Degradation state of organic matter in surface sediments from the Southern Beaufort Sea: a lipid approach

For the next decades significant climatic changes should occur in the Arctic zone. The expected destabilisation of permafrost and its consequences for hydrology and plant cover should increase the input of terrigenous carbon to coastal seas. Consequently, the relative importance of the fluxes of terrestrial and marine organic carbon to the seafloor will likely change, strongly impacting the preservation of organic carbon in Arctic marine sediments. Here, we investigated the lipid content of surface sediments collected on the Mackenzie basin in the Beaufort Sea. Particular attention was given to biotic and abiotic degradation products of sterols and monounsaturated fatty acids. By using sitosterol and campesterol degradation products as tracers of the degradation of terrestrial higher plant inputs and brassicasterol degradation products as tracers of degradation of phytoplanktonic organisms, it could be observed that autoxidation, photooxidation and biodegradation processes act much more intensively on higher plant debris than on phytoplanktonic organisms. Examination of oxidation products of monounsaturated fatty acids showed that photo- and autoxidation processes act more intensively on bacteria than on phytodetritus. Enhanced damages induced by singlet oxygen (transferred from senescent phytoplanktonic cells) in bacteria were attributed to the lack of an adapted antioxidant system in these microorganisms. The strong oxidative stress observed in the sampled sediments resulted in the production of significant amounts of epoxy acids and unusually high proportions of monounsaturated fatty acids with a <i>trans</i> double bond. The formation of epoxy acids was attributed to peroxygenases (enzymes playing a protective role against the deleterious effects of fatty acid hydroperoxides in vivo), while <i>cis/trans</i> isomerisation was probably induced by thiyl radicals produced during the reaction of thiols with hydroperoxides. Our results confirm the important role played by abiotic oxidative processes in the degradation of marine bacteria and do not support the generally expected refractory character of terrigenous material deposited in deltaic systems

Monitoring abiotic degradation in sinking versus suspended Arctic sea ice algae during a spring ice melt using specific lipid oxidation tracers

publisher: Elsevier articletitle: Monitoring abiotic degradation in sinking versus suspended Arctic sea ice algae during a spring ice melt using specific lipid oxidation tracers journaltitle: Organic Geochemistry articlelink: http://dx.doi.org/10.1016/j.orggeochem.2016.05.016 content_type: article copyright: © 2016 Elsevier Ltd. All rights reserved

Monitoring photo-oxidative and salinity-induced bacterial stress in the Canadian Arctic using specific lipid tracers

Publisher policy: author can archive post-print on open access repository after an embargo period of 18 months.Publisher's version/PDF cannot be used. Must link to publisher version with DOI. Author's post-print must be released with a Creative Commons Attribution Non-Commercial No Derivatives License

Synthesis of Nitrogenated Heterocycles by Asymmetric Transfer Hydrogenation of N-(tert-Butylsulfinyl)haloimines

Highly optically enriched, protected, nitrogenated heterocycles with different ring sizes have been synthesized by a very efficient methodology consisting of the asymmetric transfer hydrogenation of N-(tert-butylsulfinyl)haloimines followed by treatment with a base to promote an intramolecular nucleophilic substitution process. N-Protected aziridines, pyrrolidines, piperidines, and azepanes bearing aromatic, heteroaromatic, and aliphatic substituents have been obtained in very high yields and diastereomeric ratios up to >99:1. The free heterocycles can be easily obtained by a simple and mild desulfinylation procedure. Both enantiomers of the free heterocycles can be prepared with the same good results by changing the absolute configuration of the sulfur atom of the sulfinyl group.This work was generously supported by the Spanish Ministerio de Ciencia e Innovación (MICINN; grant no. CONSOLIDER INGENIO 2010, CSD2007-00006, CTQ2007-65218 and CTQ2011-24151) and the Generalitat Valenciana (PROMETEO/2009/039 and FEDER). O.P. thanks the Spanish Ministerio de Educación for a predoctoral fellowship (grant no. AP-2008-00989)

Transcriptional responses of winter barley to cold indicate nucleosome remodelling as a specific feature of crown tissues

We report a series of microarray-based comparisons of gene expression in the leaf and crown of the winter barley cultivar Luxor, following the exposure of young plants to various periods of low (above and below zero) temperatures. A transcriptomic analysis identified genes which were either expressed in both the leaf and crown, or specifically in one or the other. Among the former were genes responsible for calcium and abscisic acid signalling, polyamine synthesis, late embryogenesis abundant proteins and dehydrins. In the crown, the key organ for cereal overwintering, cold treatment induced transient changes in the transcription of nucleosome assembly genes, and especially H2A and HTA11, which have been implicated in cold sensing in Arabidopsis thaliana. In the leaf, various heat-shock proteins were induced. Differences in expression pattern between the crown and leaf were frequent for genes involved in certain pathways responsible for osmolyte production (sucrose and starch, raffinose, γ-aminobutyric acid metabolism), sugar signalling (trehalose metabolism) and secondary metabolism (lignin synthesis). The action of proteins with antifreeze activity, which were markedly induced during hardening, was demonstrated by a depression in the ice nucleation temperature

Ionic liquids improve citronellyl ester synthesis catalyzed by immobilized Candida Antarctica lipase B in solvent-free media.

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Degradation of sterols and terrigenous organic matter in waters of the Mackenzie Shelf, Canadian Arctic

Sterols and their biotic and abiotic degradation products were quantified in suspended particulate matter (SPM) from surface waters in the Mackenzie River mouth to the Beaufort Sea shelf (Canadian Arctic). 24-Ethylcholesterol (sitosterol) and 24-methylcholesterol (campesterol) appeared to be extensively degraded by bacterial and especially autoxidative degradation in the samples. Degradation was most extensive in some samples from the outer boundaries of the plume, which exhibited much higher sitosterol/campesterol ratio values than previously observed in studies of the Beaufort Sea. The lack of reactivity of specific planktonic sterols such as cholesterol, 24-methylcholesta-5,22E-dien-3β-ol (epi-brassicasterol) and 24-methylenecholesterol and the good correlation between the abundances of sitosterol, campesterol and dehydroabietic acid (DHAA, a biomarker of Pinaceae resin) oxidation products allowed us to attribute the main origin of these two sterols to terrigenous vascular plants. A good correlation was observed between the extent of autoxidation and salinity, suggesting that the free radical oxidation is enhanced via contact with seawater. Laboratory incubation of Mackenzie River SPM in Milli-Q water and seawater confirmed this proposal. To explain the specific induction of autoxidation on vascular plant-derived material, a mechanism involving homolytic cleavage of photochemically produced hydroperoxides resulting from the senescence of higher plants on land is proposed. Cleavage could be catalyzed by redox-active metal ions released from SPM in the mixing zone of riverine water and marine water. The greatest extent of degradation observed at outer boundaries of the plume is attributed to preferential settling of lithic material relative to less dense higher plant debris increasing the proportion of highly degraded vascular plant material in the SPM. The results are important for this ecologically vulnerable region, where destabilization of permafrost by global warming is expected to increase the input of terrigenous C to coastal seas. Autoxidation, which until now has received little attention, plays a key role in the degradation of vascular plant-derived lipids in surface waters and should be taken into consideration during future studies of terrigenous organic matter degradation

A new way to conduct enzymatic synthesis in an active membrane using ionic liquids as catalyst support

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