Influence of RTIL Nanodomains on the Voltammetry and Spectroelectrochemistry Of Fullerene C\u3csub\u3e60\u3c/sub\u3e in Benzonitrile/Room Temperature Ionic Liquids Mixtures

The cyclic voltammetry of fullerene C60 was examined in mixed benzonitrile/RTIL solvents in order to probe the effect of nanodomains in the mixed RTIL/benzonitrile solutions and their effect upon the voltammetry. In probing the interactions of the fullerides (up to C603−) with RTILs, BMIm+ (1-butyl-3-methylimidazolium, mostly planar) and tetraalkylammonium (more spherical/flexible) salts were used. In order to investigate these shifts in more detail, the ΔE12° (=E°1–E°2) and ΔE23° (=E°2–E°3) values, which were independent of the reference potential, were used. At higher concentrations of the RTILs, greater stabilization of the more highly charged fullerides were observed. These shifts were attributed to the interaction of the fullerides with nanodomains of the RTIL. This was further confirmed by examining the shifts in the E1/2 values of non-RTIL and RTIL salts at constant ionic strength and the changes in diffusion coefficient with %RTIL. The observed shifts in the E1/2 values with increased concentration of the RTIL salts could not be explained by ion pairing equilibria alone. Changes in the visible and near infrared spectra between benzonitrile and mixed benzonitrile/RTIL spectra were most significant for C603−, where voltammetric evidence indicates the strongest interaction between the fullerides and the RTIL. Among the RTILs studied, preliminary DFT calculations showed that the more flexible tetraalkylammonium ion was able to stabilize the C60-anionic species better than the planar BMIm+ species, under similar solution conditions

Electrochemistry and Spectroelectrochemistry of 1,4-Dinitrobenzene in Acetonitrile and Room-Temperature Ionic Liquids: Ion-Pairing Effects in Mixed Solvents

Room-temperature ionic liquids (RTILs) have been shown to have a significant effect on the redox potentials of compounds such as 1,4-dinitrobenzene (DNB), which can be reduced in two one-electron steps. The most noticeable effect is that the two one-electron waves in acetonitrile collapsed to a single two-electron wave in a RTIL such as butylmethyl imidazolium-BF4 (BMImBF4). In order to probe this effect over a wider range of mixed-molecular-solvent/RTIL solutions, the reduction process was studied using UV–vis spectroelectrochemistry. With the use of spectroelectrochemistry, it was possible to calculate readily the difference in E°’s between the first and second electron transfer (ΔE12° = E1° – E2°) even when the two one-electron waves collapsed into a single two-electron wave. The spectra of the radical anion and dianion in BMImPF6 were obtained using evolving factor analysis (EFA). Using these spectra, the concentrations of DNB, DNB–•, and DNB2– were calculated, and from these concentrations, the ΔE12° values were calculated. Significant differences were observed when the bis(trifluoromethylsulfonyl)imide (NTf2) anion replaced the PF6– anion, leading to an irreversible reduction of DNB in BMImNTf2. The results were consistent with the protonation of DNB2–, most likely by an ion pair between DNB2– and BMIm+, which has been proposed by Minami and Fry. The differences in reactivity between the PF6– and NTf2– ionic liquids were interpreted in terms of the tight versus loose ion pairing in RTILs. The results indicated that nanostructural domains of RTILs were present in a mixed-solvent system

Spectroscopic Evidence of Nanodomains in THF/RTIL Mixtures: Spectroelectrochemical and Voltammetric Study of Nickel Porphyrins

The presence and effect of RTIL nanodomains in molecular solvent/RTIL mixture were investigated by studying the spectroelectrochemistry and voltammetry of nickel octaethylporphyrin (Ni(OEP)) and nickel octaethylporphinone (Ni(OEPone)). Two oxidation and 2–3 reduction redox couples were observed, and the UV–visible spectra of all stable products in THF and RTIL mixtures were obtained. The E° values for the reduction couples that were studied were linearly correlated with the Gutmann acceptor number, as well as the difference in the E° values between the first two waves (ΔE12° = |E1° – E2°|). The ΔE12° for the reduction was much more sensitive to the %RTIL in the mixture than the oxidation, indicating a strong interaction between the RTIL and the anion or dianion. The shifts in the E° values were significantly different between Ni(OEP) and Ni(OEPone). For Ni(OEP), the E1° values were less sensitive to the %RTIL than were observed for Ni(OEPone). Variations in the diffusion coefficients of Ni(OEP) and Ni(OEPone) as a function of %RTIL were also investigated, and the results were interpreted in terms of RTIL nanodomains. To observe the effect of solvation on the metalloporphyrin, Ni(OEPone) was chosen because it contains a carbonyl group that can be easily observed in infrared spectroelectrochemistry. It was found that the νCO band was very sensitive to the solvent environment, and two carbonyl bands were observed for Ni(OEPone)− in mixed THF/RTIL solutions. The higher energy band was attributed to the reduced product in THF, and the lower energy band attributed to the reduced product in the RTIL nanophase. The second band could be observed with as little as 5% of the RTIL. No partitioning of Ni(OEPone)+ into the RTIL nanodomain was observed. DFT calculations were carried out to characterize the product of the first reduction. These results provide strong direct evidence of the presence of nanodomains in molecular solvent/RTIL mixtures

Visible and Infrared Spectroelectrochemistry of Zinc and Manganese Porphinones: Metal vs. Porphyrin Reduction

The visible and infrared spectroelectrochemistry of zinc and manganese porphinones and porphinediones was carried out in THF solutions. The aim of this work was to use FTIR spectroelectrochemistry and DFT calculation to determine whether the reduction was centered predominantly on the metal or the macrocycle. For zinc(II), the first one-electron reduction must occur on the macrocyclic ring because the metal’s d-orbitals are filled (d10). The carbonyl bands on the macrocyclic ring were used to probe the electronic structure because they can be readily observed in the infrared spectra. The results of this study are complementary to previous spectroelectrochemical studies that have been reported for the iron and cobalt complexes of the same macrocycles. As expected for the formation of a π-radical anion species, significant downshifts in the carbonyl bands were observed. DFT calculations showed that the behavior of the porphinedione complexes were most sensitive to the electronic structure of the M(OEPdione)− species. If a MI species is formed, the two carbonyl groups will be downshifted by similar energies. For MII-radical anions, one carbonyl will be downshifted significantly, and the second one will be downshifted by a small amount. On the basis of this criterion, it was determined that cobalt(I) and iron(I) complexes were formed, while zinc and manganese formed π-radical anion species. The visible spectroelectrochemistry was also consistent with these electronic structures

Probing the Effects of Nano-Domains on the Redox Products in Molecular Solvents-RTILs Mixtures

Room temperature ionic liquids (RTIL) have been very attractive as replacements for molecular solvents (MS) in many areas in chemistry. The use of the RTIL in mixture with MS as reaction media will reduce the cost and viscosity of RTILs. The formation of RTIL nano-domains (nano-structures) in the mixture may lead to partitioning of solutes between the MS and the RTIL phase, where the properties and reactivity would be more like those in pure ionic liquids. In the present work, analytical approaches have been employed to probe the presence and effects of RTIL nano-domains on redox processes in the mixture. A focus was on substrates that undergo multi-electron reductions/oxidations, such as: dinitrobenzene, fullerene and metalloporphyrins. Throughout our investigation, there was strong evidence of the presence of RTIL and MS domains in the mixture system. Correlation of the potential shifts with acceptor properties of the mixture enabled to evaluate the extent of ion paring interactions within the molecular and RTIL domains. Influence of RTIL domains on the transport properties of the solution was evaluated versus the change in the viscosity of the mixture. The impact of RTIL domains on the electronic structures of redox products was examined using several spectroscopic methods, including UV-visible, infrared and NMR spectroscopy. Computational tools such as chemometrics, voltammetric simulations and DFT calculations were used to complement the experimental analysis

Modeling of a pragmalinguistics analysis of a discussion forum

International audienceIn this paper we present, a modeling of an expertise in pragmatics. We follow knowledge engineering techniques and observe the expert when he analyses a social discussion forum. Then a number of models are defined. These models emphasize the process followed by the expert and a number of criteria used in his analysis. Results can be used as guides that help to understand and annotate discussion forums. We aim at modeling other pragmatics analysis in order to complete the base of guides; criteria, process, etc. of discussion analysi

In Situ Study of the Photodegradation of Carbofuran Deposited on TiO\u3csub\u3e2\u3c/sub\u3e Film under UV Light, Using ATR-FTIR Coupled to HS-MCR-ALS

The in situ study of the photodegradation of carbofuran deposited on a TiO2 catalyst film under UV light was carried out using the ATR-FTIR technique. The data were analyzed using a Hard–Soft Multivariate Curve Resolution-Alternating Least Squares (HS-MCR-ALS) methodology. Using S-MCR-ALS, four factors were deduced from the evolving factor analysis of the data, and their concentrations and spectra were determined. These results were used to draw qualitative and quantitative analyses of the major products of carbofuran photodegradation. The results of this analysis were in good agreement with GC-MS results and with reported mechanisms. Hard-MCR-ALS was then used to refine the spectra and concentrations, using a multistep kinetic model. The rate constant for the first step in the photodegradation of carbofuran was found to be 2.9 × 10–3 min–1. The higher magnitude of the correlation (96.87%), the explained variance (99.87%) and LOF (3.01), are good indicators of the reliability of the outcome of this approach. This method has been shown to be an efficient approach to study in situ photodegradation of pesticides on a solid surface

Investigating the relationship between vitamin D and cancer requires dosing the bio-available non-hydroxylated vitamin D storage in cancer tissues

International audienceIn a recent article published in CancerShui et al. observed no statistically significant relationship between circulating 25-hydroxyvitamin D (25(OH)D) and fatal prostate cancer (PCa) 1. However, an association between CYP2R1 SNPs and fatal PCa is found 1. CYP2R1 is the hydroxylase involved in the conversion of vitamin D into 25(OH)D. In the classical vitamin D endocrine system,activation of vitamin D into 1,25(OH)2D requires two successive hydroxylation steps. The first one is catalyzed by CYP2R1 in the liver and the second one by CYP27B1 in the kidneys. Then, 1,25D is released in the blood circulation and behaves as an endocrine hormone. The conversion of 25(OH)Dinto the active hormone 1,25(OH)2D by CYP27B1 is under stringent control. However, the first hydroxylation step catalyzed in the liver by CYP2R1 is constitutive and is not believed to be subjected to tight regulation. This has two important consequences: i) the regulation of liver CYP2R1 has retained little attention, and ii) circulating non-hydroxylated vitamin D is rapidly metabolized by liver CYP2R1. Therefore, 25(OH)D concentrations are considered to reflect vitamin D inputsand are used to determine the vitamin D status. A major breakthrough in our understanding on the nonskeletal effects of vitamin D is the recent discovery of autocrine/paracrine vitamin D systemsin many tissues 2 .This autocrine/paracrine signalingensures the local bioactivation of 25(OH)D into 1,25(OH)2D by extra-renal CYP27B1. In autocrine/paracrine vitamin D systems, the vitamin D metabolites are produced, act and are degraded locally without affecting serum 25(OH)D levels. Shui and coll rightly pointed out that local synthesis of 1,25(OH)2D from 25(OH)D can occur,because CYP27B1 is expressed in the prostate. However, the authors do not mention that CYP2R1 is also expressed in prostate tissue

Modélisation d'une analyse pragma-linguistique d'un forum de discussion

National audienceWe present in this paper, a modelling of an expertise in pragmatics. We follow knowledge engineering techniques and observe the expert when he analyses a social discussion forum. Then a number of models are defined. These models emphasises the process followed by the expert and a number of criteria used in his analysis. Results can be used as guides that help to understand and annotate discussion forum. We aim at modelling other pragmatics analysis in order to complete the base of guides; criteria, process, etc. of discussion analysi