Food Chemistry 152 (2014) 363–369

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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

A pilot study of NMR-based sensory prediction of roasted coffee bean

extracts
Feifei Wei a,b, Kazuo Furihata a, Takuya Miyakawa a, Masaru Tanokura a,⇑
a
Department of Applied Biological Chemistry, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
b
Japan Society for the Promotion of Science, 8 Ichiban-cho, Chiyoda-ku, Tokyo 102-8472, Japan

a r t i c l e i n f o a b s t r a c t

Article history: Nuclear magnetic resonance (NMR) spectroscopy can be considered a kind of ‘‘magnetic tongue’’ for the
Received 6 August 2013 characterisation and prediction of the tastes of foods, since it provides a wealth of information in a non-
Received in revised form 1 November 2013 destructive and nontargeted manner. In the present study, the chemical substances in roasted coffee bean
Accepted 28 November 2013
extracts that could distinguish and predict the different sensations of coffee taste were identified by the
Available online 4 December 2013
combination of NMR-based metabolomics and human sensory test and the application of the multivar-
iate projection method of orthogonal projection to latent structures (OPLS). In addition, the tastes of com-
Keywords:
mercial coffee beans were successfully predicted based on their NMR metabolite profiles using our OPLS
NMR
Sensory analysis
model, suggesting that NMR-based metabolomics accompanied with multiple statistical models is con-
Sensory prediction venient, fast and accurate for the sensory evaluation of coffee.
Multivariate analysis Ó 2013 Elsevier Ltd. All rights reserved.
OPLS
Roasted coffee beans

1. Introduction
The development of artificial tongues to mimic the chemical
sense of taste has received a great deal of attention (Savage,
2012). Such sensors could provide quality control in foods and
agriculture, in addition to aiding in the development of new fla-
vours and furthering our understanding of other aspects of human
biology. Nuclear magnetic resonance (NMR) spectroscopy, which
provides a wealth of information in a nondestructive and nontar-
geted manner, has been widely applied in food chemistry to obtain
metabolite profiles of various kinds of biofluids and foods, such as
milk (Hu, Furihata, Ito-Ishida, Kaminogawa, & Tanokura, 2004; Hu,
Furihata, Kato, & Tanokura, 2007), mango juice (Koda, Furihata,
Wei, Miyakawa, & Tanokura, 2012a) and rice wine (Koda, Furihata,
Wei, Miyakawa, & Tanokura, 2012b). Recently, NMR metabolomic
fingerprints have been successfully correlated with the sensory
features of sour cherry juice (Clausen, Pedersen, Bertram, & Kid-
mose, 2011) and tomatoes (Malmendal et al., 2011), suggesting
that NMR spectroscopy could be a very useful ‘‘magnetic tongue’’
for the characterisation and prediction of the taste of foods.
Coffee is one of the most important internationally traded prod-
ucts. The distinctive flavour of coffee is certainly the principal rea-
⇑ Corresponding author. Tel.: +81 3 5841 5165; fax: +81 3 5841 8023.
E-mail addresses: aweiffcn@mail.ecc.u-tokyo.ac.jp (F. Wei), afuriha@mail.ecc.
u-tokyo.ac.jp (K. Furihata), atmiya@mail.ecc.u-tokyo.ac.jp (T. Miyakawa), amtanok@
mail.ecc.u-tokyo.ac.jp (M. Tanokura).
son for its high acceptability and enjoyment throughout the world.
Although knowledge about the chemical composition of coffee
bean extracts has been advanced in the past few decades, much
about the flavour still remains unclear due to the lack of data about
the specifics of coffee sensations. At the present time, human
assessment is still the principal method for the sensory evaluation
of coffee (Nebesny & Budryn, 2006). However, paying sensory ana-
lysts to assess every variety and origin of coffee bean extracts is
prohibitively expensive and the result is unavoidably subjective.
Therefore, in the present study, the utility of NMR spectroscopy
as a potential tool to analyse the taste of coffee bean extracts
was investigated.
In our previous studies, the chemical composition of green cof-
fee bean extracts (Wei, Furihata, Hu, Miyakawa, & Tanokura, 2010),
roasted coffee bean extracts (Wei, Furihata, Hu, Miyakawa, &
Tanokura, 2011), and their changes during the roasting process
(Wei et al., 2012) and according to variety and origin (Wei et al.,
2012) have been thoroughly studied by NMR-based comprehen-
sive analysis. Here, we further sought to identify the chemical sub-
stances in roasted coffee bean extracts that could distinguish and
predict the differential sensations of coffee taste by the combina-
tion of NMR-based metabolomics and human sensory tests and
application of the multivariate projection method of orthogonal
projection to latent structures (OPLS).
When structured noise is present in a data set X (or Y), tradi-
tional projection techniques, such as partial least squares (PLS)
regression can produce systematic variation of X (or Y), having a

0308-8146/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.foodchem.2013.11.161
364 F. Wei et al. / Food Chemistry 152 (2014) 363–369
component uncorrelated to Y (or X). OPLS provides a way to re-
move systematic variation from an input data set X not correlated
to the response set Y; in other words, to remove variability in X
that is orthogonal to Y (Trygg & Wold, 2002). The purpose of the
present study was to develop a novel method to predict the tastes
of coffee using NMR-based metabolomics. To achieve this, an OPLS
model was established using the NMR spectroscopic analysis of
roasted coffee bean extracts and the sensory features evaluated
by the human sensory test as X and Y, respectively. Then, the cor-
related X–Y variations were analysed to investigate the relations
between chemical components and sensory descriptors. Finally,
the taste of four kinds of commercial roasted coffee beans was suc-
cessfully predicted based on their NMR metabolite profiles using
our OPLS model.
2. Materials and methods
2.1. Coffee beans
Green coffee beans of the arabica type from Brazil and Colombia
and of the robusta type from Indonesia were supplied by San-Ei
Gen F.F.I., Inc. (Osaka, Japan). The green coffee beans from Colom-
bia and Indonesia were roasted to light (L value 25.9 ± 0.4) and
dark (L value 18.2 ± 0.2) roasting levels with a Fuji Royal R-105
roaster (Fuji Kouki Co., Ltd., Osaka, Japan), while those from Brazil
were roasted to a medium roasting level (L value 22.9 ± 0.4) to use
as a standard sample in human sensory tests, and then all the
roasted coffee beans were milled with a Panasonic MK-61 M-G
miller (Osaka, Japan). Each L value was measured using the Hunter
colour system of ground coffee beans (particle size < 1000 lm)
with a ZE-6000 colour metre (Nippon Denshoku Industries Co.,
Ltd., Tokyo, Japan). All roasted coffee beans were sealed under a
vacuum and stored at 20 °C until use.
For the sensory prediction experiments, four kinds of commer-
cial coffee beans were purchased from a local supermarket in the
city of Tokyo (Japan). The packaging for each of these samples in-
cluded a description of the sensory features (see Table S1 in the
supplementary data), and the beans were stored at 20 °C until
analysis.
2.2. NMR spectroscopic analysis
For NMR spectroscopic observations, the crushed beans (1.5 g)
were incubated at 95 °C in a closed plastic tube with D2O
(3.50 ml, 99.7%; Shoko Co., Ltd., Tokyo, Japan) for 1 h. The extracts
were cooled on ice for 15 min and then centrifuged at 5000g at 4 °C
for 5 min. The supernatants (500 ll) were moved to new tubes, and
a trace amount of 4,4-dimethyl-4-silapentane-1-sulphonate (DSS;
Wako Pure Chemical Industries, Ltd., Osaka, Japan) was added as
an internal reference, with a chemical shift set to 0 ppm. The coffee
bean extracts were then transferred into 5 mm NMR tubes.
One-dimensional (1D) 1H NMR spectra were measured at
500 MHz on an Agilent (Varian) Unity INOVA-500 spectrometre
(Agilent Technologies, Inc., Santa Clara, CA). The H2O signal was
suppressed by the presaturation method, and the parameters for
observation were: number of data points, 64 k; spectral width,
8000 Hz; acquisition time, 4.0 s; delay time, 2.0 s; and number of
scans, 128.
The free-induction decay (FID) NMR data were processed by
MestReNova software (Version 8.0.1; MestReC, Santiago de Com-
postela, Spain). The signal assignments of the components in arab-
ica coffee bean extracts were carried out in our previous studies
based on the analysis of two-dimensional (2D) NMR spectra (Wei
et al., 2010; Wei et al., 2011). To obtain information about the com-
ponents of the roasted robusta coffee bean extracts, the signal
assignments were carried out by comparing the NMR spectra with
those of arabica coffee bean extracts.
2.3. Quantitative descriptive analysis (QDA)
For sensory evaluation, the roasted coffee beans were mechan-
ically brewed by an electric coffee maker (Model HCD-6GJ; Toshiba
Co., Tokyo, Japan). The ground coffee bean powder (24 g) was
placed in filter paper inside a funnel over a glass pot, and then
about 360 ml of coffee bean extract was brewed at 85 °C for about
7 min from 420 ml of ion-exchange water in a tank. The extract
was immediately cooled to 5–10 °C by a Graham condenser kept
at 5 °C (pre-cooled). Each coffee bean extract was transferred into
a 250 ml glass bottle (DURANÒ; SCHOTT, Mainz, Germany) which
was sealed with a lid. Each glass bottle was randomly numbered
except for the standard sample (Brazil, medium roasted, L value
22.9 ± 0.4).
The sensory evaluation was performed by 13 trained assessors
(3 females and 10 males; 27 40 years old) from San-Ei Gen F.F.I.,
Inc. (Osaka, Japan). At the time of the study, all the assessors had
been working in the field of flavour and beverage development
for at least 3 years, and they had all previously passed the requisite
tests on the identification and differentiation of the five basic
tastes. Before the evaluation sessions, the assessors selected 7
descriptors that aptly described the taste of coffee. Each descriptor
was characterised as a reference substance (see Table S2 in the
supplementary data).
In the evaluation sessions, the coffee bean extracts were ar-
ranged in random order at 10–15 °C in a water-bath without
reheating, in order to keep the sensory properties stable during
the course of the experiment. All evaluations were undertaken in
an odour-free test room under fluorescent light. The room temper-
ature and humidity were kept at 23–26 °C and 52–72% with air-
conditioners. The samples were approximately 10 ml in volume
and served in 50 ml plastic containers. Assessors tasted a standard
before tasting samples as necessary during the session. A cup of
water was prepared as a mouth rinse between each evaluation.
The attributes were marked on a 15 cm unstructured line scale an-
chored at 1.5 (weak), 13.5 (strong) and a centre point, respectively,
for each descriptive term. The sensory analysis was carried out
using QDA in triplicate (n = 3). This experiment was carried out
in accordance with The Code of Ethics of the World Medical Asso-
ciation (Declaration of Helsinki) for experiments involving
humans.
2.4. Multivariate analysis of 1H NMR
For multivariate analysis, all the 1H NMR spectral data (four
kinds of standard roasted coffee bean extracts, n = 6; four kinds
of commercial coffee bean extracts, n = 1) were referenced, phased,
baseline corrected, aligned and normalised by MestRe Nova, and
then the data between 0.40 and 10.00 ppm were reduced into
0.04 ppm spectral buckets (bins). The residual water signals
(H2O; bins 4.76–4.88 ppm) were removed. In order to avoid spuri-
ous principal components (PCs), areas of dramatically varying
caffeine signals (N1CH3, N3CH3, N7CH3, C8H; bins 3.04–3.40, 3.68–
3.84, 7.60–7.80 ppm) (D’Amelio, Fontanive, Uggeri, Suggi-Liverani,
& Navarini, 2009; Wei et al., 2010) were also removed, and the max
bin of signal C8H in the caffeine molecule (among bins 7.60–
7.80 ppm) was picked up, renamed ‘‘bin caffeine’’ and used in the
further multivariate data analysis.
The resulting data sets (standard roasted coffee bean extracts)
were then imported into SIMCA-P+ version 12.0 (Umetrics,
Umeå, Sweden) to perform Principal Component Analysis (PCA).
Prior to PCA, the data were mean-centred and then scaled using
the scaling type of Pareto. Hotelling’s T2 region, shown as an ellipse
 F. Wei et al. / Food Chemistry 152 (2014) 363–369
in the score plots, defined the 95% confidence interval of the mod-
elled variation, and the quality of the PCA model was described by
Rx2 (0.688) and Q2 (0.56) values. Rx2 was defined as the proportion
of variance in the data explained by the model and indicates good-
ness of fit. Q2 was defined as the proportion of variance in the data
predictable by the model and indicates predictability.
2.5. Multivariate analysis of QDA
QDA results were conducted with ANalysis Of VAriance (ANO-
VA) by using the JMP10 software package (SAS Institute, Inc., Cary,
NC) and were considered to be significantly different at p < 0.01.
Then, a Tukey’s test (p < 0.05) was used to find significant differ-
ences between different coffee samples in each taste quality. The
correlations among the obtained data were calculated using the
Pearson’s correlation coefficient and p values less than 0.05 were
considered to be statistically significant.
2.6. Prediction of sensory features
For the standard OPLS model, the combined data sets (1H NMR
data as variable X; corresponding QDA data as variable Y) of the
standard roasted coffee bean extracts were imported into SIMCA-
P+, mean-centred and then scaled using the scaling type of Pareto
for the variable X and Centred for the variable Y. The confidence le-
vel for membership probability was considered to be 95%, and the
quality of the model was described by R2X (0.687), R2Y (0.986) and
Q2 (0.97). Markers for the sensory descriptors were identified from
the NMR signals that showed a strong correlation (|p| P 0.05 and |p
(corr)| P 0.5 in S-plots, see Fig. S2 in the supplementary data) to
the OPLS predictive scores for the sensory descriptors.
For the predictive OPLS model, the NMR data of the commercial
coffee bean extracts were added into the standard OPLS model
leaving the corresponding Y sections blank. The Hotelling’s T2
was set to 95%, and the quality of the model was described by
R2X (0.909), R2Y (0.997) and Q2 (0.976).
3. Results and discussion
3.1. NMR analysis
The 1H NMR spectra of the standard roasted coffee bean ex-
tracts are shown in Fig. 1, and exhibit complicated signal patterns
because of overlaps and chemical-shift perturbations. As shown in
Fig. 1, for both roasted arabica and robusta coffee bean extracts, 26
components were identified: 3 isomers of chlorogenic acids (i.e.,
3-caffeoylquinic acid (3-CQA), 4-caffeoylquinic acid (4-CQA) and
5-caffeoylquinic acid (5-CQA)), quinic acid, c-quinide, syllo-quinic
acid, a-(1-3)-L-arabinofuranose, a-(1-5)-L-arabinofuranose, b-(1-
3)-D-galactopyranose, b-(1-6)-D-galactopyranose, b-(1-4)-D-man-
nopyranose, acetate, c-butyrolactone, caffeine, choline, citrate,
2-furylmethanol, formate, myo-inositol, lactate, lipids, malate,
N-methylpyridinium, nicotinic acid, 5-(hydroxymethyl)furfural
(5-HMF) and trigonelline. Because the caffeine molecules formed
complexes with chlorogenic acids, the chemical shifts of caffeine
varied dramatically in different sample matrices of roasted coffee
bean extracts (D’Amelio et al., 2009), which was considered to be
the reason for the failure in alignment. Since the unwelcome chem-
ical-shift perturbations give a more complex multivariate model
that includes spurious PCs and that may be misleading for the
identification of marker compounds, areas of varying caffeine sig-
nals were removed, leaving only the max bin of signal C8H to rep-
resent the distribution of caffeine in the roasted coffee bean
samples.
365
To determine which chemical substances were significantly
correlated with the variety and roasting level of the coffee beans
used for preparing extracts, PCA was applied to the 1H NMR spectra
of 24 independent data sets from roasted robusta and arabica cof-
fee bean extracts, at light or dark roasting levels (n = 6 each). As
shown in Fig. S2A in the supplementary data, the PCA models using
projections into two dimensions (PC1 of 0.378 and PC2 of 0.212)
showed statistically significant separation among the standard
roasted coffee bean extracts, indicating that the most significant
differences in composition are from varying roasting levels (PC1)
rather than species (PC2).
The PC1 loading plot indicates components responsible for vari-
ables contributing to the classification according to the roasting le-
vel. As shown in Fig. S2B, the negative side of the PC1 loading plot
reveals that the contents of chlorogenic acids, trigonelline, caffeine,
5-HMF, citrate, malate and acetate are higher in the roasted coffee
bean extracts at the light roasting level, while the positive side
indicates that the levels of quinic acids, quinide, N-methylpyridini-
um, mannose and lipids are higher at the dark roasting level.
The PC2 loading plot indicates components responsible for dis-
tinguishing the species of roasted coffee bean extracts but not the
roasting level. As shown in Fig. S2C, the contents of chlorogenic
acids, caffeine, lactate, quinide, quinic acids and lipids are higher
in the roasted robusta coffee bean extracts, whereas the levels of
polysaccharides, acetate, citrate, malate, formate, trigonelline,
N-methylpyridinium and 5-HMF are higher in the roasted arabica
coffee bean extracts. In our previous study, the green coffee bean
extracts of arabica was found to contain higher levels of sucrose,
trigonelline, citrate and malate (Wei et al., 2012). In the present
study, no sucrose was found but higher levels of acetate, formate
and 5-HMF were detected in the roasted arabica coffee bean ex-
tracts. These findings are in accordance with previous reports that
sucrose in green coffee beans is closely related with the formation
of aliphatic acids and 5-HMF in roasted coffee beans (Murkovic &
Bornik, 2007).
3.2. Quantitative descriptive analysis
The results of the QDA mean are shown in Fig. 2. The light
roasted arabica coffee bean extracts were characterised by sour-
ness; the dark roasted arabica and robusta coffee bean extracts
seemed to taste very similar to each other, as observed by QDA.
Consistent with the NMR results, the differences between species
of the roasted coffee bean extracts also tended not to be obvious
with the deepening of roasting. However, NMR showed higher sen-
sitivity in species discriminations even at dark roasting levels, as
shown in Fig. S2(A), while QDA provided very similar sensory char-
acteristics. Among the 7 taste descriptors evaluated in the human
sensory test, the ANOVA analysis indicated that umami is not sig-
nificantly related with the variety or the roasting level of the coffee
bean extracts. Therefore, we removed the taste of umami from our
further analysis.
To further investigate the significant differences in each taste
descriptor among the coffee bean extracts, the Tukey’s test was
carried out and the results are shown in Table S3 in the supple-
mentary data. There were significant differences between the light
roasted arabica coffee bean extracts and the other extracts with re-
spect to the taste of sweetness. Significant differences in coffee
body, sourness, and bitterness were observed between all coffee
bean extracts, except between the dark roasted robusta and arab-
ica coffee bean extracts. The taste of astringency was found to be
significantly varied according to the roasting level but not the vari-
eties of the coffee beans. The only significant difference in saltiness
was between the light roasted robusta and arabica coffee bean
extracts.
366 F. Wei et al. / Food Chemistry 152 (2014) 363–369

(A) quinic acids

quinic acids and polysaccharides and quinide

arabica
β-(1-6)-D-galactopyranose myo-inositol
N-methylpyridinium
caffeine β-(1-4)-D-mannopyranose lipids robusta
2-furylmethanol
γ-quinide
nicotinic acid

acetate
(B) choline
5-hydroxymethylfurfural
citrate and γ -butyrolactone
trigonelline formate β-(1-3)-D-galactopyranose malate
trigonelline α-(1-5)-L-arabinofuranose
α-(1-3)-L-arabinofuranose arabica
lactate
chlorogenic acids
robusta

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0
1
H (ppm)

Fig. 1. Assigned 1H NMR spectra of arabica (solid black line) and robusta (dashed grey line) roasted coffee beans at (A) dark roasting levels and (B) light roasting levels.

sweetness** and even sweetness; saltiness changed positively with sourness;

arabica (light)
10.0 and coffee body showed positive correlations with both sweetness
8.0 arabica (dark) and astringency.
umami 6.0 body** robusta (light)
4.0
robusta (dark) 3.3. Correlations between chemical components detected by NMR and
2.0
sensory descriptors
0.0

bitterness** astringency**
sourness** saltiness**
Fig. 2. Spider web plot of the sensory descriptors for the four tested coffee bean
samples. The symbol ‘‘⁄⁄’’ indicates a significant difference (p < 0.01) as calculated
by ANOVA.
To characterise the correlations between different sensory
descriptors, the Pearson’s correlation coefficients were calculated.
These are summarised in Table 1. Negative correlations of sourness
with bitterness, sweetness, astringency and body were observed;
bitterness showed positive correlations with body, astringency
To show the correlation between the chemical components and
the sensory descriptors of roasted coffee bean extracts, all possible
correlations between the NMR signals and the analysed sensory
descriptors were sought by OPLS models. Although the extraction
time for the NMR analysis was made much longer than that for
the human sensory test in order to obtain a high enough concen-
tration for NMR observation, the relationship between NMR-visible
components and sensory features was still credible, since the same
extraction time was used for all kinds of coffee bean samples in the
same analytical platform, NMR or QDA. In fact, only the relative
variations among differential coffee bean extracts can be under
consideration by the OPLS model, while the variations between
the NMR and QDA samples were removed as so-called structured
noise (Trygg & Wold, 2002).
The score plot of the standard OPLS model is shown in Fig. 3(A).
Similar to the PCA results derived from NMR only, the four kinds of

Table 1
Pearson’s correlation coefficients between sensory descriptors.

Sweetness Body Astringency Saltiness Sourness Bitterness Umami

Sweetness 0.39a 0.04 0.13 0.43a 0.33a 0.09
Body 0.39a 0.46a 0.04 0.60a 0.67a 0.02
a
Astringency 0.04 0.46 0.11 0.30a 0.56a 0
Saltiness 0.13 0.04 0.11 0.32a 0.08 0.02
Sourness 0.43a 0.60a 0.30a 0.32a 0.68a 0.08
Bitterness 0.33a 0.67a 0.56a 0.08 0.68a 0.07
Umami 0.09 0.02 0 0.02 0.08 0.07
a
p < 0.05 in Pearson’s correlation comparison.
 F. Wei et al. / Food Chemistry 152 (2014) 363–369 367

(A) arabica (light) On the other hand, the levels of the water-soluble degradation
arabica (dark) products of chlorogenic acids during the coffee bean roasting pro-
30 robusta (light) gress, such as quinic acid, syllo-quinic acid and quinide, increased
robusta (dark)
20 along with the bitter taste of coffee. Our present study suggests
that those degradation products of chlorogenic acids that have a
10
strong bitter taste (Blumberg, Frank, & Hofmann, 2010), rather
OPLS2

0 than the chlorogenic acid itself, are more likely to directly contrib-
ute to the bitterness of roasted coffee. It has been reported that
-10
trigonelline is not a dominant contributor to roasted coffee bitter-
-20 ness (Belitz, 1975), and alkylpyridiniums may indeed be responsi-
-30
ble for a portion of the perceived bitterness in the coffee brew
(Stadler, Varga, Hau, Vera, & Welti, 2002).
-40 We found that the coffee body positively correlated with the
-50 -40 -30 -20 -10 0 10 20 30 40
content of polar lipids, mannose, quinide and quinic acids, but neg-
OPLS1
atively correlated with that of arabinose, galactose and trigonel-
line. The polar lipids are important surface-active agents, which
(B) sourness
help to form and stabilise foam and emulsion and have previously
0.08 been related with the formation of coffee body (Buffo & Cardelli-
Freire, 2004). Polysaccharides are known to be responsible for
0.06
the increase of coffee viscosity (Navarini et al., 1999). We have pre-
0.04 saltiness viously reported that the concentration of water-soluble mannose
OPLS2

astringency
0.02
body
0
sweetness
-0.02
-0.04
-0.15 -0.1 -0.05 0 0.05
OPLS1
Fig. 3. OPLS (A) score plot of X–Y and (B) the scatter plot of Y derived from the 1H
NMR spectra (X) and QDA (Y) of the roasted coffee bean samples.
roasted coffee bean extracts were significantly different from each
other even if their sensory characteristics were taken into account.
According to the scatter plot of sensory descriptors (see Fig. 3(B)),
the transition from the upper-left corner to the bottom-right cor-
ner of the map shows the simultaneous decrease of the sourness
and saltiness and increase of the bitterness, body, sweetness and
astringency. In general, light roasted arabica coffee bean extracts
are characterised by sourness as well as saltiness; dark roasted
arabica coffee bean extracts are instead characterised by a more
marked astringency and bitterness. On the other hand, the dark
roasted robusta beans are characterised by bitterness, body and
sweetness. However, none of the descriptors was found to be the
marked sensory characteristic of light roasted robusta beans by
the present model, indicating the relatively plain or mild features
of light roasted robusta beans compared to the samples.
To characterise the correlations between NMR signals and the
analysed sensory descriptors, the correlation coefficients were cal-
culated by S-plots for each sensory descriptor. In the S-plot of a gi-
ven sensory descriptor, which is available in the supplementary
data (Fig. S2), variables fulfilling the covariance of |p| P 0.05 and
the correlation of |p (corr)| P 0.5 were selected and considered
as having a relationship with the given descriptor. According to
our previous signal assignment (Wei et al., 2011), the captured
components and their correlations with each descriptor were sum-
marised as shown in Table 2.
It has been described that chlorogenic acids have a mild bitter
taste and might contribute to the bitterness of coffee drinks (Cam-
pa, Doulbeau, Dussert, Hamon, & Noirot, 2005). However, whether
chlorogenic acid is actually bitter in taste remains a matter of con-
troversy. Here, we observed a negative correlation between chlor-
ogenic acid and the bitterness of coffee; that the content of
chlorogenic acids was reduced along with the bitter taste of coffee.
is constantly increased during the roasting progress due to its low-
bitterness
er thermal lability (Wei et al., 2012). Therefore, it is reasonable to
suppose that mannose might be the major contributor to coffee
body.
In contrast to bitterness and body, the sour taste of coffee was
negatively correlated with the content of lipids, quinide and quinic
acids, and positively correlated with that of chlorogenic acids, cit-
0.1
rate, malate, formate, acetate, trigonelline, arabinose and galactose.
Malic, citric, phosphoric and acetic acids have been identified as
the major contributors to coffee sourness (Degenhardt, C., S., & F.,
2006). Consistent with these previous reports, we observed a high-
er level of organic acids, such as citrate, malate, formate and ace-
tate, in roasted coffee bean extracts with a significant sour taste.
In particular, the increased concentration of aliphatic acids in the
arabica coffee bean extracts at a light roasting level might have
been derived from the degradation of sucrose, which is present
at a higher level in the green coffee bean extracts of arabica (Gin,
Balzer, Bradbury, & Maier, 2000; Wei et al., 2012).
Coffee sweetness is found to be positively related to lipids, qui-
nic acids, mannose, and quinide, and negatively related to chloro-
genic acids, citrate, formate, malate, trigonelline, arabinose and
galactose. Interestingly, almost all of the components positively re-
lated with the sweet taste of coffee are not sweet themselves. Con-
versely, quinic acids and quinide are even slightly bitter. Coffee
sweetness is increased along with coffee bitterness. These results
appear to be in conflict with the previous reports that an increase
in saccharide, which enhances the sweet taste, will inhibit the bit-
ter taste (Malmendal et al., 2011). In fact, the relationship between
sweetness and other tastes such as bitterness is variably affected at
low intensities/concentrations (i.e., their tastes strengthen each
other or weaken each other) and might be symmetrically suppres-
sive only at medium and high concentrations (Keast & Breslin,
2003). On the other hand, the components negatively related with
coffee sweetness, such as citrate and malate, have a very strong
sour taste. It has been reported that the relationship between
sweetness and sourness is variably affected at low intensities/con-
centrations but symmetrically suppressive at medium and high
intensities/concentrations. This might partially explain the trends
between sweetness and bitterness and the mutually suppressive
relationship between sweetness and sourness observed in our
present study.
Similar to bitterness, coffee astringency was positively related
with lipids, quinic acids, mannose, and quinide and negatively re-
lated with chlorogenic acids, citrate, malate, trigonelline, arabinose
and galactose. Consistent with previous reports on cranberry juice
368 F. Wei et al. / Food Chemistry 152 (2014) 363–369

Table 2
Correlation between coffee bean components and sensory descriptors highlighted by OPLS Models.a

Compound name Bin No. (ppm) or Sweetness Bitterness Sourness Astringency Saltness Body
bin name
p p (corr) p p (corr) p p (corr) p p (corr) p p (corr) p p (corr)
3-CQA 5.36 0.13 0.87 0.11 0.88 0.13 0.89 0.09 0.75 0.07 0.53
4-CQA 7.40 0.14 0.88 0.12 0.70 0.14 0.91 0.11 0.78 0.06 0.59
5-CQA 5.32 0.18 0.87 0.13 0.90 0.11 0.56 0.10 0.58 0.14 0.58
Acetate 1.96 0.07 0.50 0.19 0.56
Caffeine Caffeine 0.18 0.85
Citrate 2.76 0.07 0.56 0.05 0.64 0.07 0.59 0.06 0.71 0.05 0.63
Formate 8.44 0.09 0.57 0.09 0.58 0.10 0.51
Lactate 1.36 0.09 0.54
Lipids 0.92 0.08 0.57 0.09 0.74 0.08 0.60 0.09 0.74 0.09 0.73
Malate 2.60 0.11 0.70 0.08 0.74 0.11 0.75 0.08 0.73 0.13 0.87
N-methylpyridinium 8.72 0.05 0.60
Quinic acid 2.00 0.12 0.65 0.12 0.79 0.12 0.69 0.12 0.75 0.12 0.78
Syllo-quinic acid 2.08 0.13 0.66 0.16 0.94 0.13 0.67 0.17 0.98 0.16 0.93
Trigonelline 4.40 0.13 0.76 0.12 0.78 0.14 0.82 0.10 0.66 0.12 0.77
a-(1-3)-L-arabinofuranose 5.20 0.06 0.65 0.06 0.70 0.06 0.53
a-(1-5)-L-arabinofuranose 5.08 0.07 0.63 0.08 0.90 0.05 0.61 0.09 0.92 0.06 0.61 0.08 0.87
b-(1-3)-D-galactopyranose 4.64 0.14 0.85 0.13 0.87 0.08 0.70 0.10 0.79 0.10 0.72 0.10 0.54
b-(1-4)-D-mannopyranose 4.72 0.09 0.58 0.14 0.82 0.17 0.94 0.09 0.56
b-(1-6)-D-galactopyranose 4.44 0.16 0.50 0.10 0.52 0.16 0.54 0.11 0.75 0.10 0.50 0.13 0.86
c-Quinide 2.52 0.10 0.56 0.13 0.83 0.10 0.56 0.13 0.89 0.13 0.83
a
Only one bin of each compound were picked up, values of |p| < 0.05 and |p (corr)| < 0.5 in S-plots were excluded or shown as blank.

(Peleg & Noble, 1999), quinic acids contribute to both bitterness

and astringency. According to a previous study, astringency might sourness
rness
be strongly related with the pH of coffee (Rubico & Mcdaniel,
1992). It has been reported that the acidic component decreases 30
Mokha-blended
bitter
bitterness
Mild-blended
and the pH increases along with the change from light to dark sourness
Kilimanjaro-blended
20
roasting levels (Fuse, Kusu, & Takamura, 1997). Therefore, it is rea- saltiness Dark roast-blended
sonable that the astringency of coffee is increased during the roast- 10 astringency
OPLS2

ing progress. 0
Similar to coffee sourness, the salty taste of coffee was posi- body bitterness
-10 sweetness
tively related with most of the acids as well as with all of the poly-
saccharides except mannose, and negatively related with -20 light roasted arabica
chlorogenic acids and caffeine. Although the well-known salty sub- dark roasted arabica
-30
stances such as sodium ions and potassium ions cannot be directly light roasted robusta
dark roasted robusta
detected by NMR spectroscopy, it has been proved that green cof- -40
-50 -40 -30 -20 -10 0 10 20 30 40
fee beans are rich in a variety of metal ions, such as Na+ and K+ OPLS1
(Anderson & Smith, 2002). In fact, there is a strong correlation be-
Fig. 4. Score and scatter plots of the predictive OPLS model including the four
tween sourness and saltiness at even low concentrations/intensity
commercial roasted coffee bean samples.
of such metal ions (Keast & Breslin, 2003). Furthermore, in accor-
dance with our findings, the taste of coffee brewed with metal
ion-rich mineral water is more acidic than that brewed with dist-
data), suggesting NMR-based metabolomics combined with multi-
iled water (Pangborn, Trabue, & Little, 1971).
variate statistical analysis could be used in sensory prediction for
roasted coffee bean products.
3.4. NMR-based sensory predictions The major advantage of the NMR-based sensory prediction with
multiple statistical methods (such as the OPLS model), known as
The predictive OPLS model was established using the NMR the ‘‘magnetic tongue’’, is that it can provide a faster, cheaper,
spectra of standard roasted coffee bean extracts and their corre- and more accurate and objective way to predict the taste of food
sponding sensory features evaluated by human sensory test, as than the human tongue itself. This advance in technology will shed
well as the NMR spectra of four kinds of commercial coffee bean increased light on the field of quality control in foods and agricul-
extracts without the QDA value. As shown in Fig. 4, all four kinds ture. However, it also should be noted that one of the potential lim-
of commercial coffee bean extracts, namely Mokha taste, Mild itations of the ‘‘magnetic tongue’’ is that it cannot determine the
taste, Kilimanjaro taste and Dark roast taste, are located in the exact taste of a certain chemical component the way a human ton-
PC1 and PC2 positive area, indicating their chemical makeup and gue can. It can predict the sensory characteristics of food only by
sensory features are similar to those of dark roasted arabica coffee catching the relative change in the concentrations of the chemical
bean extracts. According to the loading plots of sourness and bit- components. This means that the chemical component with no
terness and the localisation of the commercial coffee bean extracts change in its concentration will be ignored by the OPLS model even
in the score plot, Mokha taste has the highest level of sourness fol- if it may make a considerable contribution to the sensory charac-
lowed by Mild taste, Kilimanjaro taste and Dark roast taste. Mean- teristics of the food. At the same time, all the chemical components
while, Dark roast taste has the highest level of bitterness followed sharing the same trends of change in their concentrations may be
by Kilimanjaro taste, Mild taste and Mokha taste. These predictive captured as markers by the OPLS model for the given sensory
results are exactly in agreement with the marked sensory features descriptor, e.g., bitterness, irrespective of whether they actually
of the commercial coffee beans (see Table S2 in the supplementary taste bitter.
 F. Wei et al. / Food Chemistry 152 (2014) 363–369
In summary, the OPLS model was established to clarify the cor-
relation between the composition and sensory features of coffee
bean extracts, by combining the NMR metabolic profiling and the
QDA evaluated by human sensory test. The biomarker analysis
using the OPLS model increased our understanding about the rela-
tionship between the chemical components in roasted coffee bean
extracts and their tastes. Furthermore, we successfully predicted
the tastes of four kinds of commercial coffee bean extracts based
on their NMR metabolite profiles using the predictive OPLS model,
suggesting it is convenient, fast and accurate for the sensory eval-
uation of coffee.
Acknowledgments
We thank Yuriko Imayoshi and Yasunori Sugawara of San-Ei
Gen F.F.I., Inc. for providing the coffee beans and performing sen-
sory assessment in this study. This work was supported by the Ja-
pan Society for the Promotion of Science (JSPS) Postdoctoral
Fellowship for Foreign Researchers.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.foodchem.2013.
11.161.
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