Multiple wavelength (365-475 nm) complete actinometric characterization of Corning Lab Photo Reactor using azobenzene as a highly soluble, cheap and robust chemical actinometer.

The characterization of commercially available Corning Lab Photo Reactor by actinometry at different wavelengths (365, 385, 405 and 475 nm) using azobenzene E ↔ Z photoisomerization is reported. By comparison with photon fluxes determined externally using a radiometer, this method based on NMR spectroscopy is rapid, cheap, robust, reproducible and can applied to UVA-visible range, compared to previously described chemical actinometric protocols. Recalculation of isatin N-phenylhydrazone isomerization quantum yield at 405 nm gave almost the same value as the literature data ([Formula: see text] = 0.

Electrochemical sulfonylation of imidazoheterocycles under batch and continuous flow conditions.

An efficient and versatile protocol for the C-H sulfonylation of imidazoheterocycles electrochemical activation was established under batch and flow conditions. The selective C-H bond functionalization proceeded under catalyst- and oxidant-free conditions and tolerated a wide range of functional groups. Various sodium sulfinates as well as imidazo[1,2-]-pyridines, -pyrimidine, -quinolines, and -isoquinolines, imidazo[1,2-]pyridazine, imidazo[2,1-]thiazoles and benzo[]imidazo[1,2-]thiazoles reacted successfully.

Roles of Hydration for Inducing Decomposition of 2-Deoxy-d-ribose by Ionization of Oxygen K-Shell Electrons.

To experimentally investigate the role of hydration in the initial process of the decomposition of 2-deoxy-d-ribose (dR), which is a major component of the DNA backbone, we used mass spectrometry to monitor the ions desorbing from hydrated dR films exposed to monochromatic soft X rays (560 eV). The X-ray photons preferentially ionize the K-shell electrons of the oxygen atoms in DNA. Hydrated dR samples were prepared under vacuum by exposing a cooled (∼150 K) dR film deposited on a Si substrate to water vapor.

Oxidative Neutralization of Mustard-Gas Simulants in an On-Board Flow Device with In-Line NMR Monitoring.

The fast and effective neutralization of the mustard-gas simulant 2-chloroethyl ethyl sulfide (CEES) using a simple and portable continuous flow device is reported. Neutralization takes place through a fully selective sulfoxidation by a stable source of hydrogen peroxide (alcoholic solution of urea-H O adduct/MeSO H freshly prepared). The reaction progress can be monitored with an in-line benchtop NMR spectrometer, allowing a real-time adjustment of reaction conditions.

Distinct expression of interleukin (IL)-36α, β and γ, their antagonist IL-36Ra and IL-38 in psoriasis, rheumatoid arthritis and Crohn's disease.

Interleukin (IL)-36α, IL-36β and IL-36γ are expressed highly in skin and are involved in the pathogenesis of psoriasis, while the antagonists IL-36Ra or IL-38, another potential IL-36 inhibitor, limit uncontrolled inflammation. The expression and role of IL-36 cytokines in rheumatoid arthritis (RA) and Crohn's disease (CD) is currently debated. Here, we observed that during imiquimod-induced mouse skin inflammation and in human psoriasis, expression of IL-36α, γ and IL-36Ra, but not IL-36β and IL-38 mRNA, was induced and correlated with IL-1β and T helper type 17 (Th17) cytokines (IL-17A, IL-22, IL-23, CCL20).

[CLOVES syndrome: a malformational syndrome closely resembling Proteus syndrome].

Background: CLOVES syndrome (Congenital Lipomatous asymmetric Overgrowth of the trunk with lymphatic, capillary, venous, and combined-type Vascular malformations, Epidermal nevi, Skeletal anomalies) is a sporadic malformational syndrome that has recently been described (mutation of PIK3CA), with asymmetric body hypertrophy, lipomatous hamartoma of the trunk and numerous malformations.

Patients And Methods: We report a case of CLOVES syndrome initially diagnosed as Proteus syndrome, revealed by infection of a dorsal lipomatous hamartoma. The patient presented with both right lower limb hypertrophy and capillary and venous-lymphatic malformations, associated with dorsal capillary malformations, left cervico-facial hypertrophy, and cervical epidermal hamartoma, all of which are consistent with Proteus syndrome.

Modeling proton-induced damage on 2-deoxy-D-ribose. Conformational analysis.

Modeling proton-induced damage in biological systems, in particular in DNA building blocks, is of major concern in studies on cancer proton therapy. This is indeed an extremely complex process and analysis of the mechanism at the molecular level is of crucial interest. Such collision reactions of protons on biological targets induce different reactions: excitation and ionization of the biomolecule, fragmentation of the ionized species, and charge transfer from the projectile ion toward the biomolecular target.

High pain catastrophizing scores in one-fourth of patients on biotherapy for spondylarthritis or rheumatoid arthritis.

Objectives: To measure catastrophizing scores in patients on biotherapy for spondyloarthritis (SpA) or rheumatoid arthritis (RA).

Methods: The first 140 outpatients or day-hospital patients seen at a teaching hospital rheumatology department for biotherapy administration completed the validated French version of the Pain Catastrophizing Scale (PCS, total score ranging from 0 to 52); a questionnaire on perceived support and past, current, and future disease activity; and a questionnaire on perceived understanding of their disease by family and co-workers.

Results: PCS scores were significantly higher in the 54 SpA patients than in the 86 RA patients (20.

Highly controlled synthesis of nanometric gold particles by citrate reduction using the short mixing, heating and quenching times achievable in a microfluidic device.

Homodispersed 1.8 nm gold nanoparticles were obtained reproducibly in high yields using the classical Turkevich protocol at a high concentration in a continuous flow capillary reactor. The microfluidic reactor made from commercially available items permitted short mixing, heating and quenching times which are the key parameters of this synthesis.

Double-strand break induction and repair in V79-4 hamster cells: the role of core ionisations, as probed by ultrasoft X-rays.

Purpose: To compare the induction of double-strand breaks (DSB) in cells irradiated by 250 and 350 eV ultrasoft X-rays and assess the residual yield of breaks 2 hours post irradiation in order to unravel the correlation between the sharp increase in cell-killing efficiency of ultrasoft X-rays above versus below the carbon-K threshold (284 eV) and the induction of core events in DNA atoms.

Materials And Methods: V79-4 hamster cells were irradiated with synchrotron ultrasoft X-rays at isoattenuating energies of 250 eV and 350 eV. DSB were quantified using pulse field gel electrophoresis.

Highly selective and sensitive Hg2+ fluorescent sensors based on a phosphane sulfide derivative.

A series of fluorescent sensor molecules based on a phosphane sulfide derivative were designed and synthesized. The effect of the distance between the complex entities as well as the number and the length of fluorophores was investigated using both steady-state and time-resolved fluorescence methods. The complexation behavior of these sensor molecules, which have a distinct affinity for Hg(2+), is reported.

Induction and repairability of DNA damage caused by ultrasoft X-rays: role of core events.

Purpose: To investigate the severity of damage induced in plasmid DNA by ultrasoft X-rays at different energies, in order to unravel the correlation between the sharp increase in cell-killing efficiency of ultrasoft X-rays above versus below the carbon K-threshold and the induction of core events in DNA atoms.

Materials And Methods: Bluescript (pBS, tight packing) and pSP189 (pSP, loose packing) plasmids were exposed to ultrasoft X-rays at 250, 380 and 760 eV energies, respectively, above phosphorus L-, carbon K- and oxygen K-thresholds. Complex DNA lesions were assayed by the repair protein Formamidopyrimidine DNA glycosylase (Fpg) and by in vitro repair assay using whole cell-free extracts.

Synthesis, fluorescence, and two-photon absorption of bidentate phosphane oxide derivatives: complexation with pb(2+) and cd(2+) cations.

A series of fluorescent phosphane oxide derivatives based on diphenylphosphanoethane (DPPE) and diphenylphosphanomethane (DPPM) skeletons has been prepared by means of Grignard reactions and Sonogashira cross-couplings. The photophysical properties and the linear and nonlinear spectra of these compounds have been investigated. An edge-to-face conformation resulting in the formation of an excimer was confirmed by fluorescence lifetime measurements of these multichromophoric derivatives.

Highly selective and sensitive phosphane sulfide derivative for the detection of Hg2+ in an organoaqueous medium.

A new fluorescent molecular sensor for Hg2+ based on the phosphane sulfide derivative exhibits a very low detection limit in an aqueous medium (3.8 nM) with a very high selectivity over other interfering cations. The reversibility of the complexation process was also examined and was found to be successful.

High-throughput enzymatic method for enantiomeric excess determination of O-acetylated cyanohydrins.

The reaction yield and enantiomeric excess of O-acetylated cyanohydrin reaction products from a library of chiral catalysts can be analyzed by a three-step screening method. Alcohol dehydrogenase and NADH are used to analyze unreacted substrate. A lipase with absolute specificity converts one enantiomer to a quantifiable product before the remaining enantiomer is hydrolyzed with an unspecific esterase and quantified.

Amine capture strategy for peptide bond formation by means of quinolinium thioester salts.

A new and unprecedented exploitation of quinolinium thioester salts 2 in peptide bond formation is reported. These synthetic tools were assessed during the preparation of a number of dipeptides 3a-f obtained in good yields with complete stereochemical integrity. A sequential mechanism related to a prior amine capture strategy is well-established.

Dual Lewis acid-Lewis base activation in enantioselective cyanation of aldehydes using acetyl cyanide and cyanoformate as cyanide sources.

Dual activation by a chiral Lewis acid and an achiral or chiral Lewis base enabled cyanation of both aromatic and aliphatic aldehydes with acetyl cyanide and ethyl cyanoformate to provide direct access to O-acetylated and O-alkoxycarbonylated cyanohydrins, respectively, under mild conditions. With a combination of a Ti-salen catalyst and Et3N, benzaldehyde was converted to the O-acetylated cyanohydrin with 94% ee within 10 h at -40 degrees C in 89% isolated yield.

Novel extension of Meyers' methodology: stereoselective construction of axially chiral 7,5-fused bicyclic lactams.

A novel extension of Meyer's lactamization is reported for the preparation of seven-membered ring lactams 1a-d incorporating a biaryl unit. The required keto-esters 2a-c were readily accessible via the Suzuki coupling reaction. A borylation-Suzuki coupling (BSC) sequence was successfully developed for the high-yielding preparation of keto-ester 2d.