Photoinduced hydrosilylation through hydrogen abstraction: an NMR and computational study of the structural effect of silane

The hydrosilylation reaction, describing the addition of Si–H bonds to unsaturated bonds, is performed in the presence of catalysts, usually highly active platinum catalysts. This work focuses on the study of a photoinduced hydrosilylation by the use of benzophenone which promotes the addition reaction of olefin on different hydrosilanes. The reactivity of silanes towards addition onto the double bond during hydrosilylation appears to depend on their structure. It was observed that the consumption of Si–H and C[double bond, length as m-dash]C functional groups increases with the irradiation time, and reaches a maximum of approx. 51% in the case of diphenylsilane. The hydrosilylation products are determined with (1)H NMR, HSQC, DEPT, COSY and (13)C NMR. The main product corresponds to the single adduct of the silyl radical onto the double bond. Substitution of the Si–H bond by two or three phenyls groups (triphenylsilane, diphenysilane) enhances the yield of the reaction, although diphenylsilane was found to be more efficient than triphenylsilane because of its lower steric hindrance. The ketyl radical formed after hydrogen abstraction by the triplet state of benzophenone likely forms benzopinacol, a reaction which reduces the overall yield of the hydrosilylation reaction. All these experiments are in line with DFT calculations of the Gibbs free energy of the reactions involved. This sheds new light on the photoinduced hydrosilylation process and opens the way to more active combinations of photoinitiator/silane/vinylsilane systems

Different Domains of the RNA Polymerase of Infectious Bursal Disease Virus Contribute to Virulence

BACKGROUND: Infectious bursal disease virus (IBDV) is a pathogen of worldwide significance to the poultry industry. IBDV has a bi-segmented double-stranded RNA genome. Segments A and B encode the capsid, ribonucleoprotein and non-structural proteins, or the virus polymerase (RdRp), respectively. Since the late eighties, very virulent (vv) IBDV strains have emerged in Europe inducing up to 60% mortality. Although some progress has been made in understanding the molecular biology of IBDV, the molecular basis for the pathogenicity of vvIBDV is still not fully understood. METHODOLOGY, PRINCIPAL FINDINGS: Strain 88180 belongs to a lineage of pathogenic IBDV phylogenetically related to vvIBDV. By reverse genetics, we rescued a molecular clone (mc88180), as pathogenic as its parent strain. To study the molecular basis for 88180 pathogenicity, we constructed and characterized in vivo reassortant or mosaic recombinant viruses derived from the 88180 and the attenuated Cu-1 IBDV strains. The reassortant virus rescued from segments A of 88180 (A88) and B of Cu-1 (BCU1) was milder than mc88180 showing that segment B is involved in 88180 pathogenicity. Next, the exchange of different regions of BCU1 with their counterparts in B88 in association with A88 did not fully restore a virulence equivalent to mc88180. This demonstrated that several regions if not the whole B88 are essential for the in vivo pathogenicity of 88180. CONCLUSION, SIGNIFICANCE: The present results show that different domains of the RdRp, are essential for the in vivo pathogenicity of IBDV, independently of the replication efficiency of the mosaic viruses

Etude par photo-CIDNP des reactions de transfert de charge dans les systemes : "porphyrines synthetiques hydrosolubles-substrats biologiques"

SIGLECNRS T Bordereau / INIST-CNRS - Institut de l'Information Scientifique et TechniqueFRFranc

Self-Photopolymerization of Poly(disulfide) Oligomers

International audienceBase catalyst and oxidant are usually necessary to promote the polymerization of poly(disulfide) oligomers through oxidative coupling of the terminal SH groups into S− S bonds. In this study, we prove that self-polymerization of bifunctional (disulfide) oligomer films can take place in a matter of minutes under UVC irradiation (254 nm, 10.5 mW cm −2). The resulting insoluble polymer is characterized using solid-state NMR, 1 H T 2 NMR relaxation measurements, thermal analysis, and Fourier-transform infrared spectroscopy and proves to have similar composition as a model poly(disulfide) prepared under oxidative conditions, but distinct physical properties. These differences are explained by a change in polymer architecture due to a higher ratio of cyclization relative to linear polymerization. Homolytic photocleavage of internal S−S bonds creates thiyl groups close to each other, driving an increased kinetic feasibility for the cyclization reaction by radical coupling. The subsequent formation of mechanically interlocked macrocycles (polycatenane network) is proposed to account for film properties analogous to those of a cross-linked polymer

A 13C NMR Study of pyridinium phenoxide series with increasing sterical hindrance reveals the dramatic influence of torsion on their structure

International audienceThe 13C resonance signals of five twisted pyridinium phenoxides has been assigned in two different solvents (CD3OD and D6-DMSO), while the torsion angle was varied by changing the pyridinium substituents at ortho positions of the intercyclic bond. The experimental 13C chemical shifts of these compounds were adjusted using calculating shift parameters evaluated from reference compounds, revealing the changes of 13C signals due to the different interplanar angles. A dramatic modification of the structure was observed as the angle increases (transition from quinone form to zwitterion one), adding a piece of information on the still debated question: the relative contributions of the two limit forms (quinone, zwitterion) in a pyridinium phenoxide series. Then the ability of four other twist compounds, bearing no ‘‘protected’’ groups at ortho position of the phenoxide function, to rapid deuteration was studied. This property is once more related to the twist structure of pyridinium phenolates

Ring-rearrangement metathesis of substituted dihydropyrans and dihydrofurans

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First step towards understanding the behavior of oxygenated polycyclic aromatic compounds (O-PACs) in soils and groundwater

National audienceObjectives: the aim of this study is to assess O-PAC migration in groundwater in order to know if they could form large contamination plumes in groundwater and therefore trigger a risk for sensitive targets such as drinking water wells. Innovative nature of the proposed topic: O-PAC migration in groundwater and parameters controlling their behavior in soils have never been assessed whereas it is well established in literature that these compounds are toxic, persistent and always present in soils of PAH contaminated sites. Abstract Oxygenated Polycyclic Aromatic Compounds (O-PACs) are toxic, persistent, highly leachable and often abundant at PAH contaminated sites. Furthermore, many studies have proven that O-PACs could be formed during and after the application of some remediation techniques on PAH contaminated sites1,2. However, in contrast to the 16 US EPA PAHs classified as priority pollutants and due to the lack of regulations and data regarding their behavior in soils, O-PACs are not included in health risk assessment studies and monitoring programs of PAH contaminated sites. However, these aromatic compounds could as well have an impact and contribute to the risk for human beings and the Environment. This study constitutes an important step in the process of understanding the transfer of these compounds within the soil system and in determining the related parameters that could affect their behavior. Two PAH/O-PAC couples were chosen for this study: fluorene/fluorenone (FLU/FLUone) and acenaphthene/dibenzofuran (ACE/DBFUR). These compounds were primarily selected regarding their available data, the possibility of their laboratory manipulation as well as the similarity in their molecular structures. Sorption isotherms onto a non-contaminated soil were individually determined using controlled batch experiments for all four compounds. Effects of ionic strength and liquid to solid ratio (L/S) on the sorption of FLU and FLUone were furthermore investigated through controlled batch experiments. For both O-PACs and PAHs, experimental data showed that the sorption kinetics were designated by the occurrence of two distinct phases. A fast-initial phase followed by a second much slower sorption process. Sorption equilibrium was achieved within less than 24 hours of mixing while no degradation of the studied compounds was observed. For all studied compounds and in all experimental conditions, linear sorption models best fit the isotherm data. Results revealed that ACE and DBFUR were similarly adsorbed onto the soil where the values of organic carbon-water partition coefficient (Koc) were 1184 and 1153 L/kg, respectively. In the same experimental conditions, Koc of FLU (1931 L/kg) was higher than that of FLUone (1355 L/kg), showing a smaller affinity of FLUone towards the solid phase. Furthermore, decreasing the L/S ratio from 100 L/kg to 50 and 30 L/kg, increased the sorption of FLUone onto the soil by 64 and 77% respectively, while the sorption of FLU was slightly increased by 13 and 31% respectively. Moreover, increasing the ionic strength of the aqueous phase by a factor of 6 favored 2 the sorption of FLUone by 62% while the sorption of FLU slightly decreased by 13%. These results provided meaningful first information regarding O-PAC behavior in soils: highly soluble O-PACs such as FLUone could easily migrate in groundwater, form larger contamination plumes than PAHs and reach drinking water wells. In addition, the difference in PAH and O-PAC behavior when decreasing the L/S ratio and increasing the ionic strength is a first hint that mechanisms responsible for O-PAC fate and transport in soils could be different than the ones responsible for PAH retention in soils. Further studies are in progress at different scales (lab and field scales) in order to better understand the migration potential of O-PACs

Red 33 dye co-encapsulated with cetyltrimethylammonium in mesoporous silica materials

International audienceA water soluble dye, the Red 33, used in cosmetic industry was immobilized into mesoporous silica by a one-step method which consists in the introduction of the dye molecules in the precursor medium of the mesoporous silica i.e. containing surfactant and silica source. A high loading rate of 25 wt% was achieved. The resulting Red 33-silica pigment is stable in water and oil media. The characterizations carried out on this material have shown that the encapsulation is effective and that the presence of Red 33 has an effect on the structure and texture of the material. The material exhibits an excellent stability in water due to the interactions between the Red 33 molecules, the silicate species and the surfactant molecules. It has been shown that the dye molecules interact with both the silica host matrix through the NH2 and phenyl groups, as well as with the surfactant molecules, via electrostatic interactions between the polar head of the surfactant and the sulfonate group of Red 33 which undergoes no steric hindrance

Modular total syntheses of mycolactone A/B and its [ 2 H]- isotopologue

International audienceA modular total synthesis of mycolactone A/B, the exotoxin produced by Mycobacterium ulcerans has been achieved through the orchestration of several Pd-catalyzed key steps. While this route leads to a mixture of the natural product and its C12 epimer (4:1 ratio), this was inconsequential from the biological activity standpoint. Compared to previously reported routes, this synthetic blueprint allows the late-stage modification of the toxin, as exemplified with the preparation of [22,22,22-