Convex hull: A new method to determine the separation space used and to optimize operating conditions for comprehensive two-dimensional gas chromatography

It is important to develop methods of optimizing the selection of column sets and operating conditions for comprehensive two-dimensional gas chromatography. A new method for the calculation of the percentage of separation space used was developed using Delaunay's triangulation algorithms (convex hull). This approach was compared with an existing method and showed better precision and accuracy. It was successfully applied to the selection of the most convenient column set and the geometrical parameters of second column for the analysis of 49 target compounds in wastewater.     

Thin film platinum cuff electrodes for neurostimulation: in vitro approach of safe neurostimulation parameters

Thin film technology takes more and more importance in the development of biomedical devices dedicated to functional neurostimulation. Our research about the design of implant neurostimulating electrode is oriented toward thin film cuff electrodes based on a polyimide substrate covered by a chromium/gold/Pt film. The chromium/gold sputtered film serves as adhesion layer and current collector whereas platinum acts as an electrochemical actuator. The electrode surface has been designed to obey safe stimulation criteria (i.e. chemically inert noble metal, low electrode-electrolyte impedance, high electrochemical reversibility, high corrosion stability). The electrochemical behaviour of such platinum electrodes has been assessed and compared to a foil of platinum. Extensive in vitro characterisations of the both electrode types were carried out using AFM, SEM and electrochemical techniques. The role of enhanced surface roughness enabling high double layer capacitances to be achieved was clearly highlighted. The obtained results are discussed, with particular reference to thin film electrodes stability under in vitro electrical stimulation in NaCl 0.9% (physiological serum). Therefore, these thin film devices showed reversible PtOH formation and decomposition making them potentially attractive for the fabrication of implant stimulation cuff electrodes.     

Synthesis of original benzo[g]quinoxaline‐5,10‐diones by bis‐SRN1 methodology

A new heterocyclic bioreductive bis‐alkylating agent, 2,3‐bis(chloromethyl)benzo[g]quinoxaline‐5,10‐dione, was prepared in a four‐steps synthesis. It was shown to react under electron transfer conditions with 2‐nitropropane anion by an bis‐S_RN1 mechanism to give three C‐alkylation products in excellent yields. Extension of this bis‐S_RN1 reaction to various nitronate or malonate anions and S‐centered anions led to a new class of potentially active benzo[g]quinoxaline‐5,10‐dione derivatives.     

Effect of conformational changes on a one-electron reduction process: evidence of a one-electron P-P bond formation in a bis(phosphinine)

EPR spectra show that one-electron reduction of bis(3-phenyl-6,6-(trimethylsilyl)phosphinine-2-yl)dimethylsilane (1) on an alkali mirror leads to a radical anion that is localized on a single phosphinine ring, whereas the radical anion formed from the same reaction in the presence of cryptand or from an electron transfer with sodium naphthalenide is delocalized on the two phosphinine rings. Density functional theory (DFT) calculations show that in the last species the unpaired electron is mainly confined in a loose P-P bond (3.479 A), which results from the overlap of two phosphorus p orbitals. In contrast, as attested by X-ray spectroscopy, the P-P distance in neutral 1 is large (5.8 A). As shown by crystal structure analysis, addition of a second electron leads to the formation of a classical P-P single bond (P-P 2.389 A). Spectral modifications induced by the presence of cryptand or by a change in the reaction temperature are consistent with the formation of a tight ion pair that stabilizes the radical structure localized on a single phosphinine ring. It is suggested that the structure of this pair hinders internal rotation around the C-Si bonds and prevents 1 from adopting a conformation that shortens the intramolecular P-P distance. The ability of the phosphinine radical anion to reversibly form weak P-P bonds with neutral phosphinines in the absence of steric hindrance is confirmed by EPR spectra obtained for 2,6-bis(trimethylsilyl)-3-phenylphosphinine (2). Moreover, as shown by NMR spectroscopy, in this system, which contains only one phosphinine ring, further reduction leads to an intermolecular reaction with the formation of a classical P-P bond.     

Vitamin B12 as an allosteric cofactor; dual fluorescence, hysteresis, oscillations and the selection of corrin over porphyrin

Studies of the emission spectra of four Co(III) cobinamides (diaquo-, aquohydroxo-, dihydroxo- and dicyano-) show (1) that the excited states corresponding to the alphabeta and epsilon absorption bands behave like the S(1) and S(2) levels in the non-alternant hydrocarbon azulene (with emission from S(2)> S(1) in violation of Kasha's rule) and (2) that the excited states include a TICT (twisted intramolecular charge transfer) mechanism, as in the simpler cyanines, but where the TICT state gives rise to dual fluorescence instead of cis-trans isomerisation. Combined with the previously reported dual fluorescence from the S(1) level in synthetic metal corrinoids and in the naturally-occurring metal-free corrin, this provides evidence that the existence of an additional (metastable) ground state with a significantly different vibronic splitting and nuclear configuration is an intrinsic property of the basic corrin ligand (irrespective of the nature of the side-chains and the metal ion or even the absence of a metal) which distinguishes it from porphyrin. The occurrence of hysteresis (and its associated oscillations) in redox reactions of the cobinamides involving both the Co(III/II) and Co(II/I) couples indicates that the corrin ligand also has an intrinsic ability to exist in different conformations or "allosteric" forms with differing redox potential, which further distinguishes it from the porphyrin ligand. Possible links between the existence of an additional metastable ground state and of allosteric changes and the likely reasons for the selection of corrin over a porphyrin for the vitamin B(12)-dependent enzymes are discussed.     

Nitrosation of thiols and thioethers in the gas phase: A combined theoretical and experimental study

Recent studies have demonstrated the biological importance of the interaction of nitric oxide with proteins such as cytochrome-c or hemoglobin. In particular, the possibility that the nitrosonium cation, NO(+), could reversibly bind to sulfide atom type was proposed. At pH values of biological relevance, nitrosation was proposed to occur through the action of NO(+) carriers such as nitrosothiols or nitrosamines. In this context, the gas phase chemistry of protonated nitrosothiols is studied in the present work by a combination of mass spectrometry and computational methods.     

Synthesis, characterization, and coupling reactions of six-membered cyclic P-chiral ammonium phosphonite-boranes; reactive H-phosphinate equivalents for the stereoselective synthesis of glycomimetics

Stereoselective syntheses of P-chiral ammonium phosphonite-borane complexes in the gluco- and manno-like series have been developed from P(V) phostone derivatives. The coupling reactions of these phostone donors with alcohols have been investigated with particular emphasis on the influence of protecting groups and conditions on stereoselectivity. The phosphonite-borane complexes may be applied directly in the coupling reactions and the products oxidized in situ to give phostone-mimetics of disaccharides. On the basis of these studies, successful protocols were established for the synthesis of β-gluco and α- and β-manno-configured phostones of primary alcohols. Deprotection of the dimeric compounds leads to novel families of α- or β-(1→6)-linked glycomimetics.     

Hydrogenation properties of KSi and NaSi Zintl phases

The recently reported KSi-KSiH(3) system can store 4.3 wt% of hydrogen reversibly with slow kinetics of several hours for complete absorption at 373 K and complete desorption at 473 K. From the kinetics measured at different temperatures, the Arrhenius plots give activation energies (E(a)) of 56.0 ± 5.7 kJ mol(-1) and 121 ± 17 kJ mol(-1) for the absorption and desorption processes, respectively. Ball-milling with 10 wt% of carbon strongly improves the kinetics of the system, i.e. specifically the initial rate of absorption becomes about one order of magnitude faster than that of pristine KSi. However, this fast absorption causes a disproportionation into KH and K(8)Si(46), instead of forming the KSiH(3) hydride from a slow absorption. This disproportionation, due to the formation of stable KH, leads to a total loss of reversibility. In a similar situation, when the pristine Zintl NaSi phase absorbs hydrogen, it likewise disproportionates into NaH and Na(8)Si(46), indicating a very poorly reversible reaction.