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The gas-phase reactivity of ionized nitrile sulfides, R-C[triple bond]N(+)-S*, towards neutral pyridine was studied both experimentally (six sector hybrid mass spectrometer) and theoretically (density functional theory and Møller-Plesset ab initio calculations). An ionized sulfur atom transfer and a cycloaddition process respectively yielding ionized pyridine N-thioxide and a thiazolopyridinium cation were observed. Whereas the very efficient S*+ transfer reaction probably involves the intermediacy of several ion-molecule complexes, the thiazolopyridinium ion formation is likely to be initiated by an electrophilic attack of the R-C[triple bond]N(+)-S* ion on the nitrogen atom of pyridine; the resulting intermediate then undergo an intramolecular substitution of an alpha-hydrogen atom by the sulfur atom.

Since their discovery, cyclic polymers have attracted great interest because of their unique properties. Today, the preparation of these macrocyclic structures still remains a challenge for polymer chemists, and most of the preparation pathways lead to an inescapable contamination by linear by-products. As the properties of the polymers are closely related to their structure, it is of prime importance to be able to assess the architectural purity of a sample. METHODS In this work, the suitability of ion mobility spectrometry-mass spectrometry (IMS-MS) for the quantification of two isomers was investigated. A cyclic poly(L-lactide) was prepared through photodimerization of its linear homologue. Since IMS-MS can be used to differentiate cyclic polymer ions from their linear analogues because of their more compact three-dimensional conformation, the present work envisaged the use of IMS-MS for the quantification of residual linear polymers within the cyclic polymer sample. RESULTS Using the standard addition method to plot calibration curves, the fraction of linear contaminants in the sample was determined. By doing so, unrealistically high values of contamination were measured. CONCLUSIONS These results were explained by an ionization efficiency issue. This work underlines some intrinsic limitations when using IMS-MS in the context of the relative quantification of isomers having different ionization efficiencies. Nevertheless, the linear-to-cyclic ratio can be roughly estimated by this method.

Sea urchin pigments, also known as spinochromes or polyhydroxynaphthoquinones (PHNQ) have been well studied for their bioactive properties like anti-bacterial, fungicidal, antioxidant and pro-inflammatory effects. Moreover, many studies have analyzed and identified these pigments in sea urchin tests and spines but, and to the best of our knowledge, never in their body compartments or in a quantitative manner. The aim of this work was to investigate the diversity and concentration of pigments in three sea urchins localized in the same coral reef in Madagascar ( Diadema savignyi, Tripneustes gratilla and Toxopneustes pileolus). Their pigment distribution patterns were compared and linked to their behavior in order to understand better the implication of spinochromes in a sea urchin's life. Analyses and quantifications by LC-MS showed the presence of 11 different spinochromes with principally two kinds of patterns. First, D. savignyi showed a high concentration in all its body compartments with a predominance for Echinochrome A and Spinochrome D – Iso 3, a pattern close to the E. mathaei distribution found in our previous study. The presence of these pigments has been linked to their bioactive properties and suggested their implications in UV radiation protection, in reproduction, in feeding as well as in their immune systems. Secondly, T. gratilla and T. pileolus presented few spinochromes, which could explain their restricted diet and their covering behavior facing sunlight. Moreover, the absence of pigments in their gonads could be explained by their seasonal spawning occurring before our collection period. Nevertheless, the near absence of spinochromes may be counterbalanced by other bioactive compounds like their toxic proteins, which may act as either a defense mechanism or immune agents, or like carotenoid pigments already shown in sea urchin and acting as defense agents. In conclusion, spinochromes, and pigments in general, seem to play many roles in sea urchin ecology. Their highly reactive structures confer them with strong bioactive properties involved in most parts of their metabolic system and clearly participate in the survival of the sea urchins.

MALDI-MS methodology is nowadays considered as a very reliable technique to determine the chemical structures and the molecular weight distribution of a synthetic polymer. At variance, ESI-MS occupies only a small segment in the analysis of polymers mainly because of the formation of multiple charged ion distributions, which interfere with the molecular distribution in the mass spectra of synthetic polymers. In the present communication, we want to demonstrate that, when applied to fragile polymer samples, both techniques can lead to misinterpretation since in source decomposition of the ionized oligomers can sometimes not be avoided. An accurate knowledge of the source parameters and their influences is therefore a prerequisite prior to start the analysis of the MS data. Moreover, we would like to propose that the best MS methodology to analyze fragile synthetic polymers is to associate the data obtained by both the MALDI-MS and ESI-MS techniques.