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Multidimensional techniques are still an expanding niche in separation science, due to their undoubtedly increased separation power over “conventional” one-dimensional systems in unravelling highly complex samples. Food products make no exceptions and multidimensional methods are capable to accomplish both the analysis of bioactive compounds, but also the determination of minor components through their selectivity and sensitivity. The present review provides an overview of such techniques in their modes namely heart-cutting and comprehensive liquid chromatography operated under either off-line or on-line as a valuable tool in food analysis. The combinations of liquid chromatography with other chromatographic methods are not considered. The principles, advantages and disadvantages of each approach are briefly described along with significant applications in the food field. [ABSTRACT FROM AUTHOR]

Important objectives of a high-performance liquid chromatography preparative process are: purity of products isolated, yield, and throughput. The multidimensional preparative liquid chromatography method used in this work was developed mainly to increase the throughput; moreover purity and yield are increased thanks to the automated collection of the molecules based on the intensity of a signal generated from the mass spectrometer detector, in this way only a specific product can be targeted. This preparative system allowed, in few analyses both in the first and second dimensions, the isolation of eight pure compounds present at very different concentration in the original sample with high purity (>95%) and yield, which showed how the system is efficient and versatile. Pure molecules were used to validate the analytical method and to test the anti-inflammatory and antiproliferative potential of flavonoids. The contemporary presence, in bergamot juice, of all the flavonoids together increases the anti-inflammatory effect with respect to the single compound alone. [ABSTRACT FROM AUTHOR]

The color and the pungency of red chili pepper powder, depending on the carotenoid and capsaicinoid contents, are important properties for this food ingredient. In this study the patterns of these two classes of compounds have been analyzed in samples of red chili powder during one year of storage at room temperature (20–24 °C) and at low temperature (− 18 °C), in order to investigate the eventual chemical changes occurring during storage, and to find a possible correlation between the behavior of the two groups of molecules. During storage at room temperature, both carotenoid and capsaicinoid amounts were found to decrease progressively following a linear kinetics. After 12 months free carotenoids decreased to 20% of the initial value, and total capsaicinoids to 75%. All classes of carotenoids were found to be highly correlated with total capsaicinoids, thus showing that the molecules as the object of the study were subjected to similar kinetics. During storage at low temperature carotenoids decrease with lower rate (free carotenoids reached 66% of the initial value after 12 months) and capsaicinoids were almost unaltered. [ABSTRACT FROM AUTHOR]

Abstract: In this research 12 different varieties of Capsicum cultivars belonging to three species (Capsicum chinense, Capsicum annuum, Capsicum frutescens) and of various colour, shape, and dimension have been characterised by their carotenoids and capsaicinoids content. The berries were cultivated in the region Emilia-Romagna, in Northern Italy. The native carotenoid composition was directly investigated by an HPLC-DAD-APCI-MS methodology, for the first time. In total, 52 carotenoids have been identified and considerable variation in carotenoid composition was observed among the various cultivars investigated. Among the cultivars with red colour, some Habanero, Naga morich and Sinpezon showed an high β-carotene content, whereas Serrano, Tabasco and Jalapeno showed an high capsanthin content and the absence of β-carotene. Habanero golden and Scotch Bonnet showed a high lutein, α-carotene and β-carotene amounts, and Habanero orange was rich in antheraxanthin, capsanthin and zeaxanthin. Cis-cryptocapsin was present in high amount in Habanero chocolate. The qualitative and quantitative determination of the capsaicinoids, alkaloids responsible for the pungency level, has also been estimated by a validated chromatographic procedure (HPLC-DAD) after a preliminary drying step and an opportune extraction procedure. Results have also been expressed in Scoville units. Dry matter and water activity have also been established on the fresh berries. The dried peppers of each variety were then submitted to the evaluation of the total nitrogen content, measured by a Dumas system, permitting to provide information on the protein content that was found to be in the range between 7 and 16%. [Copyright &y& Elsevier]

Abstract: A novel comprehensive two-dimensional liquid chromatographic (LC×LC) system for characterization of phospholipid (PL) molecular species belonging to six phospholipid classes was developed. To tackle such a task, a silica hydrophilic interaction liquid chromatography (HILIC) column was used as the first dimension (1D), and reversed-phase liquid chromatography (RP-LC) with a C18 column was used as the second dimension (2D) in combination with mass spectrometric detection. Fraction transfer from the 1D to the 2D was performed by means of a two-position ten-port switching valve, operated under stop-flow conditions. The capability of the investigated LC×LC approach was demonstrated in the separation of phospholipid molecular species contained in two Folch-extracted cow''s milk and plasma samples. Within the phosphatidylcholine class, up to 16 and 14 different species were identified, respectively, by means of the HILIC×RP-LC–MS system employed under both positive and negative ionization mode. [Copyright &y& Elsevier]

Abstract: A non-aqueous reversed phase high performance liquid chromatography method was developed, and optimized for triacylglycerol analysis in a Brevoortia tyrannus (menhaden) oil sample. Four columns were serially coupled to tackle such a task, for a total length of 60cm of shell-packed stationary phase, and operated under ultra high pressure conditions. As detection, positive-ion atmospheric pressure chemical ionization mass spectrometry was used to attain identification of the analyzed sample components. A number of 137 triacylglycerols containing up to 19 fatty acids, with 14–22 carbon atom alkyl chain length and 0–6 double bonds, were positively identified in the complex lipidic sample. This is the first work that reports an extensive characterization of the triacylglycerol fraction of menhaden oil. [Copyright &y& Elsevier]

Abstract: Gas Chromatography–Combustion-Isotope Ratio Mass Spectrometry (GC–C-IRMS) can provide information useful to discriminate among essential oils of different geographical origin and to reveal frauds on essential oils by addition of synthetic or natural compounds from different botanical origin. The present work reports the combination of information obtained by GC–C-IRMS, Enantioselective Gas Chromatography (Es-GC), high resolution Gas Chromatography (GC-FID) and spectrophotometry (CD values). All these techniques represent useful tools to evaluate the authenticity control on lemon essential oils. The GC–C-IRMS was applied to determine the authenticity range of carbon stable isotope ratios in genuine Italian lemon essential oils industrially cold-pressed. Several commercial samples were evaluated to assess their genuineness. The IRMS results are discussed in function of the values also obtained by GC-FID, es-GC and CD values. Stable isotope ratio analysis, by GC–C-IRMS, proved to be useful to detect the presence of sophistications in lemon essential oils, even when other techniques of analysis fail. However for subtle sophistications (e.g. addition of distilled lemon oil) quality assessment must be performed by the auxiliary of more than one technique. [Copyright &y& Elsevier]

Recently, donkey milk has been indicated as a nutraceutical food thanks to some bioactive compounds interesting in the human diet; these substances are the lipids, which are characterized by the ability in conditioning indirectly or directly the intestinal environment and immunity, taking part in the prevention and treatment of some pathologies. With the aim to compare some nutritional properties of human and donkey milk, the triacylglycerol (TAG) composition and the positional isomers of donkey milk samples were analyzed by HPLC-APCI-MS on reversed phase and silver ion columns. The technique allowed the identification of 72 TAGs in the samples analyzed. Similarities and differences among the TAGs fraction of human and donkey milk can be easily determined by HPLC analysis of the lipid fraction. Donkey milk presents TAGs with partition number (PN) values starting from 30 up to 50. In human milk, the short-chain fatty acids (FAs) are not well-represented and the PN values range between 36 and 52. Other significant differences are among TAGs containing polyunsaturated fatty acids (PUFA). In fact, donkey milk presents a larger number and amount of ω3 and ω6 FAs than human milk, which contains only significant amount of ω6 FA (linoleic). Both donkey and human milk present the saturated FA preferably on the sn-2 position. Data testify a certain degree of similarity of these products in relation to their digestibility and confirm the increasing interest toward donkey milk as an alternative food for hypoallergenic diet in humans. [ABSTRACT FROM AUTHOR]

Abstract: Authenticity assessment of flavoured strawberry foods was performed using headspace-solid phase microextraction (HS-SPME) coupled to gas chromatography–combustion-isotope ratio mass spectrometry (GC–C-IRMS). An authenticity range was achieved, investigating on the carbon isotope ratio of numerous selected aroma active volatile components (methyl butanoate, ethyl butanoate, hex-(2E)-enal, methyl hexanoate, buthyl butanoate, ethyl hexanoate, hexyl acetate, linalool, hexyl butanoate, octyl isovalerate, γ-decalactone and octyl hexanoate) of organic Italian fresh strawberries. To the author''s knowledge, this is the first time that all these components were investigated simultaneously by GC–C-IRMS on the same sample. The results were compared, when applicable, with those obtained by analyzing the HS-SPME extracts of commercial flavoured food matrices. In addition, one Kenyan pineapple and one fresh Italian peach were analyzed to determine the δ 13CVPDB of the volatile components common to strawberry. The δ 13CVPDB values are allowed to differentiate between different biogenetic pathways (C3 and CAM plants) and more interestingly between plants of the same CO2 fixation group (C3 plants). Additional analyses were performed on all the samples by means of Enantioselective Gas Chromatography (Es-GC), measuring the enantiomeric distribution of linalool and γ-decalactone. It was found that GC–C-IRMS and Es-GC measurements were in agreement to detect the presence of non-natural strawberry aromas in the food matrices studied. [Copyright &y& Elsevier]

The physicochemical indices, the composition of the volatile fraction, the enantiomeric ratios of some volatile components and the oxygen heterocyclic fraction of cold-pressed Key lime oils (types A and B), Persian lime oils, and petitgrain lime oils are reported. The volatile fraction of cold-pressed Persian lime oil is characterized by a higher content of limonene, γ-terpinene and esters and a lower content of β-pinene, sesquiterpene hydrocarbons, alcohols and aldehydes than cold-pressed Key lime oils. In petitgrain oils the oxygenated compounds are present at levels higher than the peel oils. Oxypeucedanin, probably due to the extraction technology, was almost absent in cold-pressed Key lime type A, while it is present in cold-pressed Key lime type B and in Persian lime oil. The enseparation was performed by direct enantioselective GC (esGC) and by multidimensional GC (MDGC) to obtain the most appropriate antiomeric separation of all the components analyzed. The enantiomeric excess of S-(-)-α-pinene, 1S,4R-(-)-camphene, S-(-)-β-pinene, S-(-)-sabinene, and R-(-)-β-phellandrene are lower in cold-pressed Persian lime oil than in Key lime oils. [ABSTRACT FROM AUTHOR]

An investigation was performed on 124 samples of Sicilian mandarin essential oils ( Citrus deliciosa Tenore), industrially cold pressed by different extraction techniques (Brown Oil Extractor and screw press). The samples were collected during the entire productive season (from September 2008 to March 2009). The aim of the study was to determine the composition of the volatile fraction by GC/FID and GC/MS-LRI, of the non-volatile oxygen heterocyclic components by RP-HPLC/PDA and LCMS-IT-TOF, as well as the determination of the enantiomeric ratios of some volatile components by multidimensional GC (MDGC) with chiral column in the second dimension. Three new components were identified by LCMS-IT-TOF in the non-volatile fraction (demethyl-nobiletin, isosinensetin, demethyl-tangeretin). The results obtained are discussed to evaluate seasonal variation of the composition of the essential oil as well as the influence of the extraction techniques. This study gives a wide view on the composition of Sicilian mandarin ( C. deliciosa Ten.) essential oils industrially produced during the entire productive season, useful to identify quality parameters for the analytical characterization of this product. Copyright © 2010 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Bergamot oil ( Citrus bergamia) is mainly employed in the perfumery and cosmetic industries and also, in a smaller amount, in the pharmaceutical and food industries, for its fragrant notes, fixative and antimicrobial properties. Due to the presence of some phototoxic compounds in its composition, it has become a common practice to reduce or sometimes completely eliminate these substances before using the oil. Samples of treated bergamot oils have been investigated in this study (terpeneless, furocoumarin- and bergapten-free) by means of GC-FID, GC-MS, enantio-GC-FID and HPLC. The results are reported in terms of either peak areas or g/100 g. Some considerations are made in order to discuss the technologies used for treating bergamot oil. Copyright © 2009 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Abstract: A comprehensive two-dimensional liquid chromatography method has been applied for the quantification of polyphenols in red wines and compared to the most commonly employed conventional LC approach. Such methodology comprised the use of a microbore conventional HPLC column packed with totally porous particles in the first dimension and a partially porous column of conventional diameter in the second dimension. Even though a good number of applications in comprehensive LC have been reported, quantification experiments have been rarely described. To this regard, the advantages of comprehensive LC together with the employment of dedicated software capable of detecting and quantifying each peak from the 2D plot, have been taken into account for quantifying the most representative polyphenols in three different commercial Sicilian red wine samples. The optimized method has been validated in terms of linearity, sensitivity, detection and quantification limits. LODs as low as 0.02ppm were obtained using the one-dimensional HPLC-DAD method, whereas values lower than 0.10ppm were obtained by comprehensive LC. However, comprehensive LC allowed the quantification of a higher number of compounds with RSD lower than 10% thanks to its improved resolving power. The separation capabilities of comprehensive LC allowed the analysis of complex natural samples without any pre-treatment to effectively reduce the interferences coming from the matrix. [Copyright &y& Elsevier]

Abstract: There is growing interest related to rapid screening and full characterization of the constituents of plants with medicinal properties; among these, “Mate” or Yerba Maté is a tea-like beverage widely consumed in South America, obtained from the dried leaves of Ilex paraguariensis. The high content in polyphenols accounts for in vitro and in vivo antioxidant activity of the extracts obtained from this plant; on the other hand, the high complexity of the samples extracted, depending on the method employed, may preclude complete resolution by conventional HPLC techniques. For this purpose, a comprehensive two-dimensional liquid chromatography (LC×LC) system, comprised of an RP-Amide first dimension and a partially porous octadecylsilica column in the second dimension, has been compared with a one-dimensional system. The latter was operated using a partially porous octadecylsilica column, with diode array (DAD) and electrospray/ion trap-time of flight (ESI/IT-TOF) detection for the most complex extracts. The employment of the hybrid mass spectrometer allowed unequivocal identification of several compounds in the mate extracts. Using LC×LC–MS3, it was possible to discriminate between congeners of chlorogenic acids, along with monoacyl- and diacylchlorogenic acid esters. [Copyright &y& Elsevier]

Abstract: The application of gas chromatography–olfactometry (GC–O) in food flavour analysis represents to be a valuable technique to characterise odour-active, as well as character impact compounds, responsible for the characterizing odour of a food sample. The present article briefly reviews the use of GC–O in the flavour investigation of dairy products (milk and cheese), coffee, meat and fruits. Particular attention has been devoted to extraction techniques, GC–O hardware commonly utilised and olfactometric assessment methods, which can be applied to food analysis. [Copyright &y& Elsevier]

Abstract: Comprehensive two-dimensional (2D) liquid chromatographic (LC×LC) techniques can be considered innovative methods only recently developed and adopted in many configurations. The revolutionary aspect of comprehensive two-dimensional techniques, with respect to classical multidimensional (MD) chromatography, is that the entire sample is subjected to the 2D advantage. The major benefit is that the separation capacities of each dimension are multiplied, offering a high peak capacity to resolve samples of great complexity. The first part of the present review briefly describes the theoretical and practical aspects related to the development of a multidimensional comprehensive liquid chromatographic method. Applicational experiences in comprehensive liquid chromatography are then described, divided into four groups, according to the HPLC modes used in the two dimensions and to the nature of the samples analyzed. [Copyright &y& Elsevier]

A novel approach for carotenoid analysis has been developed. Orange essential oil and juice carotenoids were separated by means of comprehensive dual-gradient elution HPLC, using normal phase with a microbore silica column in the first dimension (first D), reversed phase with a monolithic C18 column in the second dimension (second D), and a 10-port switching valve as an interface. An on-line photodiode array detector was used in order to obtain absorption spectra. Peak identification was obtained by combining retention data with the UV-visible spectra. [ABSTRACT FROM AUTHOR]

The physicochemical indices, the enantiomeric distribution of some monoterpene hydrocarbons, the qualitative and quantitative composition of the volatile fraction and the oxygenated heterocyclic fraction of cold-pressed Mexican Dancy tangerine essential oils are reported. The volatile fraction is characterized by a higher content of limonene. γ-Terpinene, myrcene and α-pinene are the other most abundant hydrocarbons. Linalool is the main oxygenated compound. The oxygen heterocyclic fraction contains five polymethoxylated flavones, tangeritin being the main of them. Very little difference in the chemical and physicochemical composition of Dancy tangerine oils of different geographical origin was detected. Copyright © 2004 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Comprehensive two-dimensional (2D) chromatographic techniques can be considered innovative methods, only quite recently developed. Since their introduction to the chromatographic community, these techniques have been used in several fields and have gained an excellent reputation as valuable and powerful analytical tools. The revolutionary aspect of comprehensive multidimensional (MD) techniques, in respect to classical MD chromatography, is that the entire sample is subjected to the 2D advantage. The resulting unprecedented separating capacity makes these approaches prime choices when analysts are challenged with highly complex mixtures. Furthermore, in the case of automated systems, instrumental analysis times are roughly the same as in monodimensional applications. The present review reports various comprehensive chromatographic applications on different food matrices. The GC × GC section highlights two fundamental aspects for component separation/identification: the exceptional peak capacity and the formation of group types on the 2D space plane. The LC × LC section reports the employment in food analysis of a recently developed multidimensional normal-phase (NP)-reversed-phase (RP) high performance liquid chromatography (HPLC) system. Also reported are comprehensive LC × GC and packed column supercritical fluid chromatography (pSFC × pSFC) applications in this field. [Copyright &y& Elsevier]

The determination of the triacylglycerol (TAG) profile in real world matrices is rather difficult as these compounds present a complex composition and are characterized by similar physico-chemical properties. This investigation is based on the high-performance liquid chromatography (HPLC) multidimensional determination of the TAG profile in terms of TAG species and positional isomers in a rice oil sample. The off-line bi-dimensional system was attained through the coupling of non-aqueous reversed-phase HPLC and silver ion (Ag)-HPLC. The primary column eluate was fractionated and the fractions of interest were then injected onto the secondary column, allowing the separation of several TAG positional isomers, unresolved in the first dimension. Peak assignment was carried out by combining retention data with atmospheric pressure chemical ionisation (APCI) MS spectra information. The fatty acid distribution along the glycerol backbone, determined by Ag-HPLC, was confirmed through diglyceride ion ratios derived from APCI-MS analysis. Method validation, where both precision and accuracy were measured, was carried out in preliminary applications on standard compounds. The analytical results obtained show that rice oil TAGs follow a distribution which can be considered typical for vegetable oils. [Copyright &y& Elsevier]

The composition of the volatile fraction of faustrime essential oil has been determined by GC and CC/MS on RTX-5 and RTX-Wax columns. The enantiomeric distribution of five volatile components has been determined by direct chiral GC using a DETTBUSILβCDX column. The oil was found to contain over 57% hydrocarbons and 41-42% oxygenated compounds. The former class was characterized by limonene, β-phellandrene and γ-terpinene, representing together about 44-45% of the whole volatile fraction; among the oxygenated compounds, citronellal was the most abundant with levels up to 22-23%. The enantiomeric distribution of five components (β-pinene, sabinene, limonene, linalool and α-terpineol) yielded combined results that were unlike any other citrus peel oil. The specific enantiomeric ratios did show similarities with components found in other citrus oils. [ABSTRACT FROM AUTHOR]

A comprehensive two-dimensional HPLC system has been developed. It is based on the use of a microbore silica column operated in normal-phase (adsorption) mode (NP) in the first dimension and a monolithic type C18 column operated in reversed-phase (RP) mode in the second dimension. The interface was a 10-port, 2-position valve equipped with two storage loops. The first column was operated at a flow rate of 20 μL/min in isocratic mode, while the monolithic column flow rate was 4 mL/min and was operated in gradient mode. The sample loops had a volume of 20 μL each, and the analysis lime in the second dimension was 1 min. In this way, every fraction from the first dimension was transferred on-line to the second dimension switching the automated valve every minute. A photodiode array detector has been used after the secondary column. The use of normal- and reversed- phase mode in the two dimensions can be helpful in the separation of complex mixtures of a natural origin that contain uncharged molecules of comparable dimension, different in polarity and hydrophobicity. The use of a microbore column in the first dimension permits the injection of a small volume in the secondary column, making the transfer of incompatible solvents from the first to the second dimension possible. Since the mobile phase in the NP separation is always stronger than the mobile phase at the head of the secondary column operated in RP mode, the initial eluent strength is important in order to obtain an effective focusing of the sample. The use of a monolithic type column in the second dimension permits the performance of very fast analysis operating at higher flow rates without loss of resolution, due to a higher permeability and increased mass-transfer properties in comparison to conventional particulate columns. Due to the brief reconditioning time necessary for monolithic columns, repetitive gradients can be carried out, extending the field of application to mixtures that contain components with different polarities. The utility of the system has been demonstrated in the analysis of the oxygen heterocycic fraction of cold-pressed lemon oil, made up of coumarins and psoralens. These components may contain hydroxyl, methoxyl, isopentenyl, isopentenyloxyl, and geranyloxyl groups and oxygen-containing modification of the terpenoid side-chain groups, such as epoxides or vicinal diol groups. The relative location of the components in the 2D plane varied in relation to their chemical structure and allowed positive peak identification. The UV spectra recorded with the photodiode array detector supplied additional information that was used for the characterization of the studied sample. [ABSTRACT FROM AUTHOR]

Reports on the suitability of high-resolution gas chromatography for analysis of volatile compounds. Capability of multidimensional chromatography to provide greater resolution; Ease of collecting and handling fluids; Advantage of mobile phase compatibility between separating techniques.

• A new analytical method was validated to determine furocoumarins in finished cosmetics. • A pre-targeted analysis in Multiple Reaction Monitoring mode of 35 oxygen heterocyclic compounds was performed. • Libraries were used in combination with Linear Retention Index filter for the unambiguous identification. • The quantitative approach was based on external calibration with curves in spiked blank corrected by weighting factors. In the European Union, cosmetic products are regulated by the Cosmetics Regulation (EC) No. 1223/2009. The Analytical Working Group of the International Fragrance Association (IFRA) suggested that a new sensitive analytical method is needed to determine psoralens in finished cosmetic products. This research provides an HPLC-MS/MS method for the quality control of 20 furocoumarins, 8 coumarins and 7 polymethoxyflavones in cosmetics. Thanks to the high sensitivity of the tandem mass spectrometry detection in Multiple Reaction Monitoring mode, psoralens contained in trace have been quantified in different products. The Limits of Quantifications were in the range 0.3-74 μg L−1. A reliable identification was achieved combining the Linear Retention Index (LRI) system with the MS and MS/MS libraries. In particular, the attribution was based on the spectra similarity filtered by the LRI parameter. The robustness and reproducibility of the LRI approach was demonstrated by the comparison of the HPLC-MS/MS results here reported with those obtained in our previous study, by using an HPLC-PDA system. This method could be taken into account for quality control of furocoumarins in cosmetics, and by the main associations, such as IFRA, for the purpose of issuing new opinions. [ABSTRACT FROM AUTHOR]

Prediabetes is a risk state that defines a high chance of developing diabetes and cardiovascular disease. Oxidative stress mediated by hyperglycemia‐induced production of reactive species could play a crucial role in this context. In the present study, we investigated whether the anion exchange capability mediated by AE1 (SLC4A1), which is sensitive to oxidative stress, was altered in human red blood cells (RBCs) obtained from prediabetic volunteers. In addition, we assessed the precise composition of bioactive compounds and the potential benefits of finger lime juice extract (Citrus australasica, Faustrime cultivar) in counteracting oxidative stress‐related functional alterations. Human RBCs from normal and prediabetic volunteers were incubated with 50 µg/mL juice extract for 2 h at 25°C. Juice extract restored alterations of the anion exchange capability mediated by AE1 and prevented the structural rearrangements of AE1 and α/β‐spectrin in prediabetic RBCs. AE1 functional and structural alterations were not associated with an increase in lipid peroxidation or protein oxidation at the level of the plasma membrane. An increased production of intracellular ROS, which provoked the oxidation of hemoglobin to methemoglobin, both reverted by juice extract, was instead observed. Importantly, juice extract also induced a reduction in glycated hemoglobin levels in prediabetic RBCs. Finally, juice extract blunted the overactivation of the endogenous antioxidant enzymes catalase and superoxide dismutase and prevented glutathione depletion in prediabetic RBCs. These findings contribute to clarifying cellular and molecular mechanisms related to oxidative stress and glycation events that may influence RBC and systemic homeostasis in prediabetes, identify AE1 as a sensitive biomarker of RBC structural and function alterations in prediabetes and propose finger lime juice extract as a natural antioxidant for the treatment and/or prevention of the complications associated with the prediabetic condition. SIGNIFICANCE STATEMENT: The data obtained here reveal that structural and functional alterations related to the increase of oxidative stress and/or glycation events can still be reversible and the early application of bioactive molecules could counteract the majority of derangements in prediabetic RBCs. This study identifies finger lime as an antioxidant/anti‐glycation functional food and suggests that diet supplementation with finger lime might contribute to the prevention or attenuation of pathophysiological events linked to RBC dysfunction during the prediabetic condition. Additionally, our findings proved that measurement of anion exchange capability via AE1 remains a valid tool for monitoring the impact of oxidative stress/glycation on human RBC and systemic homeostasis. [ABSTRACT FROM AUTHOR]

The present study aimed to investigate the chemical composition and antimicrobial activity of Jasminum grandiflorum L. essential oil produced for the first time at industrial level by steam distillation. Volatile and chiral compositions were analyzed by GC-MS and GC-FID. In total 130 volatile compounds were identified, which constituted more than 98% of the oils. The results revealed significant differences in terms of volatile compounds between jasmine essential oil and the absolute. Sensorial evaluation revealed the essential oil had a youthful and dynamic character with a bright, floral scent, while the absolute had a more mature and sensual scent that was richer. Antimicrobial activity of both products against eighteen human pathogens and cosmetic contaminants was evaluated. The results showed that essential oil exhibited greater antimicrobial activity, inhibiting 8 out of 17 microbial strains within the MIC range ≤800 µg/mL, compared to 2 out of 17 in the case of the absolute. [ABSTRACT FROM AUTHOR]

Ruta angustifolia, a wild plant which largely grows in Morocco, is commonly used in folk medicine and is believed to possess several therapeutic properties. In the present work, we aimed to determine the chemical composition, antioxidant, and antimicrobial properties of the essential oil obtained from the aerial parts of Ruta angustifolia collected from the Rif region in Morocco. The employment of gas chromatography coupled to flame ionization detector and mass spectrometry detection led to the identification of five major components, representing 91.69 % of the total volatile fraction with a dominance of nonyl methyl ketone (accounting for % 86.97 % of the whole sample). The tested essential oil displayed moderate antioxidant activity and a strong antifungal effect against Fusarium oxysporum and Botrytis cinerea with MIC values equal to 7 µL/mL and 0.81 µL/mL respectively. However, no antibacterial effect was revealed against Gram-negative or Gram-positive bacterial strains. [ABSTRACT FROM AUTHOR]

The article presents the discussion on multidimensional liquid chromatography (MD–LC) becoming a very powerful analytical method. Topics include advantage of such a technique linking to the augmented separation power, as a consequence of the increased selectivity and sensitivity of the two systems; and tracing back to the instrumental complexity and reducing sensitivity.

Triacylglycerols (TAGs), as the main components of edible oils and animal fats, are responsible for the nutritional value, organoleptic features and technological properties of foods; each lipid matrix shows a unique TAG profile which can serve as fingerprint to ensure the quality and authenticity of food products. The high complexity of many foodstuffs often makes untargeted elucidation of TAG components a challenging task; thus, more efficient separation techniques may be mandatory. In this research, the TAG profile of a borage (Borago officinalis) seed oil was obtained by two-dimensional comprehensive liquid chromatography (LC×LC), by the coupling of silver thiolate and octadecylsilica monodisperse materials. A total 94 TAG compounds were identified by ion trap-time of flight detection, using atmospheric pressure ionization, with the degree of unsaturation varying from 0 to 9, and partition values ranging from 36 to 56. The group-type separation afforded by this analytical approach may be useful to quickly fingerprint TAG components of oil samples. [ABSTRACT FROM AUTHOR]

Rapid evaporative ionization mass spectrometry (REIMS) is a relatively recent MS technique explored in many application fields, demonstrating high versatility in the detection of a wide range of chemicals, from small molecules (phenols, amino acids, di‐ and tripeptides, organic acids, and sugars) to larger biomolecules, that is, phospholipids and triacylglycerols. Different sampling devices were used depending on the analyzed matrix (liquid or solid), resulting in distinct performances in terms of automation, reproducibility, and sensitivity. The absence of laborious and time‐consuming sample preparation procedures and chromatographic separations was highlighted as a major advantage compared to chromatographic methods. REIMS was successfully used to achieve a comprehensive sample profiling according to a metabolomics untargeted analysis. Moreover, when a multitude of samples were available, the combination with chemometrics allowed rapid sample differentiation and the identification of discriminant features. The present review aims to provide a survey of literature reports based on the use of such analytical technology, highlighting its mode of operation in different application areas, ranging from clinical research, mostly focused on cancer diagnosis for the accurate identification of tumor margins, to the agri‐food sector aiming at the safeguard of food quality and security. [ABSTRACT FROM AUTHOR]

The green microalga Haematococcus pluvialis has been widely studied due to its capacity to accumulate great amounts of astaxanthin, a high-value carotenoid with biological activities. In the present work, two green compressed fluid–based processes, pressurized liquid extraction (PLE) and supercritical antisolvent fractionation (SAF), are integrated to obtain an astaxanthin-enriched extract from this microalga. PLE was carried out using pressurized ethanol as solvent, for 20 min, at 10 MPa, and 50 °C as extraction temperature. Subsequently, the obtained extract was processed by SAF to further purify the carotenoid fraction. The SAF process was optimized using a 3-level factorial experimental design and considering three experimental variables: (i) CO2 pressure (10–30 MPa), (ii) percentage of water in the PLE extract (20–50%), and (iii) PLE extract/supercritical-CO2 flow rate ratio (0.0125–0.05). Total carotenoid content was evaluated in both extracts and raffinates. Best results were obtained at 30 MPa, 0.05 feed/SC-CO2 mass flow rate, and 20% (v/v) of water in the feed solution, achieving values of 120.3 mg g−1 carotenoids in extract (in the SAF extract fraction), which were significantly higher than those obtained in the original PLE extract. In parallel, a new fast two-dimensional comprehensive liquid chromatography (LC×LC) method was optimized to get the full carotenoid profile of these extracts in less than 25 min. This is the first time that the use of a C30 column is reported in an on-line LC×LC system. [ABSTRACT FROM AUTHOR]

Background: Following our previous research on the differentiation of Italian extra virgin olive oils (EVOOs) by rapid evaporative ionization mass spectrometry coupled to a tandem high resolution mass analyser, the present study deals with the evaluation of another direct mass spectrometry (direct‐MS) approach for the rapid and automatic discrimination of EVOOs. In particular, direct analysis in real time (DART‐MS) was explored as an ambient MS (AMS) source for the building of a top‐quality Italian EVOOs database and fast identification of unknown samples. A single quadrupole detector (QDa) was coupled with DART, taking advantage of a cost‐saving, user‐friendly and less sophisticated instrumental setup. Particularly, quickstrip cards, located on a moving rail holder, were employed, allowing for the direct analysis of 12 EVOO spots in a total analysis time of 6 min. The aim was to develop a reliable statistical model by applying principal component and linear discriminant analyses to clusterize and classify EVOOs according to geographical origin and cultivar, as main factors determining their nutritional and sensory profiles. Results: Satisfactory results were achieved in terms of identification reliability of unknown EVOOs, as well as false positive risk, thus confirming that the use of AMS combined with chemometrics is a powerful tool against fraudulent activities, without the need for mass accuracy data, which would increase the analysis cost. Conclusion: A DART ionization source with a compact and reliable QDa MS analyser allowed for rapid fingerprinting analysis. Furthermore, MS spectra provided quali‐quantitative information successfully related to EVOO differentiation. © 2023 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

The present review illustrates the state of the art in the field of liquid chromatography (LC) hyphenated to electron ionization mass spectrometry (EI MS). An overview of applications over the last decades is given, in order to demonstrate the benefits arisen from the use of EI for the characterization of typically LC-amenable samples. Key advantages are related to the extensive fragmentation pattern useful for structure elucidation and the absence of matrix effects, differently from the most commonly employed LC-MS interfaces (e.g., electrospray). Different interfaces which made the LC-EI MS coupling feasible are described, along with several approaches proposed to overcome well-known incompatibility issues. • The state of the art of LC-EI MS hyphenation is presented. • An overview of LC-EI MS applications over the last 25 years is given. • Key benefits and main limitations are discussed. • Recent strategies to overcome typical LC-EI incompatibility issues are described. [ABSTRACT FROM AUTHOR]

Citrus essential oils, thanks to their pleasant aroma, are certainly the most used ingredients in the formulation of hydroalcoholic fragrances. The non-volatile fraction of Citrus essential oil is composed for 10–20% of coumarins, furocoumarins and polymethoxyflavones. It is well known that furocoumarins induce photosensitization and have potential carcinogenic and mutagenic effects. It follows that furocoumarins levels in cosmetics product are constantly monitored by opinions and regulations issued by the International Fragrance Association. The aim of this research article was to quantify coumarins, furocoumarins and polymethoxyflavones in thirty commercial hydroalcoholic fragrances using supercritical fluid chromatography in combination with triple quadrupole mass spectrometry technique (SFC-QqQ-MS). According to author's knowledge, this is the first report on the determination of oxygen heterocyclic compounds in hydroalcoholic fragrances by means of SFC-QqQ-MS technique. [ABSTRACT FROM AUTHOR]

Abstract Mango (Mangifera indica) peel powder (MP), banana (Musa paradisiaca) peel powder (BP), and yellow tamarillo freeze-dried pulp (Solanum betaceum Cav.) (YT), were selected as raw materials to obtain eight microencapsulates (M1-M8) by spray-drying with maltodextrin (MD) at two air inlet temperatures (130 °C and 180 °C) and with four feed mixture compositions. Their physicochemical characterisation was performed by measuring: pH, soluble solids (°Brix), Aw, and colour CIELAB (L*, a* and b*) parameters. The morphology analysis performed by SEM, determined that the powders showed a regular and spherical microstructure. The qualitative and quantitative carotenoid analyses carried out by HPLC-PDA-APCI/MS methodology, both in the raw materials and microencapsulates, showed that the drying temperature significantly affected the carotenoid content. The major carotenoids in the samples were β -cryptoxanthin C 14:0 , β -cryptoxanthin C 16:0 , β -carotene, β -cryptoxanthin C 12:0 , β -cryptoxanthin, zeaxanthin, and lutein. Among the microencapsulates, M2 and M4 samples (dried at 130 °C) exhibited the highest values of carotenoid content with 1.025 and 1.296 mg β -carotene/100 g sample, respectively. Thermal analyses showed that the powders were stable up to 100 °C. During the storage stability test at 18 °C, the carotenoid content diminished following a first order kinetic, showing the RH strongly influences the stability of microencapsulates. Graphical abstract Unlabelled Image Highlights • Microencapsulates carotenoid-rich were obtained from mango, banana and tamarillo powders. • Spray-drying allows to develop microencapsulates from by-products of fruit drying. • The carotenoid content in microencapsulates was reduced at higher RH values during storage. [ABSTRACT FROM AUTHOR]

During the Covid-19 pandemic, health agencies worldwide have recommended frequent handwashing and sanitizing. A variety of hand gel products were made available on the market, often with fragrances added to curtail the strong smell of alcohol. Commonly used Citrus fragrances contain volatile aroma constituents and non-volatile oxygen heterocyclic compounds (OHCs), consisting mostly of polymethoxyflavones, coumarins, and furocoumarins. The latter have long been investigated for their phototoxic properties, and their safety as cosmetic product ingredients has been debated recurrently. To this concern, twelve commercial Citrus-scented products were investigated in this study. An extraction method was optimized for thirty-seven OHC compounds, obtaining absolute mean recovery values in the 73.5–116% range with only few milliliters of solvent consumption. Analysis by ultra-high-pressure liquid chromatography with tandem mass spectrometry detection evidenced that three samples did not conform to the labeling requirements for fragrance allergens (coumarin) laid down by the European Union Regulation on Cosmetic Products. The total furocoumarin (FC) content of the samples investigated was in the 0.003–3.7ppm range, with some noteworthy exceptions. Specifically, in two samples, the total FCs were quantified as 89 and 219 ppm, thus exceeding the safe limits recommended up to a factor of 15. Finally, the consistency of the volatile fingerprint attained by gas chromatography allowed drawing conclusions on the authenticity of the Citrus fragrances labeled, and several products did not conform to the information reported on the label concerning the presence of essential oils. Besides the issue of product authenticity, analytical tools and regulatory actions for widespread testing of hand hygiene products are urgent, to protect consumers' health and safety. [ABSTRACT FROM AUTHOR]

Recently, supercritical fluid chromatography coupled to mass spectrometry has gained attention as a fast and useful technology applied to the carotenoids analysis. However, no reports are available in the literature on the direct online extraction and determination by supercritical fluid extraction with chromatography and mass spectrometry. The aim of this research was the development of an online method coupling supercritical fluid extraction and supercritical fluid chromatography for a detailed targeted native carotenoids characterization in red habanero peppers. The online nature of the system, compared to offline approaches, improves run-to-run precision, enables the setting of batch-type applications, and reduces the risks of sample contamination. The extraction has been optimized using different temperatures, starting from 40°C up to 80°C. Multiple extractions, until depletion, were performed on the same sample to evaluate the extraction yield. The range of the first extraction yield, carried out at 80°C, which was the best extraction temperature, was 37.4–65.4%, with a %CV range of 2–12. Twenty-one targeted analytes were extracted and identified by the developed methodology in less than 17 min, including free, monoesters, and diesters carotenoids, in a very fast and efficient way. Quantification of the β-carotene was carried out by using the optimized conditions. [ABSTRACT FROM AUTHOR]

Polyphenols are a class of plant secondary metabolites that are recently drawing a special interest because of their broad spectrum of pharmacological effects. As they are characterized by an enormous structural variability, the identification of these molecules in food samples is a difficult task, and sometimes having only a limited number of commercially available reference materials is not of great help. One-dimensional liquid chromatography is the most widely applied analytical approach for their analysis. In particular, the hyphenation of liquid chromatography to mass spectrometry has come to play an influential role by allowing relatively fast tentative identification and accurate quantification of polyphenolic compounds at trace levels in vegetable media. However, when dealing with very complex real-world food samples, a single separation system often does not provide sufficient resolving power for attaining rewarding results. Comprehensive two-dimensional liquid chromatography is a technique of great analytical impact, since it offers much higher peak capacities than separations in a single dimension. In the present review, we describe applications in the field of comprehensive two-dimensional liquid chromatography for polyphenol analysis in real-world food samples. Comprehensive two-dimensional liquid chromatography applications to nonfood matrices fall outside the scope of the current report and will not be discussed. [ABSTRACT FROM AUTHOR]

In this work, a comprehensive two-dimensional liquid chromatography system, comprised of a ZIC-HILIC and C18 columns in the first and second dimensions, respectively, was tuned and employed for attaining high resolution profiles of the polyphenolic pattern in seven commercial berry juices. The developed HILIC × RP-LC method was validated in terms of linearity range, correlation coefficients, limit of detection, limit of quantification, precision (intra- and inter-day), and recovery. A total of 104 polyphenolic compounds belonging to different chemical classes (hydroxybenzoic and cinnamic acid derivatives, flavone glycosides, flavonols, flavonol glycosides, dihydroflavonols, and anthocyanin glycosides) have been characterized and quantified in the juices investigated. Despite the constituents being similar, a notable quantitative variation among the analyzed berry species was observed. Elderberry contained the highest amount of polyphenols (918 ± 1.10 mg 100 mL−1), followed by chokeberry (516 ± 0.08 mg 100 mL−1). On the other hand, raspberry contained the lowest amount (104 ± 1.21 mg 100 mL−1). Further, total phenolic, flavonoid, and anthocyanin contents were determined spectrophotometrically, yielding consistent results. The free-radical scavenging activity (DPPH test) and reducing power of the juices, expressed as IC50 (μL mL−1) and mg ASE mL−1, varied from 2.79 ± 0.03 (honeyberry) to 31.66 ± 0.02 (blueberry) and from 1.71 ± 0.01 (blueberry) to 8.89 ± 0.12 (chokeberry), respectively. Such a ZIC-HILIC × C18 platform based on focusing modulation, never employed so far for berry juices, showed a remarkable separation capability with high values of corrected peak capacity (up to 1372) and orthogonality (Ao up to 0.80), thus providing a great applicability to be advantageously employed for other complex food samples. [ABSTRACT FROM AUTHOR]

The present study aimed to characterize the chemical composition and evaluate the antioxidant and antibacterial activities along with the absorption, distribution, metabolism, excretion, toxicity (ADMET) study of the essential oil of Ziziphora hispanica (ZH-EO), collected from the Middle Atlas of Morocco (Boulmane). Results showed that a total of 119 volatile components, characterized by GC-FID and GC-MS analysis, which represents the 88.7% of the total of ZH-EO. ZH-EO displayed a bactericidal effect against Listeria monocytogenes, Pseudomonas aeruginosa and Enterococcus faecalis, and a bacteriostatic effect against Staphylococcus aureus. Furthermore, ZH-EO exhibited strong antioxidant activity against DPPH radical (IC50 = 1.3 mg/mL). The ADMET prediction showed good pharmacokinetic properties of the tested components. The findings obtained from this study suggest that Ziziphora hispanica essential oil could represent a source of bioactive molecules with antioxidant and antibacterial potential in the prevention against diseases related to oxidative stress and pathogenic bacteria. [ABSTRACT FROM AUTHOR]

The present contribution is focused on the evolution and current trends of comprehensive two-dimensional gas chromatography-mass spectrometry (GC × GC-MS), with respect to a review that described this specific methodology published at the beginning of 2008 (Mondello et al., 2008). In fact, since then there has been considerable evolution in the MS field, certainly exceeding that observed in GC × GC. In particular, the present paper will cover the combination of novel MS machines [single quadrupole (Q) and triple quadrupole, isotope ratio, low- and high-resolution time-of-flight (ToF), hybrid (Q-ToF)] to GC × GC systems, and will position comprehensive two-dimensional gas chromatography within the wider context of separation science. © 2014 Wiley Periodicals, Inc. Mass Spec Rev 35:524-534, 2016 [ABSTRACT FROM AUTHOR]

Pigments were extracted from cheese-ripening bacteria belonging to the species Arthrobacter arilaitensis , which plays a role in the colour of cheese. A chromatographic method was applied to characterise the pigment profile. Based on the UV–visible (UV–vis) spectra, the mass spectra, and the elution order, eight different carotenoids were identified from the strains. Four of the pigments, namely, all- E -decaprenoxanthin, all- E -sarcinaxanthin, 9- Z -decaprenoxanthin and 15- Z -decaprenoxanthin, which were present as free-form main carotenoids (i.e., non-glycosylated), have been characterised by their UV–vis and mass spectra, both in atmospheric-pressure chemical ionisation negative [APCI (−)] and positive modes. The other minor carotenoids, namely, sarcinaxanthin monoglucoside pentaacetate, decaprenoxanthin monoglucoside, decaprenoxanthin diglucoside, decaprenoxanthin-C16:0 (decaprenoxanthin-palmitate), present in very low amounts, were only detected in the APCI (−) ionisation mode. Our results provide the first chemical characterisation of the pigments produced by cheese-ripening A. arilaitensis strains, which has not previously been reported. [ABSTRACT FROM AUTHOR]

[Display omitted] Pesticide residues in food products are a critical issue concerning food safety. Recent studies have increasingly focused on developing selective, rapid, innovative, and environmentally friendly analytical methods for detecting pesticides in foodstuffs. This study presents a novel analytical method utilizing comprehensive two-dimensional liquid chromatography-tandem mass spectrometry for the simultaneous determination of one hundred and thirteen multiclass pesticides in corn products. The method simplifies the process with a single-step solid–liquid extraction and benefits from two-dimensional separation to enhance resolution and minimize matrix effects. The methodology was validated according to European Commission DG-SANTE (SANTE/11312/2021) and European Committee for Standardization (EN 15662, 2018) guidelines, obtaining acceptable analytical parameters. Limits of detection ranged from 0.2 µg/L to 30.2 µg/L and limits of quantification from 0.3 to 91.6 μg/L, all bellow regulatory limits. Accuracy, ranged from 60 to 120 % and precision, estimated by relative standard deviation, was consistently below 15.1 % in all cases. The applicability of the method was demonstrated by analyzing pesticides in five representative corn products (tortilla, corn flakes, corn cake, starch, and polenta). Sixteen pesticides were detected, all within the regulatory residue limits. Three metric tools were applied to assess the analytical process. Environmental sustainability was evaluated using the AGREE metric, while analytical performance and method applicability were assessed with the Red-Green-Blue and Blue Applicability Grade Index models, respectively, yielding promising scores (0.5, ≥ 0.55, and 0.65). These findings and the comparison to previous methods indicated that this approach represents a promising, alternative and user-friendly strategy for pesticide determination, offering effective productivity and reliable analytical performance. [ABSTRACT FROM AUTHOR]

The aim of the present work was to study the chemical composition and to evaluate, in vitro, the antibacterial, antioxidant and insecticidal properties of the essential oil obtained from Tetraclinis articulata (Vahl) (Cupressaceae) masters cones collected from the eastern region of Morocco. GC-MS and GC-FID analyses of essential oil of T. articulata cones (TA-EO) led to the characterization of 57 components, representing 91.1% of the total volatile fraction of TA-EO. The TA-EO had a bactericidal effect against all clinical multidrug bacteria. Furthermore, TA-EO displayed strong antioxidant capacity against DPPH radical. Fumigation bioassays showed that TA-EO exhibits strong toxic effect against Sitophilus granarius and Tribolium confusum. The results obtained from this study indicate that essential oil of T. articulata masters cones is promising as a source of natural antioxidant, insecticide and antibiotic can be used in the pharmaceutical and agriculture fields. [ABSTRACT FROM AUTHOR]