1 s2.0 S006641031930016X Main

CHAPTER FIVE
Magnetic resonance applications

in food analysis
Fenfen Tanga,†, Morgan Vasasa,†, Emmanuel Hatzakisa,*,
Apostolos Spyrosb,*
a
Department of Food Science and Technology, The Ohio State University, Columbus, OH, United States
b
NMR Laboratory, Department of Chemistry, University of Crete, Voutes campus, Heraklion Crete, Greece
*Corresponding authors: e-mail address: chatzakis.1@osu.edu; aspyros@uoc.gr
Contents
1. Introduction 240
2. High resolution liquid NMR spectroscopy 242
2.1 Compositional analysis and structure elucidation 242
2.2 Food authentication 255
2.3 Quality control and sensory analysis 263
3. Solid state and HR-MAS 270
3.1 Solid state NMR 270
3.2 HR-MAS NMR 273
4. Low field and MRI 278
4.1 Time-domain NMR 278
4.2 Frequency-domain NMR 281
4.3 Magnetic resonance imaging 282
References 284
Abstract
NMR is an emerging technology in the field of food analysis. Its combination with
multivariate statistics and the application of multinuclear and multidimensional exper-
iments has already established NMR as an important analytical tool for fingerprinting,
quantification and compound identification in foods, and further increases its potential
for becoming one of the main analytical approaches in this scientific area. The present
article provides a solid overview of modern NMR applications in food analysis. Studies
from the three main categories of studies, namely high resolution liquid state NMR
spectroscopy, solid state CP-MAS/HR-MAS and low resolution (low field and MRI) are
presented, and although covering heavily work after 2015, earlier key publications
within the last 7–8 years are also mentioned. Basic concepts of NMR related to specific
food analysis methodologies are briefly discussed when required. Finally, we tried to
provide a more detailed discussion on field areas that NMR may be considered as an
†
These authors contributed equally to this work.
Annual Reports on NMR Spectroscopy, Volume 98 # 2019 Elsevier Ltd 239

ISSN 0066-4103 All rights reserved.
https://doi.org/10.1016/bs.arnmr.2019.04.005
240 Fenfen Tang et al.
Our goal is to provide the reader with the current knowledge about the most important
aspects of NMR applications in various and diverse areas of food analysis.
Keywords: NMR spectroscopy, Food, Metabolomics, Composition, Relaxation, MRI, Low
field, Magnetic resonance, Sensory, Processing
1. Introduction
Food analysis is a diverse and interdisciplinary field of research that has
a significant health, societal and economic impact. It aims to characterize
food products in terms of chemical composition, traceability, safety, quality,
sensory perception and nutritional value. Food analysis approaches are used
by industry, government/control agencies and academia. The molecular
composition of a food product is generally very complex and depends on
several factors, including genetic and geographical origin, environmental/
climatological conditions, the type of farming, breeding and processing
practices and addition of adulterants or presence of contaminants. As a result,
the global chemical composition profiling and/or the analysis of individual
compounds and their relevance to food quality, authenticity and other prop-
erties can be very challenging. In general, there is no perfect method for the
analysis of all different food components in all products and current analytical
methods for food evaluation are usually complementary to each other. For
that reason, the development of more powerful and cost-effective ana-
lytical tools for increasing our capabilities to analyse foods rapidly and with
high accuracy is a continuous and demanding research effort. The most
common analytical methods for food quality assessment are mass spectrom-
etry (MS) usually coupled to liquid (LC) or gas chromatography (GC), cap-
illary electrophoresis (CE), infrared spectroscopy (IR) and nuclear magnetic
resonance (NMR) spectroscopy. In addition to those molecular analysis
methods, other methodological approaches of biological origin, such as
polymerase chain reaction (PCR) and enzyme-linked immunosorbent assay
(ELISA), are also used extensively for food analysis [1].
NMR is a technology based on the magnetic properties of several
atomic nuclei, and it is an emerging methodology for the analysis of com-
plex mixtures, such as foods. In a typical NMR experiment, the spin
nuclear magnetization of a sample that contains NMR active nuclei and
is located inside a strong field NMR magnet, is excited using radio-
frequency pulses and during its relaxation back to equilibrium a signal is
generated, recorded and Fourier transformed to provide the sample’s
Magnetic resonance applications in food analysis 241
NMR spectrum. NMR is a non-destructive analytical method that can

determine and quantify a large number of compounds simultaneously
and it is characterized by high reproducibility. It can be applied to samples
of all states of matter, although most food-related applications involve liq-
uids and solids and under carefully chosen experimental conditions [2,3] it
is an accurate and versatile quantitative tool. The main disadvantage of
NMR compared to other technologies used in food analysis is its relatively
low sensitivity. The sensitivity of the experiment depends on the instru-
mentation, mainly the type of NMR probe and the strength of the mag-
netic field, the type of the experiment (nucleus, pulse sequence,
acquisition parameters) and the nature of the sample, and these factors also
affect the spectrum resolution. More information about the principles of
NMR spectroscopy as applied on foods can be found elsewhere [4].
The most common nuclei studied in food analysis are hydrogen, deute-
rium [5], carbon-13 [6] and phosphorus-31 [7]. The NMR techniques
applied to foods include high-resolution (HR) liquid state NMR [8]
and HR solid state NMR [9,10], which are mainly used to obtain fre-
quency domain spectra; low resolution, also known as low-field NMR
(LF-NMR) or benchtop NMR [11], that has been mostly applied to pro-
vide time-domain signal (TD-NMR); and MRI [12] which produces
images based on the differences in proton spin density and/or relaxation
times between food components, mainly water and lipids. NMR has been
applied for the analysis of several different categories of foods, such as fats
and oils [13], beverages, fruits, vegetables, dairy [14] and meat products.
Representative recent applications include food authentication, quality
control, production monitoring/improvement and sensory evaluation.
Liquid state NMR is ideal for the analysis of small and medium size mol-
ecules, and thus finds applications in the determination of lipids, carbohy-
drates, antioxidants and other common food ingredients, although more
research is required for improving our capabilities for compound identifi-
cation and quantification. Larger molecules such as polysaccharides can be
also studied using liquid state NMR, although several challenges may exist.
In such cases, solid state NMR can be applied, to overcome limitations
associated with samples of limited or no solubility.
The development of multivariate statistical analysis methods
(chemometrics) and their coupling to NMR spectroscopy was a game
changing step in the field of food analysis. Chemometrics rendered NMR
to become a very powerful tool for achieving a holistic and unbiased food
assessment and explore interactions and relationships between chemical
profile and food properties, rather than a technique used only for composi-
tional analysis. Unsupervised pattern recognition techniques, such as prin-
cipal component analysis (PCA), are applied as exploratory data analysis
methodologies to observe the total variance among samples, reveal patterns
and also remove potential outliers. Supervised techniques, such as partial
least squares discriminant analysis (PLS-DA), are applied to investigate pur-
posely the variations that arise from specific variables between pre-assigned
groups/classes and determine the impact of specific variables on the model.
Model evaluation for supervised approaches needs to be conducted by
applying cross-validation, external validation and other suitable methods.
If classification is achieved, identification of statistically significant markers
and other critical compounds is normally carried out. Other statistical
approaches that are used or they have the potential to be applied in
NMR-based food analysis are linear discriminant analysis (LDA), artificial
neural network (ANN) and independent components analysis (ICA). There
are various platforms, such as R packages, MATLAB®, SAS and various soft-
ware that can be used for statistical data analysis. Advances in big data analysis
and machine learning, as well as the development of databases are expected
to increase the number and the quality of NMR applications in complex
food analysis-related problems. Although multivariate statistical analysis is
an invaluable tool for marker identification, univariate analysis, such as t-tests
and ANOVA are still tools of specific importance. There are excellent
reviews in literature that provide comprehensive descriptions and detailed
information about chemometrics and their combination with NMR [15].
In this review we focus on the most recent applications of NMR in food
analysis, emphasizing on studies that were published after 2014, although
important earlier studies will be also mentioned. We cover the most impor-
tant NMR approaches, namely high resolution liquid state NMR, high
resolution solid state NMR, low field NMR and MRI and we present appli-
cations in various food analysis areas, such as authentication, quality control
and compositional analysis.
2. High resolution liquid NMR spectroscopy

2.1 Compositional analysis and structure elucidation
High resolution liquid state NMR spectroscopy represents the majority of
applications in food analysis and involves the use of instruments with
superconducting magnets that generate strong magnetic fields. The main
reasons for the popularity of this approach are the high quality of NMR
spectra obtained, which are characterized by excellent resolution and higher
sensitivity compared to other NMR-based approaches, as a result of the strong

magnetic fields and the sharp signals. However, HR solution state NMR is
still less sensitive compared to other analytical techniques, and the limits of
detection fall in the μΜ range, allowing thus the analysis of only a portion
of the molecules that exist in a food. Additional advantages of NMR include
the inherent quantitative nature of the methodology, especially for 1D appli-
cations, facile sample preparation, and the ability to utilize high throughput
technologies that are routinely available for these applications. The most com-
mon nucleus utilized in HR solution state NMR studies is proton, mainly due
to its high sensitivity, the short T1 relaxation times and the enormous amount
of structural information provided by the 1H NMR spectrum of common
food components. Interpretation of important NMR observables such as
chemical shifts, J-couplings and signal areas, which are all visible in a typical
1
H NMR spectrum, render 1H as the nucleus of choice for most food-related
applications. However, even in HR analysis, 1H NMR spectra often suffer
from low resolution and extensive overlapping between peaks, since many
foods are complex mixtures of hundreds of organic compounds.
Another challenge with 1H NMR food applications is water/solvent
suppression. Water exists in significant amounts in most food samples,
and other solvents may also exist in the final NMR sample as a result of
extractions and/or chromatographic separations. It is important to suppress
the signals of such solvents in order to obtain NMR spectra of good quality,
because protons from water and organic solvents present in high concentra-
tion in the NMR sample, produce signals that interfere with those of the
analytes of interest. Various suppression methods, such as presaturation [16],
watergate [17], jump and return, and excitation sculpting [18] have been
developed and described in the NMR literature, with presaturation being
one of the most commonly used water suppression approaches. For met-
abolomics type of analyses the first increment of the noesy pulse sequence
with presaturation is the most popular water suppression technique used,
because it provides spectra with minimal baseline distortion compared to
other methods [19]. When a mixture of solvents is present in an NMR sam-
ple, the solvent suppression can be very challenging, especially when proton
exchange is involved leading to the appearance of broad solvent signals. In
such cases, shaped pulses for off-resonance presaturation may be applied [20].
The type of the NMR probe used plays also an important role in water
suppression, with inverse probes generally being considered more effective
compared to X-nuclei-observe probes. However, when working with
inverse cryoprobes and strong magnetic fields, radiation dumping arising
from the magnetization of water during suppression may become a serious
problem. In such cases, the selection of a room temperature probe can be

a good choice, especially when working with samples for which analyte
amount or concentration is not an issue. Lyophilization can be used for
the physical removal of water from food samples, whereas vacuum and/or
gas nitrogen can be used for organic solvent removal. However, this is not
always the best option, because it may increase the sample preparation time,
cause degradation or oxidation of sensitive food ingredients, reduce the con-
centration of volatiles and also induce additional factors of variance in
chemometrics-related studies.
Heteronuclei, such as 13C, are also used extensively in food analysis,
because the 13C nucleus provides much higher resolution and spectral sim-
plicity compared to 1H NMR. The main challenge with 13C analysis is the
long experimental times due to the low sensitivity and the long T1 relaxation
times of 13C nuclei. This is not a very big problem when dealing with sam-
ples available in high amounts, or when focusing on compounds that are pre-
sent in high concentration, since in this case 13C NMR spectra with high
S/N (signal to noise) ratio can be obtained in minutes by acquiring just a
few scans. However, the low sensitivity of 13C can be an important limita-
tion when sample amount and/or analyte concentration is an issue.
X-observe NMR probes, where the inner coil is used to excite 13C or other
heteronuclei can provide heteronuclear NMR spectra with improved
sensitivity. In most cases 13C experiments are conducted using proton
decoupling and thus carbon spectra consisting of singlets are acquired.
Although proton decoupling increases sensitivity and spectral simplicity,
the elimination of signal multiplicity eliminates important structural infor-
mation from J-coupling with protons that can only be retrieved by heter-
onuclear 2D NMR experiments 31P NMR has also provided some very
interesting applications in food analysis, due to the high resolution and sen-
sitivity of 31P NMR experiments. The main problem with the 31P nucleus is
that only a small number of phosphorus-containing food ingredients can be
studied, such as for example phosphates, phospholipids, ATP and ADP.
However, the derivatization of compounds possessing labile protons that
can be replaced by phosphorus, using a suitable phosphytilated reagent,
opened up a new field for food-related 31P NMR analysis [21]. A similar
nucleus-tagging approach has also been developed using 4-fluorobenzoyl
chloride and 19F NMR [22].
Derivatization steps are generally not very common in NMR, except for
the 31P and 19F tagging protocols mentioned above. The main drawback of
such approaches is that they are destructive, in the sense that derivatization
reactions alter the molecular composition and the sample matrix, and thus
sample recovery for other analytical methodologies is not possible.
In addition to the standard 1D pulse sequences, other approaches
have also found application in HR solution state NMR food analysis.
A characteristic example is diffusion NMR, where the translational diffusion
of molecules is studied. Translational diffusion can be a valuable tool for
mixture analysis, molecular weight estimation and for studying biological
processes such as molecular binding and aggregation. The results obtained
from diffusion NMR studies can be presented either as diffusion coefficient
values of molecules or as Diffusion Ordered NMR Spectroscopy (DOSY)
spectra, after applying Inverse Laplace Transformation. DOSY is a pseudo-
2D plot where compounds are separated along the horizontal axis based on
their chemical shifts, like in a typical 1D experiment, and across the vertical
axis according to their diffusion coefficients. Although diffusometry may be
considered as a separate field, many food-related applications involve the use
of HR probes and the acquisition of HR 1D slices and thus it is considered in
this section of the article. Diffusion NMR experiments require pulse field
gradients (PFGs) that are used to dephase and rephase the magnetization
in order to spatially encode the location and velocity of compounds.
A diffusion experiment typically involves an initial RF pulse, a dephasing
step using PFGs, a delay time to allow the compounds to undergo transla-
tional diffusion, re-phasing the magnetization using another PFG and finally
acquiring the FID. Multiple consecutive experiments are recorded by vary-
ing the gradient strength, and the diffusion coefficient is measured by plot-
ting signal intensity as a function of gradient strength. The loss of signal
intensity depends on NMR parameters such as gradient strengths and delays
between gradients, but also on the diffusion coefficient of the compound
producing the signal, which thus can be accurately measured.
Most diffusion NMR studies in food analysis involve the 2D DOSY
representation, and a. recent application deals with the self-association
of anthocyanins [23]. More specifically, the authors investigated the
intra- and inter-molecular association processes between malvidin-3-O-
coumaroylglucoside and malvidin-3-O-glucoside by combining standard
1D NMR with DOSY. Lu et al. also applied DOSY NMR in combination
with other NMR techniques for the determination of various organic com-
pounds of interest in yogurt [24] and Bellomaria et al. used DOSY and
TOCSY to characterize proteins in nutraceutical formulations [25] and
for the determination of their molecular weight. Other applications include
the analysis of markers in valerian-hop liquid herbal products [26], the
virtual separation of important ingredients in manuka honey [27], the deter-

mination of glucose in fruit juices [28] and the analysis of sucrose in various
beverages, namely orange juice, pineapple juice and a sports drink [29].
Interestingly, in the last two studies the quantification of glucose and sucrose
was performed using 1D slices of the DOSY spectra. In another case, instead
of the 2D DOSY representation, the diffusion coefficient values were
measured in order to identify the degree of glycerol esterification by n-acyl
and trans acyl chains in fish oil [30].
Another NMR technique with only limited applications in food analysis,
despite its potential to elucidate complex interactions between small and
large molecules is saturation transfer difference (STD) NMR. STD NMR
is based on spin diffusion and can provide information about binding epi-
topes and dissociation constants of complexes, although it works only on
systems where weak or moderate binding takes place. Sun et al. combined
STD with WaterLOGSY, a method where the magnetization from water is
transferred to the complex and free ligand, to investigate the interactions
between cinnamaldehyde and its metabolite, cinnamic acid, with human
serum albumin [31]. The authors also studied the impact of other food addi-
tives, on the binding constants between cinnamaldehyde/cinnamic acid and
human serum albumin. The interactions between human salivary proline-
rich proteins and tannins that are present in foods have been also recently
studied [32]. Additionally, Tang et al. investigated the molecular mechanism
of the binding of 3,4,5-tri-O-caffeoylquinic acid to human serum albumin
using STD [33], and Fernandes et al. applied STD NMR to elucidate the
mechanism of anthocyanin binding to pectin [34].
Other advanced NMR techniques with a great potential in food analysis
include TOCSY combined with chemical shift-selective filters (CSSFs), an
innovative quantification method with high selectivity. CSSF deals with the
inevitable signal overlapping present in the 1D 1H NMR spectra of complex
food sample matrices and compared to the conventional 2D TOCSY, it is
faster and provides higher spectral resolution. Schievano et al. quantified the
most commonly present sugars in honey using CSSF-TOCSY without
sample extraction [35]. Also, regular 2D NMR experiments can sometimes
have difficulties in resolving the signals of complex isomeric mixtures and
CSSF-TOCSY combined with INEPT provides a solution for this problem
based on the resolution provided by 1D 13C NMR spectra [36]. Gouilleux
has published several articles comprehensively discussing the principle and
applications of Ultrafast 2D NMR as a real-time reaction monitoring
tool [37], in screening analysis [38] and in combination with other
techniques [39]. Ultrafast intermolecular single quantum coherence spec-

troscopy has also been applied for the analysis of viscous liquid foods by
Cai et al [40]. In a review by Giraudeau et al., it was argued that quanti-
tative Ultrafast 2D NMR, although not yet supported by a vast number
of research applications, has a promising future in food analysis [41], and
Akoka and Giraudeau have evaluated the utility of ultrafast 2D NMR in
metabolomics [42]. Reddy et al. illustrated the capability of maximum-
quantum (MaxQ) NMR for the characterization of extra virgin olive oil
polyphenols, due to this technique’s high resolution and sensitivity [43].
Fig. 1 displays the one pulse NMR spectra of olive oil samples followed
by two dimensional 5Q–1Q, 4Q–1Q, and 3Q–1Q correlation spectra.
Other methods that have been used for NMR spectral elucidation of
metabolomic mixtures [44], such as a novel selective TOCSY approach,
are also promising tools on food analysis.
HR liquid state NMR is the approach that is most commonly coupled to
chemometrics, compared to other NMR methodologies. For this reason,
the development of experimental protocols that produce reliable and repro-
ducible NMR spectra are of specific importance. It is difficult or even
impossible to provide a general sample preparation protocol applicable for
all cases, due the large differences in the structure and properties of various
food ingredients and the significant variations observed between different
food matrices. However, a usual sample preparation procedure for NMR
analysis only involves dissolution of the food product into the appropriate
NMR solvent and any necessary buffer. Characteristic examples of such sim-
ple preparation procedures include the analysis of edible oils [45], juices [46]
and beverages [47]. In several cases though, some type of analyte isolation
and purification steps, such as extraction [48], degassing [49], and centri-
fugation [50] may need to be included. The solvent selection for final
suspension and for extractions depends on the polarity of the compounds
of interest. The most common solvents are D2O or H2O/D2O for polar
molecules, DMSO-d6 and CD3OD for semi-polar and CDCl3 for non-polar
ingredients. In several cases, the use of solvent mixtures such as CD3OD:
H2O, CD3OD:H2O:CDCl3, acetic acid/H2O and acetonitrile/H2O is rec-
ommended [51]. These mixtures are usually monophasic, but this depends
on choosing the correct solvents ratio and suitably matching the food matrix.
In water based solvent mixtures, a buffer may be used to correct for un-
necessary pH dependent variations in chemical shifts. This is of specific
importance when NMR is coupled to untargeted chemometrics analysis,
where accurate spectral comparison is a very critical step. The buffer solution
Fig. 1 1H (500 MHz) one pulse NMR spectra of olive oil samples and the 2D 5Q–1Q, 4Q–1Q, and 3Q–1Q correlation spectra. Reprinted from
G.N. Manjunatha Reddy, L. Mannina, A.P. Sobolev, S. Caldarelli, Polyphenols fingerprinting in olive oils through maximum-quantum NMR spec-
troscopy, Food Anal. Methods. 11 (2018) 1012–1020 with permission from Springer Nature.
can be used during the extraction but in case there are concerns related to its
impact on the extraction procedure [52], it can also be added directly to
the extract. Often, a centrifuge step is needed after the final NMR sample
preparation step to avoid the presence of macromolecules that have a
negative impact on spectral resolution. Alternatively, the use of the Carr–
Purcell–Meiboom–Gill (CPMG) pulse sequence, which allows the elimina-
tion of the NMR signals of large molecules without performing a physical
separation can be applied. Although this pulse sequence is currently used
mostly for the analysis of biofluids, it has great potential for some HR
food-related applications as well.
In addition to untargeted analysis, NMR has been also applied for
targeted-quantitative food analysis. Because NMR is a signal ratio method,
when the measure of absolute concentrations is the goal an internal
standard needs to be added. The most common internal standards for
polar solvents such as D2O include trimethyl-silyl-propanoic acid (TSP),
4,4-dimethyl-4-silapentane-1-sulfonic acid (DSS), 3,5-dinitrobenzoic acid,
benzoic acid, maleic acid, dimethylsulfone and duroquinone [53]. For non-
polar solvents, such as CDCl3, 2,6-di-tert-butyl-4-methylphenol (BHT) is a
good choice. In any case, appropriate internal NMR standards that are not
overlapping with analyte signals, are non-toxic and have short relaxation
times are often difficult to found. Alternative approaches are the electronic
reference to assess in vivo concentrations (ERETIC) and the pulse length-
based concentration determination (PULCON). In ERETIC an electronic
reference is used [54]. ERETIC has been used in food analysis applications,
such as the quantification of benzoic acid in orange juice [55]. Although
important parameters such as frequency, phase, and intensity of the signal
can be easily controlled by the user [56], the technique requires some addi-
tional hardware for the generation and the delivery of the electronic signal
and thus is not always user friendly. PULCON seems to be a more conve-
nient approach and the quantitative analysis is based on the use of an external
standard in a separate NMR tube with predefined concentration. This
method was first introduced by Wider et al. [57] and it is now commercially
available as ERETIC2 [58] by Bruker. PULCON/ERETIC2 have been
used in a few food analysis applications, including the quality control and
quantification of bioactive principles of Lycii Fructus [59], the analysis of
molecules with overlapped resonances in the NMR spectrum [60], the auto-
mated multicomponent analysis of soft drinks [61] and the quantification
of standard compounds and natural isolates [62]. Given the difficulties in
finding an ideal internal standard and the limitations associated with its use,
as related to prevention of sample recovery for further instrumental, sensory or

clinical analysis, the number of PULCON/ERETIC2 applications is expected
to increase. Additional studies, investigating the validation and the accuracy of
the method as compared to the traditional internal standard approach and its
applicability to other nuclei in addition to 1H, may be required.
The addition of relaxation agents that reduce analyte relaxation times
and thus limit the length of the quantitative NMR analysis are also desired,
especially for 13C and 31P experiments. When working with non-polar sol-
vents such as CDCl3 the addition of small amounts of Cr(acac)3 is a common
and effective solution. For polar solvents, such as water, there are not many
options available, and more research is definitely required in that direction.
Magnesium chloride (MgCl2) has been proposed an efficient 13C NMR
relaxation agent, but it has been tested only for the determination of amino
acids and carboxylic acids [63]. Although 1D NMR is usually the method-
ology of choice for quantitative NMR food analysis, 2D NMR has also
demonstrated its potential. For example, Peterson et al. developed the
QQ-HSQC pulse sequence, which is a quick, quantitative method offered
as an alternative to an earlier variant, q-HSQC [64]. Although this approach
does not have so far significant contribution in food analysis, we believe that
it is a promising tool with great potential, especially for food systems that
generate overcrowded 1D NMR spectra. Finally, Huwang et al. recently
presented the application of a 2D 1H J-resolved NMR approach for the
analysis of heterogeneous foods [65].
HR solution state NMR has been extensively used for the quantification
and structural elucidation of many compounds that appear as common compo-
nents in foods. One of the most studied categories of molecules in foods are
lipids. NMR has been tested several times against other methods of analysis,
and was found to be very reliable [66,67]. Characteristic recent studies include
the application of 1H NMR for the measurement of the conjugated linoleic acid
present in beef muscle tissue extracts [68], the analysis of fatty acid composition
in olive oil [69], camellia oil [70], and the lipid profiling of Fossa cheese [71],
while 13C NMR has been used for the analysis of fish oil. 13C NMR is also the
most efficient method for the quantitative determination of the positional dis-
tribution of fatty acids in the glycerol skeleton of triglycerides [72,73], 31P
NMR has been recently used for the determination of phospholipids in krill
oil [74,75]. Additionally, Szlyk et al. applied 31P NMR for the determination
of polyphosphate additives, such as orthophosphate, and their ionic forms in
meat products using hexamethylphosphoroamide as an internal standard [76].
In addition to the saponifiable fraction of edible oils, NMR can be

used for the analysis of other molecules that exist in the lipid fraction [77].
For example, 1H NMR was applied for the quantification of oleocanthal
and oleacein levels in olive oil [78], the analysis of secoiridoid derivatives
and the characterization of aldehydic oleuropein and ligstroside aglycon
isomers [79]. Additionally, the oxidative and hydrolytic stability of
marine phospholipid emulsions as related to oxidative degradation and
non-enzymatic browning was investigated [80], whereas 2D 31P-1H
NMR was applied for the characterization of phospholipids in milk and
cheese [81]. Multinuclear and multidimensional NMR was also applied
for the identification of various lipid components in coffee oil [82] and
for monitoring the epoxidation reaction of coffee lipids obtained from spent
coffee grounds for the production of epoxy resins [83]. Recently the
1
H,13C-HMBC 2D experiment has been used for the analysis and structural
elucidation of trans/cis hydroperoxide isomers formed from the radical-
dependent oxidation of unsaturated fatty acids [84]. Sundekilde et al. intro-
duced a reactomics application of 1H NMR for the real-time tracking of
enzyme-assisted animal protein hydrolysis [85], and Kaufman et al. com-
bined NMR with polarimetric experiments to study the acid:base catalysis
of sugar anomerization [86].
Other food components and phytochemicals that have been elucidated
with analytical NMR experiments are terpenes [87,88], amino acids, organic
acids, steviosides [89], sugars [90], phenolics [91,92], peptides [93] and mix-
tures of various classes of compounds [94–96]. Recently, NMR enabled the
determination of xanthurenic and oleanic acids in red wines [97]. Mastihuba
et al. elucidated the mechanism of action of β-apiosidase from Aspergillus
aculeatus using NMR [98], and were able to identify the inversion of
anomeric configuration. Quantum Mechanical Total Line Shape (QMTLS)
fitting, a targeted quantitative profiling technique used in biological analysis
has broadened its application to include food science [99]. Selected green
tea catechins were quantified using QMTLS, and the results were compared
with a traditional quantification method, namely LC-MS/MS [100]. Addi-
tional studies have also demonstrated that QMTLS is a fast, reliable qNMR
tool that can be used as an alternative to chromatographic quantification [101].
Food analytical NMR challenges still exist in terms of the analysis of
minor food components that do not produce strong signals in the NMR
spectrum, and for molecules that have complex structures and thus generate
spectra with increased complexity. Minor compounds that are still not fully
resolved with NMR include various oxidation products of lipids, sterols and
vitamins. In addition, although NMR has been successfully used for the
quantification of various classes of small molecules, the analysis is usually
limited by the low resolution of the 1H NMR spectra, where many compo-
nents overlap, or the low sensitivity of the 13C NMR spectra, where minor
compounds cannot be detected under the common experimental conditions/
analysis times. Both resolution and sensitivity are improved when analyses are
performed at higher magnetic fields, and are thus expected to be less important
as food scientists obtain more access to high-field NMR instrumentation.
One of the most challenging categories of molecules not only for NMR
but also for other types of analysis is carbohydrates. Despite recent progress
in the determination of mono- and oligosaccharides [102], polysaccharide
analysis still remains challenging. From a dietary standpoint, carbohydrates
cannot be rivalled in their prevalence, and polysaccharides are particularly
notable for their organoleptic, physicochemical and health-related proper-
ties, important for the characterization and the quality assessment of foods
[103]. Because of their structural complexity, the quantitative determina-
tion and molecular characterization of polysaccharides can be challenging
when using traditional methods of analysis, such as GC and HPLC. High
resolution liquid state NMR is of particular importance for the analysis of
polysaccharides due to its robust capabilities for structural characterization,
particularly expanding to the assessment of polymerization and structural
connectivity of different residues of interest. NMR spectroscopy provides
a high-throughput, non-destructive method of analysis that allows for
broad structural elucidation of carbohydrates [104]. These aspects are
especially important for the analysis of polysaccharides, as their sizes,
structure and branching vary greatly, and there is much concerning their
structure that still needs to be understood. Paired with bioinformatics and
additional analytical techniques, NMR can provide a high degree of
structural information [105]. A typical sample preparation for the analysis
of water soluble polysaccharides using NMR involves the addition of a
D2O solution that contains an internal standard such as TSP or DSS.
When the observation of exchangeable hydroxyl –OH protons is desired,
H2O:D2O and DMSO-d6 can also be used [106]. The chemical shifts of
non-anomeric protons in 1H NMR are between 3.5 and 4.5 ppm, with
alpha-anomeric protons producing signals in the 5–6 ppm region, beta-
anomeric protons between 4 and 5 ppm, while carbon signals appear
between 60 and 110 ppm in the 13C NMR spectra [107].
NMR applications in carbohydrate analysis recently reported include the
determination of the degree of polymerization of fructo-oligosaccharides in
stevia [108], identification of gums in gelled food concentrates [109],

characterization of carrageenans [110], β-D-glucan [111], arabinogalactan
oligosaccharides in coffee [112], characterization of dietary polysaccharide
extracts of Agaricus brasiliensis fruiting bodies [113], and identification of
the RG-I domain of low molecular weight pectins [114]. 1H NMR
combined with basic hydrolysis using NaOH has been successfully used
to determine the degree of methylation, acetylation, and feruloylation of
pectin in a single experiment [115]. The result of the reaction is the release
of methanol, acetic acid, and ferulic acid, which can be rapidly quantified by
1
H NMR with high accuracy, repeatability, and reproducibility.
When the monosaccharide composition needs to be determined, poly-
saccharides need to be hydrolyzed prior to NMR analysis [116]. Hydrolysis
also needs to be performed when spectral quality is low due to the high
molecular weight of polysaccharides, leading to NMR spectra consisting
of broad lines due to the short T2 relaxation times. Since hydrolysis is the
principle process undertaken by food polysaccharides, it is important to
characterize the monomers that are derived from polysaccharide hydrolysis
as well, and thus robust methods have been established towards this goal.
However, many hydrolysis methods are destructive and may cause structural
alterations, making the end-product unreliable for analysis. De Souza et al.,
paired NMR with a two-step hydrolysis method utilizing sulphuric acid
which is a modification of the Saeman hydrolysis approach, and favourably
hydrolyzes the strong β-(1,4) linkages of cellulose, while reacting mildly
with associated monomers [117]. The authors applied this hydrolysis meth-
odology to several polysaccharides and performed quantitative analysis using
maleic acid as an internal standard. Because in those experiments the
ionic strength of the NMR solutions may be high, very long pulse durations
are needed to achieve the 90 deg. pulse required for adequate quantification.
For this reason, 3 mm NMR tubes that are less prone to ionic strength effects
are recommended [118] for such applications. The monosaccharide compo-
sition of glucans using hydrolysis and a quantitative version of HSQC exper-
iment has been also reported [119]. This approach can be an effective
alternative when dealing with signal overlapping issues, since the 2D HSQC
spectra are characterized by high resolution. Although 2D techniques are
mainly used to assist the spectral assignments of various analytes and build
trustworthy HR liquid state 1D NMR food analysis applications, they have
the potential to become attractive tools for low field NMR applications as
well, since they offer higher spectral resolution. The combination of these
sequences with other NMR tools, such as non-uniform sampling, which can
significantly reduce the NMR experimental time, further increases their

potential applications in food analysis.
To assist oligo- and polysaccharide characterization, a software program
called CASPER is available, with which 1H and 13C NMR spectra are com-
putationally generated and can be used to determine the chemical shifts of
monomeric subunits within a macromolecular structure [120]. One area of
food and nutritional studies that NMR has shown promising potential is the
study of prebiotic polysaccharides. In a study by Thambiraj et al., polysac-
charides were extracted from seeds of Lupinus luteus L., and 1H and 13C
NMR were utilized to characterize their structures. This study revealed
23 13C NMR resonances corresponding to four types of sugar rings within
the structure of the substrate. NMR was also coupled with FT-IR to reveal
that the backbone was composed of galactans and galactomannans in a
β-(1,4) glycosidic linkage, proving the strength of combining NMR with
other spectroscopic techniques in structural elucidation [121].
Much of the food waste generated in the food and beverage industry
comes from the peels, shells, and pulps of produce and vegetable products,
which contain valuable cell-wall polysaccharides. Research utilizing NMR
spectroscopy is currently being conducted on a number of these industrial
waste products, including potato pulp [122]. In that study, pectic polysac-
charides from the cell wall material within potato pulp were isolated using
both alkaline and enzymatic processes. 1H NMR was used to decipher the
structure of galactan-rich RG-I populations, using potato galactan and sugar
beet Arabinan as standards. A strong signal at chemical shift of 4.92 within
the anomeric region was assigned to the anomeric protons of α-(1 ! 4)
linked D-GalA residues and other signals belonging to H-2, H-3, H-4
and H-5 of a-D-GalA were also assigned. A study by Walia et al. examined
the Arabinan-type cell wall polysaccharides from apple pomace, in which 1H
NMR revealed signals between 3.36 and 4.47 for sugar units and 13C NMR
revealed signals at 68–85 corresponding with methines [123]. O’Shea
utilized 1H NMR to quantify the pectin yield following extraction from
apple pomace and orange pomace, and also measured the degree of pectin
methoxylation [124].
The changes that occur in the retrogradation process of starch derived
from buckwheat and glutinous rice were analysed using 1H and 13C
NMR spectrometry combined with isothermal titration calorimetry
(ITC) and differential scanning calorimetry (DSC) [125] by Lian et al. In that
study, post-retrogradation samples showed a lower intensity for a signal at δ
79, indicating a decrease in amorphous phase structures post-retrogradation.
Finally, Merkx et al. carried out the quantification of monosaccharides of

interest within food polysaccharide mixtures using the Quantum Mech-
anical Total Line Shape methodology described earlier (QMTLS) [126].
2.2 Food authentication

Typical applications of HR liquid state NMR spectroscopy in food authen-
tication deal with geographical characterization, varietal discrimination
and the detection of possible adulteration. For this type of research, the
integration of NMR spectroscopic data with univariate and multivariate
statistics and/or other methods of analysis is often necessary. As an example,
Fig. 2 displays the biplot obtained by PCA for the discrimination between
virgin olive oil samples produced by two different olive tree cultivars,
Koroneiki and Cypriot [127], using fatty acids as descriptors for the differ-
entiation. Several review article have been published already discussing
applications and technical details of NMR spectroscopy as applied for the
Cypriot Koroneiki
ω-9
2
MUFA
C18:1/C18:2
F2:42.45%
0 MUFA/PUFA
PUFA
–1
SFA
–2
–3
–4
–3 –2 –1 0 1 2 3 4 5
F1:54.69%
Fig. 2 Bi-plot obtained by pca analysis of 225 olive oil samples, showing the scores
(samples of two varieties) and the loadings (six groups of fatty acids). Reprinted from
Kritioti, G. Menexes, C. Drouza, Chemometric characterization of virgin olive oils of the
two major Cypriot cultivars based on their fatty acid composition, Food Res. Int. 103
(2018) 426–437, with permission from Elsevier.
authentication of foods. For example, Mannina and Sobolev published in

2011 a concise review of olive oil authentication and geographical/varietal
origin discrimination using high resolution NMR spectroscopy. The
authors discussed targeted analysis, metabolic profiling and metabolic finger-
printing, and also included some reports where metabolomic fingerprinting
and targeted profiling were combined studies [128]. The authors discussed
NMR and statistical protocols, providing a thorough description of the
application of NMR on olive oil characterization. Consonni and Cagliani
described in a review article published in 2010, the application of NMR
and chemometrics to assess the quality and authenticity of traditional food
products which are produced from specific locations, or made with special
recipes. The most typical example is wines labelled with Protected Desig-
nation of Origin (PDO) and/or protected geographical indication (PGI),
which indicates their unique origin. The authors discussed geographical
origin and quality and authenticity of food, covering a great variety of
commonly consumed food products [129].
Recent representative studies discussing the application of NMR in food
authentication include reports on the influence of location on the biochem-
ical composition of wild sea buckthorn [130], the varietal classification of
sweet melon and correlations between variety and sensory characteristics
[131], the determination of adulteration in hempseed oil [132], the authen-
tication of cinnamon spice [133], the geographical/varietal characterization
of wines [134] and the determination of the authenticity of roasted coffee
[135]. A comparative study of Italian PDO saffron with several commercial
saffron samples was recently conducted [136] using 1H NMR. Some unique
metabolites, namely picrocrocin and crocins, were identified as potential
authenticity markers of Italian PDO saffron. In a similar study, Dowlatabadi
et al. [137] applied 1H NMR on Iranian saffron authentication, targeting
the most common adulterants, namely safflower and tartrazine. Also, Spiteri
et al. proposed the use of 1H NMR for the detection of honey adulteration,
either independently or combined with other analytical platforms using data
fusion analysis [138]. Masetti et al. were able to distinguish the geographical
origin and cultivar of Sicilian cherry tomatoes, a PGI fruit, using 1H NMR.
Carotenoids and phospholipids naturally existing in the Sicilian cherry
tomatoes were determined as the critical chemical components responsible
for the discrimination of cherry tomatoes [139].
The vast majority of the studies described so far are based on 1H NMR
analysis, however, other nuclei such as carbon-13 and phosphorus-31 have
also been used in food authentication studies. For example, Monakhova
et al. investigated the adulteration of sunflower lecithin with soy lecithin

using 31P and 1H NMR. The authors analysed both polar and non-polar
lecithin extracts, reporting several phospholipid and other compounds,
including linolenic acid and stachyose were useful for authenticity veri-
fication [140]. In another study, Kamal et al. used 13C NMR-based
metabolomics for the biochemical profiling of Asian soy sauces [141], while
a study by Erich et al. paired 13C NMR with 1H NMR in a chemo-
metric analysis aiming to discriminate between conventional and organic
milk products [142]. Wei et al. applied similar 13C NMR metabolomic
approaches to achieve the classification of green coffee beans according to
their variety and origin, and overcome spectral misalignment issues in the
1
H NMR classification analysis, as the 13C NMR spectra were found to
be less or not at all affected by molecular interactions. Thus, a clear separa-
tion of variety and origin was evident on the PCA and OPLS-DA analysis
plots derived from the 13C NMR spectra, with sucrose, caffeine and chlo-
rogenic reported as the compounds responsible for the classification [143].
The drawback of this approach is the longer experimental times associated
with 13C NMR analysis. Site-specific natural isotopic fractionation (SNIF)
NMR is another approach with significant application in food authentica-
tion and traceability. In SNIF NMR experiments the nuclei of 2H and its
isotopic ratio with 1H is usually quantified, but there are also applications
involving the measurement of the 13C/12C isotopic ratio. Although 2H
has a spin of 1, its quadrupole moment is small and thus nucleus can still
produce spectra with high resolution and reasonable sensitivity.
Edible oils represent one of the most well-studied food products, with
NMR spectroscopy applications focusing mostly on authentication issues.
Shi et al. combined 1H NMR with PLS statistical analysis to determine
the concentrations of squalene and various sterols in seven types of vegetable
oils [144]. The results reported showed that the amounts of these com-
pounds varied significantly among different species as a result of genetic
and environmental factors. The traceability of Tuscan PGI extra virgin olive
oil was examined by 1H NMR and chemometrics by Girelli et al. [145], who
analysed 217 samples of olive oils and leaves. In another study, the 1H NMR
spectra of monovarietal extra virgin olive oils extracted from three Turkish
and one Slovenian cultivar were combined with chemometrics for oil cul-
tivar discrimination. The unique characteristic of that study was the appli-
cation of presaturation to suppress signals appearing at frequencies lower
than 5.6 ppm and belonging to the main lipid components [146]. Minor
compounds such as terpenes, phenols, diglycerides and aldehydes detected
in such spectra were found to be important cultivar biomarkers. Phenolic

compounds and other minor components were identified as important
discriminators in another study focused on the discrimination of Brazilian
plant oils of different botanical origin [147]. Zhang et al. [148] achieved
the discrimination of edible oils of plant origin, including sunflower seed,
rapeseed, sesame, soybean, peanut, corn and olive oils using 1H NMR
and multivariate statistical analysis. Alonso-Salces et al. analysed both bulk
virgin olive oils and the corresponding unsaponifiable fraction of these oil
samples, using 1H NMR for authentication purposes. They compared var-
ious types of pattern recognition models and found that PLS-DA provided
the best group discrimination model [149]. This lab also explored the use
of larger sample size for olive oil NMR authentication and implemented
IRMS for complementary information. With the larger data set, the authors
were able to improve the geographical origin discrimination ability from the
national level to regional or PDO level [150]. A 13C-INEPT (Insensitive
Nuclei Enhanced by Polarization Transfer) approach was applied for
the analysis and quantification of individual fatty acids in olive oil samples
[151]. The authors used multivariate linear regression models and compared
the INEPT results with those obtained by gas chromatography analysis.
Agiomyrgianaki et al. analysed the compositional variation of Greek
extra virgin olive oils as influenced by harvest year, cultivar and geographical
origin by using 31P and 1H NMR. The phenolic composition of olive oil
was found to be influenced by all studied factors, with harvest year being
the most highly correlated to composition. They evaluated the importance
of the three contributing factors using forward stepwise canonical discrim-
inant analysis (CDA) and classification binary trees (CBT), and several crit-
ical compounds responsible for discrimination were identified, such as the
phenolics p-coumaric acid, pinoresinol and 1-acetoxypinoresinol. Linoleic
acid was found to be the discriminatory fatty acid with the highest weight
[152]. The simple one pulse 1H NMR experiment and the multiple satura-
tion of lipid signals 1H NMR techniques as applied to olive oil classification
were evaluated by Longobardi et al. It was proposed that the combined data
of selected regions from each pulse sequence outperformed either one of the
pulse sequences [153]. Dugo et al. were able to discriminate extra virgin
olive oil (EVOO) from various regions in Italy, and suggested the use of
NMR in evaluating the quality of EVOO. The analysis of Dugo et al.
was based on the characterization of the aldehydic profile of EVOO using
band-selective NMR [154]. Unlike most of the recently published studies
on food authentication using NMR coupled with multivariate analysis,
€ and Ok investigated the geographical discrimination of olive oils using
Un
NMR combined with ANOVA analysis. Tukey’s test, one of the multiple
comparison test approaches was applied based on a number of selected and
identified NMR signals. The results showed that some compounds have the
potential to discriminate oils based on geographical origin at the regional
level [155].
Similar to vegetable oils, fats of animal origin can be studied with HR
liquid state NMR using similar experimental approaches. Picariello et al.
noted that 13C NMR can be used as a tool for identifying butterfat adult-
eration with synthetic triacylglycerols (TAGs) based on the fact that butyric
acid (C4) is only present naturally at the sn-3 position in milk fat TAGs.
Their study showed that 13C NMR analysis was capable of detecting
the adulteration of butterfat by synthetic fats to a very low level, approx.
1–2.5% w/w [156]. Fadzillah et al. conducted a study aiming at the detection
of butter adulteration with lard using 1H NMR. They applied PLS multi-
variate data analysis, and successfully correlated the added lard value with the
PLS model predicted value, suggesting that NMR has the potential to detect
and quantify lard adulteration in butter [157].
Alcoholic and non-alcoholic beverages is another food type where
HR liquid state NMR has a great potential to be established as a powerful
method of authentication. In a recent study, Brazilian lager beers made with
different raw materials have been discriminated using NMR coupled with
chemometrics. During beer processing, barley malt can be partially replaced
with adjuncts, which can influence the enzymatic reactions. NMR analysis
was able to detect the differences in the carbohydrate profile, and showed
that it can be used as a beer authentication technique for ensuring accurate
labeling [158]. Godelmann et al. applied simultaneous suppression of water
and ethanol signals on a 1H NMR fingerprinting study of 600 wine samples.
In their study, it was demonstrated that targeted and untargeted multivariate
analysis was able to differentiate wines according to grape variety and geo-
graphical origin [159]. Ferrari et al. combined FT-NIR and NMR to detect
the adulteration of red wine anthocyanins by anthocyanins extracted from
black rice. The classification using a PLS-DA model was found to be unsat-
isfactory based on comparison with FT-NIR obtained data, potentially due
to matrix effects and the limited sensitivity of NMR. However, classification
using selected aromatic bands on the 1H NMR spectrum showed a
more satisfactory performance [160]. In another varietal classification study
of wine, Silvestri et al. performed a mid-level data fusion based on data
extracted from 1H NMR, emission-excitation fluorescence and phenolic
composition measured by HPLC-DAD. They compared the classification
results of merged data with separate datasets, reporting that the combined
classification model with data fusion demonstrated superior performance.

Moreover, the information obtained by multiple analytical instrumentations
benefited sample characterization as well [161]. Caruso et al. profiled white
wines using NMR and conventional physicochemical analysis. Colour
intensity was the only parameter of significant difference in terms of vintage
year among all physical-chemical parameters tested using ANOVA. There
were several evaluated parameters that provided evidence of geograph-
ical origin differentiation of the wine samples. Multivariate analysis allowed
the geographical origin discrimination of wines, but showed poor results in
terms of production year discrimination [162]. Mazzei et al. utilized 1H
NMR based metabolomics to differentiate white wines categorized as “Fiano
Di Avellino” produced by the same grape variety but with different yeast
strains. Results obtained with spectral data processed with multivariate analysis
revealed discrimination of the wines produced with different yeast varieties
that can be attributed to differences in respective yeast metabolism [163].
SNIF NMR is now considered as an established and robust method for
wine authenticity analysis. Jiang et al. investigated Chinese wines from five
different geographical regions using SNIF-NMR combined with IRMS,
and showed that natural multi-elemental isotope ratios were able to distin-
guish the regional origin of wine [164]. Kokkinofta et al. were able to deter-
mine the cultivar, vintage effect, and geographical authenticity of Cypriot
wines using SNIF-NMR, and proposed that their results could be incor-
porated in EU’s Wine Isotopic Databank to help improve and protect
the domestic wine market [165]. A comprehensive review of the long his-
tory of application of SNIF-NMR on wine authentication in the European
Union was published by Chrisoph et al., providing detailed information
regarding SNIF-NMR wine analysis [166]. SNIF-NMR has also been
applied for the discrimination of Romanian honeys of different botanical
and geographical origin [167]. Single-element isotope ratio analysis, namely
quantitative natural abundance 13C NMR, was applied to determine the
origin authenticity of sucrose-based sugar products [168]. The utilization
of SNIF-NMR in the study of the origin of flavour compounds has been
recently growing. Remaud and Akoka used vanilla as an example of the
application of SNIF-NMR for the authentication of flavour products
[169]. Furthermore, a recently published book emphasized the applications
of SNIF-NMR on odour analysis [170].
Lee et.al characterized the profile of green tea cultivated in three different
areas with distinct climate conditions using 1H NMR. The geographical origins
of the green teas were also discriminated and the compounds responsible for
differentiation were identified. By studying chemical composition correlations

to the regional climate conditions tea authors concluded that succinate syntheses
of green tea is correlated with, and it is promoted by high temperature, long
sunlight exposure and high rainfall [171].
Clausen et al. characterized sour cherry juice made from seven different
clones/cultivars using 1H NMR and also carried out their sensory evalua-
tion. The correlation of metabolites profiled by NMR and sensory attributes
was investigated, noting that glucose and malic acid were directly correl-
ated to sweetness and sourness attributes. They also found some correlation
between other juice metabolites and sensory features [172]. To discriminate
different cultivars of mango juice, Koda et al. performed a metabolomics
analysis of band-selective 1H NMR data. Because the dominating signals
of sucrose, fructose and glucose were removed, using selective excitation
they were able to increase considerably the sensitivity of the obtained
spectra, and thus extract valuable information on minor juice components.
The compounds contributing significantly to cultivar classification were
identified as the amino acids arginine, histidine and phenylalanine [173].
A study by Vigneau and Thomas explored various model calibration, feature
selection and data pre-treatment methods for authenticating orange juice
adulterated by clementine juice, based on 1H NMR obtained composi-
tional data. Correspondingly, they found that the repeated stratified cross-
validation, Covsel, logarithmic transformation and pareto scaling led to
models of optimum performance in their study [174].
Consonni et al. performed an NMR-based metabolomics study aiming
to discriminate roasted coffee based on geographical origin. Acetate and tri-
gonelline were identified as the major contributing compounds for
continental-level geographical discrimination [175]. Roasted coffee adulter-
ation with four different adulterants, namely corn, coffee husks, barley and
soybean, was detected using 1H NMR and chemometrics [176]. A study by
Caligiani et al. was carried out to characterize different types of cocoa beans
using 1H NMR. It was reported that the metabolomic profile of cocoa beans
was mainly influenced by fermentation level, on top of botanical and geo-
graphical origin. For comparison purposes the quantitative analysis of some
of the identified compounds was provided in terms of cocoa beans of various
fermentation levels [177].
To monitor metabolomic profile changes during grape berry develop-
ment, Ali et al. [178] studied three typical Portuguese grape cultivars using
1
H NMR. Two extraction methods were used and several compounds were
elucidated using 2D NMR. The information extracted from multivariate
data analysis helped reveal the biochemical differences at four developmental

stages and changes in the sugar, organic acid and phenolic profiles were
discussed in detail. The results obtained demonstrated that Veraison stage
is a significant stage for berry development. Dastmalchi et al. investigated
wound-healing development and variations of four types of potato cultivars
using NMR-based metabolomic profiling and LC-MS-based fingerprint-
ing. Polar extracts of wound-healing tissues were analysed to differentiate
the wound-healing pattern of various cultivars and stages. The authors were
able to associate the discriminating compounds with the corresponding fac-
tors, namely cultivar and healing stage [179]. Kortesniemi et al. have studied
the impact of genotype and geographical origin on the metabolomic com-
position of sea buckthorn berries using 1H NMR. The results showed that
the two subspecies and different growth conditions can be discriminated and
associated with particular chemical compounds using multivariate analysis
[180]. Commercial cultivars of hop have been studied and characterized
by metabolomics approaches due to hop’s growing economical value. Farag
et al. conducted a comparative study of MS-based and NMR-based hop
metabolomics. LC-MS and NMR showed comparable results in terms
of cultivar differentiation, with bitter acids composition being the most
influential compositional feature. The comparative MS and NMR analysis
revealed the advantages and limitations of the two different platforms used in
metabolomics, which helps with better utilization of instrumentations for
hop and similar products’ research [181].
Honey analysis and authentication can be a challenging task due to the
compositional complexity of this highly valued product. Honey consists of a
number of various sugars with different conformations, and ring chain
tautomerism reactions that lead to various alpha- and beta-anomers as well
as pyranose and furanose ring conformers, further increases complexity.
Nevertheless, NMR has been successfully applied for determining honey
authenticity with great success. A comparison study by Bertelli et al. eval-
uated both the 1D and the 2D NMR authentication protocols of honey
adulterated with sugar syrups. They concluded that both NMR techniques
provide satisfactory results, however, data obtained by the 1D 1H NMR
protocol, which is also a simpler and faster analytical method, showed better
prediction results [182]. To discriminate the geographical origin of honey,
Consonni et al. analysed its saccharide composition using band selective 1H
NMR spectra. Full characterization of the anomeric signals of saccharides
was conducted and applied to target the main sugar components related
to a particular group of honey samples [183].
The botanical and geographical assessment of acacia honey samples of

European origin, on the basis of the floral markers content, was conducted
using NMR spectroscopy and PLS2-DA statistical analysis models [184].
In contrast to other studies, the authors analysed chloroform extracts of aca-
cia honey containing the less polar minor honey metabolites. The surface
layer of honey, so-called foam, was promoted for consumption to patients
with diabetes by a manufacturer, claiming it possessed a high content of fruc-
tose. Ivanova et al. investigated the authenticity of the promotion and the
effect of excessive thermal processing on honey for the first time using
NMR. Contrast to the claim, they reported that the surface layer honey
has higher glucose and lower fructose content, which indicates a potential
health risk of surface layer honey consumption by diabetic patients. The
same authors also reported that the ratio of glucose anomers in honey can
be used as an index for the evaluation of honey quality [185]. Schievano
et al. have developed a prediction model for geographical and entomological
origin of pot-honey. In this study the geographical marker of Brazilian
honey was identified and structurally elucidated, and the NMR spectrum
band responsible for entomological differentiation was also identified [186].
To authenticate various pre-slaughter beef productions, Osorio et al.
[187] conducted an NMR-based metabolomics study using beef urine
and muscle samples. The results demonstrated the potential of NMR as a
rapid and reliable authentication methodology for beef production systems.
The authors also identified some discriminating signals in urine spectra,
including creatinine, glucose, and hippurate, as potential biomarkers. Jung
et al. [188] applied 1H NMR and metabolomics to differentiate between
beef samples of different geographical origin. The compounds possessing
higher loadings and discriminating power were identified to be succinate
and several amino acids. One-way ANOVA tests on these compounds
showed significant differences in their mean values depending on origin,
thus they could serve as potential biomarkers for establishing the geograph-
ical origin indication of beef.
2.3 Quality control and sensory analysis

HR liquid state NMR spectroscopy is gaining popularity in the field of food
quality control and sensory analysis, although there are still fewer studies
reported in the literature compared to other NMR related food applications.
The lack of plentiful such applications may arise from the fact that food
scientists are not familiar with the potential of NMR in the field of food
quality. For that reason, we decided to provide a more detailed discussion of

published studies compared to other sections of this review, in order to help
readers become familiar with this promising analytical approach. In one of
the early studies in food quality control, NMR-based metabolomics was
conducted on meat samples obtained from pigs with various pre-slaughter
treatments. Groups were consisting of a control, under which the pigs faced
no pre-slaughter exercise stress and three different groups of pigs that
faced pre-slaughter exercise on a treadmill. The post-mortem metabolism
resulting from pre-slaughter stress plays a key role in subsequent meat qual-
ity, so understanding the effect of treatment was the goal of this study.
1
H NMR spectra were acquired from pig plasma samples and PLS regression
was applied. High correlation was shown between metabolite profile and
temperature. Large variation was seen among samples obtained from pigs
experiencing pre-slaughter stress, less so with the control samples, and a
marked difference was found between the metabolite profile of the control
pig sample and the treated samples [189]. In another study by Liu et al.
1
H NMR was paired with multivariate statistical analysis to assess the rela-
tionship between ducks that were aged for four different time periods prior
to slaughter and to observe if duck age imparts any change in metabolism
[190]. Quality characteristics, such as tenderness and colour are associated
with metabolic differences, and thus such a study was valuable in efforts
to determine duck meat quality. Representative 1H NMR spectra were
obtained from the duck meat extracts and metabolite resonances were
assigned. Analysis of the NMR spectra showed that the longest aged duck
sampled (500 days) had lower levels of alanine, betaine, and a higher
serine level, while OPLS-DA was subsequently employed to further vali-
date the observed metabolic differences. The application of NMR and
chemometrics for the characterization of Chinese Wuding chicken meat
and the evaluation of aging effects has also been recently published [191].
Several alterations in metabolites were identified and the study helped
increase our understanding of metabolic variations in chicken meat and
assess its quality.
1
H NMR was utilized to develop the fatty acid profile of lipids in two
types of pork salami at different points during ripening [192]. Lipid extracts,
which contain saturated, polyunsaturated, and monounsaturated fats were
of interest due to their nutritional impact and their contribution to key
sensory attributes. Common fatty acid chains, particularly oleyl, linoleyl,
and linolenyl could be quantified for both varieties of pork salami. This
method of analysis also enabled the quantification of total saturated fatty acid
chains present. Through the NMR methodology applied the authors were
also able to calculate saturated/unsaturated and polyunsaturated/saturated
fatty acid chain ratios for dry salami samples. In another study, Zhang
et al. assessed five different varieties of dry-cured ham using 1H NMR
spectroscopy [193]. Metabolites were extracted from the biceps femoris
tissue of each of the hams with methanol solvent. The overall metabolic
profile could be established using a 1D NOESY sequence and successive
assignments were enabled through performing 2D techniques (COSY,
TOCSY, 1H-13C HSQC, and 1H-13C HMBC) on selected samples. Thirty
three different metabolites were identified, with glutamate, lysine, alanine,
leucine, and lactate deemed as key metabolites associated with flavour con-
tributions. PCA was performed on mean centred data to assess the differen-
ces/grouping of samples, and OPLS-DA models were also developed to
facilitate the discovery of differentiating markers among groups, while metab-
olites were also quantified in the five varieties of ham. A sensory panel of
10 women and 10 men trained and experienced in the sensory evaluation
of dry-cured hams assessed the varieties based upon seven key sensory char-
acteristics. Certain key findings were determined, such that American
country-styled ham scored lowest for sourness due to its lower levels of sour
contributing metabolites, lactate, succinate, and acetate, but the highest score
for sweetness. Amino acids were found to be major contributors to flavour and
differentiation among dry-cured ham varieties. It was also shown that flavour
composition was largely due to combinations of different metabolites in
samples rather than a large contribution of a single metabolite, such as in
the case of American ham.
Straadt et al. analysed five different cross-breed pig meat extracts using
1
H NMR-based metabolomics to draw a connection between metabolic
profile and sensory data [194]. Samples were extracted from the loins and
freeze-thaw drip from the loins of pigs. For the sensory analysis, a sensory
panel consisting of nine trained participants was set up, and participants were
instructed to assess a series of attributes originating from frying the pork in
grapeseed oil. Sixteen metabolites were identified and quantified for the
samples analysed with 1H NMR spectroscopy, including seven amino acids.
A correlation was observed between identified polar metabolites and meat
sensory attributes using a Pearson correlation. The amino acid carnosine was
associated mostly to sensory effects, and several differences were obser-
ved among samples relating to the amino acids and sensory precursors.
Chakraborty and Joseph utilized 1H, 13C, and DEPT-135 NMR to assess
the ‘cooking and pressing’ technique of extracting fish oil from Sardinella
longicep tissues [195]. This method of analysis was of interest due to the
fact that contrary to other processes there are no associated toxic solvents
or chemical wastes generated, and it is overall cheaper. 1H NMR was used
to identify key peaks and abundances of fatty acids within the oil extracted
by this method, with further validation being conducted by 13C and
DEPT-135 analysis. NMR spectroscopy was used in conjunction with
several other analytical techniques in this study, including FTIR and
GC/MS, to decipher the qualities of the oil obtained from this extraction
method compared to other methods. The carbonyl region of 180–172 ppm
in the 13C NMR spectra allowed for the analysis of the positional distri-
bution of the fatty acids of the crude oils.
A study by Ruyssen et al. characterized the contribution of brining
methods and added adjunct cultures on the sensory characteristics of Gouda
cheese using 1H NMR spectroscopy. Sensory data were obtained using a
trained 20 person panel [196]. 1H NMR was used to obtain chemical
fingerprints of each of the samples which produced complex NMR spectra
where only a few signals could be identified, such as the predominant
resonances observed for lactate and acetate, which are direct products of
carbohydrate fermentation. PCA was used to successfully discriminate the
36 cheese samples into three groups based on ripening time. The study
revealed no significant differences in the metabolite profile of cheeses brined
with different salts, although there were observable differences between
those containing different adjunct cultures.
Chang et al. assessed the quality characteristics of the ‘Cheongsoo’ grape-
vine as a function of grape harvest time using NMR analysis paired with
MVSA [197]. The quality of wine was evaluated for four different grape
harvest times. Multivariate analysis methods (PCA, OPLS-DA) were used
to evaluate fruit character, wine character, and sensory characteristics includ-
ing clarity, colour, acidity, and aroma. Using these statistical tests paired with
1
H NMR, major metabolites, such as proline, tartaric acid and arginine
could be identified and used to differentiate samples from each harvest con-
dition. The identified metabolite differences corresponded to differences in
quality, such as the correlation between high proline content at late harvest
and the associated contribution to wine body. A study by Rochfort et al.
utilized 1H NMR-based metabolomics to assist in sensory analysis of wines
based upon their varieties and different shading regimes [198], and they
reported that grape variety played the largest role in metabolite variations.
PCA loading plots revealed that wine from shaded groups possessed higher
levels of maleic acid, glycerol, and some amino acids, but lower ethanol
content. This differentiation corresponded well with the results of the

sensory panel, which noted decreased mouth-feel attributes such as astrin-
gency. A supervised PLS-DA model was able to demonstrate the correct
prediction of shading effects.
Kwon et al. identified key metabolites in green coffee beans of Coffea
arabica associated with coffee quality using 1H NMR spectroscopy [199].
Green coffee beans were previously graded based on the standards of
the Alliance for Coffee Excellences (ACE), the grading criteria including
colour, aroma, sweetness, cleanness, etc. Metabolite assignments were made
using 2D NMR TOCSY and HSQC experiments. MVSA was used to
analyse the 1H NMR-obtained compositional data, although OPLS-DA
showed greater success in discrimination than PCA. High levels of sucrose
and low levels of GABA were associated with high-grade coffee beans.
However, due to the fact that there are many factors influencing the metab-
olite profile of green coffee, quality and grade could not be specifically iden-
tified just by a handful of metabolites. In a study by Wei et al., a predictive
OPLS model was constructed based on 1H NMR spectra and the qualitative
descriptive analysis of arabica and robusta coffee beans roasted at dark and
light levels [200] was attempted. PCA was used to correlate the chemical
compound identified with bean variety/roast level, and significant separa-
tion was achieved for beans of different roast level, with varietal separation
being less successful.
Watanabe et al. analysed the metabolite profile of tomatoes to assess the
impact of the utilization of pesticides and chemical fertilizers on the content
of water-soluble metabolites and mineral nutrients [201]. 1H NMR analyses
were conducted as well as 2D HSQC and TOCSY experiments to assist
in metabolite identification. PCA scores showed a clear discrimination
between organic versus non-organic grown tomatoes, although no group
separation was observed based on pesticide application. Masetti et al. used
high resolution 1H NMR spectroscopy to develop the metabolic profile
of cherry tomatoes and its variation due to climatic parameters associated
with differences in growing season [202]. Samples consisted of the lipid frac-
tion of tomatoes from each of the two cultivars that were assessed over three
years by 1H NMR spectroscopy and analysed using PCA. Within the spectra
many key compounds could be identified, including saturated fatty acid,
phospholipids, lycopene, and carotenoids. PCA analysis enabled the seasonal
discrimination between samples grown in winter and summer, with carot-
enoids being important biomarkers and showed that different varieties are
influenced differently by climatic conditions. For samples grown during
the winter no significant metabolite differences were observed by PCA analysis,

however, samples grown during the summer did show significant variability.
A study by Abreu et al. utilized 1H NMR-based metabolomic profiling
to differentiate zucchini produced under different growing conditions,
including irrigation and ventilation techniques, and to assess the potential
of different techniques in enhancing crop yield and quality [203]. Key
differentiation was sought among zucchinis irrigated with desalinated sea-
water versus groundwater and between those grown in high versus low ven-
tilation environments. The NMR spectra were assigned by 2D NMR and
provided information about amino acids, organic acids, and carbohydrates
present in zucchini. PCA analysis of the metabolite data showed that plants
grown with desalinated seawater for irrigation had increased yield, higher
glucose, fructose, and vitamin B3, and greater antioxidant activity over those
irrigated with groundwater.
Interestingly, the level of sucrose was found to be higher in plants
irrigated with groundwater, leading to enhanced sweetness. Ventilation,
on the other hand, produced no significant differences, aside from a higher
concentration of trigonelline, histidine, and phenylalanine in plants grown
with higher ventilation and groundwater irrigation.
In a study by Goulas et al. 1H NMR-based metabolic fingerprinting was
used to correlate changes in the qualitative attributes of sweet cherry fruits
with NMR spectral information as a function of storage time, with the study
observing fruits immediately upon harvest and then stored at room temper-
ature for 1, 2, 4, 6, and 8 days [204]. This study was useful in utilizing NMR
to determine the effects of relatively long-term storage on a highly perishable
product. Major metabolites of interest were sugars, phenolics, and organic
acids, while the phenolic spectral region between 8.2 and 8.6 ppm provided
information about the anthocyanin content. The aliphatic spectral region
was important for the assessment of primary metabolites, and the aromatic
region for observing secondary metabolites. The protocol assessed in this
article shows the potential of NMR fingerprinting in the assessment of sweet
cherry properties due to the rich primary and secondary metabolite informa-
tion revealed in the NMR spectra. The study revealed that antioxidant
capacity increased with shelf life, in correspondence with compounds such
as anthocyanins and other phenolics.
In a study by Grandizoli et al. the quality of commercial grape juice
from different geographical regions and characterized by the addition of
sweeteners and/or preservatives was assessed using 1H NMR spectroscopy
[205]. Additionally, homemade grape juice samples prepared without
preservatives were also obtained for analysis and to be compared with the
commercial samples. Tests were also conducted based upon samples
obtained from opened containers being stored at room temperature versus
those stored under refrigeration. Signal assignments in the 1H NMR spectra
were made using literature values, and PCA was also performed on the
1.5–3.0 ppm spectral region. One marker used for differentiation of samples
was the ethanol content, which correlates with the presence of sugars, since
a high sugar content leads to fermentation from yeast contamination. An
increase in the ethanol resonance for commercial grape juice samples,
contrary to the homemade samples, showed that the sterilization method
utilized in the preparation of homemade grape juice proved a viable method
of fermentation prevention without the use of preservatives. Acetic fermen-
tation could also be assessed in the NMR spectrum by the acetic acid singlet
arising at 2.07 ppm.
A study by Malmos et al. utilized high-resolution 31P NMR to quantify the
amount of ammonium phosphatide emulsifiers present in chocolate products
[206]. Emulsifiers, while present in small quantities, play an important role
by contributing to the quality characteristics of chocolate, including thickness,
melting point, and the possible presence of air bubbles. Thus, it is important to
establish a correlation between AMP emulsifier content and the properties of
chocolate, as well as to develop a tool for chocolate quality evaluation by reg-
ulatory bodies. Due to having 100% natural abundance, 31P was a logical tool
for the analysis of this phosphorous containing components. A lipid extraction
was performed on the samples to enable liquid-state NMR analysis of the
analytes of interest. Signals for AMP emulsifier were observed within
the monophosphate spectral region with a dominant peak at 0.0 ppm. Using
the signals identified with liquid-state NMR, the authors were able to quantify
AMP concentrations in both dark and milk chocolates between 0.25% and
1.25%, and two different AMP species could be differentiated and quantified
based upon their differences in monophosphate percentage.
In a study by Lauri et al., 1H NMR spectroscopy was used to obtain the
metabolomic fingerprint of 18 different extra virgin olive oil samples from
different companies and compare it to olive oil sensory evaluation data that,
included 11 different descriptors assessed by a team of trained panellists
[207]. Dendrograms were produced from the PC (principle component)
models produced for both sensory and NMR data. Predictive models devel-
oped using OPLS were used to test the validity of predicting certain sensory
parameters (such as bitter, tomato, rosemary, artichoke, etc.) based on the
NMR fingerprinting data. Kortesniemi et al. investigated the sensory and
chemical profiles of seven Finnish honey varieties using a multi-analytical

approach where one of the core instrumental tools was 1H NMR spectros-
copy, and including organoleptic data from a trained sensory panel [208]. 1H
NMR profiles obtained for the honey samples corresponded well with
the botanical origin of each honey and were analysed further with PCA.
Biomarkers identified with 1H NMR included high levels of isoleucine,
leucine, valine and tyrosine for Buckwheat honey, while PCA loadings
for the cloudberry-bog variety of honey revealed acetic and formic acid
are the strong biomarkers when the carbohydrate resonances are excluded
from the analysis. Sensory analysis in this study was correlated with a com-
bination of gas chromatographic-mass spectrometric/olfactometric (GC-O)
data, rather than the NMR results.
3. Solid state and HR-MAS

3.1 Solid state NMR
Solid state NMR (SS-NMR) is a powerful NMR technique that allows the
analysis of solid food samples even in cases where extractions or purification
steps are not desired and the sample needs to be analysed in its initial form. It
usually requires minimal or no sample preparation and it can be applied to
crystalline and amorphous solids, soft matter and viscous liquids. Compared
to liquid state HR and LF NMR, SS NMR has less applications in food
science. One reason for this is that currently there are no commercially avail-
able systems for high throughput applications for SS NMR. In addition,
more advanced skills are generally required by the spectroscopist to conduct
a solid state experiment compared to liquid NMR, especially the LF. The
most important reason though for the underrepresentation of SS NMR
in food analysis is its lower spectral resolution compared to the liquid state
NMR. The resolution in a SS NMR spectrum is generally decreased due to
orientation-dependent anisotropic interactions, such as chemical shift
anisotropy and dipolar coupling are not averaged by the Brownian motion
as it happens when analysing solution NMR samples. However, spectral res-
olution is excessively improved by combining strong magnetic fields and
magical angle spinning (MAS). In a MAS experiment the sample is rotated
at an angle of 54.74 deg. with respect to the magnetic field and as a result the
anisotropic interactions are significantly suppressed or even eliminated. As a
result, spectra with high resolution can be produced. The development of
advanced pulse sequences that further reduce the broadening factors provide
extra enhancement in spectral resolution. Although the instrumentation and
the pulse sequences used in SS NMR are more complicated as compared to

liquid NMR, the NMR vendors have made great progress in developing
more user friendly systems, which is important, especially in the field of food
science where the NMR expertise is not always a fact.
When hard solid foods are studied they need to be powdered and the
recommended approach is cross polarization (CP-MAS). CP-MAS was
developed to provide 13C, or other heteronuclei spectra, within sufficiently
shorter time by transferring the magnetization from 1H to the heteronuclei.
When running a CP-MAS experiment, one should be cautious of potential
sample degradation, which can be caused by high power radiation, which is
often required for experiments in solid state. In addition to CP-MAS
there are also other SS NMR techniques and pulse sequences that can be
applied, all have their advantages and limitations [209]. Researches may
select the appropriate one according to their study interest or combine var-
ious approaches to obtain more comprehensive information.
One of the earliest applications of SS NMR in food science involved the
13
C NMR analysis of xylo- and cello-oligosaccharides using CP-MAS [210].
After this pioneer work the majority of SS NMR applications in food science
are still involving the CPMAS approach in polysaccharides-related research.
Typical applications are the study of starch aging in bread [211], the effect of
flour hydration [212] on the structure and dynamics, starch polymorphism
[213,214] and reaction monitoring [215,216]. An excellent review article
by Bertocchi et al. describes a significant number of these applications
[217] and provides important technical information about experimental con-
ditions. More recent applications of SS NMR in food polysaccharides include
the analysis of cuticular fractions of berries and suberized membranes of potato
[218], the characterization of films made by banana peels-extracted pectin and
cellulose [219], and characterization of native and retrograded starches using
1D CP MAS and 2D INADEQUATE [220].
Other applications of CP MAS in foods are related to the hydration of
gluten proteins [221], the characterization of vegetable proteins extracted
from oilseed cakes [222], the analysis of the mobile and rigid components
of powder coffee [223] using CP and CP dipolar dephasing, the analysis
of the insoluble precipitates of bottled red wines [224,225], the study of
freeze-drying effects on the structure and digestibility of B-polymorphic
starches [226] and the polysaccharide composition [227] of cell walls.
Although 13C is the most common nuclei used in SS NMR, other nuclei
have been also used. For example 2H NMR was applied to study the orien-
tation and dynamics of epigallocatechin gallate into lipid bilayers [228], and
13
C–31P rotational echo double resonance (REDOR) experiments were
employed to investigate the interaction epicatechin gallate with phospho-
lipid membranes [229]. Recently, CP MAS was applied, in combination
with other techniques, such as IR and scanning electron microscopy to eval-
uate the impact of the treatment with malic acid on the structure and digest-
ibility of wrinkled pea starch [230]. Chi et al. combined NMR with X-ray
diffraction and small-angle X-ray scattering to reveal the mechanism of
starch digestion mitigation by rice protein and its enzymatic hydrolysates
[231]. CP MAS also enabled the identification of changes in helical struc-
ture based on distinct signals in the 13C NMR spectra. In another study,
Szeleszczuk et al. combined 13C CP MAS with theoretical computations
to perform the NMR signal assignment of cinnamic acid derivatives
(CADs), one of the main groups of secondary metabolites appear in food
products of plant origin [232]. One of the most important processes in
the field of food science that attracts a lot of interest is encapsulation.
Ho et al. study the capacity of a novel solid encapsulation of ethylene gas
s into amorphous α-cyclodextrins [233].
Whole foods have been also analysed with SS NMR, which is not sur-
prising as no sample pretreatment is required. Characteristic examples
include the 13C CP-MAS NMR spectra of green and black tea [234], where
signals attributed to individual components such as carbohydrates, terpe-
noids, hemicellulose and polyphenols were detected, analysis of mushrooms
for determining the ratio between proteins and polysaccharides [235], inves-
tigation of the alterations in postmortem porcine muscle properties [236]
and identification of several components in dietary fibre powders from
starches obtained from fruit seeds [237]. Another interesting application
related to dairy science is the combination of single-pulse excitation
31
P SS NMR for the quantitative and quantitative determination of soluble
and insoluble phosphates in semi-hard cow cheeses with double-quantum
filtered 23Na which was applied for the detection of Na+ ions distributions
[238]. 31P detection was also combined with Slow-Speed-Spinning SS
NMR to study the composition of bovine casein micelles, focusing on col-
loidal calcium phosphates [239], although in that study a non-whole food
approach was adopted and the milk was treated prior analysis.
Bathista et al. used SS NMR to study the effect of storage on the chemical
composition and molecular dynamics of mango starch [240]. Molecular
dynamics and potential changes in structure were investigated by running
various contact time (VCT) experiment. The contact time is an important
parameter in a CP MAS experiment and it determines for how long the
Fig. 3 13C NMR spectra of a CE-584 cowpea seeds genotype: (a) 13C CP-MAS spectrum of
the coatless grain; (b) 13C SP-MAS spectra of the coatless grain; (c) 13C CP-MAS spectra of
hydrated powder and (d) dried precipitate; (e) difference spectrum between (b) and (d).
Reprinted from A.P. Sobolev, A. Segre, R. Lamanna, Proton high-field NMR study of tomato
juice, Magn. Reson. Chem. 41 (2003) 237–245, with permission from Elsevier.
magnetization is transferred from 1H, or the abundant nuclei, to 13C, or the

dilute nuclei. By comparing the signal intensities obtained by VCT experiment
the T1ρ value, which describes the relaxation of magnetization in the rotating
frame along the B1 field, was measured. This constant can provide valuable
information about molecular motions in the microsecond range [241] which
is important for food scientists, since many conformational transitions of food
ingredients may be in that range. Recently Iulianelli et al. applied several SS
NMR techniques, including CPMAS, VCT experiment and T1ρ measures,
to assess the genotypes of Cassava, perennial woody shrub with high nutritional
importance for many countries [242]. The combination of high field and low
field SS NMR approaches revealed information about the chemical structure
and composition of cassava varieties. Liquid 1H quantitative NMR was inte-
grated with CP-MAS and single pulse (SP) MAS 13C NMR to assess the geno-
type evaluation of cowpea seeds [243]. Fig. 3, shows the CP MAS and SP MAS
13
C NMR spectra of seeds under different conditions.
3.2 HR-MAS NMR

SS NMR can be applied to powders and crystals but is can be also applied to
soft tissues using HR MAS NMR probes and produce high quality spectra
comparable to those obtained by liquid state NMR. HR-MAS for soft
tissues and semi-solid material is a very attractive option for food scientists
and offers several advantages compared to liquid state NMR especially in
terms of being non-destructive. It allows measuring solid or semi-solid
samples without changing the inner structure or loss of potentially critical
components due to extraction process. It is also an alternative NMR option
when the sample is only soluble in toxic organic solvents. A typical sample
preparation procedure for HR-MAS analysis involves a piece of sample that
is evenly packed in a rotor, often followed by adding a small amount of deu-
terated solvent and internal reference. The rotor is then placed in the NMR
instrument and start spinning at the magical angle with a certain speed rang-
ing from a few hundredths to thousands of Hz. The combination of HR
spectra obtained with no sample irrigation, with chemometric analysis, ren-
ders HR MAS as one of the most promising tools in the area of food analysis.
The existing limitation of HR-MAS is that quantification can be challenging
when needed. By combing direct polarization (HR-DPMAS), quantifica-
tion can be achieved at the cost of extensively longer experiment time.
Although the spectral resolution in 1H HR-MAS is much higher compared
to the regular SS experiments it still has signal broadening issues in some
cases, especially when solid samples and there is a narrow chemical shift win-
dows where peaks appear. Therefore, several studies would, instead, choose
13
C or 31P NMR to obtain better resolved spectrum, which is a more time-
consuming approach due to the naturally low abundance of 13C.
HR-MAS has gained popularity in food science domain although the
number of applications it is still considered small [244]. Characteristic exam-
ples include the compositional profiling of intact muscle of smoked Atlantic
salmon using 1D and 2D experiments [245], the metabolic profiling of
tomatoes for tissue differentiation and fruit ripening [246], the analysis of
tomato juice and pulp [247], the compositional characterization of lemon
juice [248], the identification of triterpenoids in olive leaf [249] and
the monitoring of compositional changes of mango during ripening
[250]. HR-MAS has been widely employed in various food authentication
studies, mainly varietal and geographical discrimination. For example, it has
been applied for studying the metabolic profile of apples from various vari-
eties [251], for achieving the geographical differentiation of Italian sweet
pepper [252], for the characterization of tomato ‘flavour varieties’ from
Spain [253], for the varietal characterization of cherry tomatoes [254] and
for the determination of the geographical origin of emmental cheese
[255] and the chemotaxonomic investigation of Hancornia speciosa
(Apocynaceae) plant varieties [256]. Chemometric analysis of spectral data
obtained by HR-MAS also enabled the evaluation of the geographical origin

of cocoa beans [257]. The simultaneous detection of important metabolites
such as amino acids, polyalcohols, organic acids, sugars, methylxanthines and
catechins was feasible; however, HR-MAS did not allow a reliable quanti-
tative analysis. However, as depicted in Fig. 4, the PCA plot obtained from
the 400 MHz HR-MAS 1H NMR fingerprints led to good separation of
cocoa beans from America, Africa and Asia/Oceania. Choze et al. applied
HR-MAS and untargeted analysis for the distinction between a transgenic
and a conventional common bean genotype. Authors were able to assess
the genetic modification because it was reflected in the metabolome as
determined by HR-MAS NMR [258]. In addition, Vermathen et al. were
able to monitor the changes in the metabolic profile of apples induced by
different production approaches [259]. In that study several univariate and
multivariate statistical methods were also employed. A recent study on vari-
ety discrimination has been conducted on persimmon [260]. Metabolic
variations were monitored by 1H HR-MAS NMR spectroscopy, as shown
Fig. 4 Score plot of orthogonal signal correction (OSC) PCA obtained from the HR MAS
1
H NMR fingerprint dataset of cocoa beans samples from America, Africa and
Asia/Oceania. Reprinted from A. Marseglia, D. Acquotti, R. Consonni, L. Cagliani, G.
Palla, A. Caligiani, HR MAS 1H NMR and chemometrics as useful tool to assess the geo-
graphical origin of cocoa beans—comparison with HR 1H NMR, Food Res. Int. (Ottawa,
Ont.) 85 (2016) 273–281, with permission from Elsevier.
in Fig. 5, during the development period of two different cultivars and

correlations between the levels of metabolites such as amino acids, organic
acids and carbohydrates were performed.
HR-MAS has been used in food processing and food quality evaluation
as well. HR-CPMAS and HR-DPMAS have also been used to assisting
incorporating green tea catechins in cheese system to extend the shelf-life
[261]. Heude et al. have investigated using HR-MAS to assess the freshness
of fish, and found two indicators [262]. Combined with PCA, HR-MAS
was utilized to characterize dry-fermented sausages during the manufac-
turing process [263]. The high spectral resolution enabled the complete
metabolic characterization of intact dry fermented sausages and enabled
the monitoring of the alterations related with the fermentation and curing
processes. Other meat-related applications include the post mortem moni-
toring of lactate formation in the muscle of rabbit [264], the identification
of the geographical origin of dried beef [265] and investigations of the
relationship between specific metabolites and pectoralis muscle dystrophy
in chicken [266]. The impact of genetic, processing and environmental
factors on the metabolic profile of four marmande type tomato varieties
was explored by Iglesias et al. [267]. Authors combined HR-MAS with
OPLS-DA and found that organic acids and the fructose/citric acid and
glucose/citric acid ratios are the main factors of discrimination. The fatty
acid composition of Jatropha curcas seeds under different agronomical
practices was also achieved by using 1H HR-MAS NMR [268]. This is a
promising application that allows the determination of lipids directly in
the seeds, without extraction and has the potential of been employed in
other seeds and foods with a high oil content. Ribó et al. used HRMAS
1
H and 13C NMR in combination to sensory analysis, to investigate poten-
tial changes in the biochemical profile of almonds due to aging and to
electron beam irradiation [269]. Direct polarization methods were used
instead of CP MAS in order to focus on the mobile part of the lipid fraction.
HR-MAS has been used in analysing starchy food by a number of
researchers due to the insolubility of starch, which limits the application
of liquid state NMR. Huang et al. have attempted to distinguish diffe-
rent potato cultivars by examining lyophilized potato peel using both
HR-CPMAS and HR-DPMAS, and identified a group of components that
contribute the most variations between cultivars, that is also related to
periderm russeting difference [270]. Rice, as a main staple food world widely
with high starch content, has been studied on cultivar differentiation
using HR-MAS [271].
Fig. 5 400 MHz HR MAS 1H NMR spectra of persimmon during the process of development (from September (S) to March (M)). Reprinted from
A.D. da C. Santos, F.A. Fonseca, L.M. Dutra, M. de F.C. Santos, L.R.A. Menezes, F.R. Campos, N. Nagata, R. Ayub, A. Barison, 1H HR-MAS NMR-based
metabolomics study of different persimmon cultivars (Diospyros kaki) during fruit development, Food Chem. 239 (2018) 511–519, with permission
from Elsevier.
4. Low field and MRI

Low-field and benchtop NMR approaches are becoming more and
more popular nowadays [272,273] and are on their way to become more
prominent and enjoy increased applications in industrial food analysis
because of their low cost, user-friendly interface and less demanding oper-
ational requirements, especially regarding cryogens which are necessary for
high resolution magnet systems. LF-NMR uses small size cryogen-free per-
manent magnets instead of superconducting magnets, which may fit better
in an industrial environment and has been proposed as an alternative and
more practical choice [274]. LF NMR instruments range from 40 to
100 MHz and modern console and electronic interfaces have been devel-
oped to increase the resolution and S/N performance of benchtop NMR
spectrometers, which has been the inherent disadvantage of this technique
due to the use of less powerful magnets. Furthermore, mobile and compact
NMR devices developed during the last decade have the advantage of being
transportable, and thus may be used in on-site studies that transfer the lab to
field [275]. Traditionally, low-field NMR applications in foods mostly
involved MRI, relaxometry and diffusion studies [276], however, benchtop
spectrometer commercial availability and the development of chemometrics
have renewed interest in LF time-domain NMR and opened new space and
opportunities for spectroscopic LF-NMR applications in food analysis. The
application of LF-NMR in different types of foods has been reviewed
recently [277–280]. Bertram [281] and Colnago et al. [282] have summa-
rized 1H NMR relaxometry applications in meat science, and an updated
review of applications of NMR relaxometry and imaging for the analysis
of dairy products has also been just published [283]. Applications of
NMR relaxometry on cereal products [284] and for the determination of
wheat protein content and quality have also been reviewed [285].
4.1 Time-domain NMR

The vast majority of low field NMR studies have been focusing on
time-domain NMR measurements, rather than frequency. Time-domain
NMR studies take advantage of the differences in molecular mobility
between various food components [286], as reflected in the longitudinal (T1)
and transverse (T2) relaxation times of protons, usually those of water. The
separation of multiple types of water protons based on the deconvolution of
T1 and T2 measurements provides information on regions of different
mobility in foods, and thus is important in defining the compositional, phys-

icochemical and textural properties of foods, and the effect of processing,
storage and other factors of quality control and industrial interest.
In studies related to meat quality control, relaxometry was used to evaluate
the effect of ultrasound-assisted immersion freezing on the microstructure,
quality and water distribution of porcine longissimus muscles during frozen
storage [287], and of sub-freezing storage (6, 9 and 12 °C) on the quality
and shelf life of beef [288]. The textural properties and gelling of meat
products such as p^ate [289] and sausages [290] have also been studied by
NMR relaxometry. Cooking has also been studied in detail, examples
including the effects of heating temperature and time on braised beef [291],
and the effect of deep-frying temperature on moisture distribution and quality
of beef jerky [292]. The dry-curing of ham was studied with the help of
fast field cycling NMR relaxometry [293], while water migration and
water-protein interactions during lamb meat air-drying were also the subject
of investigation [294]. Finally, NMR relaxometry was used to study in detail
several important factors related to meat batters, such as water-holding capac-
ity in the presence of salt and polyphosphates [295], protein hydration states
and water/fat mobility [296,297], chopping time and heating [298].
Due to its importance in fish quality traits, cold/frozen storage has been
investigated in detail for a variety of fish products, such as yellow fin tuna
[299], salted sardines [300], salmon [301] and mackerel [302]. LF-NMR
relaxometry has also been evaluated as a non-invasive tool for monitoring
the changes induced to caviar during cryopreservation at 4 °C for extended
periods (11 months) and the effect of the salting treatment [303]. LF-NMR
has also been used to evaluate the efficiency of different packaging technolo-
gies for catfish fillets [304], and determine the applicability of green and
emerging packaging technologies with extended shelf-life, such as the treat-
ment of packaged herring fillets using atmospheric cold plasma [305].
Capitani et.al have used a portable NMR instrument to monitor the water
status at different ripening points of entire Hayward kiwifruits in a non-
destructive manner [306,307]. Fundo et al. used the water transverse relaxa-
tion times (T2) to understand storage stability of fresh-cut ‘Rocha’ pears [308],
while Sun et al. employed LF-NMR to investigate the distribution, state and
content changes of water in fresh jujubes during storage at low (4 °C) or room
(25 °C) temperatures [309]. Huang et al. [310] used low field relaxometry to
study water dynamics in different ginger cultivars as affected by the presence of
different organic solutes, while Zhu et al. studied the softening of sweet
cherry due to water migration and loss as observed through LF-NMR T2
relaxometry [311]. Fig. 6 depicts the redistribution of vacuolar water during

cold storage of sweet cherry fruits as observed through T2 relaxation measure-
ments. The effects of hot-air oven dehydration of Fuji apple slices and the
pulsed electric fields treatment on apples have been evaluated using NMR
relaxometry [312]. This methodology has also been very helpful in the opti-
mization of freezing conditions for minimal fruit damages during the freezing
process for blueberries [313] and mandarins [314]. TD-NMR was evaluated,
along with near- and mid-infrared spectroscopies, as a possible predictor of
various orange fruit quality parameters, and it was reported that NMR relax-
ation parameters in combination with chemometrics could be correlated
successfully with peel thickness and total pectin content [315].
The effect of storage time and sugar concentration on the quality character-
istics of two important apple products, apple jam [316] and apple jelly [317] was
studied by proton T2 relaxometry and MRI. In recent LF-NMR studies related
to corn, Ma et al. investigated the effect of konjac glucomannan addition on past-
ing and rheological properties of corn starch [318], while Yang et al. studied
cornmeal fermentation [319]. Other noteworthy applications include the study
the moisture content and water dynamics of cubed apples upon microwave
vacuum drying [320] and the use of LF-NMR to monitor the fermentation
process of natto soybeans [321].
Fig. 6 Change of moisture distribution of sweet cherry fruit by transverse relaxation T2

using LF-NMR during storage at 4 °C. T21: cell wall protons; T22: cytoplasmic water; T23:
vacuolar water. Reprinted from D. Zhu, J. Liang, H. Liu, X. Cao, Y. Ge, J. Li, Sweet cherry
softening accompanied with moisture migration and loss during low-temperature
storage, J. Sci. Food Agric. 98 (2018) 3651–3658, with permission from John Wiley and Sons.
1D and 2D NMR relaxometry of multiple proton populations present in

bread was used as a tool to investigate bread staling and the physico-chemical
changes induced by it [322]. The effect of different ingredients, such as
maltitol [323], high bran [324], fenugreek fibre [325], fermented glutinous
rice [326] or chickpea flour [327] on bread quality during bread-making
and storage has been investigated by proton NMR relaxometry. In another
application, TD NMR relaxometry was used to evaluate the impact of ingre-
dients and baking protocols on the quality of gluten-free cakes [328], and it has
contributed towards the understanding of the microstructure of gluten-free
baked products [329]. NMR relaxometry has also been shown to be a valuable
tool to describe the entire cooking process of pasta [330].
Recently, NMR relaxometry was used to assess the oxidation and the
morphology of polyunsaturated fatty acids in butter, rapeseed oil, soybean
oil, and linseed oil, by generating 2D graphical maps of T1 versusT2
[331]. Chen et al. [332] demonstrated the practicability of using
LF-NMR as a fast and accurate method for the quantification of water
and oil in fried starchy food model systems. Applying this line of research
on a real food system, Wang et al. used LF-NMR to determine the water
and oil contents in French fries, and evaluate frying oil quality during deep
frying [333].
Confectionary gels and gelatin-based soft candies formulated using dif-
ferent traditional [334] and novel [335] low-calorie sweeteners have also
been studied using NMR relaxometry. TD-NMR applications for the
detection of milk quality and adulteration [336], edible oil differentiation
[337], and the authentication of herbs [338] demonstrate the breadth of
applicability of this technique in food analysis.
4.2 Frequency-domain NMR

In recent years low-resolution and low field NMR spectroscopy utilizing
benchtop permanent magnet NMR spectrometers has been successfully
employed for detecting various food adulterations. Despite the challenge
of poor spectrum resolution, it has been successfully applied for the authen-
tication of such abundantly consumed food commodities as coffee, oil and
meat. 16-O-methylcafestol (16-OMC), a compound proposed as a unique
component of Robusta coffee beans, was validated as a marker to distinguish
Arabica coffee beans from Robusta using low field NMR spectroscopy
[339,340]. Jakes et al. [341] demonstrated the successful authentication
of beef versus horse meat using 1H NMR spectroscopy at 60 MHz in
combination with chemometrics. Parker et al. [342] applied LF-NMR spec-

troscopy, also at 60 MHz, to successfully differentiate frying oils from edible
oils. More recently, Gouilleux et al. [343] proposed the use of ultrafast 2D
NMR as a method to enhance the resolving power of low-field NMR of
food samples compared to 1D NMR within reasonable experimental time.
Ultrafast 2D NMR was then used successfully by these authors for edible oil
analysis and adulteration with a low-field 43 MHz NMR system. Since spec-
tral resolution is one of the main limitations of LF-NMR spectroscopy, the
development of fast 2D NMR experiments in combination with advanced
acquisition methods, such as non-uniform sampling (NUS), may in the future
succeed to address this problem and make possible the acquisition of higher
resolution spectra with adequately resolved NMR signals using benchtop
LF NMR systems. This will undoubtedly increase the scope and breadth of
possible applications of LF-NMR spectroscopy in food analysis.
4.3 Magnetic resonance imaging

Although MRI is mainly known for its use in medical diagnosis and biome-
dical research, it is also extensively applied in various fields of food science.
MRI can produce three dimensional proton density maps of materials, and
since water is a big component of practically all foods, MRI can be used to
produce images of foods and their texture, and analyse the content of foods
in a non-invasive manner. The contrast in MRI images of foods can be
provided also by the difference in 1H relaxation times (Τ1, Τ2) of water
in different food regions. The primary advantage of MRI is that it is
non-destructive, thus allowing real-time monitoring and assessment of food
products. Comparative studies between conventional methods of food
analysis/ characterization and MRI have been conducted frequently, aiming
to explore MRI as a novel alternative methodology for multiple property
measurements with minimal sample preparation requirements. Depending
on the specific case, the sample varies between whole food products, such
as fruits, and cut pieces of food material which can be placed in an MRI
instrument for scanning.
Bajd and coworkers have used both MRI [344] and multiparametric
magnetic resonance microscopy [345] for the characterization of dry-cured
ham tissues. Caballero et al. [346] examined the suitability of different MRI
acquisition sequences (spin echo, gradient echo and turbo 3D), algorithms
for MRI analysis and predictive data mining techniques for studying the sen-
sory attributes of dry-cured loins. Frelka et al. used MRI to assess the effect of
repetitive freeze/thaw cycles on the quality attributes of chicken breast meat
[347]. Dry-curing of ham at different steps of the manufacturing process

(raw, salted, post salted, half-cured and cured) was studied using MRI, in
order to better understand the structural changes occurring during this
important processing procedure [348]. MRI has also been used as a high
throughput technique to measure the mass fat fraction of salmon steaks with
good accuracy, within about 1 min per steak sample [349].
A number of studies utilizes in tandem both relaxometry and MRI in
order to develop suitable methodologies for food-related analytical prob-
lems, since frequently relaxation times are also determining MRI signal
intensity. A combination of LF-NMR and MRI was used to monitor the
hot-air drying procedure and changes in the distribution of water of broccoli
[350] and matsutake mushrooms [351] during the drying process. Li and
coworkers developed a methodology to detect adulteration of prawns with
different types of hydrocolloids (gelatin, carrageenan, agar, amorphophallus
konjac and xanthan gum) based on LF-NMR and MRI [352], as depicted
in Fig. 7. Zhang et al. used low field MRI to quantify lipid tissue in live
Fig. 7 Proton density weighted images of prawns injected with different hydrocolloids
of increasing concentration. Reprinted from M. Li, B. Li, W. Zhang, Rapid and non-invasive
detection and imaging of the hydrocolloid-injected prawns with low-field NMR and MRI,
Food Chem. 242 (2018) 16–21, with permission from Elsevier.
Chinese mitten crabs and demonstrated the potential of this approach for
grading commercial live crabs or advising crab farmers on breeding and
fattening processes [353]. Xia et al., used NMR and MRI to analyse the
water dynamics of turbo flesh during frying, boiling and stewing, and dem-
onstrated the potential of this approach for the rapid and non-destructive
analysis during food processing [354].
T2 relaxation and MRI were used to study the changes induced on fresh
noodles during storage at room temperature [355], and the inhibitive effect
of polyols on the deterioration of gluten network and noodle texture [356].
In MRI and relaxometry studies of similar scope, the effect of frozen storage
on the quality of frozen pre-cooked noodles was investigated by Liu et al.
[357], while Nakanishi et al. used T2 relaxometry to examine the effect
of tomato sauce on pasta boiling [358]. Zhu et al. used LF-NMR in
combination with chemometrics to develop models for detecting peanut
oil adulteration with soybean, rapeseed and palm oil above the 30% thres-
hold [359]. Song et al. developed a novel variable temperature sample probe
that can accommodate large food samples and is suitable for the direct NMR
and MRI investigation of food phase transitions [360].
Researchers have applied MRI coupled with chemometrics to distin-
guish different cultivation fertilization effects on wine grapes [361] and pre-
dict grape split [362]. MRI is an excellent tool for the study of fruit ripening
and maturity [363] and its application for the postharvest quality monitoring
of fruits has been recently reviewed [364]. Besides, numerous studies have
been published dealing with LF-NMR and MRI as applied for the study
of food processing and storage conditions, such as the effect on meat by
freeze-thaw cycles [365] sausage fermentation [366], and duck egg salting
[367]. Finally, cooking and ready to eat foods have also received attention,
as for example in studies of oil and moisture distribution in fried potatoes
[368] and frozen-cooked noodles [369].
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CHAPTER FIVE

Magnetic resonance applications

Annual Reports on NMR Spectroscopy, Volume 98 # 2019 Elsevier Ltd 239

NMR spectrum. NMR is a non-destructive analytical method that can

2. High resolution liquid NMR spectroscopy

sensitivity compared to other NMR-based approaches, as a result of the strong

problem. In such cases, the selection of a room temperature probe can be

virtual separation of important ingredients in manuka honey [27], the deter-

techniques [39]. Ultrafast intermolecular single quantum coherence spec-

as related to prevention of sample recovery for further instrumental, sensory or

In addition to the saponifiable fraction of edible oils, NMR can be

stevia [108], identification of gums in gelled food concentrates [109],

significantly reduce the NMR experimental time, further increases their

Finally, Merkx et al. carried out the quantification of monosaccharides of

2.2 Food authentication

authentication of foods. For example, Mannina and Sobolev published in

et al. investigated the adulteration of sunflower lecithin with soy lecithin

in such spectra were found to be important cultivar biomarkers. Phenolic

classification model with data fusion demonstrated superior performance.

differentiation were identified. By studying chemical composition correlations

data analysis helped reveal the biochemical differences at four developmental

The botanical and geographical assessment of acacia honey samples of

2.3 Quality control and sensory analysis

quality. For that reason, we decided to provide a more detailed discussion of

content. This differentiation corresponded well with the results of the

the winter no significant metabolite differences were observed by PCA analysis,

chemical profiles of seven Finnish honey varieties using a multi-analytical

3. Solid state and HR-MAS

the pulse sequences used in SS NMR are more complicated as compared to

magnetization is transferred from 1H, or the abundant nuclei, to 13C, or the

3.2 HR-MAS NMR

obtained by HR-MAS also enabled the evaluation of the geographical origin

in Fig. 5, during the development period of two different cultivars and

4. Low field and MRI

4.1 Time-domain NMR

mobility in foods, and thus is important in defining the compositional, phys-

relaxometry [311]. Fig. 6 depicts the redistribution of vacuolar water during

Fig. 6 Change of moisture distribution of sweet cherry fruit by transverse relaxation T2

1D and 2D NMR relaxometry of multiple proton populations present in

4.2 Frequency-domain NMR

combination with chemometrics. Parker et al. [342] applied LF-NMR spec-

4.3 Magnetic resonance imaging

[347]. Dry-curing of ham at different steps of the manufacturing process

[45] P. Jansson, B. Kay, Aldehydes identified in commercially available ω-3 supplements

[97] M. Forino, A. Gambuti, L. Moio, NMR-based systematic analysis of bioactive

fruiting bodies: chemical characterization and bioactivities at different levels of

[130] S.R.P. Madawala, C. Brunius, A. Adholeya, S.B. Tripathi, K. Hanhineva, E. Hajazimi,

[146] _l.S. Ozdemir,

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[212] L. Calucci, L. Galleschi, M. Geppi, G. Mollica, Structure and dynamics of flour by

[229] Y. Uekusa, M. Kamihira-Ishijima, O. Sugimoto, T. Ishii, S. Kumazawa, K. Nakamura,

[263] A.B. Garcı́a-Garcı́a, S. Lamichhane, D. Castejón, M.I. Cambero, H.C. Bertram, 1H

[280] M.F. Marcone, S. Wang, W. Albabish, S. Nie, D. Somnarain, A. Hill, Diverse

[330] P. Littardi, A. Diantom, E. Carini, E. Curti, F. Boukid, Y. Vodovotz, E. Vittadini,

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