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 N2-phenylhydrazone isomerization quantum yield at 405 nm gave almost the same value as the literature data ([Formula: see text] = 0.0013) and confirmed the robustness and applicability of this methodology.

Electrochemical sulfonylation of imidazoheterocycles under batch and continuous flow conditions.

An efficient and versatile protocol for the C-H sulfonylation of imidazoheterocycles via 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-a]-pyridines, -pyrimidine, -quinolines, and -isoquinolines, imidazo[1,2-b]pyridazine, imidazo[2,1-b]thiazoles and benzo[d]imidazo[1,2-b]thiazoles reacted successfully. Interestingly, significant acceleration and higher yields were obtained under microfluidic conditions.

Metal-Free ATRP Catalyzed by Visible Light in Continuous Flow.

ATRP of methyl methacrylate catalyzed by Eosin Y, an inexpensive and an environmental benign dye, was performed in a continuous flow reactor made of FEP tubing and irradiated by visible light green LEDs. The reaction under flow conditions was significantly more rapid and controlled compared to that in batch giving 90% of polymerization after only 3 h of irradiation. The formed polymers in flow have M n measured by GPC and DOSY NMR in accordance with the theoretical values and show low dispersities (Ð < 1.5). The livingness of the polymers has been confirmed by LED on and LED off experiments and by the synthesis of block copolymers. The protocol described herein serves as a "proof of concept" of using Eosin Y as a photocatalyst for controlled polymerization and of using 1D and 2D NMR for polymer characterization. The protocol could be replicated in the future for other reversible-deactivation radical polymerizations.

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-H2 O2 adduct/MeSO3 H freshly prepared). The reaction progress can be monitored with an in-line benchtop NMR spectrometer, allowing a real-time adjustment of reaction conditions. Inherent features of millireactors, that is, perfect control of mixing, heat and reaction time, allowed the neutralization of 25 g of pure CEES within 46 minutes in a 21.5 mL millireactor (tR =3.9 minutes). This device, which relies on affordable and nontoxic reagents, fits into a suitcase, and can be deployed by police/military forces directly on the attack site.

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.

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. The coordination of Hg(2+) induces a photoinduced electron transfer from fluorophore to the complexed mercury and results in a significant decrease of the fluorescence. Theses sensors exhibit very low detection limits in CH(3)CN/H(2)O (80/20 v:v) and excellent sensitivity to Hg(2+) over other potentially interfering cations such as Na(+), K(+), Mg(2+), Ca(2+), Cu(2+), Ag(+), Zn(2+), Cd(2+) and Pb(2+).

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. Upon complexation with heavy metal ions such as Pb2+ and Cd2+, a red shift of the one- and two-photon excitation spectra was observed in the absorption and emission spectra. Furthermore, enhancement of the electron-withdrawing character of the phosphane oxide resulted in a significant enhancement of the two-photon absorption cross-section, leading to the first biphotonic Cd2+ sensors combining high affinity for Cd2+, large two-photon absorption cross-sections, and significant enhancement of the two-photon excited fluorescence in the presence of the cation. Such derivatives are highly promising for incorporation into devices for the detection of heavy metal ions in water and effluents.

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. [structure: see text]

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. Additionally, a tripeptide 3g was prepared according to a "safety-catch" approach, thus demonstrating the important potential of these new synthetic tools in the design of new safety-catch linkers exploitable in Solid-Phase Peptide Synthesis (SPPS).

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. Cyclization of the resulting keto-esters 2a-d or keto-acids 5a,c,d in the presence of (R)-phenylglycinol afforded the desired lactams 1a-d in high yields (72-93%) and excellent diastereoselectivities (>95%). This methodology provides a facile stereoselective access to new axially chiral bridged biaryls.