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Onions are known not only for their culinary importance but also for their nutritional and health-promoting properties. Both properties are closely linked to their content of organosulfur compounds, which account for up to 5% of the dry weight of an onion. Given the importance of these compounds, suitable analytical methods are required for their study. Two techniques should be highlighted in this context: gas chromatography coupled to mass spectrometry (GC-MS), and liquid chromatography coupled to mass spectrometry (LC-MS). In this study, eight different onion varieties were analyzed using two distinct analytical techniques: direct thermal desorption–gas chromatography–mass spectrometry (DTD-GC-MS) and high-resolution mass spectrometry (HRMS) on an LC-ESI-QqTOF instrument. Each method identified different organosulfur compounds, with LC-HRMS targeting 15 non-volatile compounds, such as cysteine sulfoxides, and GC-MS targeting 18 volatiles, such as disulfides and trisulfides. The results obtained were studied using Pearson correlations and principal component analysis. No precise correlation was found between the initial organosulfur compounds in onions and their hydrolysates. Consequently, although GC is one of the most employed techniques in the scientific literature, the use of LC-HRMS or a combination of both techniques may offer a more comprehensive and accurate description of the metabolomic profile of onions. [ABSTRACT FROM AUTHOR]

The characteristic collision energy to obtain 50% fragmentation, expressed as the characteristic collision voltage (CCV), was used as a tool to discriminate different classes of polymers. The CCV value of different polymers was determined in a quadrupole ion trap mass spectrometer. Good linear correlation (0.980 < [R.sup.2] < 0.999) between the CCV values and precursor ion mass was found for all polymers studied. The position of the various linear trend lines varied among the various polymers, which allowed their grouping based on the respective CCV values. The collision energy necessary to drive fragmentation was decreasing in the order of polyethers > polymethacrylates > polyesters > polysaccharides. This suggests that polysaccharides fragment most easily (low CCVs), while polyethers require the highest collision energy among the polymers studied. The effect of end group on the CCV was also studied, showing a minor influence in most cases. In addition, the applicability of CCV as discriminator was studied for a mixture of (1) polylactic acid (PLA), (2) poly(tetramethylene glycol) (PTMEG), and (3) PLA-block-PTMEG-block-PLA block copolymer. Differences between the CCV values of four nominally isobaric polymers (of which two were copolymers and two were homopolymers) were observed. These results demonstrate that the insertion of a 'weak' link into a polymer chain significantly affects the energy required for fragmentation. 10.1021/ac101936v

The collision energy or collision voltage necessary to obtain 50% fragmentation (characteristic collision energy/ voltage, CCE or CCV) has been systematically determined for different types of molecules [poly(ethylene glycols) (PEG), poly(tetrahydrofuran) (PTHF), and peptides] over a wide mass (degrees of freedom) range. In the case of lithium-cationized PEGs a clear linear correlation (R2 > 0.996) has been found between CCE and precursor ion mass on various instrument types up to 4.5 kDa. A similar linear correlation was observed between CCV and the mass-to-charge ratio. For singly and multiply charged polymers studied under a variety of experimental conditions and on several instruments, all data were plotted together and showed correlation coefficient [R.sup.2] = 0.991. A prerequisite to observe such a good linear correlation is that the energy and entropy of activation in a class of polymers is likely to remain constant. When compounds of different structure are compared, the CCV will depend not only on the molecular mass but the activation energy and entropy as well. This finding has both theoretical and practical importance. From a theoretical point of view it suggests fast energy randomization up to at least 4.5 kDa so that statistical rate theories are applicable in this range. These results also suggest an easy method for instrument tuning for high-throughput structural characterization through tandem MS: after a standard compound is measured, the optimum excitation voltage is in a simple proportion with the mass of any structurally similar analyte at constant experimental conditions. 10.1021/ac902463q

This short review article is dedicated to the Phosphonodithioformate-Amine Coupling (PAC) reaction. This reaction occurs by mixing phosphonodithioformate with amine without any catalyst and produces, according to a fast second order kinetics, phosphonothioamide. This reaction was applied to the functionalization of liposomes and opens new possibilities for the functionalization of synthetic or biologic materials. [ABSTRACT FROM AUTHOR]

The presence of an isobaric contaminant can drastically affect MS and MS/MS patterns leading to erroneous structural and quantitative analysis, which is a real challenge in mass spectrometry. Herein, we demonstrate that MS and MS/MS structural analysis of a compound can be successfully performed despite the presence of an isobaric interference with as low as few millidaltons mass difference by using pseudo-MS3 . To this end, in-source collisional excitation (in-source CID) and the Survival Yield (SY) technique (energy-resolved collision induced dissociation MS/MS) were performed on two different source geometries: a Z-spray and an orthogonal spray (with a transfer capillary) ionization sources on two different mass spectrometers. By using soft ionization conditions, the SY curve for the mixture is a linear combination of the SY curves from the pure compounds demonstrating the presence of two components in the mixture. In the case of harsher ionization conditions, the SY curve of the mixture perfectly overlaps the SY curve from the pure analyte. This observation demonstrates the isobaric interference has been completely removed by in-source CID fragmentation, independently of the source design, leaving then the analyte precursor ions only. Therefore, by measuring the MS spectrum in harsh ionization conditions and according to SY criterium, the compound of interest can be made free from isobaric interference paving the way for, for example, unequivocal HPLC-MS as well as HPLC-MS/MS structural and quantitative analysis despite the presence of a co-eluting isobaric interference. [ABSTRACT FROM AUTHOR]

The active site of the [NiFe]-hydrogenase contains a pentacoordinated iron atom; therefore, a vacant coordination site is available for substrate binding. Nonetheless, most organometallic models of the [NiFe]-hydrogenase failed to reproduce this key feature of the active site. In order to rationalize such behavior, quantum chemical calculations were carried out on a series of [Fe(CN) 2 (CO) n (dithiolate)] 2- n = 1,2 complexes, where dithiolate denotes the ligands (CF 3 ) 2 C 2 S 2 2- , (CO 2 Me) 2 C 2 S 2 2- , Ph 2 C 2 S 2 2- , C 6 Cl 2 H 2 S 2 2- , C 6 H 4 S 2 2- , C 2 H 4 S 2 2- , and C 3 H 6 S 2 2- . Structural and energetic features are discussed, and a topological analysis based on two scalar fields, the one-electron density and the electron localization function (ELF), has been attempted to describe the nature of the metal-ligand bonds. The present approach contributes to better understand the ability of noninnocent dithiolene to strongly labilize one CO whereas innocent dithiolate cannot. The methodology developed throughout the paper could be useful in the field of the CO-releasing molecules.