Food Research International 51 (2013) 729–747

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Food Research International

journal homepage: www.elsevier.com/locate/foodres

Review

Diverse food-based applications of nuclear magnetic resonance (NMR) technology

Massimo F. Marcone a,⁎, Sunan Wang a, William Albabish a, Shaoping Nie b, Dinesh Somnarain a, Art Hill a
a
Department of Food Science, University of Guelph, 50 Stone Road East, Guelph, Ontario, Canada N1G 2W1
b
State Key Laboratory of Food Science and Technology, Nanchang University, 235 Nanjing East Road, Nanchang, Jiangxi Province, 330047, China

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

Article history: Nuclear magnetic resonance (NMR) spectroscopy is one of the most common investigative techniques used
Received 15 December 2011 by both chemists and biochemists to identify molecular structures as well as to study the progress of chem-
Accepted 21 December 2012 ical reactions. Magnetic resonance imaging (MRI), another type of NMR technology, has extensively been
used in medical radiology to obtain soft tissue images for diagnostic purposes in medicine. Food scientists
Keywords:
have also explored the use of both NMR and MRI and continue to develop a wide range of applications for
Nuclear magnetic resonance (NMR)
Magnetic resonance imaging (MRI)
food analysis and food processing. This review begins with a brief introduction to NMR and then focuses
Foods on current diverse NMR applications in food research and manufacturing. Topics covered include chemical
compositional analysis and structural identification of functional components in foods, determination of
composition and formulation of packaging materials, detection of food authentication, optimization of food
processing parameters, and inspection of microbiological, physical and chemical quality of foods. This review
also emphasizes the pros and cons of specific NMR applications in the analysis of representative foods such as
wine, cheese, fruits, vegetables, meat, fish, beverages (i.e. tomato juice and pulp, green tea, coffee) and edible
oils, as well as discussing both the challenges and future opportunities in NMR applications in food science.
© 2013 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 730
2. Potential applications of NMR/MRI for compositional analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 730
2.1. Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 730
2.2. Fat and fatty acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 732
2.3. Protein/amino acids (AAs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 733
3. Potential applications of NMR/MRI for structural analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 733
4. Potential applications of NMR/MRI for inspection of microbiological, physical and chemical quality of foods . . . . . . . . . . . . . . . . . 734
5. Application of NMR in food packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 735
6. Potential application of NMR/MRI in food authentication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 735
6.1. Honey . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 735
6.2. Salmon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 735
6.3. Olive oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 736
6.4. Beverages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 736
7. Potential applications of NMR/MRI for on-line monitoring of food processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 736
8. Specific NMR/MRI applications to some representative foods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 737
8.1. Wine and beer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 737
8.2. Fruit and vegetable juice and pulp, green tea, and coffee . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 737
8.3. Edible oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 742
8.4. Cheese . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 742
8.5. Fruits and vegetables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 742
8.6. Meat and fish . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 743
9. Conclusion and future research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 743
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 744

⁎ Corresponding author. Tel.: +1 519 824 4120x58334; fax: +1 519 824 6631.
E-mail addresses: mmarcone@uoguelph.ca (M.F. Marcone), swang@uoguelph.ca (S. Wang).

0963-9969/$ – see front matter © 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.foodres.2012.12.046
730 M.F. Marcone et al. / Food Research International 51 (2013) 729–747

1. Introduction capability of currently available on-line food quality sorting method-

Nuclear magnetic resonance (NMR) can be applied to a wide
range of liquid and solid matrices without altering the sample or pro-
ducing hazardous wastes. Although the sensitivity and detection
limits of NMR still need to be improved, NMR still has several advan-
tages relative to other common analytical tools such as high pressure
liquid chromatography (HPLC), gas chromatography (GC) and mass
spectrometry (MS).
NMR technology was initially used in the late 1940s to elucidate the
structure of molecules in organic chemistry (Gutowsky, Kistiakowsky,
Pake, & Purcell, 1949). However the diverse applications of NMR spec-
troscopy in food science were delayed until the 1980s, primarily due
to lack of scientific expertise, high cost of equipment, and the absence
of NMR parts designed specifically for food purposes, although pulsed
NMR had been applied to foods and related materials earlier than this.
With the development of NMR instrumentation and improved pro-
grams to collect and analyze the data, NMR's applicability has recently
rapidly expanded in the field of food science and technology. A wide
range of NMR food-related research has covered various fields of food
science, including food microbiology, food Chemistry, food engineering
and food packaging (as shown in Table 1) (Belton, Engelsen, & Jakobsen,
2005; Chen et al., 2010; Nestor et al., 2010; Vilen et al., 2010). As illus-
trated in Fig. 1, the numbers of these studies are dramatically increased
in recent years.
A solid background with regards to NMR principles has been well
documented (Belton, Gil, Webb, & Rutledge, 2003; Belton et al., 2005;
Engelsen, Belton, & Jakobsen, 2005; Farhat, Belton, & Webb, 2007;
Gudjonsdottir, Belton, & Webb, 2009; Hills, 1998; Renou, Belton, &
Webb, 2011; Webb, Belton, Gil, & Delgadillo, 2001). Nowadays, NMR
analysis is often based on the behavior (relaxation) of NMR active nuclei
(i.e. 1H, 13C which are the most widely used for food applications) in a
magnetic field and a pulsed Radio Frequency (RF) irradiation. Relaxa-
tion describes a complex process of the nuclei from excitation [due to
splitting of the nuclear spin levels (Zeeman effect) by applied magnetic
field] to equilibrium (Novoa-Carballal, Fernandez-Megia, Jimenez, &
Riguera, 2011).
Based on the principle of NMR, magnetic resonance imaging (MRI)
further permits visual observation of the interior of foods. MRI offers
not only information about the chemical composition and internal
structure of certain foods, but also permits monitoring of internal
compositional and structural modification of foods when they experi-
ence different agricultural practices (i.e. harvest, postharvest) and
industrial possessing. The former would automatically expand the
ologies, which have typically only been used to monitor external
properties such as color, size, shape or externally visible defects
(Chayaprasert & Stroshine, 2005). The latter would provide a better
understanding of the impacts of these external factors on the
physiochemical properties (Herrero et al., 2007; Renou, Foucat, &
Bonny, 2003).
The progress in research of NMR use on foods has been addressed
in several recent reviews with a limited scope focusing on NMR
applications either in particular foods, such as wine (Ogrinc, Kosir,
Spangenberg, & Kidric, 2003); dairy foods (Mariette, 2009) or specific
applications, such as identification of food authenticity (Mannina &
Segre, 2002) and investigation into the correlations between water
distribution and mobility, water holding capacity and meat quality
(Pearce, Rosenvold, Andersen, & Hopkins, 2011), or assessment or
inspection of the quality parameters of fruits (Butz, Hofmann, &
Tauscher, 2005). Due to the importance and versatility of NMR/MRI
applications in food science and technology, a comprehensive review
would help to identify future trends of NMR application in food
science.
This review provides a comprehensive summary of diverse applica-
tions of NMR in both food research and manufacturing, followed by de-
tailed information on the use of NMR in certain foods (i.e. wine, cheese,
fruit, vegetable, meat, fish, tomato juice, pulp, green tea, coffee, oil).
2. Potential applications of NMR/MRI for compositional analysis
Due to the fact that many foods are proton-rich, with protons origi-
nating, e.g., from water, fat, carbohydrates, and proteins; proton NMR
becomes the most common type of NMR to determine these abundant
food components. The components are essential for human nutrition
and also influence the intrinsic properties of food during processing,
storage, and transportation.
2.1. Water
In NMR spectroscopy, the signal of water in food samples has been
frequently investigated for the determination of water content and
water distribution in foods (Butz et al., 2005; Ciampa, Dell'Abate,
Masetti, Valentini, & Sequi, 2010; Otero & Préstamo, 2009; Pearce et
al., 2011; Sequi, Dell'Abate, & Valentini, 2007). In fact, magnetic reso-
nance imaging (MRI) permits visual observations of the spatial and
molecular distribution of water with its food matrix environment.
For example, MRI offers visualized bi-dimensional and partial image

Table 1
Example of NMR spectroscopy applications in specific topics of food science.

Selected application Representative Examples States of food Reference

Liquid Solid

Quantitative analysis Water/moisture Soybean X Chen et al. (2010)

Conformational analysis
Nutritional or functional aspects
Packaging materials
Quality Control
Process control
contents
Lipid (fatty acid) Arctic char X Nestor et al. (2010)
Heifers meat X Ballerini et al. (2002)
Beef, chicken and pork X Keeton et al. (2003)
Milk X Hu, Furihata, Kato, and Tanokura (2007)
Mustard seeds and rapeseeds X Pedersen, Munck, and Engelsen (2000)
Protein (amino acid) Orange and grapefruits juice X Belton et al. (1996)
Mustard seeds and spring rapeseeds Pedersen et al. (2000)
Polysaccharides Carrageenan gum X Vilen, Lundqvist, Jouanneau, Helbert, and Sandstrom (2010)
Metabolites Green tea X Lee et al. (2010)
Isoflavones Methanolic soybean extract X Caligiani, Palla, Maietti, Cirlini, and Brandolini (2010)
Irradiation Polymer X Pentimalli et al. (2000)
Authenticity Virgin olive oil X Alonso-Salces et al. (2010)
Food additives Banned dyes–Sudan dyes X Di Anibal, Callao, and Ruisánchez (2011)
Rheology Wheat doughs X Lopes-da-Silva, Santos, Freitas, Brites, and Gil (2007)
Salting and storing Wild and farmed Atlantic cod X Gudjonsdottir et al. (2010)
(Gadus morhua)
 M.F. Marcone et al. / Food Research International 51 (2013) 729–747
Fig. 1. The distribution of scientific publication regarding the applications of NMR in the field of food science and Technology in ISI web of science during 1971–2011 (adapted date
from citations).
on internal morphological organization of certain foods (such as high
water content foods). The intensity of the signal in the various zones
of the sample may be directly proportional to water molecule con-
tent. Specifically, darker areas in an image may mean that there are
less water/protons. The area could contain a high concentration of
ions and or contrast agent, etc. which enhances relaxation, causing
the area to become darker (Butz et al., 2005).
The use of MRI also permits the quantification of water content
and water distribution by magnetic resonance parameters (i.e., T1
and T2), which provide information about physical (distribution,
compartmentalization) and chemical (mobility, interactions with
macromolecules) water properties. By repetitive measures of the
same samples, MRI can detect variations in the water concentration,
as well as changes in water interaction with cellular tissues of these
foods. This variation may associate with maturity, damage, decay, or
other quality related factors of fruits and vegetables (Butz et al.,
2005). Variations may also be caused by various factors, such as envi-
ronmental and climate conditions in which the raw materials were
produced, and the processing of these raw materials into food prod-
ucts (Butz et al., 2005; Ciampa et al., 2010; Otero & Préstamo, 2009;
Pearce et al., 2011; Sequi et al., 2007).
Most recently, MRI results illustrated the importance of changes
occurring in water content among cherry tomatoes according to the
season (i.e. winter, spring and summer) (Ciampa et al., 2010), all of
which impact their shelf life and storage conditions. MRI provided
information about water content and its spatial organization in the
different zones of cherry tomatoes. NMR parameters (T2 and T1)
were measured in the cellular tissues (i.e. pericarp and endocarp) of
Pachino cherry tomato fruits. Variations of T1 and T2 represented
the change of water molecular motion and its distribution within
the fruit, caused by seasonal variations (summer, spring and winter)
(Ciampa et al., 2010). On the basis of the information regarding
water content and its distributions within the product, geographical
place of cultivation could be distinguished among 70 cherry
tomatoes (Sequi et al., 2007). In yet another study, different impacts
731
of pressure processing (i.e. pressures of 100 and 200 MPa) on the
quality of strawberry products were also found (Otero & Préstamo,
2009).
In order to determine the accuracy and precision of NMR-based
water content determination techniques, comparative studies have
been carried out. Keeton et al. (2003) compared the moisture con-
tents obtained by NMR analysis for meat products, including beef,
deboned chicken with skin, pork, and all-beef hot dogs, with those
obtained using the AOAC officially described analytical methods
which consisted of forced air oven drying. The NMR results for mois-
ture in beef, chicken, and pork were 40.42%, 74.37%, and 73.75%, re-
spectively, being in good agreement with those obtained using
AOAC Official Methods (i.e. 40.39%, 74.57%, and 73.94%, respectively)
(Keeton et al., 2003).
2D MRI was also used successfully to monitor moisture transpor-
tation in two different multicomponent food systems: one had a
low water activity contrast that results in a slow moisture transport
(hours), another one had a high water activity contrast that results
in a fast moisture transport (days) (Ramos-Cabrer, Van Duynhoven,
Timmer, & Nicolay, 2006).
It should be noted that the signal through the MRI studies of the
water content of food samples comes directly from the water signal
of the sample, except in those samples that have a high content in
fatty acids. However, if the component of interest has much lower
concentration in the foods, the water must be presaturated, since
the strong water signal overlaps the signal of other interesting com-
ponents. Presaturation is one of the widely used ways to eliminate a
strong solvent signal (i.e. water signal), in which a long low-power
pulse is applied on the solvent (water) resonance as part of the
pulse. After saturating the solvent (water) resonance at the transmitter
frequency, a non-selective pulse with a wide excitation profile) is then
applied to place all remaining spins in the transverse plane for
detection. It should also be noted that due to the complexity of food
stuff, research regarding food water interactions have been heavily con-
centrated in model systems, such as using protein hydration as a model
732 M.F. Marcone et al. / Food Research International 51 (2013) 729–747
for foodstuffs, which have been well summarized in a recent review by
Belton (2011).
2.2. Fat and fatty acids
The capability of NMR spectroscopy for fat analysis of different
foods includes not only for determining total fat contents but also
for identifying fatty acid composition of the fat. Up to date, NMR has
been dedicated to fat and oil quantification in a variety of agri-food
products (i.e. animal and vegetable oil and fat). Colnago, Azeredo,
Marchi Netto, Andrade, and Venâncio (2011) well demonstrated rel-
evant theories and concepts.
1
H NMR with a presaturation method to suppress the signal of
H2O has successfully determined the fat contents in their milk sample
to be 3.6 ± 0.1% (Hu et al., 2007). The value obtained by NMR was in
good agreement with that determined by the Rose–Gottlieb method,
which determines fat content by gravimetric analysis after fat extrac-
tion with diethyl ether (ethoxyethane) (Hu et al., 2007).
In order to quantify more compounds in milk, quantitative 2D
NMR experiments, were further performed, since the 1H NMR spec-
trum of milk was very crowded, and many signals overlapped. 10%
D2O was added to milk to adjust the NMR lock and shim system
and to obtain good 1H– 13C HSQC (heteronuclear single quantum co-
herence) spectra. The resulting spectrum is two-dimensional (2D)
with one axis for 1H and the other for 13C. This 2D NMR permits quan-
tification of milk compounds, which may be overlapping, or weak sig-
nals in the 1H NMR spectra. Considering the addition of D2O to milk,
concentrations of milk compounds were compensated during the
data processing. 1H– 13C HSQC 2D NMR spectra revealed unsaturated
fatty acids (0.9 mM monounsaturated fatty acids and 0.3 mM polyun-
saturated fatty acid) as well as 24.0 mM saturated fatty acid. The fatty
acid content determined by 1H– 13C 2D NMR seemed higher than that
obtained by gas chromatography which could be due to the losses in
the sample pre-treatment for GC analysis.
Gas chromatography (GC) has traditionally been used as a recog-
nized analytical technique for fatty acid analysis and thus has been fre-
quently used to validate NMR analysis results. Miyake, Yokomizo, and
Matsuzaki (1998) compared the results from 13C-NMR (300 MHz)
and GC for the n−6 polyunsaturated fatty acid composition in palm,
olive, safflower and corn oils. NMR analysis revealed that the various
oils contained 11.2%, 14.3%, 43.7% and 60.2%, respectively, while GC
yielded results of 13.5%, 15.5%, 44.9% and 60.6% respectively, which
are in a very close agreement (Miyake et al., 1998).
Igarashi (2000) also reported that a good correlation existed be-
tween 1H-NMR (500 MHz) data and those obtained by GC in the de-
termination of the n − 3 fatty acid content in unrefined bonito and
tuna oils produced in Japan, and also in salmon oil produced in
Norway. They observed that a good correlation (R 2 = 0.994, relative
error b 5%) existed between the 1H-NMR data and the GC data, with
regard to the molar proportions of DHA to DHA quantification with
ethylene glycol dimethyl ether (EGDM) (an internal standard). Once
again, the use of NMR appears to be a very promising tool for fatty
acid analysis of foods (Igarashi, 2000).
Besides GC, fat content analysis by NMR/MRI was also very compa-
rable to other analytical assays. Fat content in eight heifer longissimus
dorsi muscle slices (2 mm thick) was determined with MRI by
Ballerini et al. (2002). By improving image by a segmentation method
and selected median filters in their study, MRI was successful in
measuring the fat percentage and its distribution in the sample, with
the mean fat content determined by MRI having a good correlation
with the results obtained by chemical analysis. Although the re-
searchers did not specify what kind of chemical analysis was used in
their paper, they successfully employed MRI for quantitative evaluation
of fat percentage in a visual, fast and non-destructive manner (Ballerini
et al., 2002).
Additionally, NMR results for the fat content in beef, chicken and
pork were 46.00%, 7.15%, and 3.88%, respectively, these results being
in agreement with those obtained by Soxhlet ether extraction
methods, namely 45.84%, 7.24%, and 3.74% respectively (AOAC Official
Method 960.39) (Keeton et al., 2003). This observation proved that
fat content analysis from NMR was also very comparable to the
above mentioned AOAC methods (Keeton et al., 2003). In another
study, Ruan, Chang, Chen, Fulcher, and Bastian (1998) reported that
the MRI derived moisture content of cheese slices was 39.9% ± 0.5%,
which corresponded closely to the results (39.8% ± 0.3%) obtained
by the official oven-drying method for cheese slices (Ruan et al.,
1998). It has also been found that fat content of minced pork samples
by NMR agreed with results by Fosslet fat analyzer (AOAC Official
Method 976.21) (Sorland, Larsen, Lundby, Anthonsen, & Foss, 2005).
Measurements from three non-destructive methods (NIR, NMR
and Fatmeter) were used to determined lipid contents of herring
(Clupea harengus L) from both a Danish research vessel and commer-
cial catches. Specifically, Fatmeter measurements were conducted in
the frequency range of microwave radiation (i.e. 2 GHz–720 MHz).
NIR spectra were measured with an InfraProver, II Fourier transform
spectrometer at region from 4500 to 9996 cm −1. NMR measure-
ments were performed on a Maran Benchtop Pulsed NMR analyzer
at 23.2 MHz. After comparing results from the three above methods
(i.e. NIR, NMR, and Fatmeter), researchers concluded that Fatmeter
appeared to have the lowest cost per analysis and can be operated
after basic training, but is not suited for measurements of whole her-
ring. NMR appeared to be the most expensive technique, yet MRI was
the most suitable for measurements of whole herring with the
highest precision therefore holding the highest potential as a produc-
tion line measurement for sorting the raw material into more homog-
enous batches of foods (Nielsen, Hyldig, Nielsen, & Nielsen, 2005).
Conversely, NIR was found to lie in between the two methods men-
tioned above in terms of cost and applicability (Nielsen et al., 2005).
Since no particular method is perfect, the combination of NMR
with other analytical methods may give better analytical results.
Keeping this in mind, NMR has been combined with micro-oven dry-
ing methods for the rapid determination of moisture and fat in both
raw and processed products, including five primary meat categories
(such as beef, chicken, pork, ham, and turkey). Researchers further
quantified the performance of such combinations. NMR results were
compared with results obtained by AOAC moisture determination
Methods 950.46 (Forced Air Oven Drying) and AOAC fat determina-
tion Method 960.39 (Soxhlet Ether Extraction). NMR combined with
micro-oven drying methods yielded much more consistent results
with these AOAC methods compared to each method performed
alone (Leffler et al., 2008).
Since 1993, NMR has become an AOCS Official Method (American
Oil Chemists' Society, 2004), to determine solid fat contents (SFC) of
fats and oils in the food industry, particularly in the bakery, confection-
ery and margarine industries (Campos, Ollivon, & Marangoni, 2009;
Marangoni & Rousseau, 1995; Timms, 2003; Vereecken, Foubert,
Smith, Sassano, & Dewettinck, 2010). Solid fat content (SFC) refers to
a solid/liquid ratio of lipid at various temperatures. Many properties of
foods containing lipid, such as spreadability, firmness, mouthfeel, pro-
cessability and stability of margarine and butter, are associated with
SFC.
In some cases, SFC results lead to further information about the
properties of lipids, such as polymorphism and crystallization. In a
study on the graininess phenomenon, beef tallow (BT)-based short-
ening was exposed to temperature fluctuation cycles of 5–20 °C to in-
duce granular crystals. This leads to the graininess phenomenon
referring to an unexpected growth of granular crystals in such fat
products as shortenings and margarines, which ultimately impair
the consistency and plasticity of these fat products and it is consid-
ered as a structural defect of fat products. NMR analyzer was success-
ful in determining SFC of BT-based shortening and further obtaining
 M.F. Marcone et al. / Food Research International 51 (2013) 729–747
the isothermal crystallization behavior of the surrounding materials
and granular crystals based on SFC. Such results not only demonstrat-
ed the possibility of NMR to determine SFC, but also to monitor some
structural defects like the graininess phenomenon.
A combination of 1H NMR and 13C NMR was able to provide in-
sights into triacylglycerol polymorphs, which include α, β′ and β
polymorphs, which in turn influence the quality of final products
(Adam-Berret, Rondeau-Mouro, Riaublanc, & Mariette, 2008). 1H
NMR provided discrimination between α and β polymorphs by mea-
suring proton spin–lattice or spin–spin relaxation times, which was
further confirmed by high-field 13C NMR by obtaining relaxation in-
formation on each triacylglycerol carbon site.
Additionally, 1H NMR holds a possibility for determining the
quality of foods according to results based on fat compositional
analysis. 1H NMR spectral data allowed visualizing the compositional
change of virgin olive oil at room temperature while protected from
light. The presence and intensity of 1H NMR signals of some targeted
chemicals (i.e., hydroperoxide) permit a stability evaluation of this
virgin olive oil. The presence of hydroperoxide (primary lipid oxida-
tion products) indicated that oxidative degradation of virgin olive
oil occurred. Such an approach to investigate the oxidation process
of edible oils or meat fat was reported by other investigators
(Guillén & Ruiz, 2001, 2006; Stefanova, Vasilev, & Vassilev, 2011).
On the other hand, NMR results can also provide stock breeding infor-
mation. Genetic selection of chicken was based on NMR fat composi-
tional analysis of abdominal fat and total body fat of chicken
(Jaturasitha, Srikanchai, Kreuzer, & Wicke, 2008). 1H NMR spectral re-
sults were also able to reveal the relationship between gamma-ray ir-
radiation (at doses of 0.5, 2.5, 5.0, 7.5, 10.0, and 15.0 kGy) and fatty
acid compositions of irradiated chicken meat, thereby permitting a
possibility of NMR to monitor the irradiation processing via changes
of fatty acid compositions in foods (Stefanova et al., 2011). All the
above studies using NMR for the characterization and quantitation
of fat have served as ample evidence of the diversity, efficiency and
specificity of NMR for such determinations.
2.3. Protein/amino acids (AAs)
The amino acid profile is considered an important component af-
fecting the characteristics of protein-based food. These characteristics
are nutrient values, thermal stability and functional properties to
name a few. 1H NMR holds out the possibility of investigating the
total quantity of protein in foods as well. For instance, Pedersen et
al. (2000) found that the mean of protein contents in 17 winter
mustard seeds and 20 spring rapeseeds were 28.02% and 20.80%, re-
spectively, by means of low-field 1H nuclear magnetic resonance
(LF-NMR) (Pedersen et al., 2000). NMR can also be used to further
look at the amino acid composition of food. For example, Consonni,
Cagliani, Guantieri, and Simonato (2011) found that several amino
acids have distinct 1H NMR spectral peaks when testing Amarone
wine, including leucine at 0.88, 1.44, and 3.37 ppm, threonine at
1.42 and 4.38 ppm, alanine at 1.45 and 3.65 ppm, proline at 2.01,
2.08, 2.35, 3.38, and 4.11 ppm and choline at 3.20 ppm (Consonni et
al., 2011). This data permits the use of NMR to investigate vintage
and aging effects on foods based on the changes of those compounds
and others (i.e. sugars, and aromatic compounds).
In another comparison study, Belton et al. (1996) applied NMR to
investigate the amino acid profiles in a variety of fruit juices and vin-
egar. The mean ratio of alanine to arginine in grape varieties was 1.8
which is similar to published data obtained from other methods, with
similar results also found in orange juice and grapefruit juice. The
only exception is that c-aminobutyric acid was around half the
expected value than that from the published data. Again, NMR can
successfully provide rapid measurements when dealing with large
sample sizes (Belton et al., 1996).
733
3. Potential applications of NMR/MRI for structural analysis
The use of NMR relaxation time not only permits compositional
analysis of foods, but also insights into food structure. In MRI, the
NMR relaxation time allows for quantification of the image contrast,
therefore enabling visualized monitoring of structural changes in
foods during processing and storage. Information obtained from this
data often lead to the determination of the desired structures,
which could impact the final physical and mechanical properties of
food. Two major subjects studied by NMR/MRI include 1) structural
elucidation of specific food compounds; 2) quantification of micro-
structural changes occurring in foods.
Several reviews have collectively well-documented primary
research on the first subject (i.e. structural elucidation of specific food
compounds). A variety of foods have been targeted in these reviews,
including carbohydrates (i.e., carrageen from Gigartina lanceata
and G. chapmanii (Falshaw & Furneaux, 1998) or from bacteria
Solieria chordalis, Cystoclonium purpureum, Calliblepharis jubata and
Calliblepharis ciliat (Deslandes, Bodeaubellion, Floch, & Penot, 1990).
These reviews also covered chitin and chitosan (Kumirska et al.,
2010), food colloids (Mariette, 2009), annatto food coloring (E160b)
(Scotter, 2009), betanidin (a aglycon of the red-violet beet pigment
betanin) (Mabry, 2001), and cellulose and its derivatives (Kono et al.,
2002). In another study, diterpene phenols and other phenolic com-
pounds from spices, such as rosemary and sage (Ho, Wang, Wei,
Huang, & Huang, 2000), were reported. Until now, NMR techniques
continue to garner scientific interest in the identification and structure
determination of food compounds in a variety of foods. Some represen-
tative examples of structural studied food compounds include
fructooligosaccharides from roots and leaves of Stevia rebaudiana
(Bert.) Bertoni (de Oliveira et al., 2011); Aminoreductone (AR) found
in heated Long-life (LL) milk and lactose–a-lactalbumin model system
(Shimamura, Kurogi, Katsuno, Kashiwagi, & Ukeda, 2011), chitosan
and carboxymethyl starch tablets (Wang, Assaad, Ispas-Szabo,
Mateescu, & Zhu, 2011). With the concept that the properties of foods
is from a network of different components rather than a single compo-
nent, NMR has also been exploited for structural investigation of com-
plex food components, such as tea polyphenols (TP) with oat β-glucan
(Wu et al., 2011).
In terms of the second subject (i.e., quantification microstructural
changes of foods), most recently, a review by Mariette (2009) well
documented the possible applications of low field magnetic field
spectrometers (frequencies b 25 MHz) for investigating the composi-
tion and microstructural changes in a variety of foods under different
processing or storage conditions (Mariette, 2009). Both NMR relaxa-
tion (one, two and multidimensional NMR) and diffusometry are
well documented. The NMR relaxation behavior of components in-
cludes solid, liquid-like relaxation, solid and liquid fat relaxation, ice
relaxation, biopolymer relaxation, and water relaxation. In terms of
water relaxation, if the diffusion coefficient is slow compared to the
relaxation rate, water relaxation (i.e., T2) behavior (multi-exponen-
tial) has been used as a probe of the microstructure or to quantify
the water holding capacity of foods. The microstructural changes di-
rectly influence the final functionality of these foods and ultimately
their sensory properties (Mariette, 2009). On the other hand, in
samples where the diffusion coefficient is fast compared to the
relaxation rate, water relaxation behavior (average and a single
mono-exponential) has been extensively investigated in studies of
changes in macromolecular food structure resulting from processing
operations (Mariette, 2009). Foods that have been reviewed include
ice cream, cake, whipped creams, cheese, potato, bread, milk, eggs,
and chocolate (Mariette, 2009).
Keeping these applications in mind, Oztop et al. (2010) selected a
whey protein-based gel to serve as a delivery model system for foods,
and NMR spectrometry was employed to monitor spatial distribution
of water in whey protein-based gels during swelling at a pH of 2.5, 7,
734 M.F. Marcone et al. / Food Research International 51 (2013) 729–747
and 10 solutions. MRI demonstrated a distinct spatial distribution of
water in whey protein-based gels during swelling at the three differ-
ent pHs. They found that the diffusion of water into gels causes more
significant microstructural changes in the gel at lower pH of 2.5 than
that at higher pH. These results prove MRI/NMR to be a potential
technique to monitor and improve the understanding of swelling of
whey protein gels or other properties of other delivery systems
(Oztop et al., 2010).
The study of the crystalline structures of starch is another applica-
tion for NMR/MRI. Different crystalline structures that are found in
starch from different food sources include A-type, B-type, C-type and
V-type crystalline structures. Knowing the crystalline structure of starch
allows for the identification of the botanical origins of the starch. A-type
crystalline structure is commonly derived from cereal starch like
corn, wheat or rice, with amylopectin having short lateral chains and
branching points close to each other; B-type crystalline structure is usu-
ally derived from fruits and tuber starches with amylopectin having
long side chains and distant branching points. Whereas C type starch
is a crystalline structure of a mixture of A and B-type crystalline struc-
tures and is usually found in legumes (i.e. pea). On the other hand,
V-type starch crystalline structure is derived from modified starch or
endosperm of some native starch granules. 13C CP/MAS NMR spectros-
copy (75.46 MHz) has been reported to be able to distinguish these
crystalline structures of starch, therefore demonstrating the possibili-
ties of NMR spectroscopy in identifying the origins of starches, as well
as well as providing insights into the changes of these crystalline struc-
tures under different processing conditions (Barsby, Donald, & Frazier,
2001; Therien-Aubin & Zhu, 2009).
1
H-NMR spectroscopy has also successfully directed the structural
characterization in the denatured states (A-state) of α-lactalbumin, a
major whey protein in cow milk (Alexandrescu, Evans, Pitkeathly,
Baum, & Dobson, 1993). The NMR spectrum of α-lactalbumin in the
A-state had intense chemical shift dispersions with random coil confor-
mation indicating that most of the long-range tertiary structure of the
A-state is more disordered and nonspecific. These results, however,
disagreed with other publications (Dolgikh et al., 1981; Ewbank &
Creighton, 1991; Semisotnov et al., 1991). This study demonstrated a
mechanism by which an unstructured polypeptide chain folds, specifi-
cally tertiary interactions and non-native structure in the A-state. The
structural information such as the mechanisms for protein folding is
considered crucial to the onset of various diseases in cattle such as
bovine spongiform encephalopathy (BSE) aka ‘mad cow disease’.
4. Potential applications of NMR/MRI for inspection of
microbiological, physical and chemical quality of foods
NMR/MRI has been used to monitor food quality in a variety of
studies that assess microbiological, physical, and chemical properties
in different foods (Gostan, Moreau, Juteau, Guichard, & Delsuc, 2004;
Gudjónsdóttir, Jónsson, Bergsson, Arason, & Rustad, 2011; Pykett,
2000; Zehl et al., 2011).
MRI has been intensively used to inspect the microbiological
quality of fruits and vegetables (Pykett, 2000) as well as meats
(Gudjónsdóttir et al., 2011). Traditionally, control of microbiological
quality in food relies on microbiological testing of representative
samples at various stages of production and/or of the final products.
Such approaches only provide a certain degree of assurance of food
safety and quality, as these methods use representative samples
that depend on the distribution of microorganisms in samples,
whereas MRI provides full real time image of microorganisms in
foods. MRI was able to rapidly distinguish cucumbers with fungus
(Mycosphaerella sp.) infection from healthy cucumbers (Hall, Evans,
& Nott, 1998). NMR was also capable of monitoring fish deterioration
based on correlation between NMR parameters with total viable
counts (TVC) of H2S-producing bacteria (Gudjónsdóttir et al., 2011).
Physical properties such as texture are considered one of the main
economically important quality indicators in foods (Bourne, 2002) for
both consumers and producers. NMR techniques, especially MRI, have
the potential for detecting various quality factors related textures or
defects in fruits, and vegetables (Chen, Mccarthy, & Kauten, 1989; Hall
et al., 1998). Scientists indicate a correlation between MRI image
changes and textural changes of certain fruits, and vegetables under dif-
ferent conditions (harvest, postharvest, storage). When a defect or an
abnormal condition occurs, it is observed quite clearly in the MRI
image. Based on this observation, MRI revealed textural changes of sev-
eral fruits such as melons, peaches, and pineapples during bruising and
ripening (Hall et al., 1998). Specifically, gradient-echo MRI images were
used to differentiate between healthy yellow melons from melons with
internal necrosis. Spin-echo MRI distinguished healthy peaches from
bruised peaches. Multi-echo MRI image also identified unripe pineap-
ples from the ripe. Similarly, Chen et al. (1989) showed the feasibility
of NMR imaging to detect the textural changes of fruits and vegetables
under various conditions such as dry regions, bruising, worm damage,
stage of maturity, and presence of voids, seeds, and pits via display
changes in intensities of the images (Chen et al., 1989). Butz et al.
(2005) also reviewed the use of NMR/MRI to measure water states
and water-related properties of fruits, including apples, pears, peaches,
kiwi fruits and oranges (Butz et al., 2005). This review gathers ample ev-
idence of the applications of NMR/MRI for assessing or inspecting qual-
ity parameters of a variety of fruits, such as ripeness, defects, and decay,
as well as differentiating between unaffected tissue, brown tissue, and
cavities during various conditions, such as postharvest, storage, and
transportations (Butz et al., 2005).
In addition to its ability to assess physical properties of certain
foods, NMR/MRI can also be used to investigate chemical attributes
related to product quality. For instance, NMR is used to investigate
the diffusion of two aroma compounds, ethyl butanoate and linalool,
in matrices of carrageenan at low concentration (1%) and in some dif-
ferent gelling states (Gostan et al., 2004). The results of these studies
further help to explain the impacts of structural and textural changes
on aroma and taste perception of foods.
A recent study by Zehl et al. (2011) demonstrated the potential of
NMR with regard to quality control of medicinal herbal products (Zehl
et al., 2011) by monitoring their unique bioactive compounds. Re-
searchers highlighted for the first time that LC-NMR and off-line NMR
analysis are capable of identifying flavonoids and ellagic acid deriva-
tives (Drosera rotundifolia and D. anglica, 2′-O-galloylhyperoside, with
myricetin-3-O-β-glucopyranoside and kaempferol-3-O-(2″-O-galloyl)-
β-galactopyranoside in four Drosera species (D. anglica, D. intermedia,
D. madagascariensis, and D. rotundifolia), which are traditionally used
for the treatment of respiratory tract diseases. Due to the successfully
obtained results of qualitative and quantitative investigation of flavo-
noids and ellagic acid derivatives, Zehl et al. (2011) highly appreciated
NMR identification which boasts of simple sample preparation, low
cost, and simplicity of analysis system. They further provide a recom-
mendation of NMR technique as it is well suited for quality control of
herbal medicinal products.
In a recent review, quantitative water analysis by NMR (MRI) also
became a tool to measure meat quality (Pearce et al., 2011). The topics
covered in this review included water distribution and mobility, water
holding capacity as they relate to meat quality, such as muscle structure,
juiciness and tenderness of meat. In other studies, the applications of
NMR have been expanded to investigate a variety of factors influencing
meat quality related to water, including animal growth rate and age,
slaughter procedure, pre-slaughter stress, cooling rate of carcasses,
aging, and storage temperature on the final meat products (Honikel,
2004; Honikel, Kim, Hamm, & Roncales, 1986; Ruiz-Cabrera, Foucat,
Bonny, Renou, & Daudin, 2005). All these studies amply displayed the
potential of NMR methodology for quantifying overall organoleptic
properties of meat as well as providing information on how to optimize
processing conditions to obtain desired organoleptic properties.
 M.F. Marcone et al. / Food Research International 51 (2013) 729–747
Similar approaches have been applied to study the impact of differ-
ent moisture levels (12%–45%) on the relaxation properties of wheat
flour dough, which in turn becomes a good indicator of the elastic prop-
erties of dough (Ruan et al., 1999; Yi & Kerr, 2009). It should be noted
that elastic properties can be measured directly using Magnetic Reso-
nance Elastography (MRE) (Gruwel, Latta, Matwiy, & Tomanek, 2010).
MRE is a phase-contrast MRI technique, which is used to map spatial
displacement patterns corresponding to harmonic shear waves initiat-
ed by the mechanical oscillations of a specially designed actuator
attached to the object (Gruwel et al., 2010). MRE has been used to de-
termine shear stress in pre-packaged fruit puddings (Gruwel et al.,
2010).
Frias, Foucat, Bimbenet, and Bonazzi (2002) also used NMR/MRI to
examine drying profiles of rice during processing, whereas, Castell-
Palou et al. (2011) established NMR methodology on how to profile
the drying of cheese as function of temperature and air rates. All this in-
formation obtained from NMR/MRI has lead to the optimal processing
of these particular products (Castell-Palou et al., 2011; Frias et al.,
2002). Successful examples of usage of NMR techniques to optimize
fish processing for quality improvements have been covered in a recent
review (Erikson, Standal, Aursand, Veliyulin, & Aursand, 2012).
NMR spectroscopy combined with statistical analysis techniques is
one of the promising tools for food quality control. One of such com-
binations is SGF profiling with NMR, which is fully automatically
performed sample transfer, measurement, data analysis and reporting
for quality control of fruit juices (Spraul et al., 2009). Having established
a spectral database (>6000 reference juice including 1500 fully authen-
tic samples, taken by SGF inspector), NMR allowed identification and
qualification of 28 different compounds in a mixture simultaneously
(Spraul et al., 2009). In fact, it also enabled the detection of fraudulent
addition of sugar, citric acid, lemon juice (e.g., apple juice), or
galacturonic acid (in indicator of exhaustive enzymatic treatment).
This technique was also capable of distinguishing the extraction of
juice from different parts (i.e. peels) and origins of fruit, as well as rip-
ened or unripened fruits (Spraul et al., 2009).
5. Application of NMR in food packaging
The quality of the packaged food is also directly related to the char-
acteristics of the packaging with the proper selection and optimizing of
packaging providing better maintenance, storage and handling of foods.
NMR holds the promise to be able to investigate packaging material
properties and optimize food packaging materials. In one study,
the effects of gamma irradiation (at a range of 1–100 kGy) on food pack-
aging polymers (polystyrene, poly-butadiene, styrene–acrylonitrile,
high impact polystyrene and acrylonitrile–butadiene–styrene) were
determined by NMR (Pentimalli et al., 2000). Researchers found that
polystyrene is an ideal polymer for packaging food that may undergo ir-
radiation. In another study by Lamanna, Piscioneri, Romanelli, and
Sharma (2008), 1H NMR was used to monitor degradation of Robiola
cheese in air (without package) and in a composite paper foil package
during a 7 day period at room temperature (15 °C). The spectrum of
the cheese aqueous extract showed more variation in the concentration
of certain chemical compounds occurring in the cheese exposed to air
during the 7 day storage period, compared with those of cheeses stored
in the package (Lamanna et al., 2008). All these findings proved NMR's
ability to evaluate the performances of various kinds of packages with
respect to its ability to preserve food in different storage conditions, in
addition to it being a promising tool for selecting desired food package
materials.
6. Potential application of NMR/MRI in food authentication
Food authentication is one of the major concerns in regard to food
quality. NMR/MRI techniques applied to detect authentication within
different foods has been reported extensively. (Bertelli et al., 2010;
735
Cuny et al., 2008; Ellis et al., 2012; Masoum et al., 2007; Rinke et al.,
2007; Schievano, Peggion, & Mammi, 2010). The potential use of
NMR in food authentication has been applied to several foods and
beverages, such as milk and cheese (Brescia, Monfreda, Buccolieri, &
Carrino, 2005), beef (Shintu, Caldarelli, & Franke, 2007), truffles
(Mannina, Cristinzio, Sobolev, Ragni, & Segre, 2004), vanillin
(Tenailleau, Lancelin, Robins, & Akoka, 2004), pistachios (Zur, Heier,
Blaas, & Fauhl-Hassek, 2008), and saffron extracts (Yilmaz, Nyberg,
Mølgaard, Asili, & Jaroszewski, 2010). The scope of NMR in food au-
thentication will be extended as the instrumentation decreases in
price and becomes more widely accessible allowing more regulatory
agencies around the world to opt-in for using NMR as the analytical
testing method of choice for their samples while allowing the sample
to remain intact if it should be required during legal prosecution or
any other reasons. Some representative foods cited in the following
section include honey, salmon, olive oil, tea and beer.
6.1. Honey
The use of NMR in honey authentication dates back to one of the ear-
liest studies, in which citrus honey was investigated by deuterium
NMR (Lindner, Bermann, & Gamarnik, 1996). In 2007, site-specific nat-
ural isotopic fractionation measured by nuclear magnetic resonance
(SNIF-NMR) was used to investigate honey authentication. Theories be-
hind SNIF-NMR have been well documented (Martin, Akoka, & Martin,
2006). Specifically in the study of Cotte et al. (2007), SNIF-NMR enabled
the determination of (D/H) ratio in the three isotopomers of ethanol:
CH2DCH2OH (I), CH3CHDOH (II) andCH3CH2OD (III). The isotope exam-
ined in this study of honey is deuterium and the isotopic ratio is mea-
sured in the ethanol obtained by fermenting honey sugars. The (D/H)II
and (D/H)III ratios were correlated with the climatic conditions of the
botanical species and the nature of water in the samples, while the
(D/H)I ratio was related to photosynthetic sugar metabolism (Cotte et
al., 2007). Analyzing (D/H)I ratios provide specific values for certain or-
igins (Cotte et al., 2007).
In recent years, limited production of honey caused a rise in honey
prices, and in turn, a rise in honey adulteration by producers through
the addition of different commercial sugar syrups. Lolli, Bertelli,
Plessi, Sabatini, and Restani (2008) initially conducted a study using
2D HR-NMR which allowed for the determination of the botanical or-
igin of unifloral honey, obtaining both efficient and versatile results
(Lolli et al., 2008). Later, 1D NMR proved to be a more effective, sim-
pler, and faster technique than 2D NMR in detecting adulteration in
honey without using any sample pre-treatments, yielding results
that were comparable to those obtained using FTIR with a 92.5% cor-
rect prediction rate (Bertelli et al., 2010). Schievano et al. (2010) used
1
H NMR to identify the botanical origin of unifloral and polyfloral
honey, with minimal preparation, yielding 100% correct sample
identification.
6.2. Salmon
Farmed salmon practice has grown dramatically from 6% to 58%
during 1985 to 2000, this increase in farmed salmon is attributed to
its lower price and higher omega− 3 FA content compared to the
wild variety. Farmed salmon, however, poses a risk of much higher
concentrations of organocholorine compounds (polychlorinated bi-
phenyl (PCBs), dioxans) and chlorinated pesticides (toxaphene and
dieldrin, along with other contaminants (Hites, Foran, Carpenter, et
al., 2004; Hites, Foran, Schwager, et al., 2004). Due to preference,
price, and the risk involved with farmed salmon, mislabeling the
type of salmon as well as the origin is a common occurrence in
some fish markets. 1H NMR with support of data processing using
support vector machine (SVMs) was capable of distinguishing be-
tween wild and farmed salmon including their origins with a high ac-
curacy based on their muscle lipid profiles (Masoum et al., 2007). The
736 M.F. Marcone et al. / Food Research International 51 (2013) 729–747
previous technique was furthermore refined by the use of 13C NMR to
look at the lipids extracted from the muscle. 13C NMR spectra have a
larger chemical shift scale than the 1H NMR spectra yielding a better
observation of the peaks and eliminating any overlaps (Aursand et al.,
2009).
6.3. Olive oil
Virgin olive oils (VOOs) have been produced for thousands of
years in countries around the Mediterranean Sea, with their quality
being linked to their geographical origin as well as processing
methods. The European Union (EU) has very strict rules associated
with the labeling, of VOOs in terms of the specific production region
and production method. Due to the high market prices of VOOs, the
fraudulent act of mislabeling the origin of VOOs, and the adulteration
of the VOOs occur very often. Although several analytical methods al-
ready exist for the detection of VOO adulteration, NMR fingerprinting
was proven to be a much more effective method in the authentication of
VOOs based on their geographical origin (Alonso-Salces, Moreno-Rojas,
et al., 2010). For authentication purpose, several variables have been
studied, including 1H, 13C, and/or 31P NMR analyses, unsaponifiable
fraction of VOOs and phenolic compounds in the polar fraction of
VOOs (Alonso-Salces, Holland, et al., 2010; Christophoridou, Dais,
Tseng, & Spraul, 2005).
6.4. Beverages
The use of NMR for food authentication also extends to beverages
as well. 1H NMR spectroscopy showed potential in the discrimination
of green tea according to the country of origin or with respect to qual-
ity (Le Gall, Colquhoun, & Defernez, 2004). 1H NMR was able to detect
simultaneously the catechins, the amino, organic, phenolic, and fatty
acids, and the sugars from a single green tea extract. It was also capa-
ble of detecting catechins, caffeine, 5-galloyl quinic acid, and 2-O-
(â-L-arabinopyranosyl)-myo-inositol, all of which are associated to
tea quality (Le Gall et al., 2004). Another application field for NMR
spectroscopy is to examine the source of the raw material used for
making juices. 1H NMR has also been shown to be very accurate in
the determination of the origin or quality of juices (Cuny et al.,
2008; Rinke et al., 2007).
NMR spectroscopy is also widely used in alcoholic beverages for
authentication purposes, as these beverages command higher prices
in the market place. Unfortunately, as with VOOs, this increases the
risk of fraud by adulteration and deliberate mislabeling. Zivania, a tra-
ditional Cypriot alcoholic beverage was tested with 1H NMR spectros-
copy to determine the country of origin for authenticity purposes
(Petrakis et al., 2005). The results obtained were slightly less accurate
than traditional methods but they were still deemed to be acceptable.
Beer, the third most popular drink in the world after water and tea
(Nelson, 2005) is enjoyed and consumed in many cultures. Due to the
high prices commanded by some beers, adulteration practices includ-
ing mislabeling of the place of origin unfortunately also exist with this
popular alcoholic beverage. Initially beer was characterized chemical-
ly by high resolution 1H NMR observing many distinct chemicals
between different beers as well as the potential of NMR (Duarte et
al., 2002). Further experimentation explored the potential NMR spec-
troscopy for quality control of beer (Duarte et al., 2004). The same
group explored the potential of NMR spectroscopy to observe the
composition of beer and relate it to the brewing site and date of produc-
tion, showing the potential to use PCA/NMR to monitor and control the
beer production process (Almeida et al., 2006). The quality control of
beer was explored a year earlier (Lachenmeier et al., 2005) with the
results obtained suggesting that NMR could be used for quality control
and authentication of beer.
7. Potential applications of NMR/MRI for on-line monitoring of
food processing
The use of traditional analytical methods for on-line process mon-
itoring and process optimization is challenging, as these methods are
time consuming and sample-destructive. Numerous non-destructive
methods have been used to evaluate the quality of foods including
light transmission, X-ray transmission, sonication and vibration.
However, these approaches failed to provide information about mul-
tiple (or complex) physical properties of some foodstuffs (Chen et al.,
1989). The use of NMR/MRI for online monitoring of the process is
one such promising alternative. NMR/MRI has been initially success-
fully developed for online analysis of bio-processes in life science,
this is due to its capability of shortening the time delay for offline
sample preparation and analyses (Kara, Mueller, & Liese, 2011). Re-
cently, food scientists have also successfully extended the scope of
such usage to food on-line processes.
Gudjónsdóttir and his co-researchers, demonstrated the possibility
of using a low-field proton nuclear magnetic resonance (LF-NMR) ana-
lyzer (at a frequency of 20 MHz) for on-line process control during pro-
cessing of cold water shrimp (Pandalus borealis). Specifically, they
attempted to determine the impact of polyphosphate concentrations
and length of pre-brining and freezing on physicochemical properties
of shrimp muscles. Prior to cooking the shrimp at 80 °C for 15 s, three
specific steps were performed. LF-NMR was capable of rapidly detecting
physicochemical property changes in shrimp muscle after each of these
three treatments. The changes include protein content, phosphate
levels, and moisture content as well as water-holding capacity (WHC).
They also pointed out that further optimization is necessary in regard
to measurement settings, number of sample replicates, the size of ana-
lyzing surface as well as suitable probe selection. The same research
group also confirmed that LF-NMR can differentiate wild farmed cod
from farmed cod processed pre-rigor and post-rigor in terms of the
muscular structure and physical properties (Gudjonsdottir et al.,
2010). They highly recommended that LF-NMR can be considered a
valuable on-line control tool to optimize the salting and sorting process
of these types of cods that are slightly salted.
In addition, the use of an LF-MRI (5.55 MHz) sensor and conveyor
system for online determination of the internal browning in whole
apples was reported by Chayaprasert and Stroshine (2005). Such
non-destructive detection of internal defects makes it possible to
distinguish healthy apples and apples with internal browning, and
expand the capability of currently available on-line quality sorting,
which are typically used on to monitor external properties such as
color, size, shape, or externally visible defects (Chayaprasert &
Stroshine, 2005). Another researcher has also tried to employ a Maran
bench top NMR spectrometer (15 MHz) for on-line determination of
the gelatinization temperatures of corn starch, when combined with
other food components, like sugar (i.e. glucose and sucrose) and various
gums (i.e., xanthan) (Gonera & Cornillon, 2002). This allowed for the
monitoring of changes occurring in starchy foods on the addition of
other ingredients. NMR-spectroscopy also has potential for the analysis
and determination of fine structures in carrageenan. Quantitative anal-
ysis of carrageenan is important for ingredient suppliers and food man-
ufacturers. Specific applications of such analysis range from screening
tools and quality control to studying the processing parameters and
structural components. This approach helps understand the possible
commercial or industrial value of raw extracts obtained from red
seaweeds as well as the influence of processing parameters such as
temperature and pH on the structure, which ultimately allows suppliers
to develop and deliver a consistent consumer product (van de Velde,
Knutsen, Usov, Rollema, & Cerezo, 2002). In a review by van de Velde
et al. (2002), both 1H NMR and 13C NMR were documented in detail re-
garding their potentials of qualitative and quantitative analysis of carra-
geenan samples. 13C-NMRspectroscopy can be used for distinguishing
the polysaccharides of the agar and carrageenan groups. Since the pairs
 M.F. Marcone et al. / Food Research International 51 (2013) 729–747
of dyads G–D and G–L, as well as G–DA and G–LA, are diastereoisomeric
and give different spectra, such differences were noticeable for the
anomeric carbon resonances. Quantification of different carrageenan ori-
gins in a sample by 1H-NMR is based on the resonances of the a-anomeric
protons in certain regions (van de Velde et al., 2002).
Another possible use of NMR is to resolve the diffusivity of aroma
compounds within various food matrixes (Gostan et al., 2004;
Juteau-Vigier et al., 2007; Savary, Moreau, & Cayot, 2010). Gostan et
al. (2004) evaluated the effectiveness of NMR Diffusion Ordered Spec-
troscopy (DOSY) investigating self-diffusion of small aroma solutes
(ethyl butanoate and linalool) in natural polysaccharide polymers
(iota-carrageenan matrix), thickeners in the food industry (Gostan et
al., 2004). This approach worked well for estimating the diffusion and
partition properties of another aroma compound (ethyl hexanoate) in
carrageenan matrices (Juteau-Vigier et al., 2007). Savary et al. (2010)
formulated eight polysaccharide composite gels composed of sucrose
(35%, w/w), starch (1.4%, w/w), carrageenan (0.05% (w/w), 0.33%
(w/w), 0.80% (w/w)) with (Ci) or with pectin (P) at 0.40% (w/w)
using different salts (K+, Na+ and/or Ca2+). These gels can be used to
flavor commercial dairy products and can cause them to impart differ-
ent textural properties. 1H pulsed-field gradient (PFG) NMR spectra
successfully recorded the diffusion of ethyl butyrate in all eight textured
gels (Savary et al., 2010). All these above experimental trials promote a
better understanding of the performance of aroma food delivery
systems, therefore leading the development of new food products.
8. Specific NMR/MRI applications to some representative foods
8.1. Wine and beer
Due to the fact that water, ethanol, and acetic acid comprise the
major proton containing components in the full bottle of spoiled wine,
therefore measurement of the intensity of their peaks in the 1H NMR
spectrum should able to determine the degree of wine spoilage
(Weekley et al., 2003). Several researchers studied spoilage properties
of bottled wines by measuring the acetic acid content down to the
level of complex sugars, phenols, and trace elements in wine (Lopez-
Rituerto et al., 2009; Sobieski et al., 2006; Weekley et al., 2003).
Currently, there are cases in which dissolved cocaine has been
smuggled illegally with the aid of wine bottles. Gambarota et al.
(2011) have tackled this issue by detecting dissolved cocaine reso-
nances in intact wine bottles. This was accomplished through a stan-
dard clinical MR scanner, within a scan time of 1 min detectable at
levels of 5 mM (i.e. ~ 1.5 g/L). This technique can examine suspicious
cargo since it allowed non-destructive and rapid content characteri-
zation (Gambarota et al., 2011). These studies emphasize the utiliza-
tion of a full bottle NMR approach, being applicable to any type of
wine (Sobieski et al., 2006; Weekley et al., 2003).
This area of research extends to other alcoholic beverages as well
(Table 2). The synergetic combination of 1H NMR with FTIR-
attenuated total reflectance (ATR) can separate different beers based
on alcoholic content (Duarte et al., 2004). This provided rapid informa-
tion regarding different types of beer fermentation, a crucial aspect in
beer production. Rodrigues et al. (2010) identified six useful organic
acids; acetic, citric, lactic, malic, pyruvic, and succinic acids. Organic
acids play an important role in beer, not only contributing to flavor,
color, and aroma but they also are good indicators of fermentation per-
formance. This established PLS-NMR method for organic acid quantifi-
cation in beer, provides important information on the product's
quality and history (Rodrigues et al., 2010).
8.2. Fruit and vegetable juice and pulp, green tea, and coffee
In addition to wine and beer, research on other beverages such as to-
mato juice with pulp, green tea, and coffee can also benefit from NMR
and MRI technology. Methods comprising 1H HR-MAS NMR have
737
determined the chemical composition of tomato juices and total pulp
from two tomato cultivars, i.e. Red Setter and Ciliegino (Sobolev et al.,
2003) including a variety of aliphatic groups in amino acids and organic
acids. The fluid section was measured with standard HR NMR and
tomato pulps were analyzed by magic angle spinning (MAS) NMR. In
particular, valine, isoleucine, threonine, alanine, glutamate, glutamine,
aminobutyrate (4-aminobutanoate), asparagine, aspartate, citrate (2-
hydroxypropane-1,2,3-tricarboxylate), acetate and malate were identi-
fied. The comparison between the juice and pulp spectra reveals all the
water-soluble substances that are present in the pulp extracted from
the juice. 1H HR-MAS NMR has advantages, allowing the study of
semi-liquid or semi-solid samples without extraction (mostly food)
and obtaining a spectral resolution as if the sample were liquid.
Coffee is a popular beverage containing the stimulant caffeine; the
worlds' most widely consumed psychoactive substance. Many major or
minor compounds in coffee have aroused scientific interest, including caf-
feine, formic acid, trigonelline and 5-hydroxymethylfurfural (5-HMF).
Among these compounds, caffeine and trigonelline are associated
with bitter taste, formic acid determines the level of acidity of coffee
and hydroxymethylfurfural (5-HMF) serves as an indicator of quality
deterioration during coffee roasting.
Signal assignment of many major constituents present in coffee
(i.e. caffeine, formic acid and trigonelline) has been performed using
1
H NMR techniques. The sensitivity and precision of NMR for quantita-
tively determining some major or minor compounds in coffee have
been described in a recent study (del Campo et al., 2010). Specifically,
1
H NMR was used to quantitate the content of caffeine, formic acid,
trigonelline, and 5-hydroxymethylfurfural (5-HMF) in their commer-
cial soluble coffees at 30 °C. 1H NMR spectra of these coffees reveal
that they contain 4.2% caffeine, 2.6% formic acid, 2.4% for trigonelline,
and 7.3% for 5-HMF. Since previous studies only established the qualita-
tive analysis of caffeine, formic acid, and trigonelline by 1H NMR (Bosco,
Toffanin, De Palo, Zatti, & Segre, 1999). This study was considered the
first to report the quantitative procedures of the NMR technique for
chemical analysis of coffee (del Campo et al., 2010).
One study established a quantitative NMR methodology for formic
acid determination in apple juice (Berregi, del Campo, Caracena, &
Miranda, 2007). Five varieties of Spanish Basque cider apples were se-
lected in this study, including Moko, Patzuloa, Txalaka, Urtebi Haundi
and Urtebi Txiki. The researchers optimized the 1H NMR acquisition
conditions to ensure that the signal for formic acid appears at
8.2–8.4 ppm without overlapping with signals of other chemicals.
They also successfully validated their technique by an enzymatic
method, in which formic acid is quantitatively oxidized to bicarbon-
ate by nicotinamide–adenine dinucleotide (NAD+) in the presence
of enzyme formate dehydrogenase (FDH). The amount of formic
acid was determined by measuring the absorbance of NADH at
340 nm to determine formic acids (Berregi et al., 2007).
Quality predictions for green tea are often performed by highly
trained tea tasters using a sensory testing. This process, however,
can be rather inconsistent as it is somewhat subjective leading
Tarachiwin et al. (2007) to introduce new methods involving meta-
bolic profiling and finger printing using 1H NMR. In this study, dried
ground green tea leaves were mixed with D2O, incubated at 60 °C,
centrifuged to separate the supernatant containing the hydrophilic
metabolites, which was then filtered and mixed with a buffer before
testing. Subsequently, 1H NMR was able to identify the levels of chem-
ical constituents in Japanese green tea in different frequency regions.
More specifically, theanine (δ 1.10, 2.12, 2.39, 3.19 ppm) and quinic
acid (δ 1.88, 1.97, 2.05 ppm) at δ 0.5–3.0 ppm, whereas caffeine
(δ 3.27, 3.43, 3.89 ppm), arginine (δ 3.22, 3.47 ppm), myo-inositol
(δ 3.30 ppm), chlorogenic acid (δ 3.89, 4.22 ppm), and quinic acid
(δ 3.56 and 4.01 ppm) were observed at δ 3.0–4.5 ppm, after excluding
sucrose and fructose signals, 2-O-β-L-arabinopyranosyl-myo-inositol
(δ 5.19 ppm), p-coumaryl quinic acid and/or cinnamic acid (δ 7.51,
7.75 ppm), EGCG (δ 6.61, 7.02, 7.14 ppm), and ECG (δ 6.91, 7.02 ppm)

Table 2
Specific NMR/MRI applications to some representative foods.
Foods Sample information
Wine Entire bottle-unopened Rioja red
wine
Entered bottle
Entire bottles of UC Davis
Cabernet Sauvignon (1950–1977)
Entire bottles wine +phantoms of
wine+ cocaine, or water+cocaine
Beer
10 ml beer sample dissolved in
solution
Tomato Juice Puree for pulp analysis
and Pulp Puree extracts containing 30% D2O,
with DSS (3-trimethylsilyl-
1-propanesulfonic acid, sodium
salt), placed in a 5 mm NMR tube
Two tomato cultivars, Red Setter and
Ciliegino
Green tea 53 Japanese dried first-crop green
tea leaves or Ichiban cha
600 μL solution contain 200 μL of
0.2 M buffer solution containing
3 mM DSS and 400 μL D2O water tea
extract
Research objective
To monitor the levels of important
metabolites of wine during the
alcoholic and malolactic
fermentation processes
To estimate spoilage
To measure spoilage indicators
(such as acetic acid).
To detect complex sugars, phenols,
and trace elements in full intact
wine bottles
To detect cocaine dissolved in wines
using a non-invasive and non de-
structive method
To determine the spectral
parameters
To quantify the major organic acids
in beer, acetic, citric, lactic, malic,
pyruvic and succinic acids
To determine properties of beer and
fermentation performance.
To obtain high resolution proton
spectrum of tomato pulps and
tomato juices.
To identify, quantify, analyze and
compare the results between tomato
pulps and juices.
To produce a Japanese green tea
quality prediction method using
metabolic profiling and finger
printing of 1H NMR spectra.
Allowing for consistent and accurate
judging between different tea
qualities.
Type NMR
1
H qNMR
1 1
H NMR
1
H NMR and selected
bottles with 13C NMR
Water suppressed 1H MRS
using a 3 T clinical scanner
FTIR-ATR and 1H NMR
Partial least squares
(PLS)-NMR spectroscopy
1
H NMR — neosypr1d pulse
sequence (Bruker library)
1
H High Resolution Magic
angle spinning(HR-MAS)NMR
for tomato pulps
High-resolution inverse probe.
Liquid state NMR for tomato juice
Non-targeted 1H NMR based
metabolomics.
Presaturation pulse sequence used
to suppress the residual water signal
738
Observations Reference
Quantitative nuclear magnetic resonance allowed simultaneous detection of Lopez-Rituerto et al. (2009)
ethanol, acetic, malic, lactic, and succinic acids, and the amino acids proline
and alanine, besides the ratio proline/arginine through grape fermentation
corresponding to the Tempranillo variety.
H NMR with optimized 1331 water suppression pulse sequence Sobieski, Mulvihill, Broz, and
detected ppm ethyl alcohol and 2.1 ppm oxidation products (acetic acid or Augustine (2006)
acetaldehyde) in full bottles of wine.
Oxidative change of a bottle of wine can be detected within 10 min
Lack of correlation was observed between acetic acid concentrations and wine Weekley, Bruins, Sisto, and
age. The sensitivity of the acetic acid measurement is less than 0.1 g/L Augustine (2003)
The integrity of the cork and hence the quality of the bottle seal against oxygen
M.F. Marcone et al. / Food Research International 51 (2013) 729–747
leakage with time was found to be important factors to prevent acetic acid
contamination
Ethanol concentration does not correlate well with year and varies between 10
and 20%
Peaks of 3 main groups in the cocaine molecule (aliphatic ring, methyl, and Gambarota et al. (2011)
aromatic proton) are observed
The separation of beers mainly according to their alcoholic content; two Duarte, Barros, Almeida, Spraul, and
groups characterized by the predominance of dextrin, one group of Gil (2004)
alcohol-free beers characterized by the predominance of maltose, and one
group where glucose were found to predominate
PLS1-NMR proved to be an effective rapid method for analyzing the major Rodrigues et al. (2010)
organic compounds in beer
Out of the 6 compounds measured, compared to other analytical methods,
malic and pyruvic acid was slightly overestimated, and there was apparent
overestimation for citric acid
Detailed assignment of HR NMR spectra of Red Setter tomato juice was Sobolev, Segre, and Lamanna (2003)
obtained :
− In the high-field region of the proton spectrum, the resonances are
mostly due to aliphatic groups of amino acids and organic acids of
the tricarboxylic acid metabolic cycle.
− In the middle field region (from 3.2 to 5.3 ppm), the resonances are
mostly due to saccharides and major components (D-glucose and
D-fructose)
− In the low-field region (from 5.5 to resonances are mostly due to
minor components of tomato juice such as aromatic amino acids,
phenolic compounds and formate
All water-soluble substances present in both pulp and juice.
Both liquid state NMR and HR-MAS NMR produced consistent re-
sults, except HR-MAS NMR was also able to detect insoluble sub-
stances such as lipids
Information on the quality evaluation of Japanese green tea was provided via Tarachiwin, Ute, Kobayashi, and
1
H NMR Fukusaki (2007)
NMR offered higher reliability in results over the traditional method of
testing Japanese green tea quality. specifically to quantitative and qualitative
evaluate sensory quality of green tea is derived from the metabolites
(e.g. caffeine, theanine, EGCG, ECG, EGC, and EC) in the matter of easier
sample preparation and quicker results
The PLS regression model of green tea have correlation coefficient R2 (good-
ness to fit): 0.987, correlation coefficient Q2 (goodness of prediction): 0.671,
root mean squared error of estimation (rmsEE): 1.82, and root mean squared
error of prediction (rmsEP): 9.22
Foods
Sample Research objective
information
Tea sample dissolved and placed in
5 mm NMR tube
Fresh green tea leaves from
Hannam, Dosun and Seogwang areas
in South Korea
Coffee Commercial soluble coffees include:
Baque Natural Eroski Tueste Natural,
Fortaleza Natural Marcilla Creme
Express Natural, Nescafe Alta Rica,
Nescafe Classic Natural, Nescafe
Expresso, Nescafe Solo and Spar
Tueste Natural
600 μL placed in a 5 mm outer
diameter NMR tube
Edible Oils 200 μL directly transferred to 5 mm
NMR tube
Edible vegetable oils include soybean
(6), canola (3), sunflower (5), corn
(5), rice (2), and olive (8)
Olive oil sample in (20 μL) dissolved
in solution and placed into 5 mm
NMR tube
Olive oil from the Adriatic district in the
Molise region (southern central Italy)
963Virgin olive oils (VOOs) from
Italy (661), Spain (144),Greece (97),
France (39), Turkey (14), Cyprus (6),
and Syria (2)
40 μL of each samples dissolved into
200 μL deuterated chloroform —
placed in a 2 mm NMR capillary
Olive, hazelnut and sunflower oils
Lettuce Water soluble extract and lipidic
fraction extract were prepared and
placed into 5-mm NMR tube
Supernatant from processed mixture
into 5 mm NMR tube
Onions 2-cm thick equatorial slice of yellow
type onion bulbs 5 ×5 mm piece into
NMR tube
2 control treatments:
(1) raw onion, 0.1 MPa, 20 °C;
(2) raw onion, vacuum packed
(0 MPa)
2 treatments:
(1) high pressure (20–200 MPa,
5 min)
(2) thermal treatment (40 to 90 °C,
30 min)
Freeze dried sample to exert water,
prepared solution of 700 μL into
5 mm NMR tubes
Type NMR
To investigate the effects of climate
conditions on green tea metabolites
To quantify caffeine, formic acid,
trigonelline and 5 (hydroxymethyl)
furfural (5-HMF) in soluble coffees
To develop an effective, simple
method of analyzing fatty acid
contents in edible oils and compare
the method to official AOAC method
of gas chromatography
To investigate the influence of
harvest period and method on the
composition of olive oil
To determine authentication of
virgin olive oil by identification of
geographical origin at the national,
regional and or protected
designation of origin (PDO) level.
To perform a composition analysis
To identify and assign in details the
1
H NMR spectra of lyophilized
lettuce
To compare the water soluble
metabolites between wild type
lettuce and GM modified lettuce and
detect any differences.
To study the effects of high pressure
and thermal processing on
membrane permeability and
integrity in plant tissue using 1H
NMR
To verify that 1H NMR is a useful re-
liable tool to measure changes in cell
membrane permeability
To determine the range of pressure
that would induce changes in onion
tissue membrane permeability
To investigate the extracted
metabolites in raw onions and
aqueous onion solution using a fast
effective method. To compare the
Observations Reference
1
H NMR 500 MHz, NOESTPRESAT differences were observed in the OPLS-DA score plots derived from the 1H Lee et al. (2010)
pulse to suppress water signal. NMR green tea spectra between the Hannam and Dosun areas, between the
Dosun and Seogwang areas, and between the Hannam and Seogwang areas
(P b 0.05)
Green tea metabolome have been found to be d influenced by climatic con-
ditions (sun exposure time, precipitation, and temperature) in different area
500 MHz 1H NMR Solvent suppres- For 10 measurements by 1H NMR, the coefficients of variation obtained are del Campo, Berregi, Caracena, and
sion using the Watergate pulse 4.2%, 2.6%, 2.4% and 7.3% for caffeine, formic acid, trigonelline and 5-HMF, Zuriarrain (2010)
sequence respectively, throughout 5 days
Results from 1H NMR are in good agreement (P> 0.05) with those from the
reference methods (HPLC standard method determines caffeine, trigonelline
and 5-HMF and commercial enzymatic method determines formic acid)
1
H NMR Using 1H NMR provided similar results to gas chromatography results (at Barison et al. (2010)
significance levels higher than 95%). However, unlike CG, 1H NMR proved to
be a rapid, simple, robust and sensitive.
There was no need for sample pre-treatment such as extraction, allowing 1H
NMR technique to be environmentally and economically friendly
1
H NMR Volatile compounds (hexanal, trans-2-hexenal, sn-1,3-diglycerides, and D'Imperio et al. (2010)
M.F. Marcone et al. / Food Research International 51 (2013) 729–747
squalene) significantly. decreased in concentration significantly during the
ripening period (Pb 0.05)
ΔK parameter and the amount of hexanal were much higher in olives that
were obtained via a shaker, whereas olives that were obtained using a comb
had lower levels
1
H NMR Partial least-squares discriminant analysis (PLS-DA) model recognized 94% of Alonso-Salces et al. (2010)
Greek, 81% of Italian, and 75% of Spanish oils in the training-test sets and
predicted correctly 88% of Greek oils and 69% of the samples from Italy and
Spain in the cross-validation and 81% of Greek, 79% of Spanish, and 66% of
Italian oils in the external validation
PLS-DA correctly classified Greek and non-Greek VOOs (>90%)
δ13C of olive oils could discriminate Greece, Spain, and Italy VOOs (the mean
value of δ13C follows a order of Italianb Greekb Spanish oils)
1
H NMR spectroscopy Separation between these three oils of different botanical origin and Fauhl, Reniero, and Guillou (2000)
permitted the detection of their mixtures
1 13 31
1D and 2D H, C and P-NMR A large number of water soluble metabolites were identified, as well as Sobolev, Brosio, Gianferri, and Segre
metabolites extracted in organic solvents were identified as well. (2005)
1D 1H NMR, 600.13 MHz NMR results on their own did not derive any information; however after proper Sobolev et al. (2010)
2D NMR, 1H–1H TOCSY, and 1H–13C statistical analysis. different levels of metabolites were correlated with the GM
HSQC lettuce and wild type lettuce. The highest impact was noted in the trend of glu-
cose and fructose content which was inverted when compared to the wild type.
1 1
H NMR H NMR proved to be an effective method to quantify cell membrane damage Gonzalez et al. (2010)
Carr–Purcell–Meiboom–Gill (CPMG) in plant tissue. It was possible to distinguish between different degrees of
pulse sequence membrane damage.
This method will allow for the selection of the best food processing method
based on the impact on tissue integrity
The greatest percent of weight loss was observed in the frozen sample with
an average of 16.7% . The weight losses increased along with increase in
temperature during thermal treatments. For all the high pressure treatments
below 200 MPa, the percentage of weight loss was insignificant.
300 MHz (7.05 T) 3 main saccharides. 17 amino acids and 5 organic acids were detected with Tardieu, De Man, and This (2010)
1D, 2D 1H (COSY sequence) NMR the use of NMR spectroscopy. The results were similar to other methods.
spectroscopy Using NMR spectroscopy proved to be a simultaneous and direct detection
method.
(continued on next page)
739

Table 2 (continued)
Foods Sample information
Onions
Sweet pepper 253 Italian sweet peppers (Capsicum
annum L.)
101 peppers belonged to cv. “Corno”
152 peppers belonged to cv. “Cuneo”.
25 mg fresh sweet pepper for 1D and
freeze dried for 2D NMR.
Potatoes Five potato varieties (Sava, Berber,
Ditta, Bintjemedio-dry-matter and
Bintje-high-dry-matter) stored at
4 °C and 95% relative humidity for
two and eight months,
For cooked potatoes, whole potatoes
were peeled and boiled in water for
20–25 min
Apples Slices
Mango Mango fruits (“Tommy Atkins”
cultivar)
Rice Rice
Cocoa beans Fermented cocoa beans (Forastero,
Criollo, and Trinitario) from different
countries (Ecuador, Ghana, Grenada,
and Trinidad)
Dried fermented cocoa beans extracts
re-dissolved in 1 mL of D2O/CD3OD
(8:2 v/v) containing 0.1% of TSP
Diluted samples, 5 mm NMR sample
tube
Maize Processed seeds in solution placed in
standard 5 mm NMR tube
Dry samples were dissolved in a D2O
phosphate buffer (100 mM, pH7.2)
containing trimethylsilylpropionate
(TSP, 1 mM) as internal standard.
Research objective
results from H NMR to
high-performance liquid chroma-
tography (HPLC), mass spectroscopy
(MS, MS/MS), and thin layer chro-
matography (TLC and PLC)
To produce a detailed chemical
characterization of sweet pepper,
and identify major compounds by
means 1D and 2D NMR using a fresh
sweet pepper samples without
sample preparation.
To predict sensory texture quality
attributes of cooked potatoes,
including hardness, cohesiveness,
adhesiveness, mealiness, graininess
and moistness.
To investigate the correlation
between advanced image analysis
features determined in different
regions of raw potatoes, and sensory
texture attributes of cooked
potatoes.
To perform texture analysis during
ripening and storage
To study the composition of mango
during ripening using solid state and
liquid state NMR in an intact mango
pulp and mango juice respectively.
Prove HR-MAS NMR to be a non de-
structive analytical tool for fruit
analysis.
To analyze the water distribution
and structural changes
To quantitatively and qualitatively
analyze the composition of
fermented cocoa beans and to
distinguish between varieties and
geographical region
To compare metabolites of maize
seeds from the transgenic maize
variety 33P67 to the traditional
variety.
740
Type NMR Observations Reference
400 MHz 1H and 13C NMR Using HRMAS-NMR, metabolic profile of sweet pepper was observed and Ritota, Marini, Sequi, and Valentini
HRMAS-NMR (high resolution magic recorded. (2010)
angle spinning nuclear magnetic With PLS-DA analysis, the 1H NMR spectra reveals that the metabolites mainly
resonance) H contributing to the discrimination between the two cultivars considered were
sugars and organic and fatty acids.
PLS-DA analysis allowed for the determination of geographical origin of the
M.F. Marcone et al. / Food Research International 51 (2013) 729–747
pepper sample: For cv. “Corno”. an acceptable discrimination was obtained with
an overall non-error rate of 92.1%; For cv. “Cuneo”, an acceptable discrimination
was obtained with an overall non-error rate of 94.7%
NMR-imaging (MRI) Potentially, MRI data from raw potatoes could used to predict sensory attri- Thybo et al. (2004)
butes is related to the texture of cooked potatoes.
Compared with the MRI features from horizontal and vertical regions, the
highest prediction was obtained by the MRI features from the full region
within the potato, For hardness, 76% of the variation was predicted; for ad-
hesiveness 54% and for moistness 50% of the variance was predicted,
resulting in correlation coefficients of 0.86, 0.72 and 0.69, respectively. For
mealiness and graininess, the variances were below 55%. the vertical region
seemed to predict y better (46%) than both the full and the horizontal regions
The MR-image features predicted 70% of the variation in hardness of the
cooked potato.
MRI A significant correlation was found between acidity and texture analysis Létal et al. (2003)
parameters such as sum average, sum variance and sum entropy.
The dynamics of Texture analysis parameters during the periods of
maturation and storage were described by polynomial functions
Water suppression and 2D NMR Main sugars (glucose, fructose and sucrose) and approximately 40 metabolites Gil et al. (2000)
HR-MAS NMR using 400 MHz 1H and were identified in mango samples at different ripening stages
and 100 MHz 13C for the intact In mango pulps, sucrose predominates over fructose and glucose at most
mango pulp ripening stages
NMR spectra for the juice sample Citric acid is the most abundant organic acid in the unripe mango, decreasing
was produced using a 600 MHz 1H dramatically through the ripening process.
NMR
1
H NMR Internal hollows were observed in all examined cooked rice grains, and we Horigane et al. (1999)
propose a mechanism to explain their formation. The origin of these hollows
was hypothesized to be cracks or fissures, and hollows resulted from sealing
of such lacerations by gelatinized starch in the peripheral layer in
combination with expansion of the grain during cooking.
1 1
H NMR spectra of hydroalcoholic H NMR successfully quantified amino acids, polyalcohols, organic acids, Caligiani, Acquotti, Cirlini, and Palla
extracts sugars, methylxanthines, catechins, and phenols in different varieties of (2010a)
cocoa beans
1
H NMR analysis could be used as a rapid method for cocoa bean quality
control by quantifying methylxanthines and catechins.
600 MHz Bruker 1H NMR and 2D The 1H spectra from both seed lines turned out to be identical, however Piccioni, Capitani, Zolla, and
1
H–1H and 1H–13C transgenic extracts, higher levels of ethanol, citric acid, glycine–betaine, Mannina (2009)
trehalose, and an unknown compound were observed that allow for a
distinction between the two varieties (transgenic and nontransgenic seed
maize samples).
Several compounds (ethanol, lactic acid, citric acid, lysine, arginine, glycine–
Foods
Sample Research objective
information
Whey protein Whey protein isolate (WPI)
gels containing 95.6% protein
WPI gels — in 8 slices. 6.2 mm
thickness of each slice
Soybean 2 g of strip sample of Chinese Soy
protein isolate (SPI) placed in
15 mm NMR tube
Methanolic extract of defatted
soybean — solution in 5 mm NMR
tube
Cheese Cheese made from pasteurized
cow's milk
Cheese placed in drying chamber at
1, 3, 6, 9, 13 and 26 days of drying
Beef 600 μL of supernatant transferred
into 5 mm NMR tube
40 authentic raw beef samples from
Australia, Korea, New Zealand, and
the United States
Prepared liquefied sample — 5 mm
NMR tube
Fish 8–10 mg of white muscle sample
Smoked Atlantic salmon (S. salar)
Samples minced and placed in
10 mm sample tubes (Atlantic cod)
15 mg sample (Arctic char, Central
Sweden)
Manuka honey Diluted samples
Type NMR
To quantify changes in geometry
and water content of whey protein
gels and detect swelling whey
protein gels in solutions at 3
different pHs.
To observe the state of water in
texture soybean protein (TSP) and
the changes of water states and
distribution in TSP when extruded at
different feed moisture contents and
cooking temperatures.
To investigate fingerprint soybean
extracts, such as amino acids,
carbohydrates, organic acids,
emphasizing on isoflavones
quantification
To investigate determine moisture
profiles of cheese during drying
To evaluate the metabolite profile of
beef post mortem, and monitor the
changes occurring during the aging
of beef
To identify metabolites in raw beef
that will enable geographical
location of the beef origin to be
identified
To detect and identify the main
components in smoked salmon.
To identify what changes may occur
in the metabolite profile of smoked
Atlantic salmon during storage
To detect physical and chemical
differences between wild and
farmed cod (pre and post rigor) in
terms of effect of brine injection,
brining, and freezing
To obtain nutritional value of fish,
such as PUFA composition and major
small metabolites in intact muscle of
arctic char
To accurately and rapidly measure
the levels of methylglyoxal in
Manuka honey.
Observations
1.03 T NMR spectrometer —
proton NMR-MRI images — T1 and
T2 times
1
H Using low field nuclear magnetic
resonance (LF-NMR) 22.6 MHz, used
Carr–Purcell–Meiboom–Gill (CPMG)
sequence to measure spin–spin
relaxation time (t2)
1 1
H NMR, 14.1 T, 600 MHz. Used
selective water signal irradiation
A time-domain nuclear magnetic
resonance (TD-NMR)
1
H NMR, 300 MHz
1 1
H NMR, 600 MHz, NOESY-PRESAT
pulse sequence to suppress residual
water signal
1 1
H-HRMAS NMR spectroscopy.
500.13 MHz (11.7 T)
A low-field Brukermq 20 Benchtop
NMR analyzer with 20 MHz proton
frequency
1
H HR-MAS NMR spectroscopy
600 MHz
11.7 T Bruker Avance III 500 MHz
NMR (1H resonances with water
suppression
Reference
betaine, raffinose, trehalose, R-galactose, and adenine) were identified for the
first time in maize with 1H NMR
Approximate 40 water-soluble metabolites in the maize seed extracts were
identified.
MRI can be used to monitor the rate and extent of how whey protein-based Oztop, Rosenberg, Rosenberg,
gel swell at different aqueous environments McCarthy, and McCarthy (2010)
At pH 7 and 10, mass uptake of WPI gel correlated with volume change of
WPI gels (R2= 0.99)
The results from both methods were consistent. It was found that water Chen, Wei, and Zhang (2010)
spreads in a homogenous manner, and the intensity of water distribution
increased as total water content increased.
Freezable and non-freezable water content determined by differential scan-
ning calorimeter (DSC) were correlated to the results of spin–spin relaxation
time constants T22 and T21 from NMR at the correlation coefficients were 0.96
(pb 0.01) and 0.54 (p b0.05), respectively.
H NMR analysis provided accurate results, with the advantages of minimal Caligiani, Palla, Maietti, Cirlini, and
sample preparation, and rapid acquisition time of data. Brandolini (2010)
M.F. Marcone et al. / Food Research International 51 (2013) 729–747
A proposed diffusion model satisfied both the drying curve (mean relative Castell-Palou, Rossello, Femenia,
error (MRE) = 0.4% and percentage of explained variance (%var) =99.7%) Bon, and Simal (2011)
and the moisture profiles (average MRE= 4.4% and %var = 94.5%)
The predicted moisture content (TD-NMR method) is correlated with
vacuum oven methods (according to the International Dairy Federation (IDF,
1982) standard norm 4A0 (r2 = 0.999)
Aging of sample was shown to effect metabolites, specifically the Graham et al. (2010)
concentration of amino acids due to an increase in proteolysis.
H NMR proved to be effective in identifying metabolites in aqueous raw beef, Jung et al. (2010)
which helped to identify the geographical origin of beef.
Succinate and various amino acids such as isoleucine, leucine, methionine,
tyrosine, and valine could potentially be used as markers to distinguish be-
tween various raw beef samples
H-HRMAS spectra of smoked salmon shows the presence of FAs, Castejón et al. (2010)
triacylglycerides and phospholipids, carbohydrates, nucleoside derivatives,
osmolytes, amino acids, dipeptides, various organic acids (acetic acid,
succinic acid, lactic acid, fumaric acid and formic acid), pyrimidine derivative
uracil as well as ethanol (a fermentative degradation product of sugars).
This method proved to be a rapid non-destructive technique to identify
valuable information in foods. Estimation of DHA and other polyunsaturated
FAs by direct analysis was achieved without chemically preparing the sample
and extract lipids as usually required by other methods.
Muscle structure information for the farmed and wild cod as well as the state Gudjonsdottir et al. (2010)
of the water in the muscle during brine injection, brining and during rigor
tension was attained — NMR can be used to optimize the salting and storing
process of wild and farmed cod
n−3 FA, EPA and DHA in fish oil were determined using 1H HR-MAS NMR Nestor et al. (2010)
spectroscopy in intact muscles. provide fatty acid profile and major metabo-
lites of fish without hydrophilic and lipophilic extraction
qNMR method worked for quantifying methylglyoxal in Manuka honey Donarski, Roberts, and Charlton
without chromatographic separation or a derivatization procedure (2010)
Result also showed that other methods may have overestimated [MGO]
741
742 M.F. Marcone et al. / Food Research International 51 (2013) 729–747
were also observed. The x-axis of the spectrum is the delta scale
(δ) with units of ppm and the y-axis is an intensity scale. These
above-mentioned compounds were targeted in this study because
they are all relevant in regard to the quality of green tea. Again,
this 1H NMR based study proved the possibility of the use of NMR for
quality evaluation of beverages by determining the quality related
chemical constitutes in food with simple sample preparation and
short analysis time (Tarachiwin et al., 2007).
8.3. Edible oils
1
H NMR spectroscopy provides a possible alternative to conven-
tional chromatographic methods for determining the composition of
oils. Fauhl et al. (2000) separated olive oil, hazelnut and sunflower
oils based on geographic origin (Fauhl et al., 2000). In a more recent
study, Alonso-Salces, Moreno-Rojas, et al. (2010) identified olive oil
samples from five different countries (Spain, Italy, Greece, Tunisia,
Turkey, and Syria) and their corresponding unsaponifiable fractions
using 1H NMR spectra(Alonso-Salces, Moreno-Rojas, et al., 2010).
This study suggested that they contain complementary information
which would enhance the classification of olive oil according to
their geographical origin. Likewise, several studies have shown that
NMR spectroscopy is a powerful tool for characterizing olive oils
according to cultivar, geographical origin, quality, and genuineness
(D'Imperio et al., 2010). Few studies, however, have used this tech-
nique to investigate the effect of the harvesting method on olive oil
composition. D'Imperio et al. (2010) focused on this area of research.
Harvesting methods such as the use of combs or shakers can influence
the composition of unsaturated fatty acid chains and volatile com-
pounds in raw olives. This affects olive oil quality as it specifically in-
creases in acidity and peroxide values while also causing a decrease in
total polyphenol content. In general, the mechanical harm to fruits
during harvest can increase several autoxidative processes which
are detrimental to olive quality (D'Imperio et al., 2010).
8.4. Cheese
The potential of NMR to study cheese has been intensively reported
with some specific topics, such as determining its geographic origin,
molecular mobility of water, water holding capacity (Hinrichs et al.,
2004; Karoui & De Baerdemaeker, 2007; Summer et al., 2003). In
addition, Consonni and Cagliani (2008) analyzed Italian Parmigiano
Reggiano cheese for the identification of ripening and geographical
discrimination using NMR. During the ripening process, cheese compo-
nents encounter modifications in their chemical, physical and enzymat-
ic properties. Researchers realized that the amino acid content may be
influenced by the ripening and production location showing a high
content of leucine and isoleucine in the early ripening stages while
the later ripening stages had high threonine content. When a Parmigiano
Reggiano cheese was compared with a Grana type cheese from Eastern
Europe, the latter was rich in lactate, butanoate, acetate, leucine and
isoleucine whereas the former had large amounts of other compounds,
such as, threonine. These free amino acids and fatty acids also
contributed to distinctive taste features of those cheeses (Consonni &
Cagliani, 2008). With NMR technology, other researchers were able to
differentiate Asiago cheese produced in alpine farms from the same
cheese produced commercially in larger operations (Schievano, Pasini,
Cozzi, & Mammi, 2008). Results indicated that the FA composition of al-
pine farm cheeses had a higher unsaturated FA content (oleic, linoleic,
linolenic, and conjugated linoleic acids) compared to the industrially
produced cheese. Such differences in FA composition can be accounted
for due to the diet of cattle on high-concentrate diets, compared to
cattle on Alpine farms where production consists of milk from cattle
grazing on natural pasture grasses at higher elevations. This further
demonstrates the importance of the cattle's diet which has the ability
to directly affect the quality of milk and milk products such as cheese.
In a review, several other applications of NMR for cheese analysis
have been summarized, including the use of MRI to examine the gross
microstructure of cheese and to identify the location of holes and slits
within cheese for quality control purpose; the use of NMR to measure
moisture and fat content, as well as chemical compounds in Parmigia-
no Reggiano cheese for investigation of ripening (Everett & Auty,
2008). This review also introduced that the utility of NMR to evaluate
water mobility and to identify the more mobile bulk water trapped
within the casein matrix and a less mobile water phase bound direct-
ly to the casein in mozzarella cheese. In addition, NMR results has also
revealed that ice crystals opened up the protein matrix for permitting
the development of water pockets during the freezing of Mozzarella
cheese, as well as diffusion of water molecules and fat globules in
cheese (Everett & Auty, 2008).
8.5. Fruits and vegetables
By means of the quantification of certain NMR parameters (i.e. T1,
T2, and diffusion coefficient (DC) to obtain information about several
processes and material properties (such as ice crystallization, and
water mobility), the use of NMR methods to identify compositions
and evaluate quality has also been popular amongst a wide-range of
fruits and vegetables (Brusewitz & Stone, 1987; Chen et al., 1989).
Studies have applied NMR to leafy vegetables, lettuce samples
(Lactucasativa) with a large number of water soluble metabolites were
distinguished along with key organic solvents (Sobolev et al., 2005).
“The safety testing of genetically modified organisms (GMOs) is a
high priority for regulatory authorities, and there is a need for tech-
niques capable of detecting any unintended effect following a genetic
modification” (Piccioni et al., 2009). With the increasing awareness of
genetically modified (GM) foods, Sobolev et al. (2005) used NMR to
study GM lettuce. This 2010 study compared levels of water soluble me-
tabolites between GM lettuce and wild type lettuce resulting in differ-
ences in both the glucose and fructose content. Piccioni et al. (2009)
touched upon differences between transgenic and traditional maize.
Transgenic maize revealed higher levels of certain compounds, includ-
ing mainly ethanol, citric acid, glycine–betaine, and trehalose.
Kerr, Kauten, McCarthy, and Reid (1998) studied ice formation and
freezing properties in a variety of foods such as potatoes, carrots, peas,
and chicken legs. Freezing is a very important tool in the food industry,
allowing for the longer preservation of food. Being able to detect
freezing times, patterns, and time to completion is important for the
improvement of food quality. Using MRI, the freezing behavior charac-
teristics were monitored noninvasively in the different foods, the ice
formation correlated to the loss of NMR signal intensity, as well as the
time of ice formation to the time of the loss of signal. (Kerr et al., 1998).
NMR data regarding correlation of distribution during cooking
correlated to texture attributes of potato have also successfully been
demonstrated (Mortensen, Thybo, Bertram, Andersen, & Engelsen,
2005; Thybo et al., 2004). For example, in a study by Mortensen et al.
(2005), a pulsed NMR analyzer was employed to determine dry matter
(DM) content, and investigate water characteristics and water transi-
tion between two bins (low DM and medium DM) of potatoes of the
Sava variety during cooking. DM content was of interest in the study,
since DM content is relevant for potato texture and plays a role in the
mobility of the water (Mortensen et al., 2005). These studies not only
demonstrated the sensitivity of MRI for determination of structural
changes with respect to water association during processing and final
texture of the potato, but also gave scientific support for the develop-
ment of NMR methodology for the prediction of sensory texture attri-
butes of other fruits and vegetables.
MRI texture analysis (TA) was used to study the effects of ripening
and storage of sliced apples. Here TA refers to a series of techniques
used for the quantification of spatial variation of gray tones in MR im-
ages. Certain TA parameters were calculated from MR images of apple
varieties during ripening and long-term storage. Different apple
 M.F. Marcone et al. / Food Research International 51 (2013) 729–747
varieties are found to have different dynamics of TA parameters for
maturation and storage periods. These TA parameters of particular in-
cluded skewness and kurtosis (among histogram-based parameters),
and variance of absolute gradient (among gradient-based parameters).
In addition, different gray level nonuniformities (among run length
matrix-based parameters) and especially some co-occurrence
matrix-derived parameters such as correlation, sum average, sum vari-
ance and sum entropy (within 1-, 3-, and 5-pixel neighborhoods) were
also found. These above mentioned TA parameters were associated
with chemical and physical characteristics (firmness of fruits, bruising,
soluble solids content (SSC), titratable acids) or three apple varieties
(i.e. Topaz, Redspur and Idared) (Létal, Jirák, Šuderlová, & Hájek,
2003). MRI texture analysis also applied to study other fruits, such as
pears (Lammertyn et al., 2003; Zhou & Li, 2007).
HR NMR spectroscopy has been shown to be a valuable method for
the analysis of low molecular weight compounds in fruit juices while
allowing the simultaneous identification of several sugars, organic
acids, amino acids and other minor components such as phenolic
compounds (Duarte et al., 2006). Gil et al. (2000) applied high resolu-
tion 1H NMR to examine the composition of natural mango juices (Gil
et al., 2000). The value of this study lies in the ability to identify spoil-
age and microbial contamination (specifically Penicillium expansum)
hence 1H NMR enables earlier detection of the juice compositional
degradation.
Gonzalez et al. (2010) studied the effects of high pressure and
thermal processing on onion cell membranes. In particular, mem-
brane permeability and cell compartmentalization were the focus
since they are an integral aspect of plant tissue texture (Gonzalez et
al., 2010). 1H-NMR proved to be an effective method for the quantifi-
cation of cell membrane damage in onions and allowed for the com-
parison of the impact of different food processes based on tissue
integrity. These findings can be extended towards other samples
since the quality of fruits and vegetables are related to the degree of
tissue integrity.
Researchers have been able to use 1H NMR to obtain information
on the composition of a variety of fermented cocoa beans (Caligiani,
Acquotti, Cirlini, & Palla, 2010b). The study determined the amino
acids, polyalcohols, organic acids, sugars, methylxanthines, catechins,
and phenols in cocoa beans from different countries (Ecuador, Ghana,
Grenada, and Trinidad) demonstrating the method to be a rapid
method for country identification and quantification of beans. Chen
et al. (2010) used LF-NMR to observe the distribution and state of
water in soybeans. The distribution of water was homogeneous, and
the intensity of distribution increased remarkably with total water
content (Chen et al., 2010). This proves to be a useful approach to un-
derstand the role of water (in different states) in the extrusion
cooking process, which is a popular manufacturing process for pre-
paring a variety of foods, such as cereals, and snacks.
8.6. Meat and fish
NMR technology continues to be explored in a wide range of dif-
ferent meats (i.e. pork, beef and chicken). Several NMR parameters
have been found associated with variations of water mobility as con-
sequences of the mediations of water macromolecule interactions
and changes in tissue structure, including spin–lattice (T1) and
spin–spin (T2) relaxation times, magnetization transfer ratio (MTR),
and apparent diffusion coefficient (ADC).
The use of MRI permits the quantification of the above mentioned
parameters, which has been used not only to determine chemical
composition, muscle structure, and quality of meat, but also to
study carcass composition, adipose tissue distribution, connective
tissue, and muscle fiber type. These parameters have also been corre-
lated with meat properties including pH, water-holding capacity,
moisture, texture and sensory attributes (Bonny, Laurent, & Renou,
2000; Cernadas, Carrion, Rodriguez, Muriel, & Antequera, 2005;
743
Graham et al., 2010; Herrero et al., 2007; Jung et al., 2010; Mitchell,
Scholz, Wang, & Song, 2001; Renou et al., 2003; Ruiz-Cabrera, Gou,
Foucat, Renou, & Daudin, 2004; Shaarani, Nott, & Hall, 2006).
Recent studies have quantified beef (Graham et al., 2010; Jung et
al., 2010). The aim of the study by Graham et al. (2010) was to eval-
uate the ability of 1H-NMR to characterize the changes in amino
acids, nucleotides, and sugars during post mortem aging. Significant-
ly, this method required minimal sample preparation to analyze beef
samples and demonstrated that aging does affect the concentration of
different metabolites. Their study revealed an increase in proteolysis
that ultimately affected the concentration of amino acids.
In order to obtain information regarding the correlations between
MRI, texture, and physicochemical parameters, three model systems:
fibrinogen–thrombin gels (FTG), meat emulsions (ME), and meat
emulsion supplemented with fibrinogen–thrombin (ME-FT) were
used in a study. MRI parameters (T2, T1, and apparent diffusion coef-
ficient) indicated that systems with fibrinogen and thrombin (FTG
and ME-FT) presented a structure with many and large pores, bulk
water, and higher translational motion of water (Herrero et al., 2007).
The increasing awareness of BSE has caused both an interest in and
concern amongst individuals when trying to determine the geographi-
cal origin of beef. Jung et al. (2010) used 1H NMR spectroscopy coupled
with multivariate statistical analyses to differentiate the geographical
origin of beef samples. Samples were examined with the use of metab-
olite profiling data. This identified potential marker candidates includ-
ing amino acids and succinate which distinguish beef origin.
The main components of smoked salmon have also been identified
using NMR spectroscopy (Castejón et al., 2010). This includes the de-
termination of docosahexaenoic acid (DHA) and other polyunsaturat-
ed FAs along with carbohydrates, amino acids, dipeptides, and
organic acids. Their study created a novel possibility in the determi-
nation of ω − 3 FAs for fish and processed fish products. Consequent-
ly, these methods avoided preparation (chemical pre-treatment) and
extraction which are essentially required by other methods. Similarly,
Nestor et al. (2010) targeted the avoidance of extractions and deter-
mined the FA composition, the eicosapentaenoic acid (EPA) and
DHA in Arctic char. This study achieved direct information regarding
the nutritional value of the fish, with a simple analytical technique
(Nestor et al., 2010).
Further applications of NMR analysis to fish sample processing
methods were demonstrated with regards to salting (Gudjonsdottir
et al., 2010). Salting fish has been a traditional preservation technique
for centuries in many cultures. These methods involved in the pro-
duction of salting cod can impact the distribution of water in cod
muscle tissues as well as protein denaturation. By investigating the
water distribution, it indicated that salting and rehydration processes
did irreversibly change the cells. These analytical methods have prov-
en to be rapid and non-destructive techniques that can produce valu-
able information in an extensive amount of food samples.
9. Conclusion and future research
Research applications described above illustrate that NMR and
MRI are valuable tools to study metabolic processes, composition,
structural, and physical states of foods, as well as tools for food quality
and process control (Sobolev et al., 2005; Tarachiwin et al., 2007).
Spyros and Dais (2009) envisioned that NMR in the future will “play
an important role in this field that encompasses many potential appli-
cations in food science and analysis” (Spyros & Dais, 2009).
Among many, one of those applications that will become increas-
ingly important is to explore the connections between food and
health sciences. For examples; Weissleder, Poss, Wilkinson, Zhou,
and Bogdanov (1995) have made rehydration and dehydration pro-
cesses for a food gel suitable for monitoring the controlled release
and hydrogel volume erosion of an implant in vivo; and Marciani
et al. (2007) have used MRI to investigate the behavior of lipid
744 M.F. Marcone et al. / Food Research International 51 (2013) 729–747
emulsions in the human stomach. Another type of application that
will become more important is verification of labeling claims about:
region or species or breed of origin, health properties of pronutrients;
and production or processing systems such as organic or minimally
processed (Caligiani, Acquotti, Cirlini, & Palla, 2010b; Figueiredo et
al., 2006; Marciani et al., 2007; Weissleder et al., 1995).
Modifications of NMR instruments are also needed to improve
the sensitivity to enable improved detection and quantification of food
components. Researchers have made credible attempts; Haiduc, Trezza,
van Dusschoten, Reszka, and van Duynhoven (2007) designed an
NMR-Mouse that employs new magnet geometry, and Hollingsworth
and Johns (2004) and Callaghan (2006) developed techniques to mea-
sure non-NMR parameters such as flow and rheological properties, also
known as velocimetry MRI or Rheo-NMR (Callaghan, 2006; Haiduc et
al., 2007; Hollingsworth & Johns, 2004). Improvements will also be real-
ized using synergistic combinations of NMR/MRI and other tools, such as
impedance spectroscopy, ultrasound or laser scattering, and rheological
measurements (Mariette, 2009). For examples, researchers have intro-
duced a novel low-cost Halbach-array based NMR system which
facilitates the simultaneous use of multi-sensor techniques on the same
sample; and other workers proposed that low-field NMR technologies
along with polarization techniques can contribute to the development
of stable, robust and portable NMR devices (Adams et al., 2009;
Trabesinger et al., 2004).
In another study, a site-specific natural isotope fractionation-
nuclear magnetic resonance (SNIF-NMR) methodology has been de-
veloped to detect added beet or cane sugar in maple syrup. When
beet sugar was added, the deuterium/hydrogen (D/H) value obtained
by SNIF-NMR is in good agreement with the values (AOAC Official
Method 995.17); however, when cane sugars, or blends of beet and
cane sugars, or corn sweeteners were added, SNIF-NMR was unable
to perform precise and accurate measurements as before, unless
AOAC Official Method 984.23 (Corn Syrup and Cane Sugar in Maple
Syrup) was used with SNIF-NMR (Martin et al., 2001).
In food science, barriers to development of NMR spectroscopy in-
struments are primarily due to high cost, the expertise involved, and
safety issues related to magnetic field maintenance. Low-field NMR
and MRI are relatively more accessible to food researchers due to
lower cost and easier maintenance, but their applications are still lim-
ited. It should also be noted that all applications of NMR and/or MRI
appears to be research oriented at the present time (Table 1).
Extending the application of NMR techniques beyond research to in-
dustrial process and quality control is still to come. In order to ensure
proper data acquisition and analysis, more NMR-trained staff are
needed in the aspect of food application. Food researchers also face
challenge to establish standard operation procedures (SOPs) of
NMR/MRI analysis for specific categorized food products (i.e. wine,
potatoes) due to the complex nature of foods. Once SOPs are
established, researchers are able to compare their results of NMR/
MRI for further improvements. On the other hand, NMR permits di-
verse food-based application, but still has limitation. Integrating
with other analyses will provide a full picture of results.
References
Adam-Berret, M., Rondeau-Mouro, C., Riaublanc, A., & Mariette, F. (2008). Study of
triacylglycerol polymorphs by nuclear magnetic resonance: Effects of temperature
and chain length on relaxation parameters. Magnetic Resonance in Chemistry, 46(6),
550–557.
Adams, R. W., Aguilar, J. A., Atkinson, K. D., Cowley, M. J., Elliott, P. I., Duckett, S. B., et al.
(2009). Reversible interactions with para-hydrogen enhance NMR sensitivity by
polarization transfer. Science, 323(5922), 1708–1711.
Alexandrescu, A. T., Evans, P. A., Pitkeathly, M., Baum, J., & Dobson, C. M. (1993). Structure
and dynamics of the acid-denatured molten globule state of alpha-lactalbumin: A
two-dimensional NMR study. Biochemistry, 32(7), 1707–1718.
Almeida, C., Duarte, I. F., Barros, A., Rodrigues, J., Spraul, M., & Gil, A. M. (2006). Composi-
tion of beer by 1H NMR spectroscopy: Effects of brewing site and date of production.
Journal of Agricultural and Food Chemistry, 54(3), 700–706.
Alonso-Salces, R. M., Holland, M. V., Moreno-Rojas, J. M., Mariani, C., Bellan, G., Reniero, F.,
et al. (2010). Multivariate analysis of NMR fingerprint of the unsaponifiable fraction of
virgin olive oils for authentication purposes. Food Chemistry, 118(4), 956–965.
Alonso-Salces, R. M., Moreno-Rojas, J. M., Holland, M. V., Reniero, F., Guillou, C., &
Heberger, K. (2010). Virgin olive oil authentication by multivariate analyses
of 1H NMR fingerprints and δ13C and δ2H data. Journal of Agricultural and Food
Chemistry, 58(9), 5586–5596.
American Oil Chemists' Society (2004). Official methods and recommended practices
of the American Oil Chemists' Society (6th ed.). Champaign, Ill: The Society.
Aursand, M., Standal, I. B., Prael, A., McEvoy, L., Irvine, J., & Axelson, D. E. (2009). 13C
NMR pattern recognition techniques for the classification of Atlantic salmon
(Salmo salar L.) according to their wild, farmed, and geographical origin. Journal
of Agricultural and Food Chemistry, 57(9), 3444–3451.
Ballerini, L., Hogberg, A., Borgefors, G., Bylund, A. C., Lindgard, A., Lundstrom, K., et al.
(2002). A segmentation technique to determine fat content in NMR images of
beef meat. IEEE Transactions on Nuclear Science, 49(1), 195–199.
Barison, A., da Silva, C. W., Campos, F. R., Simonelli, F., Lenz, C. A., & Ferreira, A. G.
(2010). A simple methodology for the determination of fatty acid composition in
edible oils through 1H NMR spectroscopy. Magnetic Resonance in Chemistry,
48(8), 642–650.
Barsby, T. L., Donald, A. M., & Frazier, P. J. (2001). Starch: Advances in structure and function.
Cambridge: Royal Society of Chemistry.
Belton, P. (2011). Spectroscopic approaches to the understanding of water in foods.
Food Reviews International, 27, 170–191.
Belton, P. S., Delgadillo, I., Holmes, E., Nicholls, A., Nicholson, J. K., & Spraul, M. (1996).
Use of high-field 1H NMR spectroscopy for the analysis of liquid foods. Journal of
Agricultural and Food Chemistry, 44(6), 1483–1487.
Belton, P. S., Engelsen, S. B., & Jakobsen, H. J. (2005). Magnetic resonance in food science:
The multivariate challenge. Cambridge: Royal Society of Chemistry.
Belton, P. S., Gil, A., Webb, G., & Rutledge, D. (2003). Magnetic resonance in food science:
Latest developments. Cambridge: Royal Society of Chemistry.
Berregi, I., del Campo, G., Caracena, R., & Miranda, J. I. (2007). Quantitative determination
of formic acid in apple juices by 1H NMR spectrometry. Talanta, 72(3), 1049–1053.
Bertelli, D., Lolli, M., Papotti, G., Bortolotti, L., Serra, G., & Plessi, M. (2010). Detection of
honey adulteration by sugar syrups using one-dimensional and two-dimensional
high-resolution nuclear magnetic resonance. Journal of Agricultural and Food Chemistry,
58(15), 8495–8501.
Bonny, J. M., Laurent, W., & Renou, J. P. (2000). Detection of susceptibility effects using
simultaneous T-2* and magnetic field mapping. Magnetic Resonance Imaging,
18(9), 1125–1128.
Bosco, M., Toffanin, R., De Palo, D., Zatti, L., & Segre, A. (1999). High-resolution 1H NMR
investigation of coffee. Journal of the Science of Food and Agriculture, 79(6), 869–878.
Bourne, M. C. (2002). Food texture and viscosity: Concept and measurement/Malcolm C.
Bourne: Academic Press.
Brescia, M. A., Monfreda, M., Buccolieri, A., & Carrino, C. (2005). Characterisation of the
geographical origin of buffalo milk and mozzarella cheese by means of analytical
and spectroscopic determinations. Food Chemistry, 89(1), 139–147.
Brusewitz, G. H., & Stone, M. L. (1987). Wheat moisture by NMR. Transactions of the
ASAE — American Society of Agricultural Engineers, 30(3), 858–862.
Butz, P., Hofmann, C., & Tauscher, B. (2005). Recent developments in noninvasive tech-
niques for fresh fruit and vegetable internal quality analysis. Journal of Food Science,
70(9), R131–R141.
Caligiani, A., Acquotti, D., Cirlini, M., & Palla, G. (2010a). 1H NMR study of fermented
cocoa (Theobroma cacao L.) beans. Journal of Agricultural and Food Chemistry,
58(23), 12105–12111.
Caligiani, A., Acquotti, D., Cirlini, M., & Palla, G. (2010b). 1H NMR study of fermented
cocoa (Theobroma cacao L.) beans. Journal of Agricultural and Food Chemistry.
Caligiani, A., Palla, G., Maietti, A., Cirlini, M., & Brandolini, V. (2010). 1H NMR finger-
printing of soybean extracts, with emphasis on identification and quantification
of isoflavones. Nutrients, 2(3), 280–289.
Callaghan, P. T. (2006). Rheo-NMR and velocity imaging. Current Opinion in Colloid &
Interface Science, 11(1), 13–18.
Campos, R., Ollivon, M., & Marangoni, A. G. (2009). Molecular composition dynamics
and structure of cocoa butter. Crystal Growth & Design, 10(1), 205–217.
Castejón, D. D., Villa, P. P., Calvo, M. M. M. M., Santa-María, G. G., Herraiz, M. M., &
Herrera, A. A. (2010). 1H-HRMAS NMR study of smoked Atlantic salmon (Salmo
salar). Magnetic Resonance in Chemistry, 48(9), 693–703.
Castell-Palou, A., Rossello, C., Femenia, A., Bon, J., & Simal, S. (2011). Moisture profiles in
cheese drying determined by TD-NMR: Mathematical modeling of mass transfer.
Journal of Food Engineering, 104(4), 525–531.
Cernadas, E., Carrion, P., Rodriguez, P. G., Muriel, E., & Antequera, T. (2005). Analyzing
magnetic resonance images of Iberian pork loin to predict its sensorial characteristics.
Computer Vision and Image Understanding, 98(2), 345–361.
Chayaprasert, W., & Stroshine, R. (2005). Rapid sensing of internal browning in whole
apples using a low-cost, low-field proton magnetic resonance sensor. Postharvest
Biology and Technology, 36(3), 291–301.
Chen, P., Mccarthy, M. J., & Kauten, R. (1989). NMR for internal quality evaluation of
fruits and vegetables. Transactions of ASAE, 32(5), 1747–1753.
Chen, F. L., Wei, Y. M., & Zhang, B. (2010). Characterization of water state and distribution
in textured soybean protein using DSC and NMR. Journal of Food Engineering, 100(3),
522–526.
Christophoridou, S., Dais, P., Tseng, L. H., & Spraul, M. (2005). Separation and identifi-
cation of phenolic compounds in olive oil by coupling high-performance liquid
chromatography with postcolumn solid-phase extraction to nuclear magnetic
resonance spectroscopy (LC-SPE-NMR). Journal of Agricultural and Food Chemistry,
53(12), 4667–4679.
 M.F. Marcone et al. / Food Research International 51 (2013) 729–747
Ciampa, A., Dell'Abate, M. T., Masetti, O., Valentini, M., & Sequi, P. (2010). Seasonal
chemical–physical changes of PGI Pachino cherry tomatoes detected by magnetic
resonance imaging (MRI). Food Chemistry, 122(4), 1253–1260.
Colnago, L. A., Azeredo, R. B. V., Marchi Netto, A., Andrade, F. D., & Venâncio, T. (2011).
Rapid analyses of oil and fat content in agri-food products using continuous wave free
precession time domain NMR. Magnetic Resonance in Chemistry, 49, S113–S120.
Consonni, R., & Cagliani, L. R. (2008). Ripening and geographical characterization of
Parmigiano Reggiano cheese by 1H NMR spectroscopy. Talanta, 76(1), 200–205.
Consonni, R., Cagliani, L. R., Guantieri, V., & Simonato, B. (2011). Identification of
metabolic content of selected Amarone wine. Food Chemistry, 129(2), 693–699.
Cotte, J. F., Casabianca, H., Lheritier, J., Perrucchietti, C., Sanglar, C., Waton, H., et al.
(2007). Study and validity of 13C stable carbon isotopic ratio analysis by mass spec-
trometry and 2H site-specific natural isotopic fractionation by nuclear magnetic
resonance isotopic measurements to characterize and control the authenticity of
honey. Analytica Chimica Acta, 582(1), 125–136.
Cuny, M., Vigneau, E., Le Gall, G., Colquhoun, I., Lees, M., & Rutledge, D. N. (2008). Fruit
juice authentication by 1H NMR spectroscopy in combination with different
chemometrics tools. Analytical and Bioanalytical Chemistry, 390(1), 419–427.
D'Imperio, M., Gobbino, M., Picanza, A., Costanzo, S., Della Corte, A., & Mannina, L.
(2010). Influence of harvest method and period on olive oil composition: An
NMR and statistical study. Journal of Agricultural and Food Chemistry, 58(20),
11043–11051.
de Oliveira, A. J. B., Gonçalves, R. A. C., Chierrito, T. P. C., dos Santos, M. M., de Souza, L.
M., Gorin, P. A. J., et al. (2011). Structure and degree of polymerisation of
fructooligosaccharides present in roots and leaves of Stevia rebaudiana (Bert.)
Bertoni. Food Chemistry, 129(2), 305–311.
del Campo, G. G., Berregi, I. I., Caracena, R. R., & Zuriarrain, J. J. (2010). Quantitative
determination of caffeine, formic acid, trigonelline and 5-(hydroxymethyl)furfural
in soluble coffees by 1H NMR spectrometry. Talanta, 81(1–2), 367–371.
Deslandes, E., Bodeaubellion, C., Floch, J. Y., & Penot, M. (1990). 13C-NMR spectroscopy
and chemical-analysis of the carrageenans of 4 red algae (Gigartinales). Plant
Physiology and Biochemistry, 28(1), 65–69.
Di Anibal, C. V., Callao, M. P., & Ruisánchez, I. (2011). 1H NMR and UV–visible data
fusion for determining Sudan dyes in culinary spices. Talanta, 84(3), 829–833.
Dolgikh, D. A., Gilmanshin, R. I., Brazhnikov, E. V., Bychkova, V. E., Semisotnov, G. V.,
Venyaminov, S., et al. (1981). Alpha-lactalbumin: Compact state with fluctuating
tertiary structure? FEBS Letters, 136(2), 311–315.
Donarski, J. A., Roberts, D. P. T., & Charlton, A. J. (2010). Quantitative NMR spectroscopy
for the rapid measurement of methylglyoxal in manuka honey. Analytical Methods,
2(10).
Duarte, I., Barros, A., Almeida, C., Spraul, M., & Gil, A. M. (2004). Multivariate analysis of
NMR and FTIR data as a potential tool for the quality control of beer. Journal of
Agricultural and Food Chemistry, 52(5), 1031–1038.
Duarte, I., Barros, A., Belton, P. S., Righelato, R., Spraul, M., Humpfer, E., et al. (2002).
High-resolution nuclear magnetic resonance spectroscopy and multivariate analysis
for the characterization of beer. Journal of Agricultural and Food Chemistry, 50(9),
2475–2481.
Duarte, S., Gregoire, S., Singh, A. P., Vorsa, N., Schaich, K., Bowen, W. H., et al. (2006).
Inhibitory effects of cranberry polyphenols on formation and acidogenicity of
Streptococcus mutans biofilms. FEMS Microbiology Letters, 257(1), 50–56.
Ellis, D. I., Brewster, V. L., Dunn, W. B., Allwood, J. W., Golovanov, A. P., & Goodacre, R.
(2012). Fingerprinting food: Current technologies for the detection of food
adulteration and contamination. Chemical Society Reviews, 41, 5706–5727.
Engelsen, S. B., Belton, P. S., & Jakobsen, H. J. (2005). Magnetic resonance in food science:
The multivariate challenge. Cambridge: Royal Society of Chemistry.
Erikson, U., Standal, I. B., Aursand, I. G., Veliyulin, E., & Aursand, M. (2012). Use of NMR
in fish processing optimization: A review of recent progress. Magnetic Resonance in
Chemistry, 50, 471–480.
Everett, D. W., & Auty, M. A. E. (2008). Cheese structure and current methods of analysis.
International Dairy Journal, 18(7), 759–773.
Ewbank, J. J., & Creighton, T. E. (1991). The molten globule protein conformation
probed by disulphide bonds. Nature, 350(6318), 518–520.
Falshaw, R., & Furneaux, R. H. (1998). Structural analysis of carrageenans from the
tetrasporic stages of the red algae, Gigartina lanceata and Gigartina chapmanii
(Gigartinaceae, Rhodophyta). Carbohydrate Research, 307(3–4), 325–331.
Farhat, I. A., Belton, P. S., & Webb, G. A. (2007). Magnetic resonance in food science: From
molecules to man. Cambridge: RSC Publishing.
Fauhl, C., Reniero, F., & Guillou, C. (2000). 1H NMR as a tool for the analysis of mixtures
of virgin olive oil with oils of different botanical origin. Magnetic Resonance in
Chemistry, 38(6), 436–443.
Figueiredo, I. M., Pereira, N. R., Efraim, P., Garcia, N. H., Rodrigues, N. R., Marsaioli, A., Jr.,
et al. (2006). 1H NMR, a rapid method to monitor organic acids during cupuassu
(Theobroma grandiflorum Spreng) processing. Journal of Agricultural and Food
Chemistry, 54(12), 4102–4106.
Frias, J. M., Foucat, L., Bimbenet, J. J., & Bonazzi, C. (2002). Modeling of moisture profiles
in paddy rice during drying mapped with magnetic resonance imaging. Chemical
Engineering Journal, 86(1–2), 173–178.
Gambarota, G., Perazzolo, C., Leimgruber, A., Meuli, R., Mangin, P., Augsburger, M., et al.
(2011). Non-invasive detection of cocaine dissolved in wine bottles by 1H magnetic
resonance spectroscopy. Drug Testing and Analysis, 3(9), 544–547.
Gil, A. M., Duarte, I. F., Delgadillo, I., Colquhoun, I. J., Casuscelli, F., Humpfer, E., et al.
(2000). Study of the compositional changes of mango during ripening by use of
nuclear magnetic resonance spectroscopy. Journal of Agricultural and Food Chemistry,
48(5), 1524–1536.
Gonera, A., & Cornillon, P. (2002). Gelatinization of starch/gum/sugar systems studied
by using DSC, NMR, and CSLM. Starch-Starke, 54(11), 508–516.
745
Gonzalez, M. E., Barrett, D. M., McCarthy, M. J., Vergeldt, F. J., Gerkema, E., Matser, A. M.,
et al. (2010). 1H-NMR study of the impact of high pressure and thermal processing
on cell membrane integrity of onions. Journal of Food Science, 75(7), E417–E425.
Gostan, T., Moreau, C., Juteau, A., Guichard, E., & Delsuc, M. A. (2004). Measurement of
aroma compound self-diffusion in food models by DOSY. Magnetic Resonance in
Chemistry, 42(6), 496–499.
Graham, S., Kennedy, T., Chevallier, O., Gordon, A., Farmer, L., Elliott, C., et al. (2010).
The application of NMR to study changes in polar metabolite concentrations in
beef longissimus dorsi stored for different periods post mortem. Metabolomics,
6(3), 395–404.
Gruwel, M. L. H., Latta, P., Matwiy, B., & Tomanek, B. (2010). Characterization of food
stuffs using Magnetic Resonance Elastography. Food Research International, 43(8),
2087–2092.
Gudjonsdottir, M., Belton, P. S., & Webb, G. A. (2009). Magnetic resonance in food
science: Challenges in a changing world. Special publication, Vol. 319. (pp. 253)
Cambridge: Royal Society of Chemistry.
Gudjonsdottir, M., Gunnlaugsson, V. N., Finnbogadottir, G. A., Sveinsdottir, K.,
Magnusson, H., Arason, S., et al. (2010). Process control of lightly salted wild and
farmed Atlantic cod (Gadus morhua) by brine injection, brining, and freezing—A
low field NMR study. Journal of Food Science, 75(8), E527–E536.
Gudjónsdóttir, M., Jónsson, Á., Bergsson, A. B., Arason, S., & Rustad, T. (2011). Shrimp
processing assessed by low field nuclear magnetic resonance, near infrared
spectroscopy, and physicochemical measurements—The effect of polyphosphate
content and length of prebrining on shrimp muscle. Journal of Food Science,
76(4), E357–E367.
Guillén, M. a. D., & Ruiz, A. (2001). High resolution 1H nuclear magnetic resonance in
the study of edible oils and fats. Trends in Food Science & Technology, 12(9),
328–338.
Guillén, M. D., & Ruiz, A. (2006). Study by means of 1H nuclear magnetic resonance of
the oxidation process undergone by edible oils of different natures submitted to
microwave action. Food Chemistry, 96(4), 665–674.
Gutowsky, H. S., Kistiakowsky, G. B., Pake, G. E., & Purcell, E. M. (1949). Structural
investigations by means of nuclear magnetism. 1. Rigid crystal lattices. Journal of
Chemical Physics, 17(10), 972–981.
Haiduc, A. M., Trezza, E. E., van Dusschoten, D., Reszka, A. A., & van Duynhoven, J. P. M.
(2007). Non-invasive ‘through-package’ assessment of the microstructural quality
of a model food emulsion by the NMR MOUSE. LWT — Food Science and Technology,
40(4), 737–743.
Hall, L. D., Evans, S. D., & Nott, K. P. (1998). Measurement of textural changes of food by
MRI relaxometry. Magnetic Resonance Imaging, 16(5–6), 485–492.
Herrero, A. M., Cambero, M. I., Ordonez, J. A., Castejon, D., Romero de Avila, M. D., & de
la Hoz, L. (2007). Magnetic resonance imaging, rheological properties, and physi-
cochemical characteristics of meat systems with fibrinogen and thrombin. Journal
of Agricultural and Food Chemistry, 55(23), 9357–9364.
Hills, B. (1998). Magnetic resonance imaging in food science. New York: Wiley.
Hinrichs, R., Götz, J., Noll, M., Wolfschoon, A., Eibel, H., & Weisser, H. (2004). Character-
isation of the water-holding capacity of fresh cheese samples by means of low
resolution nuclear magnetic resonance. Food Research International, 37(7), 667–676.
Hites, R. A., Foran, J. A., Carpenter, D. O., Hamilton, M. C., Knuth, B. A., & Schwager, S. J.
(2004). Global assessment of organic contaminants in farmed salmon. Science,
303(5655), 226–229.
Hites, R. A., Foran, J. A., Schwager, S. J., Knuth, B. A., Hamilton, M. C., & Carpenter, D. O.
(2004). Global assessment of polybrominated diphenyl ethers in farmed and wild
salmon. Environmental Science and Technology, 38(19), 4945–4949.
Ho, C. T., Wang, M., Wei, G. J., Huang, T. C., & Huang, M. T. (2000). Chemistry and
antioxidative factors in rosemary and sage. BioFactors, 13(1–4), 161–166.
Hollingsworth, K. G., & Johns, M. L. (2004). Rheo-nuclear magnetic resonance of emulsion
systems. Journal of Rheology, 48(4), 787–803.
Honikel, K. O. (2004). From meat to products — Ageing mincing heating salting.
Fleischwirtschaft, 84(5), 228–234.
Honikel, K. O., Kim, C. J., Hamm, R., & Roncales, P. (1986). Sarcomere shortening of
prerigor muscles and its influence on drip loss. Meat Science, 16(4), 267–282.
Horigane, A. K., Toyoshima, H., Hemmi, H., Engelaar, W. M. H. G., Okubo, A., & Nagata, T.
(1999). Internal hollows in cooked rice grains (Oryza sativa cv. Koshihikari)
observed by NMR micro imaging. Journal of Food Science, 64(1), 1–5.
Hu, F., Furihata, K., Kato, Y., & Tanokura, M. (2007). Nondestructive quantification of
organic compounds in whole milk without pretreatment by two-dimensional
NMR spectroscopy. Journal of Agricultural and Food Chemistry, 55(11), 4307–4311.
Igarashi, M. (2000). Spin–spin relaxation process of 23Na-NMR in Na-loaded NaY.
Molecular Crystals and Liquid Crystals, 341, 1241–1244.
Jaturasitha, S., Srikanchai, T., Kreuzer, M., & Wicke, M. (2008). Differences in carcass
and meat characteristics between chicken indigenous to northern Thailand
(Black-boned and Thai native) and imported extensive breeds (Bresse and Rhode
Island red). Poultry Science, 87(1), 160–169.
Jung, Y., Lee, J., Kwon, J., Lee, K. S., Ryu, D. H., & Hwang, G. S. (2010). Discrimination of the
geographical origin of beef by 1H NMR-based metabolomics. Journal of Agricultural
and Food Chemistry, 58(19), 10458–10466.
Juteau-Vigier, A., Atlan, S., Deleris, I., Guichard, E., Souchon, I., & Trelea, I. C. (2007).
Ethyl hexanoate transfer modeling in carrageenan matrices for determination of
diffusion and partition properties. Journal of Agricultural and Food Chemistry,
55(9), 3577–3584.
Kara, S., Mueller, J. J., & Liese, A. (2011). Online analysis methods for monitoring of
bioprocesses. Chimica Oggi/ Chemistry Today, 29(2), 38–41.
Karoui, R., & De Baerdemaeker, J. (2007). A review of the analytical methods coupled
with chemometric tools for the determination of the quality and identity of dairy
products. Food Chemistry, 102(3), 621–640.
746 M.F. Marcone et al. / Food Research International 51 (2013) 729–747
Keeton, J. T., Hafley, B. S., Eddy, S. M., Moser, C. R., McManus, B. J., & Leffler, T. P. (2003).
Rapid determination of moisture and fat in meats by microwave and nuclear
magnetic resonance analysis—PVM 1:2003. Journal of AOAC International, 86(6),
1193–1202.
Kerr, W. L., Kauten, R. J., McCarthy, M. J., & Reid, D. S. (1998). Monitoring the formation
of ice during food freezing by magnetic resonance imaging. LWT — Food Science and
Technology, 31(3), 215–220.
Kono, H., Yunoki, S., Shikano, T., Fujiwara, M., Erata, T., & Takai, M. (2002). CP/MAS 13C
NMR study of cellulose and cellulose derivatives. 1. Complete assignment of the
CP/MAS 13C NMR spectrum of the native cellulose. Journal of the American Chemical
Society, 124(25), 7506–7511.
Kumirska, J., Czerwicka, M., Kaczynski, Z., Bychowska, A., Brzozowski, K., Thoming, J.,
et al. (2010). Application of spectroscopic methods for structural analysis of chitin
and chitosan. Marine Drugs, 8(5), 1567–1636.
Lachenmeier, D. W., Frank, W., Humpfer, E., Schäfer, H., Keller, S., Mörtter, M., et al.
(2005). Quality control of beer using high-resolution nuclear magnetic resonance
spectroscopy and multivariate analysis. European Food Research and Technology,
220(2), 215–221.
Lamanna, R., Piscioneri, I., Romanelli, V., & Sharma, N. (2008). A preliminary study of
soft cheese degradation in different packaging conditions by 1H-NMR. Magnetic
Resonance in Chemistry, 46(9), 828–831.
Lammertyn, J., Dresselaers, T., Van Hecke, P., Jancsók, P., Wevers, M., & Nicolaï, B. M.
(2003). MRI and X-ray CT study of spatial distribution of core breakdown in
‘Conference’ pears. Magnetic Resonance Imaging, 21(7), 805–815.
Le Gall, G., Colquhoun, I. J., & Defernez, M. (2004). Metabolite profiling using 1H NMR
spectroscopy for quality assessment of green tea, Camellia sinensis (L.). Journal of
Agricultural and Food Chemistry, 52(4), 692–700.
Lee, J. -E., Lee, B. -J., Chung, J. -O., Hwang, J. -A., Lee, S. -J., Lee, C. -H., et al. (2010).
Geographical and climatic dependencies of green tea (Camellia sinensis) metabolites:
A 1H NMR-based metabolomics study. Journal of Agricultural and Food Chemistry,
58(19), 10582–10589.
Leffler, T. P., Moser, C. R., McManus, B. J., Urh, J. J., Keeton, J. T., & Claflin, A. (2008).
Determination of moisture and fat in meats by microwave and nuclear magnetic
resonance analysis: Collaborative study. Journal of AOAC International, 91(4),
802–810.
Létal, J., Jirák, D., Šuderlová, L., & Hájek, M. (2003). MRI ‘texture’ analysis of MR images
of apples during ripening and storage. LWT — Food Science and Technology, 36(7),
719–727.
Lindner, P., Bermann, E., & Gamarnik, B. (1996). Characterization of citrus honey by
deuterium NMR. Journal of Agricultural and Food Chemistry, 44(1), 139–140.
Lolli, M., Bertelli, D., Plessi, M., Sabatini, A. G., & Restani, C. (2008). Classification of
Italian honeys by 2D HR-NMR. Journal of Agricultural and Food Chemistry, 56(4),
1298–1304.
Lopes-da-Silva, J. A., Santos, D. M., Freitas, A., Brites, C., & Gil, A. M. (2007). Rheological
and nuclear magnetic resonance (NMR) study of the hydration and heating of
undeveloped wheat doughs. Journal of Agricultural and Food Chemistry, 55(14),
5636–5644.
Lopez-Rituerto, E., Cabredo, S., Lopez, M., Avenoza, A., Busto, J. H., & Peregrina, J. M.
(2009). A thorough study on the use of quantitative 1H NMR in Rioja red wine
fermentation processes. Journal of Agricultural and Food Chemistry, 57(6), 2112–2118.
Mabry, T. J. (2001). Selected topics from forty years of natural products research:
Betalains to flavonoids, antiviral proteins, and neurotoxic nonprotein amino
acids. Journal of Natural Products, 64(12), 1596–1604.
Mannina, L., Cristinzio, M., Sobolev, A. P., Ragni, P., & Segre, A. (2004). High-field nuclear
magnetic resonance (NMR) study of truffles (Tuber aestivum vittadini). Journal of
Agricultural and Food Chemistry, 52(26), 7988–7996.
Mannina, L., & Segre, A. (2002). High resolution nuclear magnetic resonance: From
chemical structure to food authenticity. Grasas Y Aceites, 53(1), 22–33.
Marangoni, A. G., & Rousseau, D. (1995). Engineering triacylglycerols: The role of
interesterification. Trends in Food Science & Technology, 6(10), 329–335.
Marciani, L., Wickham, M., Singh, G., Bush, D., Pick, B., Cox, E., et al. (2007). Enhancement
of intragastric acid stability of a fat emulsion meal delays gastric emptying and
increases cholecystokinin release and gallbladder contraction. American Journal of
Physiology — Gastrointestinal and Liver Physiology, 292(6), G1607–G1613.
Mariette, F. (2009). Investigations of food colloids by NMR and MRI. Current Opinion in
Colloid & Interface Science, 14(3), 203–211.
Martin, Y. L., Christoph, N., Blanch-Cortes, A. I., Dennis, J., Giraudon, S., Guillon, C., et al.
(2001). Detection of added beet or cane sugar in maple syrup by the site-specific
deuterium nuclear magnetic resonance (SNIF-NMR (R)) method: Collaborative
study. Journal of AOAC International, 84(5), 1509–1521.
Martin, G., Akoka, J. S., & Martin, M. L. (2006). SNIF-NMR—Part 1: Principles. In G. A.
Webb (Ed.), Modern magnetic resonance, part 3. Dordrecht, Netherlands: Springer
p. 1629.
Masoum, S., Malabat, C., Jalali-Heravi, M., Guillou, C., Rezzi, S., & Rutledge, D. N. (2007).
Application of support vector machines to 1H NMR data of fish oils: Methodology
for the confirmation of wild and farmed salmon and their origins. Analytical and
Bioanalytical Chemistry, 387(4), 1499–1510.
Mitchell, A. D., Scholz, A. M., Wang, P. C., & Song, H. (2001). Body composition analysis
of the pig by magnetic resonance imaging. Journal of Animal Science, 79(7),
1800–1813.
Miyake, Y., Yokomizo, K., & Matsuzaki, N. (1998). Determination of unsaturated fatty
acid composition by high-resolution nuclear magnetic resonance spectroscopy.
Journal of the American Oil Chemists' Society, 75(9), 1091–1094.
Mortensen, M., Thybo, A. K., Bertram, H. C., Andersen, H. J., & Engelsen, S. B. (2005).
Cooking effects on water distribution in potatoes using nuclear magnetic reso-
nance relaxation. Journal of Agricultural and Food Chemistry, 53(15), 5976–5981.
Nelson, M. (2005). The barbarian's beverage: A history of beer in ancient Europe. London;
New York: Routledge.
Nestor, G., Bankefors, J., Schlechtriem, C., Brännäs, E., Pickova, J., & Sandström, C.
(2010). High-resolution 1H magic angle spinning NMR spectroscopy of intact
Arctic char (Salvelinus alpinus) muscle. Quantitative analysis of n−3 fatty acids,
EPA and DHA. Journal of Agricultural and Food Chemistry, 58(20), 10799–10803.
Nielsen, D., Hyldig, G., Nielsen, J., & Nielsen, H. H. (2005). Lipid content in herring
(Clupea harengus L.) — Influence of biological factors and comparison of different
methods of analyses: Solvent extraction, Fatmeter, NIR and NMR. LWT — Food
Science and Technology, 38(5), 537–548.
Novoa-Carballal, R., Fernandez-Megia, E., Jimenez, C., & Riguera, R. (2011). NMR
methods for unravelling the spectra of complex mixtures. Natural Product Reports,
28(1), 78–98.
Ogrinc, N., Kosir, I. J., Spangenberg, J. E., & Kidric, J. (2003). The application of NMR and
MS methods for detection of adulteration of wine, fruit juices, and olive oil. A
review. Analytical and Bioanalytical Chemistry, 376(4), 424–430.
Otero, L., & Préstamo, G. (2009). Effects of pressure processing on strawberry studied
by nuclear magnetic resonance. Innovative Food Science & Emerging Technologies,
10(4), 434–440.
Oztop, M. H., Rosenberg, M., Rosenberg, Y., McCarthy, K. L., & McCarthy, M. J. (2010).
Magnetic resonance imaging (MRI) and relaxation spectrum analysis as methods
to investigate swelling in whey protein gels. Journal of Food Science, 75(8),
E508–E515.
Pearce, K. L., Rosenvold, K., Andersen, H. J., & Hopkins, D. L. (2011). Water distribution
and mobility in meat during the conversion of muscle to meat and ageing and the
impacts on fresh meat quality attributes—A review. Meat Science, 89(2), 111–124.
Pedersen, H., Munck, L., & Engelsen, S. (2000). Low-field 1H nuclear magnetic resonance
and chemometrics combined for simultaneous determination of water, oil, and
protein contents in oilseeds. Journal of the American Oil Chemists' Society, 77(10),
1069–1077.
Pentimalli, M., Capitani, D., Ferrando, A., Ferri, D., Ragni, P., & Segre, A. L. (2000).
Gamma irradiation of food packaging materials: An NMR study. Polymer, 41(8),
2871–2881.
Petrakis, P., Touris, I., Liouni, M., Zervou, M., Kyrikou, I., Kokkinofta, R., et al. (2005).
Authenticity of the traditional cypriot spirit “zivania” on the basis of 1H NMR spec-
troscopy diagnostic parameters and statistical analysis. Journal of Agricultural and
Food Chemistry, 53(13), 5293–5303.
Piccioni, F., Capitani, D., Zolla, L., & Mannina, L. (2009). NMR metabolic profiling of
transgenic maize with the Cry1Ab gene. Journal of Agricultural and Food Chemistry,
57(14), 6041–6049.
Pykett, I. L. (2000). NMR — A powerful tool for industrial process control and quality
assurance. IEEE Transactions on Applied Superconductivity, 10(1), 721–723.
Ramos-Cabrer, P., Van Duynhoven, J. P., Timmer, H., & Nicolay, K. (2006). Monitoring of
moisture redistribution in multicomponent food systems by use of magnetic
resonance imaging. Journal of Agricultural and Food Chemistry, 54(3), 672–677.
Renou, J. P., Belton, P. S., & Webb, G. A. (2011). Magnetic resonance in food science: An
exciting future. Cambridge, UK: Royal Society of Chemistry.
Renou, J. P., Foucat, L., & Bonny, J. M. (2003). Magnetic resonance imaging studies of
water interactions in meat. Food Chemistry, 82(1), 35–39.
Rinke, P., Moitrier, S., Humpfer, E., Keller, S., Mörtter, M., Godejohann, M., et al. (2007).
An 1H-NMR-technique for high throughput screening in quality and authenticity
control of fruit juice and fruit juice raw materials — SGF-profiling. Fruit Processing.
Ritota, M., Marini, F., Sequi, P., & Valentini, M. (2010). Metabolomic characterization of
Italian sweet pepper (Capsicum annum L.) by means of HRMAS-NMR spectroscopy and
multivariate analysis. Journal of Agricultural and Food Chemistry, 58(17), 9675–9684.
Rodrigues, J. E., Erny, G. L., Barros, A. S., Esteves, V. I., Brandao, T., Ferreira, A. A., et al.
(2010). Quantification of organic acids in beer by nuclear magnetic resonance
(NMR)-based methods. Analytica Chimica Acta, 674(2), 166–175.
Ruan, R., Chang, K., Chen, P. L., Fulcher, R. G., & Bastian, E. D. (1998). A magnetic reso-
nance imaging technique for quantitative mapping of moisture and fat in a cheese
block. Journal of Dairy Science, 81(1), 9–15.
Ruan, R., Wang, X., Chen, P. L., Fulcher, R. G., Pesheck, P., & Chakrabarti, S. (1999). Study
of water in dough using nuclear magnetic resonance. Cereal Chemistry, 76(2),
231–235.
Ruiz-Cabrera, M. A., Foucat, L., Bonny, J. M., Renou, J. P., & Daudin, J. D. (2005). Assess-
ment of water diffusivity in gelatine gel from moisture profiles. I—Non-destructive
measurement of 1D moisture profiles during drying from 2D nuclear magnetic res-
onance images. Journal of Food Engineering, 68(2), 209–219.
Ruiz-Cabrera, M. A., Gou, P., Foucat, L., Renou, J. P., & Daudin, J. D. (2004). Water transfer
analysis in pork meat supported by NMR imaging. Meat Science, 67(1), 169–178.
Savary, G., Moreau, C., & Cayot, N. (2010). Impact of the composition of polysaccharide
composite gels on small molecules diffusion: A rheological and NMR study. Food
Research International, 43(1), 364–368.
Schievano, E., Pasini, G., Cozzi, G., & Mammi, S. (2008). Identification of the production
chain of Asiago d'Allevo cheese by nuclear magnetic resonance spectroscopy and
principal component analysis. Journal of Agricultural and Food Chemistry, 56(16),
7208–7214.
Schievano, E., Peggion, E., & Mammi, S. (2010). 1H nuclear magnetic resonance spectra
of chloroform extracts of honey for chemometric determination of its botanical or-
igin. Journal of Agricultural and Food Chemistry, 58, 57–65.
Scotter, M. (2009). The chemistry and analysis of annatto food colouring: A review.
Food Additives and Contaminants Part a—Chemistry Analysis Control Exposure &
Risk Assessment, 26(8), 1123–1145.
Semisotnov, G. V., Rodionova, N. A., Razgulyaev, O. I., Uversky, V. N., Gripas, A. F., &
Gilmanshin, R. I. (1991). Study of the “molten globule” intermediate state in
protein folding by a hydrophobic fluorescent probe. Biopolymers, 31(1), 119–128.
 M.F. Marcone et al. / Food Research International 51 (2013) 729–747
Sequi, P., Dell'Abate, M. T., & Valentini, M. (2007). Identification of cherry tomatoes
growth origin by means of magnetic resonance imaging. Journal of the Science of
Food and Agriculture, 87(1), 127–132.
Shaarani, S. M., Nott, K. P., & Hall, L. D. (2006). Combination of NMR and MRI quantita-
tion of structure and structure changes for convection cooking of fresh chicken
meat. Meat Science, 72(3), 398–403.
Shimamura, T., Kurogi, Y., Katsuno, S., Kashiwagi, T., & Ukeda, H. (2011). Demonstration
of the presence of aminoreductone formed during the Maillard reaction in milk.
Food Chemistry, 129(3), 1088–1092.
Shintu, L., Caldarelli, S., & Franke, B. M. (2007). Pre-selection of potential molecular
markers for the geographic origin of dried beef by HR-MAS NMR spectroscopy.
Meat Science, 76(4), 700–707.
Sobieski, D. N., Mulvihill, G., Broz, J. S., & Augustine, M. P. (2006). Towards rapid through-
put NMR studies of full wine bottles. Solid State Nuclear Magnetic Resonance, 29(1–3),
191–198.
Sobolev, A. P., Brosio, E., Gianferri, R., & Segre, A. L. (2005). Metabolic profile of lettuce
leaves by high-field NMR spectra. Magnetic Resonance in Chemistry, 43(8),
625–638.
Sobolev, A. P., Segre, A., & Lamanna, R. (2003). Proton high-field NMR study of tomato
juice. Magnetic Resonance in Chemistry, 41(4), 237–245.
Sobolev, A. P., Testone, G., Santoro, F., Nicolodi, C., Iannelli, M. A., Amato, M. E., et al.
(2010). Quality traits of conventional and transgenic lettuce (Lactuca sativa L.) at
harvesting by NMR metabolic profiling. Journal of Agricultural and Food Chemistry,
58(11), 6928–6936.
Sorland, G. H., Larsen, P. M., Lundby, F., Anthonsen, H. W., & Foss, B. J. (2005). On the
use of low-field NMR methods for the determination of total lipid content in
marine products. Magnetic Resonance in Food Science: The Multivariate Challenge,
20–27.
Spraul, M., Schutz, B., Rinke, P., Koswig, S., Humpfer, E., Schafer, H., et al. (2009).
NMR-based multi parametric quality control of fruit juices: SGF profiling. Nutrients,
1(2), 148–155.
Spyros, A., & Dais, P. (2009). 31P NMR spectroscopy in food analysis. Progress in Nuclear
Magnetic Resonance Spectroscopy, 54(3–4), 195–207.
Stefanova, R., Vasilev, N., & Vassilev, N. (2011). 1H-NMR spectroscopy as an alternative
tool for the detection of γ-ray irradiated meat. Food Analytical Methods, 4(3),
399–403.
Summer, A., Franceschi, P., Bollini, A., Formaggioni, P., Tosi, F., & Mariani, P. (2003).
Seasonal variations of milk characteristics and cheesemaking losses in the manu-
facture of Parmigiano-Reggiano cheese. Veterinary Research Communications, 27,
663–666.
Tarachiwin, L., Ute, K., Kobayashi, A., & Fukusaki, E. (2007). 1H NMR based metabolic
profiling in the evaluation of Japanese green tea quality. Journal of Agricultural
and Food Chemistry, 55(23), 9330–9336.
Tardieu, A., De Man, W., & This, H. (2010). Using one-dimensional (1D) and two-
dimensional (2D) quantitative proton nuclear magnetic resonance spectroscopy
(q NMR) for the identification and quantification of taste compounds in raw
onion (Allium cepa L.) bulbs and in aqueous solutions where onion tissues are
soaked. Analytical and Bioanalytical Chemistry, 398(7), 3139–3153.
Tenailleau, E. J., Lancelin, P., Robins, R. J., & Akoka, S. (2004). Authentication of the
origin of vanillin using quantitative natural abundance 13C NMR. Journal of Agricultural
and Food Chemistry, 52(26), 7782–7787.
747
Therien-Aubin, H., & Zhu, X. X. (2009). NMR spectroscopy and imaging studies of phar-
maceutical tablets made of starch. Carbohydrate Polymers, 75(3), 369–379.
Thybo, A. K., Szczypiński, P. M., Karlsson, A. H., Dønstrup, S., Stødkilde-Jørgensen, H. S.,
& Andersen, H. J. (2004). Prediction of sensory texture quality attributes of cooked
potatoes by NMR-imaging (MRI) of raw potatoes in combination with different
image analysis methods. Journal of Food Engineering, 61(1), 91–100.
Timms, R. (2003). Confectionery fats handbook: Properties, production and application.
Oily Press.
Trabesinger, A. H., McDermott, R., Lee, S. K., Muck, M., Clarke, J., & Pines, A. (2004).
SQUID-detected liquid state NMR in microtesla fields. Journal of Physical Chemistry
A, 108(6), 957–963.
van de Velde, F., Knutsen, S. H., Usov, A. I., Rollema, H. S., & Cerezo, A. S. (2002). 1H and
13
C high resolution NMR spectroscopy of carrageenans: Application in research
and industry. Trends in Food Science & Technology, 13(3), 73–92.
Vereecken, J., Foubert, I., Smith, K. W., Sassano, G. J., & Dewettinck, K. (2010). Crystalliza-
tion of model fat blends containing symmetric and asymmetric monounsaturated
triacylglycerols. European Journal of Lipid Science and Technology, 112(2), 233–245.
Vilen, E. M., Lundqvist, L. C., Jouanneau, D., Helbert, W., & Sandstrom, C. (2010). NMR study
on hydroxy protons of kappa- and kappa/mu-hybrid carrageenan oligosaccharides:
Experimental evidence of hydrogen bonding and chemical exchange interactions in
kappa/mu oligosaccharides. Biomacromolecules, 11(12), 3487–3494.
Wang, Y. J., Assaad, E., Ispas-Szabo, P., Mateescu, M. A., & Zhu, X. X. (2011). NMR imaging
of chitosan and carboxymethyl starch tablets: Swelling and hydration of the poly-
electrolyte complex. International Journal of Pharmaceutics, 419(1–2), 215–221.
Webb, G. A., Belton, P. S., Gil, A. M., & Delgadillo, I. (2001). Magnetic resonance in food
science: A view to the future. Cambridge: Royal Society of Chemistry.
Weekley, A. J., Bruins, P., Sisto, M., & Augustine, M. P. (2003). Using NMR to study full
intact wine bottles. Journal of Magnetic Resonance, 161(1), 91–98.
Weissleder, R., Poss, K., Wilkinson, R., Zhou, C., & Bogdanov, A., Jr. (1995). Quantitation
of slow drug release from an implantable and degradable gentamicin conjugate by
in vivo magnetic resonance imaging. Antimicrobial Agents and Chemotherapy,
39(4), 839–845.
Wu, Z., Ming, J., Gao, R., Wang, Y., Liang, Q., Yu, H., et al. (2011). Characterization and
antioxidant activity of the complex of tea polyphenols and oat beta-glucan. Journal
of Agricultural and Food Chemistry, 59(19), 10737–10746.
Yi, J., & Kerr, W. L. (2009). Combined effects of freezing rate, storage temperature and
time on bread dough and baking properties. LWT — Food Science and Technology,
42(9), 1474–1483.
Yilmaz, A., Nyberg, N., Mølgaard, P., Asili, J., & Jaroszewski, J. (2010). 1H NMR metabolic
fingerprinting of saffron extracts. Metabolomics, 6(4), 511–517.
Zehl, M., Braunberger, C., Conrad, J., Crnogorac, M., Krasteva, S., Vogler, B., et al. (2011).
Identification and quantification of flavonoids and ellagic acid derivatives in
therapeutically important Drosera species by LC-DAD, LC-NMR, NMR, and LC–MS.
Analytical and Bioanalytical Chemistry, 400(8), 2565–2576.
Zhou, R., & Li, Y. F. (2007). Texture analysis of MR image for predicting the firmness of
Huanghua pears (Pyrus pyrifolia Nakai, cv. Huanghua) during storage using an
artificial neural network. Magnetic Resonance Imaging, 25(5), 727–732.
Zur, K., Heier, A., Blaas, K., & Fauhl-Hassek, C. (2008). Authenticity control of pistachios
based on 1H- and 13C-NMR spectroscopy and multivariate statistics. European Food
Research and Technology A, 227(4), 969–977.