysis of CGAs by liquid chromatography/mass spectrometry
(LC/MS) and high-performance liquid chromatography (HPLC)
HPLC analysis was performed using an Agilent Technologies
(Wilmington, Del, USA) 1200 HPLC system equipped with a Supelco
(Bellefonte, PA., USA) C18 column (150 mm × 4.6 mm, 100 Å, 3
µm). Binary gradient elution was carried out using a solvent
system with phase A consisting of water/methanol (95:5 v/v)
containing 1 mL L−1 99.0% formic acid and phase B consisting of
methanol/water (60:40 v/v) containing 1 mL L−1 99.0% formic acid.
The gradient profile was as follows: 0–1 min, 0% B; 1–5 min, 0–25%
B; 5–9 min, 25% B; 9–15 min, 25–80% B; 15–16 min, 80–100% B;
16–30min, 100% B; 30–31 min, 100–0% B; 31–36 min, 0% B. The
flow rate was 0.4 mL min−1 , the column temperature was 30 ◦ C
and the injection volume was 10 µL. An Agilent 6224 time-of-flight
(TOF) LC/MS system with electrospray ionization (ESI) and a TOF
analyzer (in negative ion polarization mode for acid analyses and
in positive ion polarization mode for other phenolic compounds)
was used for ion monitoring within the range m/z 50–1700. The
voltage applied to the capillary column was 4 kV, the gas pressure
in the nebulizer was 20 psi and the fragmenter voltage was 214 V.
Assays of 5-CQA were performed in a Dionex Corporation
(Sunnyvale, CA, USA) LC system equipped with the same column
and using the same gradient parameters. The 5-CQA present in
each sample was identified by comparing its retention time and
spectrum with the standard using a photodiode array detector
(PAD). CGAs were quantified from absorbances recorded in the
chromatograms relative to external standards of 5-CQA, with
detection at 325 nm. A standardization curve was prepared
based on the following concentrations of 5-CQA standard (Sigma-
2119
Aldrich, Steinheim, Germany): 1, 5, 10, 20, 50 and 100 µg mL−1 .
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Table 1. Identification and proportions of individual isomers in total CGAs by LC/MS in raw materials before/after roasting (%/%)

Compound (abbreviation) RT (HPLC) m/z (MS/MS) C S A H L B Ch

3-O-Caffeoylquinic acid (3-CQA) 17.385 191.0875 –/– –/– –/10 42/– 2/7 –/– 46/15
179.0653
161.0534
135.0713
Glycoside of delphinidin 18.719 303.0525 –/– –/– –/– –/– –/– tr/– –/–
3-O-p-Coumaroylquinic acid (3-pCoQA) 191.0871
19.394 173.0757 –/– –/– –/– 17/– –/– –/– –/–
163.0691
5-O-Caffeoylquinic acid, chlorogenic acid (5-CQA) 191.0878
19.803 61/100 61/100 48/52 39/100 72/71 100/100 51/73
161.0536
4-O-Caffeoylquinic acid (4-CQA) 20.172 191.0872 –/– –/– –/tr 2/– tr/3 tr/tr 3/1
179.0649
163.0694
135.0707
Caffeoylshikimic acid (CSA) 21.375 179.0657 –/– –/– –/5 –/– –/19 –/– –/11
161.0538
135.0716
5-O-p-Coumaroylquinic acid (5-pCoQA) 21.361 191.0883 –/– –/– 2/8 –/– 1/– –/– –/–
3-O-Feruloylquinic acid (3-FQA) 22.084 193.1187 –/– –/– –/– –/– 10/– –/– –/–
191.0929
149.1011
3,5-Di-O-caffeoylquinic acid (3,5-diCQA) 22.487 353.1330 26/– 39/– 44/24 –/– 8/– –/– –/–
191.0897
135.0737
Derivative of p-coumaric acid 22.860 163.0705 –/– –/– –/– –/– –/– tr/tr –/–
4,5-Di-O-caffeoylquinic acid (4,5-diCQA) 23.065 353.1334 13/– –/– 6/1 –/– 5/– –/– –/–
179.0678
Caffeoylhexose 23.287 179.0659 –/– –/– –/– –/– tr/– –/– –/–
135.0722
Derivative of apigenin 24.324 269.0825 –/– –/– tr/– –/– –/– –/– –/–
Quercetin glycosides 23.407 303.0527 –/– –/– –/– –/– –/– tr/– –/–
Quercetin-3-rutinoside 23.410 463.1378 –/– –/– –/– tr/– –/– –/– –/–
300.0686

RT, retention time (min); C, chicory; S, sugar beet; A, artichoke; H, hawthorn; L, lovage; B, blueberry; Ch, chokeberry; –, not identified; tr, trace amount.

The coefficient of determination of the standardization curve RESULTS AND DISCUSSION

was 0.999. The detection limit was 0.03 µg mL−1 . The applied
method was characterized by a high recovery rate of 101.4%. The
proportions of individual CGA isomers assayed in the raw materials
were determined as a percentage of total CGAs.
Analysis of volatile compounds
Volatile compounds were identified using an Agilent 5975C VL
GC/MSD system equipped with an HP-5MS capillary column
(30 m × 0.25 mm, 0.25 µm). Extraction was performed by the
solid phase microextraction (SPME) technique using a divinylben-
zene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fibre at 70
◦
C for 20 min. The carrier gas used was helium at a flow rate 1 mL
min−1 . The temperature programme was as follows: hold for 5 min
at 35 ◦ C; increase at 30 ◦ C min−1 to 60◦ C; increase at 6 ◦ C min−1
to 200 ◦ C; increase at 30 ◦ C min−1 to 280 ◦ C. Mass spectra were
compared with data from the NIST05 library (containing 163 198
unique compounds).
Statistical analysis
All data were expressed as mean ± standard deviation (n = 3).
Statistical analyses were conducted using Student’s t test. Values
with P < 0.05 were considered statistically significant. STATISTICA
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CGAs were identified by HPLC/LC/MS. Identified compounds are
listed in Table 1 along with their proportions before and after
roasting. Based on collected data, 5-CQA was found in chicory and
sugar beet but was not detected in the other two traditional raw
materials, i.e. rye and barley. However, it was found in all novel raw
materials selected to improve the aroma of chicory coffee.
In this study the presence of several other compounds from
the CGA family was also detected. These included 3-CQA, 4-CQA,
3-O-feruloylquinic acid (3-FQA), 3,5-di-O-caffeoylquinic acid (3,5-
diCQA) and 4,5-di-O-caffeoylquinic acid (4,5-diCQA), as similarly
found by Farah et al.27 in natural coffee. However, 4-FQA, 5-FQA
and 3,4-diCQA were not detected in any tested raw material,
in contrast to the results presented by Farah et al.27 Other
CGAs were detected in artichoke and lovage before roasting,
i.e. 5-O-p-coumaroylquinic acid (5-pCoQA), and in hawthorn
before roasting, i.e. 3-O-p-coumaroylquinic acid (3-pCoQA). Apart
from the above-mentioned compounds, the following were also
detected: caffeoylshikimic acid (CSA), a derivative of p-coumaric
acid, caffeoylhexose, a glycoside of delphinidin, quercetin-3-
rutinoside, quercetin glycosides and a derivative of apigenin.
Another interesting finding is the disappearance of some of

9.0 software (StatSoft, Krakow, Poland) was used for all analyses. the above-mentioned compounds after the roasting process; for

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Table 2. 5-CQA content in traditional raw materials for chicory coffee Table 4. Content of isomers other than 5-CQA in traditional and
production estimated by HPLC novel raw materials for chicory coffee production estimated by HPLC
(mg g−1 )
Before roasting Roasted
Isomer Before roasting Roasted
% of total % of total
Raw material mg g−1 CGAs mg g−1 CGAs Chicory
3,5-diCQA 0.53 ± 0.08 ND
Chicory 1.23 ± 0.03a 61.4 0.43 ± 0.02b 99.9
4,5-diCQA 0.27 ± 0.04 ND
Sugar beet 0.03 ± 0.01a 61.0 0.02 ± 0.01b 99.0
Sugar beet
Rye ND ND ND ND
3,5-diCQA 0.02 ± 0.04 ND
Barley ND ND ND ND
Artichoke
Results are mean ± standard deviation (n = 3). Values with the same 3-CQA ND 0.05 ± 0.01
letter in a row are not statistically different at P < 0.05 (Student’s t 4-CQA ND tr
test). ND, not determined. CSA ND 0.02 ± 0.01
5-pCoQA 0.13 ± 0.02a 0.04 ± 0.01b
3,5-diCQA 2.66 ± 0.12a 0.13 ± 0.03b
4,5-diCQA 0.37 ± 0.08a 0.01 ± 0.01b
Table 3. 5-CQA content in novel raw materials for chicory coffee
production estimated by HPLC Derivative of apigenin tr ND
Hawthorn
Before roasting Roasted 3-CQA 1.07 ± 0.07 ND
% of total % of total 3-pCoQA 0.09 ± 0.02 ND
Raw material mg g−1 CGAs mg g−1 CGAs 4-CQA 0.01 ± 0.01 ND
Quercetin-3-rutinoside tr ND
Artichoke 2.90 ± 0.02a 47.8 0.27 ± 0.01b 51.7 Lovage
Hawthorn 0.19 ± 0.01a 39.4 0.04 ± 0.01b 100.0 3-CQA 0.10 ± 0.01a 0.03 ± 0.01b
Lovage 3.25 ± 0.20a 72.5 0.30 ± 0.05b 70.8 4-CQA tr 0.01 ± 0.01
Blueberry 1.07 ± 0.07a 100.0 0.53 ± 0.02b 100.0 CSA ND 0.10 ± 0.01
Chokeberry 3.97 ± 0.03a 51.2 2.11 ± 0.11b 73.5 5-pCoQA 0.04 ± 0.01 ND
3-FQA 0.46 ± 0.02 ND
Results are mean ± standard deviation (n = 3). Values with the same
letter in a row are not statistically different at P < 0.05 (Student’s t test). 3,5-diCQA 0.38 ± 0.01 ND
4,5-diCQA 0.27 ± 0.02 ND
Caffeoylhexose tr ND
Blueberry
example, 3-CQA and 3-pCoQA normally found in hawthorn and
4-CQA tr tr
5-pCoQA normally found in artichoke were not detected in those
Quercetin-3-rutinoside tr ND
raw materials after roasting. Thus it may be assumed that, as a
Chokeberry
result of roasting, other acids belonging to the CGA family are also
3-CQA 3.66 ± 0.24a 0.44 ± 0.08b
degraded in hawthorn and artichoke.
4-CQA 0.20 ± 0.02a 0.03 ± 0.01b
In turn, after roasting, some CGAs appeared that had not been
CSA ND 0.32 ± 0.02
found in the raw materials before roasting; for example, 4-CQA
detected in artichoke after roasting was not identified in that plant Results are mean ± standard deviation (n = 3). Values in a row with
prior to roasting. This is an example of isomerization.8,17 In roasted the same letter are not statistically different at P < 0.05 (Student’s t
test). ND, not determined; tr, trace.
artichoke, lovage and chokeberry, CSA was also identified, which
is a product of 5-CQA dehydratation.17,27
Some authors reported the total content of compounds
belonging to the CGA family.16 This study focused on the content ranged from 0.19 mg g−1 in hawthorn to 3.97 mg g−1 in
determination of 5-CQA content. In the tested raw materials chokeberry. These results are comparable to those reported in the
before roasting, this compound was found in highest amounts, literature.22 – 25,30 Differences may be due to different cultivation
its proportion being 48–100% of total CGAs. After roasting, the conditions for the raw materials tested by other authors. Available
proportion of 5-CQA in the raw materials amounted to 52–100% literature sources did not present contents of 5-CQA in these raw
of total CGAs. Hawthorn was an exception in this respect, as the materials after roasting. Farah et al.27 and Ferruzzi15 stated that
proportion of 5-CQA before roasting was only 39% of total CGAs. the 5-CQA content in coffee decreased as a result of roasting
Among the traditional raw materials used for the production of and that an extended time and increased temperature of roasting
chicory coffee, a significant amount of 5-CQA was contained only caused a greater reduction in its content, amounting to as much
in chicory, namely 1.23 ± 0.03 g kg−1 (Table 2). In sugar beet, only as 85–90% in dark-roasted beans. A longer roasting time resulted
0.03 g kg−1 5-CQA was detected, while no 5-CQA was detected in the loss of the entire 5-CQA content. In this study, 5-CQA
in the other two traditional raw materials, i.e. rye and barley. losses after roasting reached 55–91%, which suggests that this
Literature sources also did not indicate the presence of CGAs in compound was transformed and the process of its degradation
cereals. The main phenolic acids found in barley and rye included was progressing. The greatest losses were recorded in artichoke
ferulic, sinapic, coumaric and caffeic acids.28,29 and lovage, exceeding 90% of initial contents, similarly as in dark-
Contents of 5-CQA in the novel raw materials before and roasted coffee beans. A high loss was also found in hawthorn
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after roasting are presented in Table 3. Prior to roasting, its (79%). Contents of 5-CQA in roasted blueberry and chokeberry

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Table 5. Identification and composition of chemicals formed from pure chlorogenic acid (5-CQA) and present in roasted raw materials (% of total
volatiles)

Compound Odour description RI Coffee 5-CQA C A H L B Ch

Acetic acid Pungent 667 + 22.7 2.0 6.6 10.7 — 0.6 5.2
Hexanal Fresh, green 817 + 0.9 — 0.4 0.2 — 0.5 —
Furfural Freshly baked bread 855 + 8.4 25.0 10.7 1.7 8.9 47.5 7.0
Oxime-methoxy-phenyl 915 0.9 — 0.6 — — — —
5-Methylfurfural Almond, carmel 965 + 2.7 9.4 9.1 2.5 1.4 2.3 1.3
Phenol Sweet, tarry 982 + 16.0 — 2.3 — — — —
Hexanoic acid Sweat-like 991 + 1.3 0.3 — — — 0.2 —
3-Furylmethyl acetate 998 3.6 — 1.0 — — — —
1-Hexanol-2-ethyl 1029 1.8 0.2 — — 0.8 — 0.5
2-Methoxy-6-methyl-pyrazine Roasted nut 1086 7.3 0.8 1.0 — 1.4 — —
2-Ethylhexanoic acid 1142 2.7 — — — — — —
2,3-Dihydroxybenzaldehyde 1209 0.7 — 0.4 — — — 0.2
5-Hydroxymethyl-2-furancarboxaldehyde Cotton candy 1225 + 6.9 20.2 2.5 — 1.8 — 1.0
2-Ethylfuran 1242 1.1 — 0.4 — — — —
4-Methoxyphenol Smoky, burnt 1255 + 8.4 0.2 1.3 — 1.3 — —
2-Methoxy-4-vinylphenol (vinylguaiacol) Spicy, smoky, clove 1264 + 7.1 — 2.8 1.4 1.6 — —
4-Ethylphenol Phenolic, spicy 1356 1.3 — 0.5 1.1 0.5 — —
4-Ethylcatechol Phenolic, spicy 1454 + 6.2 — 1.1 — — — —

RI, retention index; C, chicory; A, artichoke; H, hawthorn; L, lovage; B, blueberry; Ch, chokeberry; +, compounds identified in coffee from literature.31 – 33

amounted to 50% of initial levels. In roasted chicory the content
of 5-CQA decreased by 65%, which is comparable to that in
medium-roasted coffee beans. Observations for sugar beet cannot
be compared owing to the low level of 5-CQA, which prevented
sufficiently precise determinations. The roasting process resulted
also in losses of other compounds from the CGA family in the
raw materials before and after roasting, causing changes in their
percentage contents (Table 1). These changes result from the
depletion of compounds contained in low amounts and the
potential formation of the above-mentioned isomers. In some
cases, only 5-CQA remained (in hawthorn, chicory and sugar
beet). The contents of isomers other than 5-CGA identified in the
traditional and novel materials are presented in Table 4. Significant
amounts (>1 mg g−1 ) of other isomers were found for 3,5-diCQA
in artichoke, 3-CQA in hawthorn and 3-CQA in chokeberry, but
only before roasting. In the roasted materials the amounts of
these compounds were very low or even undetectable. The
differences seen in this work may depend only on the character and
composition of the raw materials. This is because the conditions
of roasting, which undoubtedly influence the reactions, were the
same for all materials used. According to the data obtained, the
content of CGAs in the individual raw materials was different. The
amount of 5-CQA remaining after roasting depended mostly on its
concentration in the material before the process. In the novel raw
materials the presence of higher numbers of isomers other than
5-CQA in comparison with traditional chicory might be the reason
for the distinction in composition after processing.
It results from literature data on natural coffee that phenolic
volatile compounds may be formed from 5-CQA.2,4 For this reason
the present study included experimental degradation of the pure
5-CQA standard under similar conditions to those applied in
roasting the novel raw materials. Volatile compounds formed as a
result of this process were identified and are listed in Table 5. Their
amounts are expressed as a percentage of total volatiles identified
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compounds derived from CGAs ranged from 15.2% (chokeberry)
to 58.1% (chicory) of total volatiles.
They include heterocyclic compounds, acids and phenols
(oxime-methoxy-phenyl, phenol, 2,3-dihydroxybenzaldehyde, 4-
methoxyphenol, 2-methoxy-4-vinylphenol, 4-ethylphenol, 4-
ethylcatechol). The data in Table 5 also show that some of
them are present in the novel raw materials used in this study.
It is noteworthy that they were identified by other authors7
as products of thermal degradation of CGAs as well as in the
aroma of natural coffee.9 – 13 Some of them are recognized as
important odorants in coffee aroma, such as 4-methoxyphenol
and 2-methoxy-4-vinylphenol originating from 5-CQA. The latter
compound was present in roasted artichoke, hawthorn and lovage
but not in chicory (Table 5). Odours of the identified chemicals
formed from CGAs are described as caramel-like, burnt, smoky and
spicy. Taking into account the amounts and composition of the
compounds originating from 5-CQA, the most interesting new raw
material seems to be artichoke.
The results of this study confirm the opinion of other authors
that the formation pathways of the compounds discussed above
start with CGAs.7
CONCLUSIONS
1. In the traditional and proposed novel raw materials for
the production of chicory coffee, apart from 5-CQA, other
compounds from the CGA family were also identified, e.g. 3-
CQA, 4-CQA, 3,5-diCQA, 4,5-diCQA and 3-pCoQA. The highest
numbers of these compounds were recorded in chicory,
artichoke, lovage and hawthorn.
2. Among the traditional raw materials, chicory was the only
significant source of 5-CQA. The novel raw materials proved

with spectral similarity over 80%. The amounts of presented to be good sources of 5-CQA, and even such materials as

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c 2013 Society of Chemical Industry J Sci Food Agric 2014; 94: 2118–2123
Chlorogenic acid in raw materials for chicory coffee
chokeberry, artichoke and lovage contained greater amounts
of this acid than chicory.
3. 5-CQA was the predominant acid, but its content was
considerably depleted as a result of roasting. Moreover, losses
of other CGAs caused by roasting were also observed.
4. In the proposed novel raw materials for the production of
chicory coffee the same compounds were detected after
roasting as those identified after experimental degradation
of pure 5-CQA.
5. The best of the raw materials analyzed for chicory coffee
production was artichoke, since it was a good source of CGAs
and produced the highest number of volatiles during roasting,
particularly those important in coffee aroma such as 2-methoxy-
4-vinylphenol.
ACKNOWLEDGEMENT
This study was financially supported by the National Centre of
Science, Poland (grant 2011/01/B/NZ9/01060).
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