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Nowadays, there is a global concern over water quality and the impact of contamination on both natural ecosystems and human well-being. Plastics, ubiquitous in modern life, may release harmful chemicals when they reach aquatic environments. Among them, bisphenol A (BPA) and its alternatives, such as bisphenol S (BPS), bisphenol F (BPF), and others, are of special concern because their presence in water systems can have detrimental effects on human health and aquatic organisms due to their endocrine-disrupting properties. This study explores the potential of terpenoids, sustainable and environmentally friendly solvents, for efficiently removing bisphenols from contaminated environmental water. Using an in silico approach based on the Conductor-like Screening Model for Realistic Solvents (COSMO-RS) theory, more than 30 terpenoids were screened, and carvone was found to be an excellent candidate due to its high solvent capacity and low toxicity. The impact of pH, temperature, stirring conditions, and sample:extractant phase ratios on the extraction efficiency were investigated. A design of experiments revealed optimal conditions for the extraction process and demonstrated that carvone can effectively extract bisphenols (nearly 100 % for most of them) under a wide range of conditions, showing the robustness and efficiency of the extraction method, even in environmental samples. The paper provides valuable insights into the potential of terpenoids, specifically carvone, as a sustainable and eco-friendly solvent for removing bisphenol contaminants from environmental water bodies. The findings of this study offer a promising solution to address water contamination issues, aligning with the principles of Green Chemistry and contributing to a more environmentally responsible approach to water remediation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Aliphatics prevail in asteroids, comets, meteorites and other bodies in our solar system. They are also found in the interstellar and circumstellar media both in gas-phase and in dust grains. Among aliphatics, linear alkanes (n-C n H 2n+2 ) are known to survive in carbonaceous chondrites in hundreds to thousands of parts per billion, encompassing sequences from CH 4 to n-C 31 H 64 . Despite being systematically detected, the mechanism responsible for their formation in meteorites has yet to be identified. Based on advanced laboratory astrochemistry simulations, we propose a gas-phase synthesis mechanism for n-alkanes starting from carbon and hydrogen under conditions of temperature and pressure that mimic those found in carbon-rich circumstellar envelopes. We characterize the analogs generated in a customized sputter gas aggregation source using a combination of atomically precise scanning tunneling microscopy, non-contact atomic force microscopy and ex-situ gas chromatography-mass spectrometry. Within the formed carbon nanostructures, we identify the presence of n-alkanes with sizes ranging from n-C 8 H 18 to n-C 32 H 66 . Ab-initio calculations of formation free energies, kinetic barriers, and kinetic chemical network modelling lead us to propose a gas-phase growth mechanism for the formation of large n-alkanes based on methyl-methylene addition (MMA). In this process, methylene serves as both a reagent and a catalyst for carbon chain growth. Our study provides evidence of an aliphatic gas-phase synthesis mechanism around evolved stars and provides a potential explanation for its presence in interstellar dust and meteorites., (© 2024. The Author(s).)

Prebiotics are known for their health-promoting functions associated with the modulation of the colonic microbiota and the products of fermentation. Recently, single-pot syntheses of galactooligosaccharides in combination with steviol glycosides (mSG-GOS) have been developed. This work was conducted to evaluate their prebiotic effect by using faecal inoculum from healthy human donors during in vitro batch fermentations. Additionally, their relative sweetness was evaluated to determine their suitability as food ingredients. The results showed a significant growth (p < 0.05) of bacteria, including the genera Bifidobacterium, Bacteroides and Clostridium, and a corresponding increase in short-chain fatty acids (SCFA) in comparison to either positive and negative controls. The sweetness equivalence to 1 % w:v of SG-GOS was 0.8 % w:v when compared to sucrose. Considering the bacteria and organic acids analyses and their sweetness values of these new biosynthesized compounds, SG-GOS could act as a prebiotic sweetener with potential health benefits warranting further evaluation through human studies., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

This study was conducted to investigate the sweetness intensity and the potential fecal microbiome modulation of galactooligosaccharides in combination with enzymatically modified mogrosides (mMV-GOS), both generated through a patented single-pot synthesis. Sweetness intensity was performed in vivo by trained sensory panelists. The impact on the human fecal microbiome was evaluated by in vitro pH-controlled batch fermentation, and bacterial populations and organic acid concentrations were measured by qPCR and GC-FID, respectively. Significant growth ( p ≤ 0.05) during the fermentation at 10 h of bacterial populations includes Bifidobacterium (8.49 ± 0.44 CFU/mL), Bacteroides (9.73 ± 0.32 CFU/mL), Enterococcus (8.17 ± 0.42 CFU/mL), and Clostridium coccoides (6.15 ± 0.11 CFU/mL) as compared to the negative control counts for each bacterial group (7.94 ± 0.27, 7.84 ± 1.11, 7.52 ± 0.37, and 5.81 ± 0.08 CFU/mL, respectively) at the same time of fermentation. Likewise, the corresponding significant increase in production of SCFA in mMV-GOS at 10 h of fermentation, mainly seen in acetate (20.32 ± 2.56 mM) and propionate (9.49 ± 1.44 mM) production compared to a negative control at the same time (8.15 ± 1.97 and 1.86 ± 0.24 mM), is in line with a positive control (short-chain fructooligosaccharides; 46.74 ± 12.13 and 6.51 ± 1.91 mM, respectively) revealing a selective fermentation. In conclusion, these substrates could be considered as novel candidate prebiotic sweeteners, foreseeing a feasible and innovative approach targeting the sucrose content reduction in food. This new ingredient could provide health benefits when evaluated in human studies by combining sweetness and prebiotic fiber functionality.

Development of sustainable processes for hydrocarbons synthesis is a fundamental challenge in chemistry since these are of unquestionable importance for the production of many essential synthetic chemicals, materials and carbon-based fuels. Current industrial processes rely on non-abundant metal catalysts, temperatures of hundreds of Celsius and pressures of tens of bars. We propose an alternative gas phase process under mild reaction conditions using only atomic carbon, molecular hydrogen and an inert carrier gas. We demonstrate that the presence of CH 2 and H radicals leads to efficient C-C chain growth, producing micron-length fibres of unbranched alkanes with an average length distribution between C 23 -C 33 . Ab-initio calculations uncover a thermodynamically favourable methylene coupling process on the surface of carbonaceous nanoparticles, which is kinematically facilitated by a trap-and-release mechanism of the reactants and nanoparticles that is confirmed by a steady incompressible flow simulation. This work could lead to future alternative sustainable synthetic routes to critical alkane-based chemicals or fuels., (© 2021. The Author(s).)

A comprehensive study on packaging used in commercially available milk products from Spanish markets has been presented. Concentrations of four phthalates, seven parabens and BPA were determined in forty-two milk products. Eleven brands and five types of packaging (metallic aluminium bag, carton, high-density polyethylene, metal pail and polyethylene terephthalate) were included in the study. BPA showed the lowest concentrations (8.3 pg/g f.w.), far below those of phthalates (6431 pg/g f.w.) and parabens (6234 pg/g f.w.). Metallic aluminium bags were the least migrating packaging (considering plasticisers and monomers) followed by HDPE bottles, in the case of phthalates. Parabens showed their highest concentrations for fresh-milk samples. Levels found were far below the specific migration limits established by the EU and the cumulative hazard index was lower than 1, indicating that adverse health effects were not expected. In general, the results found in Spanish samples were lower than those reported in other countries., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Luo Han Guo fruit extract ( Siraitia grosvenorii ), mainly composed of mogroside V (50%), could be considered a suitable alternative to free sugars; however, its commercial applications are limited by its unpleasant off-notes. In the present work, a central composite design method was employed to optimize the transglycosylation of a mogroside extract using cyclodextrin glucosyltransferases (CGTases) from three different bacteriological sources ( Paenibacillus macerans , Geobacillus sp., and Thermoanaerobacter sp.) considering various experimental parameters such as maltodextrin and mogroside concentration, temperature, time of reaction, enzymatic activity, and pH. Product structures were determined by liquid chromatography coupled to a diode-array detector (LC-DAD), liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS), and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). Sensory analysis of glucosylated mogrosides showed an improvement in flavor attributes relevant to licorice flavor and aftereffect. Consequently, an optimum methodology was developed to produce new modified mogrosides more suitable when formulating food products as free sugar substitutes.

To improve flavor profiles, three cyclodextrin glucosyltransferases (CGTases) from different bacteriological sources, Paenibacillus macerans , Geobacillus sp. and Thermoanaerobacter sp., were used with an extract of steviol glycosides (SVglys) and rebaudioside A (RebA) as acceptor substrates in two parallel sets of reactions. A central composite experimental design was employed to maximize the concentration of glucosylated species synthesized, considering temperature, pH, time of reaction, enzymatic activity, maltodextrin concentration and SVglys/RebA concentration as experimental factors, together with their interactions. Liquid chromatography coupled to a diode-array detector (LC-DAD), liquid chromatography-mass spectrometry (LC-ESI-MS) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) were used to characterize and identify the chemical structures obtained along the optimization. To assess the impact on the sensory properties, a sensory analysis was carried out with a group of panelists that evaluated up to 16 sensorial attributes. CGTase transglucosylation of the C-13 and/or C-19 led to the addition of up to 11 glucose units to the steviol aglycone, which meant the achievement of enhanced sensory profiles due to a diminution of bitterness and licorice appreciations. The outcome herein obtained supposes the development of new potential alternatives to replace free sugars with low-calorie sweeteners with added health benefits.

This paper reports the development of an LC-ESI-MS 2 method for the sensitive determination of hydroxylated polychlorinated biphenyls (OH-PCBs) in human serum samples. Congener-specific separation was achieved by using a polar-embedded stationary phase, previously optimized for the working group, which provided better separation of isobaric compounds than the common octadecylsilane phases. MS fragmentation patterns and energies showed differences among OH-PCB congeners, mainly depending on the position of OH-group and the number of chlorine atoms in the molecule, although the most intense transitions were always those corresponding to the neutral loss of an HCl group from the quasi-molecular ion cluster. The method allowed the determination of OH-PCBs with good linearity (dynamic linear range of four orders of magnitude with R 2 higher than 0.995) and precision (relative standard deviations of absolute areas lower than 10%), and with better sensitivity than other similar methods previously described in the literature. Matrix effect has been evaluated and reduced to less than 10% by the addition of isotopically labeled standards and a 10-fold dilution of the final sample extract. The low iLODs provided by the developed method (from 1.2 to 5.4 fg µL -1 for all the OH-PCBs studied, except 4'-OHCB108, whose iLOD was 61 fg µL -1 ) allows dilution without losses of detected peaks. Finally, the applicability of the method has been demonstrated by analyzing human serum samples belonging to an interlaboratory exercise., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Atmospheric iodine plays a relevant role in climate change. Bearing in mind that most of this iodine comes from the oceans, analytical methods capable of determining iodine in a challenging matrix as seawater are necessary. In this work, the first method capable of direct determination of total inorganic iodine in seawater at subnanomolar level based on mixed-mode liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) without any sample treatment is presented. Analytical characteristics of the developed method were studied in terms of linear range, limits of detection and quantification, precision, trueness, matrix effect, and robustness. The detection limit for iodide was as low as 0.16 nM, injecting 5 μL of seawater without any sample treatment and the working linear range of four orders of magnitude was wide enough to cover the broad concentration range observed in seawater samples. Average values for repeatability and intermediate precision were 4.1% and 8.1%, respectively. The suitability of the method was demonstrated through its application to the analysis of several types of samples, including seawater samples taken at different locations along the Spanish Mediterranean coast and some domestic iodized salts. According to the results obtained, the method developed is rapid, easy to apply and to be automated, avoids sample treatment and requires only few microliters of sample. Furthermore, it has a low detection limit and allows the quantification of inorganic iodine over a wide concentration range., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Apart from alkaloids, bioactive properties of Uncaria tomentosa L. have been attributed to its phenolic constituents. Although there are some reports concerning low-molecular-weight polyphenols in U. tomentosa , its polymeric phenolic composition has been scarcely studied. In this study, phenolic-rich extracts from leaves, stems, bark and wood ( n = 14) of Uncaria tomentosa plants from several regions of Costa Rica were obtained and analysed in respect to their proanthocyanidin profile determined by a quadrupole-time-of-flight analyser (ESI-QTOF MS). Main structural characteristics found for U. tomentosa proanthocyanidins were: (a) monomer composition, including pure procyanidins (only composed of (epi)catechin units) and propelargonidins (only composed of (epi)afzelechin units) as well as mixed proanthocyanidins; and (b) degree of polymerization, from 3 up to 11 units. In addition, U. tomentosa phenolic extracts were found to exhibit reasonable antioxidant capacity (ORAC (Oxygen Radical Absorbance Capacity) values between 1.5 and 18.8 mmol TE/g) and antimicrobial activity against potential respiratory pathogens (minimum IC 50 of 133 µg/mL). There were also found to be particularly cytotoxic to gastric adenocarcinoma AGS and colon adenocarcinoma SW620 cell lines. The results state the particularities of U. tomentosa proanthocyanidins and suggest the potential value of these extracts with prospective use as functional ingredients.

Sulfatides are sulfoglycolipids found in the myelin sheath. The composition ratio of sulfatide molecular species changes with age, and it has also been associated with the pathogenesis of various human central nervous system diseases. However, profiling sulfatides in biological samples is difficult, due to the great variety of molecular species. In this work, a new, easy and reliable liquid chromatography-electrospray tandem mass spectrometry (LC-ESI(+)-MS/MS) method has been developed to profile sulfatide content in biological samples of myelin. The 'wrong-way-round' ionization effect has been described for this type of molecules for the first time, making it possible to correctly identify as many as 37 different sulfatides in mouse brain myelin samples, including molecules with different fatty acid chain lengths and varying degrees of unsaturation and hydroxylation. A chemometric analysis of their relative abundances showed that the main difference among individuals of different ages was the content of sulfatides with odd-numbered fatty acid chains, in addition to hydroxylated species., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Although qualitative strategies based on direct injection mass spectrometry (DIMS) have recently emerged as an alternative for the rapid classification of food samples, the potential of these approaches in quantitative tasks has scarcely been addressed to date. In this paper, the applicability of different multivariate regression procedures to data collected by DIMS from simulated mixtures has been evaluated. The most relevant factors affecting quantitation, such as random noise, the number of calibration samples, type of validation, mixture complexity and similarity of mass spectra, were also considered and comprehensively discussed. Based on the conclusions drawn from simulated data, and as an example of application, experimental mass spectral fingerprints collected by direct thermal desorption coupled to mass spectrometry were used for the quantitation of major volatiles in Thymus zygis subsp. zygis chemotypes. The results obtained, validated with the direct thermal desorption coupled to gas chromatography-mass spectrometry method here used as a reference, show the potential of DIMS approaches for the fast and precise quantitative profiling of volatiles in foods.This article is part of the themed issue 'Quantitative mass spectrometry'., (© 2016 The Author(s).)

A rapid and sensitive analytical method for the simultaneous determination of thirteen endocrine disruptors (five phthalates, seven parabens, and bisphenol A) in a single chromatographic run has been developed for the first time. The separation method, based on ultra-high performance liquid chromatography (UHPLC), allows the separation of all compounds (including isobaric pairs) in less than 4.1 min. The fast polarity switching mode of the triple quadrupole mass spectrometer used enables the registration of positive (phthalates) and negative (parabens and BPA) ions in the same acquisition run. A Response Surface Methodology was used for the optimization of the method. The optimum elution program starts with 0.2 min in isocratic conditions (79.8% water; 20% acetonitrile, 0.2% ammonium formate 5mM at pH 10.2), then the content of acetonitrile is linearly increased in 2 min up to 42%, and later up to 98% in 1.1 min. The analytical characteristics of the developed method were satisfactory. The method is robust and showed a linear response with determination coefficients (R(2)) higher than 0.991 in the range 5.0-2000 pg on column (or higher) for all the compounds investigated. Instrumental intra- and inter-day precision (expressed as relative standard deviation) were lower than 12% for parabens and bisphenol A, and between 5.9% and 27% for phthalates. Instrumental detection and quantification limits (iLODs and iLOQs) were in the range of medium-high femtograms (270-1300 pg on column for iLODs). Finally, the suitability of the developed method was demonstrated through its application to the analysis of commercial personal care products (shower gels) without any sample treatment, only a simple dilution, being possible to determine the simultaneous presence of phthalates, parabens, and bisphenol A in almost all the gels analyzed., (Copyright © 2015 Elsevier B.V. All rights reserved.)

The retention behavior of nine MPAEs has been studied, using commercial LC columns with octadecylsilane (ODS), phenyl, and amide-type SPs. First, it was found that the use of methanol in the mobile phase is not advisable, because induce a transesterification reaction of MPAEs in the electrospray ion source, regardless of the SP used. On the other hand, different responses were observed when representing the logarithm of retention factors (k) vs. the volume fraction of ACN (φ) in the mobile phase, for the three SPs tested. A quite linear trend was obtained for ODS (at φ values below 0.80) and Phenyl columns. On the contrary, the Amide column shows a striking U-shape trend, typical of both hydrophobic and hydrophilic retention mechanisms. Therefore, the separation process was mainly hydrophobic in the ODS and phenyl SPs, but in the amide-type a dual retention mechanism was found, showing zones with predominant hydrophobic or hydrophilic interactions, depending on both the compound and the experimental conditions. A high content of acetonitrile (>75%) and low concentration of formic acid in the mobile phase promote the hydrophilic separation mechanism for MPAEs on the amide SP. So, this dual separation mechanism can be modulated modifying the pH and content of organic modifier in the mobile phase, allowing greater flexibility to develop improved methods. Taking advantage of this, a separation method was optimized in this amide column using a Box-Wilson Central Composite experimental design, which allows separating the studied MPAEs with a time-saving of around 40% comparing to the conventional phenyl SP., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A method by hydrophilic interaction liquid chromatography coupled to tandem mass spectrometry (HILIC-MS(2)) has been successfully developed for the simultaneous analysis of bioactive iminosugars and other low molecular weight carbohydrates in Aglaonema leaf extracts. Among other experimental chromatographic conditions, mobile phase eluents, additives and column temperature were evaluated in terms of retention time, resolution, peak width and symmetry provided for target carbohydrates. In general, narrow peaks (wh: 0.2-0.6min) with good symmetry (As: 0.9-1.3) and excellent resolution (Rs>1.8) were obtained for iminosugars using an acetonitrile:water gradient with 5mM ammonium acetate in both eluents at 55°C. Tandem mass spectra were used to confirm the presence of previously detected iminosugars in Aglaonema extracts and to tentatively identify for the first time others such as miglitol isomer, glycosyl-miglitol isomers and glycosyl-DMDP isomers. Concentration of total iminosugars varied from 1.35 to 2.84mgg(-1) in the extracts of the different Aglaonema samples analyzed. To the best of our knowledge, this is the first time that a HILIC-MS(2) method has been proposed for the simultaneous analysis of iminosugars and other low molecular weight carbohydrates of Aglaonema sp. extracts., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Phthalates (PAEs) are ubiquitous toxic chemical compounds. During the last few years, some phthalate metabolites (MPAEs) have been proposed as appropriate biomarkers in human urine samples to determine PAE human intake and exposure. So, it is necessary to have fast, easy, robust and validated analytical methods to determine selected MPAEs in urine human samples. Two different instrumental methods based on gas (GC) and ultra-high performance liquid (UHPLC) chromatography coupled to mass spectrometry (MS) have been optimized, characterized and validated for the simultaneous determination of nine primary and secondary phthalate metabolites in urine samples. Both instrumental methods have similar sensitivity (detection limits ranged from 0.03 to 8.89 pg μL(-1) and from 0.06 to 0.49 pg μL(-1) in GC-MS and UHPLC-MS(2), respectively), precision (repeatability, expressed as relative standard deviation, which was lower than 8.4% in both systems, except for 5OH-MEHP in the case of GC-MS) and accuracy. But some advantages of the UHPLC-MS(2) method, such as more selectivity and lower time in the chromatographic runs (6.8 min vs. 28.5 min), have caused the UHPLC-MS(2) method to be chosen to analyze the twenty one human urine samples from the general Spanish population. Regarding these samples, MEP showed the highest median concentration (68.6 μg L(-1)), followed by MiBP (23.3 μg L(-1)), 5cx-MEPP (22.5 μg L(-1)) and MBP (19.3μgL(-1)). MMP (6.99 μg L(-1)), 5oxo-MEHP (6.15 μg L(-1)), 5OH-MEHP (5.30 μg L(-1)) and MEHP (4.40 μg L(-1)) showed intermediate levels. Finally, the lowest levels were found for MBzP (2.55 μg L(-1)). These data are within the same order of magnitude as those found in other similar populations., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Iminosugars are considered potential drug candidates for the treatment of several diseases, mainly as a result of their α-glycosidase inhibition properties. A method by hydrophilic interaction liquid chromatography tandem mass spectrometry has been optimized for the first time for the simultaneous determination of complex mixtures of bioactive iminosugars and other low molecular weight carbohydrates (LMWC) in vegetable extracts. Three hydrophilic stationary phases (sulfoalkylbetaine zwitterionic, polyhydroxyethyl aspartamide and ethylene bridge hybrid (BEH) with trifunctionally bonded amide) were compared under both basic and acidic conditions. The best sensitivity (limits of detection between 0.025 and 0.28ngmL -1 ) and overall chromatographic performance in terms of resolution, peak width and analysis time were obtained with the BEH amide column using 0.1% ammonium hydroxide as a mobile phase additive. The optimized method was applied to the analysis of extracts of hyacinth bulbs, buckwheat seeds and mulberry leaves. Iminosugar and other LMWC structures were tentatively assigned by their high resolution daughter ions mass spectra. Several iminosugars such as glycosyl-fagomine in mulberry extract were also described for the first time. Among the extracts analysed, mulberry showed the widest diversity of iminosugars, whereas the highest content of them was found in hyacinth bulb (2.5mgg -1 ) followed by mulberry (1.95 mgg -1 )., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The dependence of isothermal retention indices (I) on column temperature over a wide temperature range has been studied for solutes belonging to nine chemical functions on a capillary column coated with poly(100% dimethyl siloxane). I values for some solutes are reported for the first time on capillary columns. I values increased with increasing column temperature, with the exception of the linear alcohols and the esters, which decreased with increasing temperature, and of cyclobutanol, 2-butanone, 2-pentanone, 1-butylamine and 1-pentylamine that showed a well-defined minimum in the 358-377K range. Moreover, a minimum at the higher temperature range for longer and less polar solutes such as 1-nonanol was observed for the first time. The three trends of I vs. T were perfectly described by the extended model (I=a+bT(-1)+clnT). On the other hand, the dependence of I on the carbon atom number (z) of the solute was linear and with a slope of similar magnitude for all homologous series studied, except for the alicyclic compounds. For the latter, higher slope values and worse correlations were obtained, owing to their larger surface area and to the different conformations that they adopt in order to minimize the ring strain. In addition, due to its higher chain stiffness, an important influence of the column temperature on these slopes was observed., (Copyright © 2014 Elsevier B.V. All rights reserved.)

For the first time, four commercial ionic liquid columns (SLB-IL59, SLB-IL76, SLB-IL82 and SLB-IL100) for gas chromatography have been comprehensively evaluated in terms of efficiency, polarity and solvation properties. Grob tests and McReynolds constants showed that they were all high-efficiency columns of high polarity, but with low inertness to compounds with hydrogen bonding capabilities. The solvation parameter model was used to characterize the solvation interactions of the four columns in the 80-160°C temperature range. Results revealed that all the ionic liquids studied can be considered moderately hydrogen-bond acid and highly cohesive stationary phases, on which the dominant contributions to retention were the dipolar-type and hydrogen-bond base interactions, while π-π and n-π interactions were barely significant. The SLB-IL59 column provided the best separation of homologs, while the SLB-IL76 and SLB-IL100 columns had the most basic and the most acidic phases, respectively. A principal component analysis for the commonly used stationary phases in capillary GC showed that these commercial ionic liquid columns fill an empty area of the available selectivity space, which clearly enhances the separation capacity of this technique., (Copyright © 2013 Elsevier B.V. All rights reserved.)

An in vitro batch culture fermentation experiment was conducted with fecal inocula from three healthy volunteers in the presence and absence of a red wine extract. Changes in main bacterial groups were determined by FISH during a 48 h fermentation period. The catabolism of main flavonoids (i.e., flavan-3-ols and anthocyanins) and the formation of a wide a range of phenolic microbial metabolites were determined by a targeted UPLC-PAD-ESI-TQ MS method. Statistical analysis revealed that catechol/pyrocatechol, as well as 4-hydroxy-5-(phenyl)-valeric, 3- and 4-hydroxyphenylacetic, phenylacetic, phenylpropionic, and benzoic acids, showed the greatest increases in concentration during fermentation, whereas 5-(3'-hydroxyphenyl)-γ-valerolactone, its open form 4-hydroxy-5-(3'-hydroxyphenyl)-valeric acid, and 3,4-dihydroxyphenylacetic acid represented the largest interindividual variations in the catabolism of red wine polyphenols. Despite these changes, microbial catabolism did not produce significant changes in the main bacterial groups detected, although a slight inhibition of the Clostridium histolyticum group was observed.

Isothermal retention indices (I) of benzene, toluene, ethylbenzene, n-propylbenzene and n-butylbenzene were determined at 323-423 K on twelve WCOT capillary columns covering a broad stationary phase polarity spectrum. These I values have been tested carrying out a comparison with the NIST database values. The effect of the stationary phase polarity on I values was studied. But for the poly(3,3,3-trifluoropropylmethyl siloxane) column, a good linear correlation was found. At each temperature, the dependence on I of the alkyl chain length (z) attached to the ring of the n-alkylbenzenes was linear and of similar magnitude for the stationary phases of low to middle polarity, but lower for the more polar ones. Moreover, an important influence of the column temperature on the slope of the I vs. z plots was observed for the only non polysiloxane-type stationary phase studied, i.e., poly(ethylene glycol), due to its higher chain stiffness. Finally, different expressions describing the effect of the temperature on the retention index have been compared. I values of the n-alkylbenzenes in the 323-423 K range increase with increasing column temperature according to the Antoine-type (I=α+β(γ+T)(-1)) and the extended (I=a+bT(-1)+clnT) models. No significant differences were observed between them, except for the poly[70% bis(3-cyanopropyl) 30% dimethyl silphenylene-siloxane] column, for which the Antoine-type model was slightly better., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Introduction: Concentrations and congener profiles of polychlorinated biphenyls (PCBs) and their hydroxylated metabolites (OH-PCBs) in placenta samples from a Madrid population (Spain) are reported. Structure dependent retentions of OH-PCBs are known to occur in both humans and wildlife, making it of interest to assess placental transfer of both parent compounds and their metabolites to the developing foetus., Results: The ΣPCB concentrations found in placenta samples were in the range 943-4,331 pg/g fresh weight (f.w.), and their hydroxylated metabolites showed a 20-time lower concentration level (53-261 pg/g f.w.). The PCB profiles were surprisingly dominated by CB-52 and CB-101 accounting for more than 44% of the total PCB concentration. This is indicating a source of exposure that is not yet identified. The OH-PCB profiles were dominated by 4-OH-CB187 and 4-OH-CB146, representing >50% of the ΣOH-PCB concentration of the placenta samples. Statistical analysis of the data revealed strong correlations between the PCB congeners, among some OH-PCBs, and between OH-PCB metabolites with a meta- and para- substitution pattern. Both PCB and OH-PCB concentrations presented homogeneous distribution, what allowed the establishment of a partial least squares model that correlated the concentrations of OH-PCB with those of PCBs in placenta samples. In addition, causal correlations were observed between the concentrations of OH-PCBs and those of their corresponding PCB precursors.

This work addresses the characterization of phosphopeptides in bovine κ-casein macropeptide by reversed-phase liquid chromatography-electrospray ionization-tandem mass spectrometry (RPLC-ESI-MS(2)). Two different mass spectrometers, equipped with an ion trap (IT) or a quadrupole time-of-flight (Q-TOF) analyzer, were used to perform an accurate phosphorylation site assignment. A total of 8 phosphopeptides from 26 identified peptides were characterized. MS(2) spectra of phosphopeptides were dominated by the neutral loss of a phosphoric acid molecule (H(3)PO(4)) and sufficient informative fragment ions resulting from peptide backbone cleavages enabling the elucidation of the phosphopeptide sequence. A higher number of sequence informative b and y ions were detected using a Q-TOF instead of an IT analyzer. In addition to the well-established phosphorylation sites at Ser(149) and Ser(127), this study also revealed the presence of two minor phosphorylation sites at Thr(145) and Ser(166). These findings indicate that RPLC-ESI-MS(2) on a Q-TOF analyzer is a useful technique for identifying low-abundance phosphorylation sites in caseins.

A comparison of the most usual gas chromatographic methods for the calculation of partial molar enthalpies of solvation (Δ(sol)H(o)) has been carried out. Those methods based on the fitting of lnV(g) or ln(k/T) vs. 1/T and ln(k/T) vs. (1/T and the temperature arrangement, T(a)) are the most adequate ones for obtaining Δ(sol)H(o) values. However, the latter is the only reliable option for Δ(sol)H(o) estimation when commercial WCOT capillary columns are used, since in this case the estimation of some variables involved in the V(g) determination is less accurate or even impossible. Consequently, in this paper, Δ(sol)H(o) obtained from ln(k/T) vs. (1/T+T(a)) fitting at 373.15 and 298.15K for n-alkanes and n-alkylbenzenes on 12 commercial capillary columns coated with stationary phases covering the 203-3608 McReynolds polarity range are reported. Moreover, molar heat capacities of solvation at constant pressure (Δ(sol)C(p)(o)) have also been calculated using this method. A clear influence on Δ(sol)H(o) of the type and content of the substitution group in the stationary phase was observed. In addition, a linear relationship of Δ(sol)C(p)(o) with the van der Waals volume of the n-alkanes and the temperature gradient of density of the stationary phase was found. The effect of the size of the hydrocarbon on both thermodynamic variables was also investigated., (Copyright © 2010 Elsevier B.V. All rights reserved.)

Traditionally, the determination of hydroxylated polychlorinated biphenyls (OH-PCBs) has been carried out by gas chromatography (GC). However, the gas chromatographic behavior and sensitivity of this type of hydroxylated compounds are not always satisfactory, hence a prior derivatization of the OH-PCBs must be performed. Therefore, the development of liquid chromatographic methods should prove to be a very interesting task aimed at dealing with the instrumental determination of OH-PCBs. Taking into account that octadecylsilane stationary phases are not the most adequate for the separation of isobaric compounds, an amide-type column has been tested. For the development of the method, the Response Surface Methodology was used, based on a Box-Wilson Central Composite experimental design. The initial content of methanol in the mobile phase, the gradient time, and the concentration and the pH value of the buffer were chosen as relevant experimental parameters. A global optimum was obtained by selecting the elution time, the sensitivity and the overall resolution as responses to optimize. The developed method for liquid chromatography presented a very good resolution and sensitivity, and a reasonably short analysis time. In addition, a retention study was conducted in order to survey the different interactions that take place in the separation process, showing that hydrogen bonding is the main interaction between OH-PCBs and the amide-type stationary phase. However, a substantial contribution of dispersion forces was present in methanol contents in the mobile phase below 65%. Besides, the pH value of the mobile phase was found to be the most important parameter to control the hydrogen bond forces and therefore, to regulate the OH-PCBs separation., (Copyright © 2010 Elsevier B.V. All rights reserved.)

Sialylated O-linked oligosaccharides are involved in many biological processes, such as cell-cell interactions, cell-substance adhesion, and virus-host interactions. These activities depend on their structure, which is frequently determined by tandem mass spectrometry. However, these spectra are frequently analyzer-dependent, which makes it difficult to develop widely applicable analytical methods. In order to deepen the origin of this behavior, two couples of isomers of sialylated O-linked oligosaccharides, NeuAc alpha2-3Gal beta1-3GalNAc-ol/Gal beta1-3(NeuAc alpha2-6)GalNAc-ol and NeuGc alpha2-3Gal beta1-3GalNAc-ol/Gal beta1-3(NeuGc alpha2-6)GalNAc-ol, were analyzed by liquid chromatography/negative electrospray ionization ion trap tandem mass spectrometry (LC/ESI(-)-MS(n)) using both an ion trap and a triple quadrupole mass spectrometer. Results clearly showed that while ions obtained in the triple quadrupole instrument fitted very well with the standard fragmentation routes, in the ion trap several intense ions could not be explained by these rules, specially a fragment at m/z 597. Furthermore, this ion was observed in the mass spectrum of those isomers that sialic acid binds to GalNAc by an alpha2-6 linkage. From the MS(3) spectrum of this ion an unexpected structure was deduced, and it led to propose alternative fragmentation pathways. Molecular mechanics calculations suggested that the found atypical route could be promoted by a hydrogen bond located only in alpha2-6-linked oligosaccharides. It has also been demonstrated that this process follows a slow kinetic, explaining why it cannot be observed using an ion beam-type mass analyzer. In conclusion, ion traps seem to be more appropriate than triple quadrupoles to develop a reliable analytical method to distinguish between isomeric O-linked glycans., (2010 John Wiley & Sons, Ltd.)

Proanthocyanidins or condensed tannins are among the most abundant polyphenols compounds in our diet and may play a key role in the prevention of cardiovascular and neurodegenerative diseases and cancer. These antioxidants are widely distributed in the plant kingdom both in food plants and in non-food plants. The biological activity of plant proanthocyanidins depends on their chemical structure and concentration. However, due to their structural diversity and complexity, the qualitative and quantitative analysis of proanthocyanidins is a difficult task. Mass spectrometry has enabled great advances in the characterization of plant proanthocyanidins. Among these techniques, MALDI-TOF MS has proved to be highly suited for the analysis of highly polydisperse and heterogeneous proanthocyanidins. The objective of the present paper was to assess the potential, limitations and future challenges of the analysis of plant proanthocyanidins by MALDI-TOF MS techniques. Firstly, the fundamental of this technique, including modes of operation, advantages and limitations, as well as quantitative and qualitative operations, have been summarized. Applications of MALDI-TOF analysis to plant proanthocyanidins reported in the last decade (1997-2008) have been extensively covered, including the sample preparation protocols and conditions used for proanthocyanidin analysis, as well as the main findings regarding the determination of the structural features of different plant proanthocyanidin types (procyanidins, propelargonidins, prodelphinidins, profisetinidins and prorobinetinidins). Finally, attempts in the assessment of the molecular weight distribution of proanthocyanidins by MALDI-TOF are described.

This article describes a comprehensive characterization of bovine beta-lactoglobulin peptides glycated with an aldohexose (galactose) or a ketohexose (tagatose), derived from in vitro gastrointestinal digestion, by liquid chromatography coupled to positive electrospray ion trap tandem mass spectrometry. In addition to the dissociation pathway previously described for aldohexoses-derived Amadori compounds, i.e. formation of the pyrylium ([M+H](+)-54) and furylium ions ([M+H](+)-84) via the oxonium ion ([M+H](+)-18), another and more direct fragmentation route involving the formation of the imminium ion ([M+H](+)-150) is also reported following extensive glycation rates of beta-lactoglobulin with both carbohydrates. These results indicated that the analysis of digested proteins by LC-ESI-MS(2) on a three-dimensional ion trap monitoring neutral losses is an efficient and direct method to identify peptides glycated not only through the Amadori rearrangement but also via the Heyns rearrangement. Nevertheless, as the predominating MS(2) fragmentation pattern of the glycated peptides is derived from the sugar moiety, the sequence-informative b- and y-ions resulting from peptide backbone cleavage were undetected. To overcome this drawback, and taking advantage of multi-stage fragmentation capabilities of ion traps, the indicative Amadori and Heyns-derived imminium ions were successfully used in MS(3) analyses to identify the peptide backbone, as well as the specific glycation site. In addition, further MS(4) analyses were needed to carry out the characterization of doubly glycated peptides.

It is well documented and experimentally confirmed that hexabromocyclododecanes (HBCDs) tend to associate with several anions forming different adducts that can affect the sensitivity and the accuracy of the determinations. In the present work, two different approaches for HBCD determination have been optimised and characterised based on their repeatability and intermediate precision, linear calibration ranges, sensitivity, limits of detection and quantification and application to commercial food samples. Both methods involve the use of a triple quadrupole mass spectrometer coupled to a liquid chromatograph and the addition of different ammonium salts to the mobile phase, i.e. ammonium chloride or ammonium acetate, in order to encourage (Cl method) or try to inhibit (Ac method), respectively, the formation of the chlorine adducts of the molecular ion. Precision of the two methods investigated was similar and both approaches presented a comparable behaviour for the analysis of food samples. However, the Cl method showed higher sensitivity and the limits of detection (0.23-0.41 pg on column) and quantification (0.77-1.35 pg on column) were up to 14 times lower than those obtained applying the Ac method. All these facts make the Cl method the best choice for the quantification of HBCDs in food samples with low concentration levels.

Experimental isothermal retention indices (I) at 348, 363, 378 and 393 K of 52 solutes of varied polarity on seven different poly(cyanopropylmethylsiloxane) stationary phases with cyanopropyl group percentages between 0% and 75% have been determined by a well-proven, accurate method. Some of these I values were obtained on new stationary phases with cyanopropyl percentages never used before. The influence of column temperature and polymer polarity on I was thoroughly investigated. Finally, retention models were developed relating I values to physicochemical and molecular properties by multiple linear regression. The best model of retention index prediction for the proposed cyanosilicones involves the Abraham's descriptors.

A mass spectrometric study has been carried out to elucidate the structures of glycated peptides obtained after in vitro gastrointestinal digestion of bovine beta-lactoglobulin (beta-LG) glycated with prebiotic galacto-oligosaccharides (GOS). The digests of both native and glycated beta-LG were analyzed by MALDI-MS, LC-ESI-MS, and LC-ESI-MS/MS. MALDI-MS profiles showed marked differences mainly related to the lower intensity of ions corresponding to the digest of glycated beta-LG. Overall, 58 and 23 unglycated peptides covering 97% and 63% of the mature beta-LG sequence could be identified in the digests of native and glycated samples, respectively. The LC-ESI-MS analyses corroborated the MALDI-MS results regarding the unglycated peptides but they also enabled an extensive investigation into the digest of glycated beta-LG. Thus, a total of 19 peptides glycated with GOS from two to seven hexose units could be identified. The tandem mass spectra of glycated peptides were mostly characterized by two neutral losses of 1026/1056, 864/894, 702/732, 540/570, 378/408, and 216/246 u, corresponding to the formation of the furylium ion and its subsequent "CHOH" loss, indicative of the peptide glycation with hepta-, hexa-, penta-, tetra-, tri-, and disaccharides, respectively. Also, other minor ionic species containing the furylium ring linked to different galactose units could be also detected, showing the diversity of the fragmentation pattern of peptides glycated with larger size carbohydrates. Finally, the putative GOS glycation sites could be determined at the NH(2)-terminal Leu residue and at Lys residues located in positions 14, 47, 75, 77, 83, 91, 100, 135, and 138.

An alternative method for the enantiomer specific determination of hexabromocyclododecanes (HBCD) by LC-ESI-MS/MS using an ion trap analyser is proposed. The method is based on the formation of a chlorine adduct (m/z 676.6) of the (+/-)alpha-, (+/-)beta-, and (+/-)gamma-HBCD enantiomers and their further fragmentation into their stable quasi-molecular ion (m/z 640.6). In this way, problems related to the ion trap low mass cutoff and variable amounts of other adduct peaks in the samples are solved. Parameters affecting separation, ionisation and MS/MS detection were studied. Method performance was also evaluated: calibration curves were found linear from 20 to 400 pg microL(-1) for each enantiomer; detection limits ranged between 1.5 and 4.3 pg microL(-1); repeatability and reproducibility, expressed as relative standard deviation, were lower than 6% and 13%, respectively. The application to different types of spiked samples (pork meat, lean fish, and butter) pointed out the occurrence of matrix effects that could be solved by using labelled standards.

Isothermal retention indices (I) of 56 solutes of varied chemical nature and polarity were determined by a well-proven accurate method on poly(3,3,3-trifluoropropylmethylsiloxanes) with trifluoropropyl group percentages between 0 and 50% within the 353-413 K temperature range. The column temperature effect on the retention index for a representative set of solutes was studied. The linear model and the recent expression I = a + bT(-1) + c ln T were discussed. The retention index dependence on the polymer polarity was also investigated. Principal component analysis and multiple linear regression (MLR) were applied to obtain retention models relating the I values to physicochemical and molecular properties of the solutes chromatographed. The best model of prediction of the retention in these fluorinated stationary phases was obtained by using the Abraham's descriptors.

Isothermal Kováts retention indices may be used in GC for identification purposes, but they are also useful in characterisation of stationary phases and for studying structural and physico-chemical properties of both the analyte and the stationary phase. They are currently reported as whole numbers with an accuracy of one index unit for non-polar stationary phases. The method recommended for their calculation uses a linear regression model, although non-linear models have also been applied with good results. In both cases, a computer programme and the retention times of a series of n-alkanes that elute correctly and resolved from the other compounds are needed, conditions which cannot always be fulfilled. However, it is possible to calculate retention indices with an accuracy of 0.1 retention index units (0.2 units for packed columns) with the help of only three n-alkanes using just a pocket calculator or a computer spreadsheet. The main requirement is that at least one of the n-alkanes has a retention index differing by no more than one hundred retention index units from that of the analyte being investigated. Examples are given for different stationary phases.

The solvation parameter model has been applied to the specific retention volumes of 65 solutes of varied polarity on glass capillary columns coated with commercial and synthesized poly(methylcyanopropyl)siloxanes (CNPXX) with eight different percentages of cyanopropyl group (CNP). Their system constants were determined at 75, 90, 105 and 120 degrees C. The polymers examined do not either show any acidity (b = 0) or interact with solute pi/n electrons (e = 0); the prominent constants, dipolarity/polarizability and hydrogen-bond basicity, are of the same order (s approximately a), and the cavity formation/dispersive forces have normal values. Constants s, l and a decrease linearly with temperature for each cyanopropyl percentage. At each temperature, the constants s and a increase with polarity of polymer according to a curve, while the constant l decreases slightly. Cluster analysis shows that six CNPXX with medium to high cyanopropyl substitution integrate into a group with other high-polarity cyano-containing stationary phases taken from the literature, while the other three CNPXX with low CNP percentage form a group with other low-polarity stationary phases of different chemical nature. These clusters are supported by the dendrogram of 52 stationary phases made with the nine polymers presented here and other 43 taken from the literature.

The method of solvation model has been applied to five poly (methyl-trifluoropropyl) siloxanes (TFPSXX) prepared in our laboratories, at five trifluoropropyl (TFP) group contents, XX = 0, 11.5, 26.3, 35.5 and 50.0%, at 80, 100, 120 and 140 degrees C. Previously, specific retention volumes of 60-odd solutes of varied polarities were measured upon each of these stationary phases within the above temperature range. Constant s prevails over all other constants, TFPSXX stationary phases showing strong dipole/induced dipole forces with the solutes, moderate acidity and no basicity at all. Constant e is zero in the stationary phase without TFP groups, but has negative low-medium values for the other fluorine contents, XX from 11.5 to 50.0%, hinting at repulsive forces, as expected. Normal values for constant l, decreasing from the less cohesive TFPS00 to the more cohesive TFPS50, were found. For each TFP content constants s, a and l show a negative temperature dependence, while constant e increases as temperature increases. Constant c also decreases with increasing temperature. At each temperature, constants s and a increase with increasing %TFP (or increasing stationary phase polarity), whereas constants e and l show the opposite trend, diminishing with increasing polarity of the stationary phase. Principal component analysis shows that the five stationary phases presented in this work conform a group with other earlier synthesized trifluoropropyl siloxanes and other fluorinated stationary phases taken from literature: VB-210, QF-1, DB-200, DB-210 and PFS6, showing the same selectivity which only the fluorine atom confers. A dendrogram of 38 stationary phases supports these results.

Isothermal Kováts' retention indices are currently reported as whole numbers, and are frequently deduced from a linear least mean squares fitting of the logarithms of adjusted retention times of a number of n-alkanes versus carbon number, following an iterative method that minimises errors. The currently accepted accuracy is about one retention index unit for apolar stationary phases, and lower for polar stationary phases. This paper presents results that show how the accuracy of the retention index may be safely reported to one-tenth of a retention index unit by the use of a non-linear equation, with present day gas chromatographs without electronic flow controllers. Results are presented that prove the correctness of the retention indices found for several substances on one particular capillary column. Hints on the minimum retention times needed to achieve the 0.1 retention index accuracy are mentioned, for retention times recorded in minutes and in seconds. According to results of this paper, two chromatograms, run under the appropriate conditions, are sufficient to obtain the desired accuracy. The method proposed in this paper does not require knowledge of the hold-up time of the chromatogram.

The chromatographic behaviour of n-alkanes and other homologous series in isothermal gas chromatography has been shown to depart from the "linear" representation of the logarithms of the adjusted retention times vs. carbon number. One of the expressions proposed to describe this behaviour is tR(z)=A+exp(B+CzD). In this paper, a regression analysis shows that three of the parameters of the equation depend on different chromatographic variables such as hold-up time, average linear gas velocity, volume and polarity of the stationary phase and temperature of the column. The fourth parameter (D), responsible for the departure from the "linearity", does not depend on any chromatographic variable, and represents a gradual decrease of the contribution of the methylene groups to the general properties of n-alkanes, with no relation to the chromatographic phenomenon.

Three of the methods most often used for the clean-up and fractionation of organochlorine pesticides in lipid residue analysis by gas chromatography with electron-capture detection were compared. The overall recoveries of twenty pesticides from spiked samples were higher than 88%, the relative standard deviation being in the range 3-11% (n = 6) at the 36-80 ppb (10(9) level. The three methods were compared by analysis of variance, with no differences in precision at the 0.05 significance level. Differences in recoveries appeared in only two instances. None of the three methods seems to be significantly better than the others for the determination of the pesticides studied.