Food Chemistry

Food Chemistry 365 (2021) 130456
Contents lists available at ScienceDirect
Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem
Review
Mass spectrometry-based protein and peptide profiling for food frauds,

traceability and authenticity assessment
Mariangela Valletta a, Sara Ragucci a, Nicola Landi a, Antimo Di Maro a, Paolo Vincenzo Pedone a,
Rosita Russo a, *, 1, Angela Chambery a, *, 1
a
Department of Environmental, Biological and Pharmaceutical Sciences and Technologies, University of Campania “Luigi Vanvitelli”, 81100 Caserta, Italy
A R T I C L E I N F O A B S T R A C T
Keywords: The ever-growing use of mass spectrometry (MS) methodologies in food authentication and traceability origi
Mass spectrometry nates from their unrivalled specificity, accuracy and sensitivity. Such features are crucial for setting up analytical
Matrix-assisted laser desorption ionization strategies for detecting food frauds and adulterations by monitoring selected components within food matrices.
mass spectrometry (MALDI-TOF MS)
Among MS approaches, protein and peptide profiling has become increasingly consolidated.
Liquid-chromatography-electrospray ionization
tandem mass spectrometry (LC-ESI MS/MS)
This review explores the current knowledge on recent MS techniques using protein and peptide biomarkers for
Protein and peptide marker assessing food traceability and authenticity, with a specific focus on their use for unmasking potential frauds and
Food authenticity adulterations. We provide a survey of the current state-of-the-art instrumentation including the most reliable and
Food traceability sensitive acquisition modes highlighting advantages and limitations. Finally, we summarize the recent appli
cations of MS to protein/peptide analyses in food matrices and examine their potential in ensuring the quality of
agro-food products.
1. Introduction the global food supply system that has substantially increased the dis
tance between the food production site and consumers (Aung & Chang,
Food fraud is a broad term used to encompass any intentional vio 2014; Manning, 2016). Thus, since the raw materials come from several
lations of the agri-food chain legislation. These actions, often motivated countries, it is increasingly difficult to trace potential sources of unin
by economic gain, include “the deliberate and intentional substitution, tentional contamination. Besides intentional product frauds are not
addition, tampering, or misrepresentation of food, food ingredients, or easily detected in highly processed foods due to complex ingredients
food packaging”. Additional criteria for defining frauds entails some often provided by multiple suppliers.
forms of deception of the consumers including the use of false or Food labelling systems are constantly evolving in parallel with
misleading labelling, mystifying the product quality or the nature of a legislation to support and guarantee food quality and authenticity.
product, such as the declaration of false species, varieties or origin to Indeed, besides food intrinsic properties, some “value descriptors” such
reduce importation costs or false statements on production processes. as geographic origin, production methods, safety claims and environ
The most common food frauds are summarized in Supplementary ma mental welfare standards are increasingly used as quality indicators. In
terial, Fig. S1. Europe, the certification and the protection of origin is one of the main
Food fraud is a practice perpetrated since antiquity as witnessed by authenticity issues concerning foodstuffs. In particular, these legisla
the findings of counterfeit Roman seals on amphorae containing fraud tions include the protected designation of origin (PDO) that indicates
ulent olive oil and wine. Nowadays, the need to compete with powerful products entirely manufactured in a defined geographical area. In
businesses and manufacturers in a globalized market is among the addition, the protected geographical indication (PGI) label correlates
driving forces for food frauds, together with the growing complexity of products to a geographical area where at least one production step
Abbreviations: HRMS, high-resolution mass spectrometry; IRMS, isotope-ratio mass spectrometry; IT, ion trap analyser; FT-ICR, Fourier-transform ion cyclotron
resonance; MALDI, matrix-assisted laser desorption ionization; MS, mass spectrometry; MS/MS, tandem mass spectrometry; LC, liquid-chromatography; LTQ, linear
trap quadrupole analyser; Q, quadrupole analyser; QqQ, triple quadrupole analyser; QT, quadrupole-trap analyser; Q-TOF, quadrupole-time of flight analyser.
* Corresponding authors.
E-mail addresses: [email protected] (R. Russo), [email protected] (A. Chambery).
1
These authors share equal senior authorship.
https://doi.org/10.1016/j.foodchem.2021.130456
Received 23 March 2021; Received in revised form 22 June 2021; Accepted 22 June 2021
Available online 25 June 2021
0308-8146/© 2021 Elsevier Ltd. All rights reserved.
M. Valletta et al. Food Chemistry 365 (2021) 130456
occurred, while traditional specialities guaranteed (TSG) label provide a pressures (up to 100 MPa) that improves the resolution and sensitivity of
protection regime for traditional food products. Furthermore, optional the analysis while reducing separation times and solvent consumption.
quality terms (OPT) have been recently defined as new types of quality Based on these advantages, the use of UPLC systems has become more
schemes to protect the reputation of regional foods and to promote good and more common allowing fast analyses of food matrices even in the
practices in rural and agricultural activity. Some OPT as “mountain context of food authentication (Di Giuseppe, Giarretta, Lippert, Sever
product” and “product of island farming” were also defined to reinforce ino, & Di Maro, 2015). In addition, multidimensional-liquid-chroma
the consumer perception of special quality attributed to mountain and tography systems (LC/LC) have been also developed to improve the
island product. separation of compounds from very complex food matrices (Herrero,
Food authentication is closely related to food quality and safety since Ibáñez, Cifuentes, & Bernal, 2009).
common adulteration may affect overall food characteristics and may Chromatographic systems can be coupled with different types of
cause foodborne illnesses following consumption. Since food authenti detectors. Thermal-conductivity and flame-ionization detectors are
cation, food quality and safety attracted public attention in recent years, typically integrated with GC while ultraviolet/visible light absorbance
there is an increasing need for developing and applying more efficient detectors, diode arrays and electrochemical detectors are usually asso
tools and methodologies to analyse food components. In this framework, ciated with HPLC. Nevertheless, coupling of mass spectrometers to
the set-up of innovative technological platforms to trace food authen chromatographic techniques has offered an unrivalled sensitivity,
tication and verify product compliance with label descriptions is also reproducibility and specificity compared to other detectors. In food
desirable. analysis, hyphenated platforms based on LC-MS and GC–MS are the most
popular, also considering their high-throughput and automation capa
2. Mass spectrometry-based food authentication methodologies bility (Cacciola, Donato, Beccaria, Dugo, & Mondello, 2012; Tranchida,
Dugo, & Mondello, 2012). Regarding applications, while GC–MS is the
Even though traditional methods are extensively used for food primary technique used to analyse food volatile fractions, organic con
traceability, innovative analytical techniques relying on molecular taminants and fats, LC-MS is mainly used for the analysis of food pro
markers are nowadays among the most reliable methodologies for teins, peptides, and carbohydrates. Several recent applications in the
determining food authenticity. Because of intrinsic advantages and field of food authentication of both HPLC and GC techniques, alone or in
disadvantages of each analytical approach, the most appropriate method combination with MS, have been accurately reviewed by Santos and
for foodstuff authentication should be selected for each application to Oliveira (Santos & Oliveira, 2017).
discriminate original food products from non-original counterparts.
In this topical review, we mainly focused on electrospray ionization 2.2. Mass-spectrometry instrumentations for food protein and peptide
(ESI) and matrix-assisted laser desorption ionization (MALDI) mass analysis
spectrometry (MS)-based approaches and related chromatographic
methodologies applied to protein/peptide analyses as markers for food MS is an analytical technique that can provide both qualitative and
authentication. A brief overview is also given on other state-of-the-art quantitative information on food proteins and peptides that are ionized
mass spectroscopy instrumentation currently utilized in food analysis. and sorted on the basis of their mass/charge ratio. Given its high
reproducibility, specificity, sensitivity and high-throughput features, MS
2.1. Overview of chromatographic approaches in food analysis is emerging as a powerful tool in food research (Herrero, Simo, Garcia-
Canas, Ibanez, & Cifuentes, 2012; Wang, Wang, & Cai, 2013). Mass
Traditional chromatographic methods have been used for food spectrometry instruments consist of three parts: the ion source, the mass
authentication and traceability to obtain the rapid and reliable identi analyser, and the detector. The ion source is responsible for the ioni
fication or quantification of proteins and peptides in complex food zation of molecules in liquid, gas or dried form. The resulting ions are
matrices (Esteki, Shahsavari, & Simal-Gandara, 2019; Fanali, Dugo, & then sorted and separated by electric and/or magnetic fields according
Mondello, 2016). These applications are challenging due to the high to their mass and charge in the mass analyser. Among ionization tech
dynamic range, complexity and heterogeneity of compounds within niques, the so-called “soft ionization” techniques such ESI and MALDI,
food matrices. Nevertheless, despite the overall chemical complexity of characterized by high sensitivity in ionization with minimal in-source
foodstuffs, the chromatographic separation principle of adsorption and/ fragmentation, have evolved as methods of choice for food proteins
or partition of molecules between a mobile and a stationary phase has and peptides analysis.
proved to be advantageous to obtain unique molecular fingerprints In MALDI sources, samples are mixed with suitable matrix solutions
useful to differentiate and authenticate foods. Chromatographic tech and placed on a stainless-steel plate. Upon evaporation of the solvents,
niques can be classified according to the properties of stationary and the matrix and molecules co-crystallize. Sinapinic acid and α-cyano-4-
mobile phases, the packaging of the stationary phase or the driving hydroxycinnamic acid are well known suitable matrices for MALDI-MS
forces of separation. Gas chromatography (GC) exploits separations analysis of proteins and peptides. During the analysis, samples are
mediated by a solid stationary phase and a gas mobile phase. In this irradiated with laser beam shots (usually, nitrogen laser of 337 nm),
technique, the introduction of the sample into the chromatographic whose energy is mostly absorbed by the matrix that protects the bio
system is mainly responsible for the resolution depending on the specific molecules preventing their fragmentation. Afterwards, the matrix ions
injection system (i.e. split/splitless injection, on-column, headspace). In transfer the energy to sample molecules triggering their desorption. The
high-performance liquid chromatography (HPLC) systems, a high- resulting low charge protonated/deprotonated ions are subsequently
pressure pump delivers a liquid mobile phase through the column accelerated by an electric field and separated based on their mass/
packed with a solid stationary phase where compounds are separated on charge (m/z) ratio typically using time-of-flight (TOF) analysers.
the basis of their charge (ion-exchange chromatography), molecular In ESI, high voltages are applied to a liquid flowing through an
mass (size-exclusion chromatography) or polarity (reversed-phase emitter (usually a glass or metallic capillary). The charged droplets are
HPLC). generated at the exit of the electrospray tip through a desolvation pro
A more recent evolution of HPLC is represented by ultra-high-per cess driven by gas flow (N2) and capillary heating (100–300 ◦ C). The
formance liquid chromatography (UPLC) analytical systems. Although resulting multiply protonated ions are then focused toward the analyser
based on the same principles of HPLC, UPLC achieve enhanced separa region of the mass spectrometer. ESI sources are the most sensitive,
tion capabilities by essentially reducing the diameter of column material robust and reliable for studying, at femto-mole levels in few micro-litre
particle size at a sub-2 μm level. Compared to traditional HPLC, the sample volumes, non-volatile and thermally labile biomolecules that are
separation and quantification in UPLC are performed under higher not responsive to analyses by other conventional MS techniques.
2
The mass analysers can be distinguished into quadrupole-based, ion food spectra databases is needed. In addition, these methodologies also
traps (IT) and TOF. Quadrupoles consists of four cylindrical rods, par require a combination with other analytical techniques to fully charac
allel to each other with oscillating electric fields applied, in which ions terize potential changes in food components at a molecular level.
are separated based on the stability of their trajectories in the rods. For a
given ratio of voltages, only ions of a certain m/z will reach the detector. 2.4. Nuclear magnetic resonance
Other ions with unstable trajectories will collide with the rods. A linear
series of three quadrupoles is known as a triple quadrupole (QqQ) mass Nuclear magnetic resonance (NMR) represents a gold standard
analyser. The first (Q1) and third (Q3) quadrupoles act as mass filters, methodology for metabolite food analysis providing valuable informa
and the middle (Q2) quadrupole is usually employed as a collision cell. tion about quality, geographical origin and processing. Among several
In particular, this mass analyser is widely used mainly to carry out NMR-based strategies for investigating foodstuffs metabolite composi
quantitative determinations related to food safety and quality issues tion (i.e. target analysis, metabolic profiling, metabolic fingerprinting,
(Picó, 2015). and metabolomics), metabolomics is the most comprehensive approach
The IT mass analysers operate by storing ions in the trap and (Agapito-Tenfen, Guerra, Wikmark, & Nodari, 2013).
manipulating them by using direct current and radio frequency electric A schematic workflow of NMR-based metabolomics analyses is
fields in a series of timed events. Among IT-based mass analysers, we can shown in Fig. 1. At first, clear criteria should be defined for sample se
distinguish “dynamic” traps (i.e. 3D IT) from “static” traps (i.e. linear lection to ensure the representation of whole populations and the
trap quadrupole, LTQ, or Fourier-transform ion cyclotron resonance, FT- availability of related documentation about their properties. Sample
ICR). In a 3D IT, ions are dynamically stored in a three-dimensional preparation typically includes an extraction step, where compounds of
quadrupole in which RF and DC potentials can be scanned to eject interest are extracted from the food product using suitable solvents. For
successive m/z from the trap into the detector. In an LTQ, ions are solution-state NMR analyses, samples are resuspended in appropriate
confined radially by a two-dimensional RF field and axially by stopping NMR solvents which also contains a reference compound. Following the
potentials applied to end electrodes. In FT-ICR mass analysers, ions NMR acquisition, the set of domain signals, called free induction decay
move in a circular path in a magnetic field. The cyclotron frequency of (FIDs), are processed and converted to spectra which are then used for
the ion’s circular motion is mass-dependent. By measuring the cyclotron compound identification using multivariate statistical analyses of rele
frequency, the ion’s mass can be determined. More recent evolution of vant chemical shift values.
ion traps includes the high-resolution Orbitrap analyser in which ions Given the chemical complexity of food matrices and the high dy
are electrostatically trapped in an orbit around a central, spindle-shaped namic range of metabolites, the sensitivity of NMR is a major limitation
electrode. The electrode confines the ions so that they orbit around the of this technique, especially compared to mass spectrometry. Never
central electrode and oscillate back and forth along the central elec theless, continuous developments of hardware technology enable the
trode’s long axis. The image current from the trapped ions is detected analysis of even more small sample amounts through the use of the
and converted to a mass spectrum using the Fourier transform of the cryogenically cooled NMR probes (cryoprobes) with a substantial in
frequency signal. crease of sensitivity.
Different analysers are also combined in hybrid MS/MS instruments, A comprehensive overview of recent applications in the field of
typically endowed with higher resolving power and measurement ac compositional analysis, food authentication, quality control, and human
curacy with respect to single analysers instruments. For instance, LTQ- nutrition has been recently proposed by Consonni and co-workers
Orbitrap instruments offer a wide range of fragmentation capabilities (Consonni & Cagliani, 2019).
through coupling a higher energy collisional dissociation (HCD) cell to
the C-trap (Makarov & Scigelova, 2010; Zubarev & Makarov, 2013). 3. Isotope-ratio mass spectrometry
Ions separated by different types of analysers finally reach detectors,
typically electron multipliers or microchannel plates, that record either Among MS approaches, isotope-ratio mass spectrometry (IRMS) has
charge or current. Results are then displayed as spectra by plotting the been widely applied to food authentication and traceability, providing
relative abundance of detected ions as a function of the m/z ratio. valuable information on food geographic, chemical, and biological ori
gins by measuring relative isotopic ratios of their components (Camin,
2.3. Vibrational and fluorescence spectroscopy Bontempo, Perini, & Piasentier, 2016; Katerinopoulou, Kontogeorgos,
Salmas, Patakas, & Ladavos, 2020). In IRMS approaches, rather than
In recent years, the combination of vibrational (i.e. near-infrared, specifically examining food protein and peptides, whole food products
mid-infrared and Raman) and fluorescence spectroscopy analytical or selected animal or plant tissues are usually analysed with high
techniques with multivariate methods has resulted in the development quantitative accuracy.
of rapid approaches for the qualitative and quantitative analysis of In the present review, we focus on the application of protein and
several food matrices (Karoui, Downey, & Blecker, 2010). By this peptide biomarkers-based MS methodologies to food analyses. Alterna
analytical technique, characteristic spectra can be evaluated with che tive approaches, such as IRMS have been discussed elsewhere (Camin,
mometric methods to provide information about food origin or pro Bontempo, Perini, & Piasentier, 2016; Katerinopoulou, Kontogeorgos,
cessing. Moreover, the non-destructive nature together with the minimal Salmas, Patakas, & Ladavos, 2020) and are beyond the scope of this
sample preparation of both vibrational and fluorescence spectroscopies review. Nevertheless, a summary of the most recent applications of
make these methods promising for the rapid, efficient and reliable food IRMS for the determination of food botanical and geographical origin as
monitoring for protecting consumers from potential frauds. well as other potential applications, including those in the field of food
Several applications of vibrational spectroscopy have been applied authentication and traceability are reported in Supplementary material,
for the assessment of the authenticity of meat (Prieto, Pawluczyk, Tables S1–S6.
Dugan, & Aalhus, 2017), fish and seafood (Cozzolino & Murray, 2012),
honey (Cozzolino, Corbella, & Smyth, 2011), wine (Basalekou, Pappas, 4. Proteomic workflows for protein and peptide-based
Tarantilis, Kotseridis, & Kallithraka, 2017) and cereal grains (Caporaso, biomarker discovery for food profiling
Whitworth, & Fisk, 2018). A variety of fluorescence spectroscopy-based
analytical techniques for food quality assessment has been also previ Among the mass spectrometry and spectroscopy methodologies
ously extensively reviewed (Karoui & Blecker, 2011). currently utilized in food analysis, those based on protein and peptide
Despite the advantages of applying vibrational spectroscopy as a analyses by MS technologies are at the forefront as tools for food
large-scale fingerprinting tool for food traceability, implementation of authenticity assessment because of their sensitivity, specificity,
3
Fig. 1. NMR-based metabolomics workflow for food analysis. Critical steps, such as sample collection and preparation, spectra processing and data analysis
are depicted.
multiplexing capacity and high-throughput capability. Additional ad protein mixtures or purified proteins are subjected to proteolytic
vantages such as the relative protein/peptide stability to food processing cleavage and the resulting peptides are analysed by MS or MS/MS.
also support the development of novel protein-based MS workflows for A schematic diagram of a bottom-up proteomic workflow is shown in
food authenticity monitoring. Fig. 2A. The first developed bottom-up strategy was introduced more
Specific “fit-for-purpose” proteomic approaches can be selected for than 36 years ago by combining a two-dimensional polyacrylamide gel
the qualitative identification of species-specific peptide markers useful electrophoresis (2-DE) with peptide mass fingerprinting (PMF) by
for food authentication. Many techniques are also available for quanti MALDI-TOF MS. Search engines such as Sequest and Mascot are
tative proteomic analyses (Panchaud, Affolter, Moreillon, & Kussmann, frequently used to match and score the peptide assignment to a protein
2008). Sometimes specific markers quantification by LC-MS can be also by comparing accurate experimental and theoretical peptide masses
easily obtained by extracted ion chromatograms (XIC) by measuring from curated protein databases. Most algorithms also statistically anal
peak heights or integrating peak areas to determine peptides yse data to find the best match on probabilistic bases. This can be ach
abundances. ieved by calculating the probability that the observed match is not a
Untargeted methods might be better suited for the early stages of random event. Despite the fractionation step based on electrophoresis
food biomarker discovery workflows, while targeted approaches are (mono- or two-dimensional) is still used in bottom-up protocols, protein
usually preferred for the later steps of validation and implementation. identification by MALDI-TOF-based PMF has been now mostly replaced
by LC-ESI MS/MS methodologies. In the so-called “shot-gun” proteomic
approaches, protein enzymatic digestion is directly performed in solu
4.1. Untargeted proteomic approach
tion on complex protein mixtures without a preliminary electrophoretic
fractionation step. The resulting peptides are then separated by RP-
The boost of research output in untargeted proteomic strategies in
HPLC or UPLC coupled on-line with the mass spectrometers for MS/
food analysis during the last decade is tightly associated with the
MS analyses. Differently from PMF, protein identification by MS/MS
availability of improved high-resolution mass spectrometry (HRMS)
analysis is also based on amino acid sequencing of the peptide deduced
instrumentation and advanced user-friendly software for data process
from collision induced dissociation (CID) or higher-energy c-trap
ing. Untargeted approaches are strictly related to the “-omic” concept of
dissociation (HCD) fragmentation.
characterizing the whole proteome, defined as the set of all the proteins
In top-down strategies, ions from intact proteins generated usually
expressed by a cell or a tissue in a defined moment. A data-dependent
by electrospray ionization are subjected to CID, HCD and electron
analysis (DDA) is the most popular acquisition mode of untargeted MS
transfer dissociation (ETD) fragmentation, yielding monoisotopic mo
strategies. In DDA mode, MS/MS fragmentation spectra are acquired for
lecular weights of both the intact protein and its fragments (Fig. 2B).
a fixed number of the most abundant ions detected during a survey MS
This analysis can integrate and support information obtained from
scan. Generally, given the high dynamic range of proteins in food-
bottom-up approaches, in particular regarding the presence and locali
related matrices, for untargeted proteomic profiling, a sample prepara
zation of post-translational modifications (PTM). However, the
tion step is required for the enrichment or partial purification of a spe
complexity of multicharged isotopic clusters from intact proteins and
cific subset of target proteins or the depletion of potential interfering
their related fragments still limits the wide use of top-down strategies for
proteins (Martínez-Maqueda, Hernández-Ledesma, Amigo, Miralles, &
intact proteins high-throughput identification.
Gómez-Ruiz, 2013). Moreover, before MS analysis, a further separation
step typically based on gel electrophoresis (gel-based approach) and/or
5. Targeted proteomic approach
liquid chromatography (gel-free approach) is performed at protein and/
or peptide level. The two typical workflows currently used for protein
The limited sensitivity of shotgun proteomic approaches related to
identification and characterization using MS are based on the so-called
the high dynamic range of complex food matrices together with the high
“bottom-up” and “top-down” approaches. In top-down proteomics,
similarity in their chemical composition is one of the main limitations in
intact proteins or large protein fragments are directly subjected to gas-
food analysis. Nevertheless, proteome profiling of food samples is usu
phase fragmentation for MS/MS analysis. By contrast, in bottom-up
ally the first step for the identification of suitable peptides for the
approaches, widely used for protein identification by MS, complex
4
Fig. 2. Schematic diagrams of the bottom-up (A) and top-down (B) MS-based proteomics pipelines commonly used in food research.
development of targeted methods aimed at monitoring or quantifying reaction monitoring (MRM), multiple precursors and product ions can
species-specific biomarkers within food matrices. be selected for a targeted analysis. By restricting the acquisition mass
Indeed, differently from untargeted approaches, that focus on the range around the m/z value of the ion(s) of interest, compared to XICs
simultaneous detection of many unknown potential biomarkers, tar from full scans, targeted acquisition modes strongly increase the sensi
geted proteomic analyses can be used to detect and quantify a limited tivity of detection since mass spectrometer is allowed to dwell for a
number of specific peptide ions. This selective monitoring is especially longer time over a small mass range.
useful for the quantification of low-abundance peptides usually hardly The unique capabilities of triple quadrupole (QqQ) mass spectrom
detectable by untargeted approaches. In the acquisition modes known as eters are extremely suitable for quantitative targeted analyses. In SRM
selected ion monitoring (SIM) or selected MS/MS ion monitoring mode, the first and the third quadrupoles act as filters to select pre
(SMIM), selected m/z values of precursor ions are detected or frag defined m/z values of precursor and fragment ions of a given peptide,
mented, respectively, in a given time range or along a whole chro while the second quadrupole serves as a collision cell (Fig. 3A). Several
matographic run. Moreover, selected reaction monitoring (SRM) is a transitions (precursor/fragment ion pairs) can be monitored, yielding a
tandem acquisition mode in which both a precursor ion and an associ set of chromatographic traces in which co-eluting background ions are
ated product ion are simultaneously monitored while in multiple- filtered out increasing sensitivity up to five orders of magnitude with a
Fig. 3. Representative scheme of an SRM/MRM acquisition mode on a triple quadrupole mass spectrometer (A). A typical workflow of a targeted quantitative
analysis by mass spectrometry-based on proteotypic peptides monitoring (B).
5
linear response over a wide dynamic range in highly complex mixtures temperature (UHT) milk, several studies were focused on the analysis of
such as foods. milk thermal treatments. For example, the lactosylated counterparts of
The crucial step of targeted experiments is the selection and the some casein phosphopeptides were found to be specific to intensely
optimization of transitions subsequently used for quantitation purposes heated kinds of milk by MALDI-TOF MS and proved to be useful to
(Fig. 3B). At first, starting from a protein of interest, a set of peptides, discriminate raw and pasteurized from UHT milk (Pinto, Caira, Cuollo,
named proteotypic peptides, is selected based on their good MS re Fierro, Nicolai, Chianese, et al., 2012). Similarly, the identification of a
sponses and the unique assignment to the target protein. Then, instru PyroQ modified β-casein peptide marker allows the differentiation of the
mental parameters such as ionization and fragmentation parameters are UHT milk from mildly heated milk (Dalabasmaz, Ebner, & Pischets
optimized for each transition. Validation steps, including the determi rieder, 2017). Other peptide markers and specific markers related to
nation of the limits of detection (LOD) and quantification (LOQ), are thermal treatments were also identified by Sassi and co-workers for
required before quantifying the targeted protein within samples. bovine, water buffalo, ovine and goat milk (Sassi, Arena, & Scaloni,
Besides canonical SRM experiments performed on triple quadrupole 2015).
mass spectrometers, acquisition methods known as “pseudo SRM” are Casein tryptic peptides were used for identifying and quantifying
conducted on linear ion traps or quadrupole-time of flight (Q-TOF) in milk adulteration by MALDI-TOF and LC-ESI-Q MS analyses, allowing
struments. This scan mode is based on the acquisition, upon fragmen the detection of as low as 0.5% of bovine, ovine, buffalo, and caprine
tation of a precursor ion, of MS/MS data on a restricted mass range milk in milk mixtures (Cuollo, Caira, Fierro, Pinto, Picariello, & Addeo,
including a fragment ion of interest. Although resembling an SRM 2010). A similar approach combining MALDI-TOF with LC-ESI-Q-TOF
experiment, can be essentially viewed as a SIM focused on selected MS was used to verify the authenticity of 27 kinds of cheese of the
fragment ions. Czech food market (Kuckova, Zitkova, Novotny, & Smirnova, 2019).
Overall, targeted scanning modes are the most suitable to detect Calvano et al. described a method based on in-solution digestion of
known peptides in complex protein mixtures and already proved to be whole milk samples followed by MALDI-TOF MS analysis of the tryptic
effective tools for food product authentication (Ortea, Cañas, & Gal digests to detect cow and goat milk adulteration up to 5% (Calvano, De
lardo, 2011). Ceglie, Monopoli, & Zambonin, 2012). 2-DE in association with MALDI-
TOF MS was also successfully used to unmask powder milk in liquid milk
6. Application of protein-based mass spectrometry analyses to (Calvano, Monopoli, Loizzo, Faccia, & Zambonin, 2013) and to detect
food authentication plant protein adulterants in milk (Yang, Ghosh, & Beaudry, 2018).
Similar adulterations were also evaluated by LC-ESI-Q-TOF MS (Lu, Liu,
Food authentication is essential to verify that a given product is Gao, Lv, & Yu, 2017) and high-resolution nano-LC-ESI-Orbitrap MS/MS
complying with its label description according to specific compositional (Yang, Zheng, Soyeurt, Yang, & Wang, 2019). Moreover, the detection of
claims. Although specific regulations may differ among countries, for powdered milk in liquid whole milk was also performed by analysing
many foods more stringent requirements must be met concerning the both intact proteins and peptides through a sensitive and robust
species of origin or the variety of the organism. As a consequence, one of approach using LC-ESI-Q-TOF MS analysis combined with chemometric
the main authenticity issues is the need to monitor whether food prod tools and data fusion technologies (Du, Lu, Zhang, Gao, & Yu, 2020).
ucts from one species have been mixed with similar material derived Although these MS1-based methods are valuable tools for analysing
from a cheaper species. Protein-based mass spectrometry analyses are simple matrices, the extra specificity of MS/MS-based approaches is
being increasingly applied to food authentication (Mamone, Picariello, more accurate in preventing false positives/negatives in more complex
Caira, Addeo, & Ferranti, 2009; Mamone, Picariello, Nitride, Addeo, & mixtures by providing amino acid sequence information. Species-
Ferranti, 2013; Samperi, Capriotti, Cavaliere, Colapicchioni, Chiozzi, & specific peptides from bovine β-lactoglobulin and α-s1-casein were
Laganà, 2015). identified by nano-LC-ESI-IT MS/MS as suitable markers for the assess
We therefore reviewed significant literature studies indexed within ment of goat milk adulteration with cheaper bovine milk (Nardiello,
the Scopus database and published on different food matrices in the last Natale, Palermo, Quinto, & Centonze, 2018). Recently, high-resolution
ten years using peptides and proteins as markers for food authenticity nano-LC-tandem MS analyses on a Q-Exactive Orbitrap instrument
and traceability by mass spectrometry strategies. were applied for the first time to the characterization of lactic acid
bacteria within buffalo and bovine whey starter cultures used for
6.1. Milk and dairy products cheeses production (Russo, Valletta, Rega, Marasco, Muscariello,
Pedone, et al., 2019). In this study, bacteria identification was per
Milk and dairy products represent important diet components being formed at genus, species and sub-species level by using the sequence
sources of nutrients for both children and adults. Based on their wide regions 33–52 and 72–82 of the S16 ribosomal protein as proteotypic
consumption, milk and dairy products are among the top foods sus peptide markers. Regarding finished products, Guarino et al. (Guarino,
ceptible to adulteration with financial gains for unscrupulous producers. Fuselli, La Mantia, Longo, Faberi, & Marianella, 2010) developed an LC-
In recent years, MALDI-TOF and LC-MS protein analyses have been ESI-IT MS/MS methodology for the detection and quantification of
widely used for the detection of fraudulent practices in dairy industry sheep’s milk in goat’s and cow’s cheeses. Following plasmin digestion of
(Table 1). In particular, MALDI-TOF analysis of low molecular weight the casein fraction extracted from cheese samples, a peptide specific for
intact proteins was used to reveal potential adulterations of donkey and sheep species was at first selected. Then, a pseudo-selected reaction
goat milk with cow, ewe and buffalo milk (Di Girolamo, Masotti, Sal monitoring (pSRM) method targeting this marker peptide was optimized
vatori, Scapaticci, Muraca, & Putignani, 2014). Moreover, the addition and calibration curves were built using cheeses containing different
of frozen buffalo milk to fresh buffalo milk was detected through the percentages of the three milk types. By using this approach, the authors
analysis of phosphorylated peptides (Arena, Salzano, & Scaloni, 2016). reported the detection of 2% of sheep’s milk in goat’s and cow’s cheeses.
Peptide-based MALDI-TOF MS approaches proved to be efficient also to A similar strategy has been applied to the detection of PDO buffalo
reveal the adulteration of foods endowed with PDO, such as buffalo mozzarella adulteration with cow milk through a targeted LC-ESI-QqQ
mozzarella (Caira, Pinto, Nicolai, Chianese, & Addeo, 2016) and buffalo MRM-based approach aimed at monitoring a proteotypic phosphory
ricotta (Russo, Rega, & Chambery, 2016). lated β-casein tryptic peptide (Russo, Severino, Mendez, Lliberia,
Regarding milk processing, since the European Union Directives (92/ Parente, & Chambery, 2012). The limit of detection was three orders of
46 CEE and 94/71 CEE) set specific rules for the production of heat- magnitude lower than that declared by the methodology officially
treated milk and milk-based products such as the use of specific tem recognized by the European Commission (Reg. CE N. 273/ 2008).
peratures/times combinations for pasteurized and ultra-high An LC-ESI-quadrupole-trap (QT) pSRM-based approach was also
6
Table 1
Studies published in the last ten years reporting applications of protein and peptide-based mass spectrometry analyses to milk and dairy products, meat, fish and
seafood.
MS technique Research aim Peptide/protein biomarker* Reference
Milk and dairy MALDI-TOF Adulteration of donkey/goat milk with cow, ewe Low MW proteins (less than25 kDa) Di Girolamo et al., 2014
products and buffalo milk
Adulteration of ovine, caprine and buffalo milk with CNs and whey proteins/peptides Sassi et al., 2015
bovine milk
Adulteration of cheese with bovine, ovine, buffalo α-s1-CN peptides Cuollo et al., 2010
and caprine milk
Adulteration of sheep and goat milk with bovine CNs and β-LGB peptides Calvano et al., 2012
milk
Addition of frozen buffalo milk to fresh buffalo milk CNs; α-LAC, β-LGB peptides Arena et al., 2016
Adulteration of buffalo Mozzarella milk/curd with β-CN and α-s1-CN peptides Caira et al., 2016
bovine milk
Effects of thermal treatments on milk α-s2-CN and β-CN peptides Pinto et al., 2012
Effects of thermal treatments on milk PyroQ modified β-CN peptide Dalabasmaz et al., 2017
Adulteration of PDO buffalo ricotta with bovine milk β-LGB peptide Russo et al., 2016
2-DE MALDI-TOF Adulteration of milk with plant proteins Soy, pea and wheat proteins Yang et al., 2018
Adulteration of fresh milk with powdered milk Whey proteins and/or CNs peptides Calvano et al., 2013
LC-MS Adulteration of milk with plant proteins Soy and pea proteins Lu et al., 2017
Detection of milk powder in liquid whole milk Caseins and whey milk proteins Du et al., 2020
Cheese authenticity CNs peptides Kuckova et al., 2019
LC-MS/MS Adulteration of milk with plant proteins Soy, pea, wheat and rice proteins Yang et al., 2019
Milk authenticity β-LGB and α-s1-CN peptides Nardiello et al., 2018
Characterization of buffalo and bovine whey starter Ribosomal proteins of lactic acid Russo et al., 2019
cultures bacteria
Adulteration of goat and sheep cheeses with sheep Peptides from plasmin digestion of Guarino et al., 2010
and cow milk CNs
Detection of milk allergens in foods α-CN, β-CN, α-LAC and β-LGB Ansari et al., 2011
Detection of milk allergens in foods β-LGB, β-CN, α-s2-CN and κ-CN Lutter et al., 2011
Adulteration of PDO buffalo mozzarella with bovine β-CN Russo et al., 2012
milk
Adulteration of milk adulteration with cheese whey Caseinomacropeptide Motta et al., 2014
Meat 2-DE MALDI-TOF Detection of cattle, pork, chicken, turkey, duck and Myosin light chains Montowska et al., 2012;
goose meats 2013
Detection of buffalo, sheep and goat meats Myosin light chains peptides Naveena et al., 2018
LC-MS/MS Detection of chicken meat Myosin light chains peptides Sentandreu et al., 2010
Detection of non-meat proteins in beef burgers Soy, pea, beetroot and milk peptides Mikołajczak et al., 2018
Detection of allergenic proteins in sausages, Soy, milk and egg white peptides Montowsa & Fornal,
frankfurters and pâtés 2018
Detection of pork, beef, chicken, duck and goose Peptide markers from meat Montowska & Fornal,
meats 2017
Detection of horse, pork and beef meats Myosin and myoglobin peptides Montowska & Spychaj,
2018
Detection of beef, horse, pork and lamb meats Myosin, myoglobin, haemoglobin Orduna et al., 2015;
peptides 2017
Detection of chicken, pork, beef, duck, goose meats Meat, soy, milk and egg white Montowska & Fornal,
and allergens peptides 2019
Detection of allergenic proteins in sausages Barley, maize, oats, rice, rye Jira & Munch, 2019
peptides
Detection of allergenic proteins in sausages Lupine, pea and soy peptides Hoffmann et al., 2017
LC-MS/MS Detection of soy, milk and egg white in meat Meat, soy, milk and egg peptides Montowska et al., 2019
products
Detection of meat species in Bolognese sauce Peptide markers from meat proteins Prandi et al., 2019
Detection of horse and pork meats in halal beef Peptide markers from meat proteins Von Bargen et al., 2013;
2014
Detection of pork in beef, chevron and chicken meats Peptide markers from meat proteins Sarah et al., 2016
Detection of beef, pork, horse, and lamb meats Myoglobin peptides Watson et al., 2015
Detection of pork, beef, lamb, chicken, duck meats Soy, peanut, pea and meat peptides Li et al., 2018
and allergens
Detection of pork, chicken, duck, beef, sheep meats Peptide markers from meat proteins Wang et al., 2018
Detection of duck, goose, chicken, pork and beef Peptide markers from meat proteins Fornal & Montowska,
meats 2019
Authentication of raw pork cuts and processed Myoglobin peptides Nalazek-Rudnicka et al.,
products 2019
Fish and seafood IEF + LC-MS/MS Identification of closely related shrimp and prawn Sarcoplasmic calcium-binding Ortea et al., 2010
species proteins
2-DE MALDI-TOF and/or LC- Discrimination between Sperata seenghala and Peptides from TIM Barik et al., 2013
MS/MS Sperata aor
Differentiation of Pandalus borealis from other Peptides from arginine kinase Pascoal et al., 2012
crustaceans
Differentiation of tuna species Muscle proteins Pepe et al., 2010; 2012
Detection of pufferfish Takifugu rubripes Muscle proteins Lu et al., 2010
Discrimination of two scallop populations Mantle proteins Artigaud et al., 2014
MS coupled to spectral library Differentiation of shrimp species Muscle proteins Salla & Murray, 2013
matching Identification of scallop species Muscle proteins Stephan et al., 2014
(continued on next page)
7
Table 1 (continued )
MS technique Research aim Peptide/protein biomarker* Reference
Identification of fish species Peptides from muscle proteins Wulff et al., 2013
Differentiation of closely related flatfish Muscle proteins Nessen et al., 2016
LC-MS/MS Differentiation of shrimp species Peptides from arginine kinase Ortea et al., 2011
Differentiation of hake species Peptides from parvalbumin Carrera et al., 2011
Differentiation of wild and farmed gilthead bream Peptides from sarcoplasmic proteins Piovesana et al., 2016
DART-MS/MS Differentiation of wild and farmed salmon Peptides from muscle proteins Fiorino et al., 2019
* CN, Casein; LAC, lactalbumin; LGB, lactoglobulin; TIM, triose phosphate isomerase.
applied for the quantification of milk traces in chocolate with a limit of optimization of a targeted MRM methodology, the authors demon
detection of 1 ng/mL in the food samples under investigation (Ansari, strated the capability of simultaneous detection of legumes lupine, pea,
Stoppacher, Rudolf, Schuhmacher, & Baumgartner, 2011). Moreover, a and soy proteins in meat products with LODs in the range of 2–5 mg/kg
LC-ESI-QqQ analysis in SRM mode was applied to the determination of (Hoffmann, Münch, Schwägele, Neusüß, & Jira, 2017). Jira et al. simi
milk in protein-rich infant cereals with a detection limit of 0.2–0.5 mg/ larly investigated the presence of the six most important grain species (i.
kg (Lutter, Parisod, & Weymuth, 2011). The quantitation of milk adul e. barley, maize, oats, rice, rye and wheat) in sausages with detection
terations with cheese whey was also accomplished by monitoring spe limits below 5 mg/kg (Jira & Munch, 2019). Moreover, LC-ESI-Q-TOF
cific fragments originating from caseinomacropeptide digestion with MS/MS was applied to the analysis of ready-to-cook commercially
pepsin with a limit of detection of 1 µg/mL (Motta, Hoff, Barreto, produced burgers with the aim to detect soy, pea, milk and beetroot
Andrade, Lorenzini, Meneghini, et al., 2014). proteins, including known allergenic proteins from soy (glycinin and
β-conglycinin), pea (vicilin and provicilin) and milk (αS1-casein and
β-lactoglobulin) (Mikołajczak, Fornal, & Montowska, 2018). High-
6.2. Meat and animal ingredients in foods resolution LC-ESI-Orbitrap MS/MS proved also to be efficient for the
detection of beef, horse, pork, and lamb meat in meat mixtures by
The potential of mass spectrometry analysis of intact proteins for monitoring tryptic peptides from myosin, myoglobin and haemoglobin
meat speciation has long been recognized since the first study reporting (Ruiz Orduna, Husby, Yang, Ghosh, & Beaudry, 2015; 2017).
the determination of the molecular weights of haemoglobin and In the context of high-resolution MS-based quantitative techniques,
myoglobin from different animal species by ESI-MS (Taylor, Linforth, label-free approaches further represent a reliable, versatile and cheaper
Weir, Hutton, & Green, 1993). Subsequently, the evidence that the alternative MS technique for meat authentication. In particular, nano-
assessment of protein mass differences could be a valuable strategy for LC-ESI-Q-TOF MS/MS enabled to discriminate between pork, beef,
meat speciation was supported by the development of ESI-MS/MS ap chicken, duck and goose meats, as well as to quantify relative changes in
proaches based on the use of protein fragments (Ponce-Alquicira & protein abundance in various commercially processed meat products by
Taylor, 2000). More recently, advances in mass spectrometry instru using 20 heat-stable peptide markers (Montowska & Fornal, 2017). The
mental technologies allowed to overcome the limitations of these pio method allowed the detection of 1% (w/w) of chicken and 1% (w/w)
neering attempts (Table 1). pork in meat mixtures of the three species, as well as of 0.8% (w/w) of
A combined approach exploiting 2-DE and MALDI-TOF MS has been beef proteins in commercial poultry frankfurters. A similar approach has
used to unravel differences in protein patterns between cattle, pig, been proposed to authenticate industrially processed sausages made
chicken, turkey, duck and goose meats and their processed products. In with horse meat, pork and beef with a LOD of 5% (w/w) for pork and
this work, myosin light chain isoforms, together with some regulatory beef and 1% (w/w) for horse meat in the matrix containing the three-
proteins and metabolic enzymes, were identified as proteins markers for components (Montowska & Spychaj, 2018). The same authors also re
meat authentication (Montowska & Pospiech, 2012, 2013). Based on ported the application of the AQUA strategy (Montowska & Fornal,
these findings, Naveena et al. also utilized both two-dimensional and 2019) and an LC-ESI-QqQ analysis in MRM mode (Montowska, Fornal,
OFFGEL electrophoresis coupled to MALDI-TOF MS for the authentica Piątek, & Krzywdzińska-Bartkowiak, 2019) for the simultaneous quan
tion of raw and cooked buffalo, sheep and goat meats and their mixtures tification of meat and allergenic protein additives in meat products by
by monitoring species-specific peptide markers derived from myosin using peptide markers identified in previous studies (Fornal & Mon
light chains (Naveena, Jagadeesh, Kamuni, Muthukumar, Kulkarni, towska, 2019; Montowska & Fornal, 2017, 2018). Indeed, by MRM
Kiran, et al., 2018). analysis, a LOD of 0.14% (w/w) for milk proteins and of 0.45% (w/w)
A proteomic technique has been developed for the detection of for soy and egg white proteins was achieved in final meat products
chicken meat within mixed meat preparations by using OFFGEL iso (Montowska, Fornal, Piątek, & Krzywdzińska-Bartkowiak, 2019).
electric focusing coupled to ESI-LC-IT MS/MS (Sentandreu, Fraser, Von Bargen et al. developed an MRM method for the detection of
Halket, Patel, & Bramley, 2010). Starting from selected species-specific horse and pork in halal raw beef using species-specific tryptic marker
biomarkers, the same study reported the development of a quantitative peptides with a LOD of 0.55% (w/w). By using MRM3 mode on a QT
approach allowing the detection of up to 0.5% contaminating chicken system, the authors were able to enhance sensitivity and to detect pork
meat in pork meat by using the absolute quantification (AQUA™) stable contamination in beef down to 0.13% (w/w) (von Bargen, Dojahn,
isotope peptides (Sentandreu, Fraser, Halket, Patel, & Bramley, 2010). Waidelich, Humpf, & Brockmeyer, 2013). A similar experimental pro
High-resolution mass spectrometry was also shown to be suitable to tocol allowed the analysis of processed/highly processed food samples
reveal vegetable proteins with allergenic potential in various types of with a LOD down to 0.24% for horse or pork meat in a beef matrix (von
meat products. In particular, nano-LC-ESI-Q-TOF MS/MS analysis of Bargen, Brockmeyer, & Humpf, 2014).
sausages, frankfurters and pâtés allowed the identification of allergenic Other quantitative MRM approaches have been developed for the
proteins from soy, milk and egg white (Montowska & Fornal, 2018). rapid and reliable detection of meat species in food products. Among
Since eggs are widely used in the food industry a list of 16 potential them, myoglobin peptides were successfully used as protein markers for
peptide biomarkers for the detection of eggs in other processed foods the quantitative determination of meat species (i.e. beef, pork, horse and
was also recently reported (Gavage, Van Vlierberghe, Van Poucke, De lamb) (Watson, Gunning, Rigby, Philo, & Kemsley, 2015) and the
Loose, Gevaert, Dieu, et al., 2019). Hoffmann et al. monitored specific authentication of commercially raw pork cuts and other meat products
marker peptides for the simultaneous detection of lupine, pea and soy in (Nalazek-Rudnicka, Klosowska-Chomiczewska, Wasik, & Macierzanka,
sausages (Hoffmann, Münch, Schwägele, Neusüß, & Jira, 2017). After
8
2019). MRM was also used for the identification, at a qualitative level, of polymorphism) assays and MALDI-TOF and LC-IT MS/MS analyses of
porcine-specific peptide markers in thermally processed meat to differ protein spots from 2-DE (Pascoal, Ortea, Gallardo, Canas, Barros-
entiate pork from beef, chevon and chicken meats (Sarah, Faradalila, Velazquez, & Calo-Mata, 2012). Other combined proteomic strategies
Salwani, Amin, Karsani, & Sazili, 2016). Moreover, heat-stable specific integrating 2-DE and mass spectrometry analyses have been extensively
peptides were used to identify and simultaneously quantify eight used in the field of fish authentication (Barik, Banerjee, Bhattacharjee,
different species (i.e. pork, beef, lamb, chicken, duck, soy, peanut, and Das Gupta, Mohanty, & Mohanty, 2013; Mazzeo & Siciliano, 2016).
pea), allowing the detection of up to 0.5% (w/w) contamination of any Specifically, MALDI-TOF and LC-QT MS/MS analyses were both applied
of the eight species in self-made food mixtures (Li, Zhang, Li, Zhao, Guo, to the characterisation of electrophoretically separated sarcoplasmic
& Wang, 2018). Other heat-stable peptide biomarkers were also used for proteins of tuna species (i.e. Thunnus thynnus, Thunnus alalunga, Thunnus
the MRM-based detection of five animal species (i.e. pork, chicken, albacares, and Thunnus obesus) (Pepe, Ceruso, Carpentieri, Ventrone,
duck, beef, and sheep) in cocked meats (Wang, Zhou, Ren, Xu, Yang, Amoresano, & Anastasio, 2010; Pepe, Ceruso, Carpentieri, Ventrone,
Guo, et al., 2018). On whole finished products, proteotypic peptides Amoresano, Anastasio, et al., 2012). Skeletal muscle proteins profiling of
from eight different meat species (i.e. duck, rabbit, chicken, turkey, the pufferfish Takifugu rubripes was also performed to investigate their
buffalo, equine, deer and sheep) were identified within Bolognese sauce use as potential marker proteins for monitoring and controlling the
with LODs ranging from 0.2% to 0.8% (w/w) (Prandi, Varani, Faccini, quality of Takifugu rubripes meat (Lu, Zheng, Liu, Li, Chen, & Chen,
Lambertini, Suman, Leporati, et al., 2019). 2010). 2-DE in combination with MALDI-TOF/TOF MS analysis has been
Regarding animal ingredients, gelatin is one of the most widely used also used for the identification of potential protein biomarkers for
in the food industry as a foam stabilizer, gelling, clarifying or binding discriminating between two populations of the great scallop Pecten
agent and emulsifier. Gelatin is obtained by partial denaturation of maximus (Artigaud, Lavaud, Thebault, Jean, Strand, Strohmeier, et al.,
collagen extracted from skins, bones and connective tissues of animals 2014).
such as bovine and porcine. An accurate and sensitive nano-LC-ESI Q- To overcome the limited availability of genome sequences, fish
TOF MS/MS approach has been developed to determine the origin of species authentication by MALDI-TOF MS and spectral library matching
species in commercial food gelatines, meat mixtures and extracts pre without the electrophoretic separation step was also proposed as a
pared from meats (Grundy, Reece, Buckley, Solazzo, Dowle, Ashford, robust and reliable alternative for shrimps (Salla & Murray, 2013) and
et al., 2016). Yang and co-workers also set up a targeted strategy for scallop (Stephan, Johler, Oesterle, Näumann, Vogel, & Pflüger, 2014)
gelatin speciation (Yang, Ghosh, & Beaudry, 2018). In this work, identification. Alternatively, protein digests can be used in proteome-
species-specific peptide biomarkers were identified, characterized and wide MS/MS approaches to identify different fish species by counting
quantified by using extracted ion chromatograms by LC-ESI-Orbitrap the number of shared tandem mass spectra between the investigated
MS/MS analysis. Then, the method was tested on gelatin used in char sample and reference spectral libraries (Nessen, van der Zwaan, Grevers,
cuterie meats obtained from grocery stores, fruit-snacks and gelatin Dalebout, Staats, Kok, et al., 2016; Wulff, Nielsen, Deelder, Jessen, &
capsules allowing the detection down to 0.1% (w/w) of pork gelatin Palmblad, 2013).
(Yang, Ghosh, & Beaudry, 2018). Furthermore, a single porcine marker Selected ion monitoring of parvalbumin peptides by ESI-IT tandem
peptide from gelatin was selected to develop a sensitive MRM-based mass spectrometry was shown to be suitable for the identification of
approach to identify porcine materials within both in-house-made and relevant commercial fish species belonging to the Merlucciidae family in
commercial products down to 0.04% (w/w) (Guo, Xu, Zhou, & Huang, less than 2 h (Carrera, Canas, Lopez-Ferrer, Pineiro, Vazquez, & Gal
2018). Yilmaz and co-workers developed a nano-UPLC-ESI-Q-TOF MSE lardo, 2011). By applying a similar methodology, seven commercial
(i.e. elevated energy MS) workflow based on porcine and bovine marker closely related species of Decapoda shrimps were classified by using
peptides to identify the animal origin of gelatin in dairy products such as proteotypic peptides of arginine kinase proteins (Ortea, Cañas, & Gal
yoghurt, cheese and ice cream (Yilmaz, Kesmen, Baykal, Sagdic, Kulen, lardo, 2011). A shotgun method was developed for the proteome char
Kacar, et al., 2013). The MSE tandem MS data acquisition method is acterization of gilthead sea bream (Sparus aurata) muscle samples
based on alternating low-energy collision-induced dissociation and (Piovesana, Capriotti, Caruso, Cavaliere, La Barbera, Zenezini Chiozzi,
high-energy collision-induced dissociation, where the former is used to et al., 2016). More recently, high-resolution MS analyses on an Orbitrap
obtain precursor ion accurate mass and intensity data for quantification analyser coupled to a direct analysis in real time (DART) source allowed
and the latter is used to obtain product ion accurate mass. the discrimination of wild-type from farmed salmons belonging to Salmo
salar species (Fiorino, Losito, De Angelis, Arlorio, Logrieco, & Monaci,
6.3. Fish and seafood 2019).
The high phenotypic similarity between related marine species 6.4. Cereals
makes intentional or accidental adulteration of seafood products,
including shellfish and fish, one of the most common food frauds. As a Cereals, including rice, barley, and wheat are the most widely har
consequence, global commercial requirements on labelling and trace vested crops in the world. Given the increasing demand in the global
ability are needed to guarantee the authenticity and traceability of market, cereals production is exposed to a growing number of frauds. In
seafood trading. In the last ten years, the development of reliable the last decade, the improvements in MS technologies together with the
analytical methodologies aimed at identifying closely related marine increasing availability of genomic database, enabled the use of MS-
species represents an issue of primary relevance for the seafood industry based approaches for the analysis of cereal proteins (Table 2). Most ef
to prevent mislabelling and adulteration (Table 1). forts are finalized to identify marker peptides suitable for discriminating
One of the first approaches proposed for fish authentication was different species of high economic interests or even those representing a
focused on the assessment of intra-species variability of fourteen shrimp risk for consumers with allergies and/or intolerances.
species of commercial interest by native isoelectrofocusing (IEF) Different durum wheat cultivars were analysed by Prandi and co-
coupled to LC-ESI-IT MS/MS analysis (Ortea, Cañas, Calo-Mata, Barros- workers to determine the content of the amylase/trypsin inhibitor
Velázquez, & Gallardo, 2010). To date, this study represents the most CM3, a common wheat allergen, by using marker peptides derived from
comprehensive electrophoretic characterization of closely related the protein. The authors detected the CM3 protein at concentrations
shrimp species. The same authors further identified several species- ranging from 0.22 to 1.11 mg/g in wheat samples by a quantitative
specific peptides from Pandalus borealis potentially useful for the un analysis performed on a single quadrupole mass spectrometer by using
equivocal identification of this shrimp species by coupling a genomic an isotopically labelled standard peptide (Prandi, Faccini, Tedeschi,
approach based on PCR-RFLP (restriction fragment length Galaverna, & Sforza, 2013).
9
Table 2
Studies published in the last ten years reporting applications of protein and peptide-based mass spectrometry analyses to cereals, tree nuts and wine.
MS technique Aim of the analysis Peptide/protein biomarker Reference
Cereals LC-MS/MS Differentiation of durum wheat varieties Peptides from α-amylase inhibitor Prandi et al., 2013
CM3
Detection of common wheat in commercial durum wheat flour Peptides from α-gliadin Prandi et al., 2012
Detection of common wheat in commercial durum wheat flour and pasta Peptides from puroindoline-A Russo et al., 2014
Detection of wheat, rye and spelt in bread Peptides from gluten proteins Bönick et al., 2017
Detection of wheat gluten Peptides from gluten proteins Schalk et al., 2018
Detection of wheat in rye, millet, oats, sorghum, buckwheat and soy Peptides from gluten proteins Colgrave et al., 2015
flours
Detection of oats in processed foods Peptides from gluten proteins Dawson et al., 2018
Detection of barley in processed foods Peptides from gluten proteins Colgrave et al., 2016
Identification of wheat, rye, barley, oats, corn, soy and rice Peptides from gluten proteins Martínez-Esteso et al., 2016
Tree nuts LC-MS/MS Detection of hazelnut in foods Peptides from allergenic proteins Van Vlierberghe et al., 2020
Detection of peanut in processed foods Peptides from allergenic proteins Gavage et al., 2020
Detection of peanut and tree nuts in processed or unprocessed foods Peptides from allergenic proteins Sealey-Voyksner, et al.
2016
Detection of almond, cashew, hazelnut, peanut, pistachio, walnut in foods Peptides from allergenic proteins Korte et al., 2016
Detection of hazelnut in foods Peptides from allergenic proteins Ansari et al., 2012
Wine MALDI-TOF MS Classification of Croatian white wines Wine proteins and peptides Rešetar et al., 2016
LC-MS/MS Detection of fining agents in white wines Peptides from caseins Cereda et al., 2010
Detection of fining agents in red wines Caseins D’Amato et al., 2010
Authentication of Amaro Branzi Soluble liqueur proteins Lerma-García et al., 2014
Detection of fining agents in white wines Peptides from caseins Monaci et al., 2010; 2011
Detection of fining agents in white wines Peptides from milk and egg proteins Monaci et al., 2013
The determination of common wheat in durum wheat samples was Marker peptides from the three major hazelnut allergenic proteins
assessed by LC-ESI-QqQ MS/MS analysis, at both qualitative and (Cor a8, Cor a9 and Cor a11) have been used for the development of LC-
quantitative level, by using peptide markers from α-gliadin (Prandi, MS/MS methods for detecting hazelnut in foods. Indeed, an LC-ESI QT
Bencivenni, Tedeschi, Marchelli, Dossena, Galaverna, et al., 2012) and MS/MS method in SRM mode was developed as a valid alternative to
puroindoline A (Russo, Cusano, Perissi, Ferron, Severino, Parente, et al., immunological assays to determinate trace amounts of allergenic nut
2014). In this work, by using an MRM-based approach, Russo and co- proteins in processed foods (Ansari, Stoppacher, & Baumgartner, 2012).
workers were able to detect up to 0.01% of common wheat in raw ma In this study, synthetic peptides of eight tryptic fragments from Cor a8,
terials (kernels) and processed products (pasta). Cor a9 and Cor a11 proteins, were used to build a calibration curve
Several studies also applied MRM-based quantitative strategies to ranging between 3.1 and 4166.7 ng/mL (Ansari, Stoppacher, & Baum
cereal composition analysis within commercial food products. By gartner, 2012). Furthermore, through a comprehensive LC-ESI-Q-TOF
determining the total protein content and the gluten-enriched fractions MS/MS-based approach, additional marker peptides from the same
of sixteen cereal grains, including wheat, rye, barley and oats, Colgrave allergenic proteins were identified and their robustness for applications
and co-workers selected a pool of specific wheat markers for detecting in food processing was validated by analysing roasted and caramelized
wheat contaminations in several commercially flours, with a limit of nuts, chocolate and fermented nut milk (Van Vlierberghe, Gavage, Dieu,
detection down to 15 mg/kg in a deliberately contaminated soy flour Renard, Arnould, Gillard, et al., 2020). A similar approach was also
(Colgrave, Goswami, Byrne, Blundell, Howitt, & Tanner, 2015). Simi applied to the identification of highly conserved marker peptides for
larly, by LC-MS/MS analysis of gluten-enriched extracts from barley and peanuts and tree nuts detection in food matrices (Sealey-Voyksner,
oat cultivars, a panel of peptide markers allowed the detection of barley Zweigenbaum, & Voyksner, 2016).
and oat contamination in breakfast cereals (Colgrave, Byrne, Blundell, & Untargeted high-resolution mass spectrometry also allowed the
Howitt, 2016; Dawson, Mendoza-Porras, Byrne, Hooper, Howitt, & identification and quantification of selected proteotypic peptides from
Colgrave, 2018). Moreover, peptide markers from common wheat, spelt six allergenic nut species (almond, cashew, hazelnut, peanut, pistachio
and rye were used to detect and quantify contaminations of these crop and walnut) by a shotgun proteomic approach. By this strategy, trace nut
species in baked products with LOD values in the range 0.5%-1% contaminations in processed foods were detected and quantified by LC-
(Bönick, Huschek, & Rawel, 2017). Specific wheat gluten peptides QT MS. Furthermore, LODs below 10 μg/g, comparable with routinely
identified by LC-MS/MS were also proposed as specific markers in an used ELISA and PCR methods, were obtained for several nuts by ana
MRM-based screening for the quantification of gluten within gluten- lysing spiked matrix samples (Korte, Lepski, & Brockmeyer, 2016).
containing species (Martínez-Esteso, Nørgaard, Brohée, Haraszi, Recently, by high-resolution LC-ESI- Q-TOF MS analysis, sixteen po
Maquet, & O’Connor, 2016; Schalk, Koehler, & Scherf, 2018). tential peanut peptide biomarkers from Ara h1 and Ara h3 proteins, the
two most abundant peanut allergens, were identified in both raw and
6.5. Tree nuts processed food products, paving the way to further studies aimed at the
development of an MS-based quantitative approach for peanut detection
Tree nuts, including almonds, Brazil nuts, cashews, hazelnuts, mac in complex food matrices (Gavage, Van Vlierberghe, Van Poucke, De
adamia nuts, pecans, pine nuts, pistachio nuts and walnuts, are common Loose, Gevaert, Dieu, et al., 2020).
allergen sources with a prevalence of up to 5% in the general population
(McWilliam, Koplin, Lodge, Tang, Dharmage, & Allen, 2015). A 6.6. Wine
remarkable increase in tree nuts-driven allergy incidence could be also
likely due to the large consumption justified by their nutritional benefits In parallel with the growing attention to quality control in the wine
and wide use in the food industry (Özenç & Bender Özenç, 2015). industry, there has been an increasing demand for analytical techniques
Reliable MS-based analytical methods have been developed for the to assess wine authenticity and traceability. Regarding the development
detection and quantification of allergenic proteins from tree nuts and application of protein-based MS approaches for wine analysis, the
(Table 2) according to the EU Regulation N. 1169/2011 to establish extraction and the enrichment of proteins present at low concentration
compliance of food ingredients indicated within foodstuff labels. levels within finished products are the most critical steps. Nevertheless,
10
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the multiplex determination of these fining agents with LODs ranging Colgrave, M. L., Byrne, K., Blundell, M., & Howitt, C. A. (2016). Identification of barley-
from 0.4 to 1.1 μg/mL (Monaci, Losito, De Angelis, Pilolli, & Visconti, specific peptide markers that persist in processed foods and are capable of detecting
barley contamination by LC-MS/MS. Journal of Proteomics, 147, 169–176.
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Declaration of Competing Interest 2659–2668.
Consonni, R., & Cagliani, L. R. (2019). The potentiality of NMR-based metabolomics in
food science and food authentication assessment. Magnetic Resonance in Chemistry,
The authors declare that they have no known competing financial 57(9), 558–578.
interests or personal relationships that could have appeared to influence Cozzolino, D., Corbella, E., & Smyth, H. E. (2011). Quality control of honey using
the work reported in this paper. infrared spectroscopy: A review. Applied Spectroscopy Reviews, 46(7), 523–538.
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to determine and monitor composition and other quality characteristics in raw fish,
Acknowledgements fish products, and seafood. Applied Spectroscopy Reviews, 47(3), 207–218.
Cuollo, M., Caira, S., Fierro, O., Pinto, G., Picariello, G., & Addeo, F. (2010). Toward milk
speciation through the monitoring of casein proteotypic peptides. Rapid
This work was supported by funding from University of Campania Communications in Mass Spectrometry, 24(11), 1687–1696.
“Luigi Vanvitelli” through the VALERE program and MISE, project D’Amato, A., Kravchuk, A. V., Bachi, A., & Righetti, P. G. (2010). Noah’s nectar: The
proteome content of a glass of red wine. Journal of Proteomics, 73(12), 2370–2377.
NUTRABEST PON I&C 2014-2020 Prog. n. F/200050/01-03/X45. Dalabasmaz, S., Ebner, J., & Pischetsrieder, M. (2017). Identification of the peptide
pyroQ-betaCasein 194–209 as a highly specific and sensitive marker to differentiate
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Appendix A. Supplementary data
Journal of Agricultural and Food Chemistry, 65(49), 10781–10791.
Dawson, C., Mendoza-Porras, O., Byrne, K., Hooper, T., Howitt, C., & Colgrave, M.
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org/10.1016/j.foodchem.2021.130456. food. Peptide Science, 110, Article e24045.
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Food Chemistry 365 (2021) 130456

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Mass spectrometry-based protein and peptide profiling for food frauds,

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