Photoinduced processes in dipyrrolyl-perfluoro-cyclopentenes

The photobehavior of five photochromic dipyrrolyl-perfluoro-cyclopentenes was studied by steady state and time-resolved absorption spectroscopy. The quantum yields of the UV-photoinduced ring-closing reaction (coloration) and the visible-stimulated cycloreversion reaction (bleaching) were measured. Kinetic and thermodynamic parameters of thermal bleaching were also determined. Nanosecond time-resolved experiments showed formation of a transient, which was not a precursor of the reaction photoproduct. This transient was tentatively assigned to a radical cation formed by direct photoionization through a short-lived triplet state. The nature of the transient species was supported by photoinduced electron transfer to electron acceptors.     

Synthesis of new benzylpyridines as potential photochromic compoundsa

Photoinduced proton transfer systems such as 2‐(2′,4′‐dinitrobenzyl)pyridine derivatives have been developed in an attempt to apply the compounds to variable optical transmission materials. However their fatigue resistance property is a limitation for these applications. New benzylpyridines have been synthesized and tested. 2‐(2′,4′‐Diphenylsulfonybenzyl)pyridine was found to be photochromic in the crystalline state and in ethanolic solution (λ_max= 485 nm) upon UV flash photolysis.     

Modeling viscosity and diffusion of plasma for pure elements and multicomponent mixtures from weakly to strongly coupled regimes

An analytic model is presented that predicts viscosity and diffusion of plasma for pure elements and multicomponent mixtures, from the high-temperature low-density weakly coupled regime to the low-temperature high-density strongly coupled regime. It relies on a pseudo-ion in jellium modeling that incorporates the effect of electron screening on the ion–ion interaction in the pseudo-ionization. Mixtures are treated using approximate kinetic expressions and mixing laws applied to the excess viscosity and self-diffusion of pure elements. Comparisons are made with classical and quantum molecular dynamics results to assess its accuracy. The mean deviations are in the range 20–40% with almost no predictions further than a factor of 2 over many decades of variation. Applications of this model in the inertial confinement fusion context could help in predicting the appearance and the growth of hydrodynamic instabilities.     

Aroma analysis of fresh and preserved onions and leek by dual solid-phase microextraction-liquid extraction and gas chromatography-mass spectrometry

The lachrymatory factor (thiopropanal-S-oxide) was directly analysed on fresh onion (Allium cepa) juice by solid-phase microextraction (polyacrylate fibre) using a fast routine GC-MS method on a 10 m x 0.32 mm I.D. (4 microm thick polydimethylsiloxane film) column with splitless mode injection. The identification and quantification of thiosulphinates and zwiebelanes were obtained on the same juice extracted by diethyl ether after 80 min maceration using the same GC-MS method. Selected ion recording enhanced the differentiation possibilities and the detection limits. This dual method was used to evaluate flavour differences between onion and shallot varieties as it provides accurate profiles of all initially formed compounds. Moreover, this method allowed us to compare qualitatively and quantitatively transformed products: frozen, freeze-dried powders and sterilised products. Excepting the lachrymatory factor, frozen onion compounds were similar compared to those of fresh onion sample. Conversely, the other transformed samples have lost most of the initially formed compounds and produced mainly di- and trisulphides corresponding to the degradation of thiosulphinates and zwiebelanes. These dramatic changes can explain the very different flavours of these manufactured products compared to fresh material.     

In search of novel ligands using a structure-based approach: a case study on the adenosine A<Subscript>2A</Subscript> receptor

In this work, we present a case study to explore the challenges associated with finding novel molecules for a receptor that has been studied in depth and has a wealth of chemical information available. Specifically, we apply a previously described protocol that incorporates explicit water molecules in the ligand binding site to prospectively screen over 2.5 million drug-like and lead-like compounds from the commercially available eMolecules database in search of novel binders to the adenosine A_2A receptor (A_2AAR). A total of seventy-one compounds were selected for purchase and biochemical assaying based on high ligand efficiency and high novelty (Tanimoto coefficient ≤0.25 to any A_2AAR tested compound). These molecules were then tested for their affinity to the adenosine A_2A receptor in a radioligand binding assay. We identified two hits that fulfilled the criterion of ~50 % radioligand displacement at a concentration of 10 μM. Next we selected an additional eight novel molecules that were predicted to make a bidentate interaction with Asn253^6.55, a key interacting residue in the binding pocket of the A_2AAR. None of these eight molecules were found to be active. Based on these results we discuss the advantages of structure-based methods and the challenges associated with finding chemically novel molecules for well-explored targets.     

Theoretical interpretation of X-rays photo-absorption in medium-Z elements plasmas measured at LULI2000 facility

We analyzed the spectra of X-ray transmission through radiatively heated medium-Z plasma (Fe, Ni, Cu and Ge) measured at LULI2000 facility in the wavelength range of 2p–nd transitions. The analysis was performed using the statistical superconfiguration code SCO, two line-by-line opacity codes based on the HULLAC and FAC packages and a new hybrid statistical-detailed code SCORCG. The temperature and mass density of the samples were estimated from hydrodynamic simulations based on the cavity radiative temperature measurements. The theory–experiment agreement is relatively good in the wavelength range corresponding to the 2p–3d transitions except in the germanium case. In the wavelength range of the 2p–2d, n > 3 transitions a relatively good theory–experiment agreement was found in the copper case. As predicted by calculations the separation of the characteristic spin-orbit-split 2p–3d structures, absent in the iron measured spectrum, appears in the nickel spectrum and is visible in the copper and germanium spectra. Comparisons of the experimental transmission with calculations confirm the importance of the relativistic configuration interaction. The absorption strength of the measured germanium 2p–3d transition is much larger than that obtained from the codes. Spatial temperature and density gradients, relatively high in the germanium sample, may be at the origin of this discrepancy.     

Surface properties of hydrogenated nanodiamonds: a chemical investigation

Hydrogen terminations (C-H) confer to diamond layers specific surface properties such as a negative electron affinity and a superficial conductive layer, opening the way to specific functionalization routes. For example, efficient covalent bonding of diazonium salts or of alkene moieties can be performed on hydrogenated diamond thin films, owing to electronic exchanges at the interface. Here, we report on the chemical reactivity of fully hydrogenated High Pressure High Temperature (HPHT) nanodiamonds (H-NDs) towards such grafting, with respect to the reactivity of as-received NDs. Chemical characterizations such as FTIR, XPS analysis and Zeta potential measurements reveal a clear selectivity of such couplings on H-NDs, suggesting that C-H related surface properties remain dominant even on particles at the nanoscale. These results on hydrogenated NDs open up the route to a broad range of new functionalizations for innovative NDs applications development.     

High sensitivity of diamond resonant microcantilevers for direct detection in liquids as probed by molecular electrostatic surface interactions

Resonant microcantilevers have demonstrated that they can play an important role in the detection of chemical and biological agents. Molecular interactions with target species on the mechanical microtransducers surface generally induce a change of the beam's bending stiffness, resulting in a shift of the resonance frequency. In most biochemical sensor applications, cantilevers must operate in liquid, even though damping deteriorates the vibrational performances of the transducers. Here we focus on diamond-based microcantilevers since their transducing properties surpass those of other materials. In fact, among a wide range of remarkable features, diamond possesses exceptional mechanical properties enabling the fabrication of cantilever beams with higher resonant frequencies and Q-factors than when made from other conventional materials. Therefore, they appear as one of the top-ranked materials for designing cantilevers operating in liquid media. In this study, we evaluate the resonator sensitivity performances of our diamond microcantilevers using grafted carboxylated alkyl chains as a tool to investigate the subtle changes of surface stiffness as induced by electrostatic interactions. Here, caproic acid was immobilized on the hydrogen-terminated surface of resonant polycrystalline diamond cantilevers using a novel one-step grafting technique that could be also adapted to several other functionalizations. By varying the pH of the solution one could tune the -COO(-)/-COOH ratio of carboxylic acid moieties immobilized on the surface, thus enabling fine variations of the surface stress. We were able to probe the cantilevers resonance frequency evolution and correlate it with the ratio of -COO(-)/-COOH terminations on the functionalized diamond surface and consequently the evolution of the electrostatic potential over the cantilever surface. The approach successfully enabled one to probe variations in cantilevers bending stiffness from several tens to hundreds of millinewtons/meter, thus opening the way for diamond microcantilevers to direct sensing applications in liquids. The evolution of the diamond surface chemistry was also investigated using X-ray photoelectron spectroscopy.