New polydentate ligand and catalytic properties of the corresponding ruthenium complex during sulfoxidation and alkene epoxidation

Bis(diimine)-ruthenium complexes constitute a class of catalysts with good activity for oxidation reactions, such as sulfoxidation and epoxidation. The synthesis and the full characterization of a new ruthenium complex bearing an original pentadentate ligand (L5pyr for 2,6-bis-(6-ethyl-2,2'-bipyridyl)-pyridine) is reported. Comparison of its activity with regard to[Ru(bpy)2(CH3CN)2](2+) and [Ru(bpy)2(py)(CH3CN)](2+) during alkene and sulfide oxidation allowed us to conclude that the addition of a fifth pyridine ligand in the coordination sphere improves the efficiency of the catalyst. Moreover, under these oxidation conditions a hydroxylation of the ligand L5pyr led to a better activity than its analogue [Ru(bpy)2(py)(CH3CN)](2+), especially during epoxidation of alkenes by PhI(OAc)2.     

Rapid amperometric detection of Escherichia coli in wastewater by measuring β-D glucuronidase activity with disposable carbon sensors

An assay on the indirect amperometric quantification of the β-D-Glucuronidase (GLUase) activity was developed for the rapid and specific detection of Escherichia coli (E. coli) in complex environmental samples. The p-aminophenyl β-D-glucopyranoside (PAPG) was selected as an electrochemical substrate for GLUase measurement and the p-aminophenol (PAP) released during the enzymatic hydrolysis was monitored by cyclic voltammetry with disposable carbon screen-printed sensors. The intensity of the measured anodic peak current was proportional to the amount of GLUase, and therefore to the number of E. coli in the tested sample. Once the substrate concentration and pH values optimized, a GLUase detection limit of 10 ng mL⁻¹ was achieved. Using a procedure involving a filtration step of the bacteria followed by their incubation with the substrate solution containing both the nonionic detergent Triton X-100 as permeabilization agent and the culture media Luria broth to monitor the growth, filtered bacterial cells ranging from 5 × 10⁴ to 10⁸ UFC/membrane were detected within 3 h. The amperometric assay was applied to the determination of fecal contamination in raw and treated wastewater samples and it was successfully compared with conventional bacterial plating methods and uidA gene quantitative PCR. Owing to its ability to perform measurements in turbid media, the GLUase amperometric method is a reliable tool for the rapid and decentralized quantification of viable but also nonculturable E. coli in complex environmental samples.     

Brønsted Acid-Catalyzed Enantioselective Cycloisomerization of Arylalkynes

The first example of an enantioselective carbocyclization of an alkyne-containing substrate catalyzed by chiral Brønsted acids was achieved. The use of the 2-hydroxynaphthyl substituent on the alkyne as a directing group constituted the key parameter enabling both efficient regioselective protonation of the carbon–carbon triple bond and chiral induction. The key cationic intermediate could be depicted either as a cationic vinylidene ortho-quinone methide or a stabilized vinyl cation. Atropoisomeric phenanthrenes derivatives were produced in high yields and good enantioselectivities under mild, metal-free reaction conditions in the presence of chiral N-triflylphosphoramide catalysts. The carbenic nature of the cationic intermediate was also exploited to describe an example of alkyne/alkane cycloisomerization.     

Kinetics and Bacterial Inactivation Induced by Peroxynitrite in Electric Discharges in Air

The mechanism of bacterial inactivation by electric discharges (non-thermal plasma) is examined on the basis of the action of the formed peroxynitrite and hydrogen peroxide on the external membrane of bacteria. A model accounts for the gas to liquid transfer of the active species which react with the bacterial wall at the liquid surface or /and in the bulk solution. Direct exposure to the glidarc discharge induces a pseudo zero order decay of the bacterial concentration, followed by a pseudo 1st order step for low concentrations. Post-discharge reactions develop after switching off the discharge according to a 1st order mechanism and show that active species drift in the solution. Additionally the bactericidal properties of pure water exposed to the discharge (i.e., ??Plasma Activated Water??) was evidenced even 24?h after performing the plasma treatment.     

Synthesis of new carbamoyl dithiophosphates

The synthesis of new organophosphorus compounds containing a carbamoyl unit is performed by nucleophilic addition or cycloaddilion on substituted acetylisocyanates.     

New Carbamoyl Organophosphorus Compounds

Abstract

The syntheses of various organophosphorus compounds, which contain a function with potentially agropharmaceutical properties (acylureas [1], acylsemicarbazides [2] or imidazolidinetriones [3]) are described.     

FTIR spectroscopic analyses of the temperature and pH influences on stratum corneum lipid phase behaviors and interactions

A thermotropic investigation of different lipid dispersions containing ceramide 3 (CER3) or sphingomyelin (SPM), perdeuterated palmitic acid (PA-d(31)) and cholesterol (CH) or cholesterol sulfate (CS) at pH 5.2 and 7.4 used as model membranes, has been carried out by Fourier transform infrared (FTIR) spectroscopy in order to estimate the importance of these lipids and of the temperature and pH for the maintenance of the structural organization of the stratum corneum (SC) lipid lamellae. The results obtained for the CER3 and SPM mixtures at pH 5.2 and 7.4 indicated that the little size of the polar headgroup of CER3 compared with that of SPM could permit a more closely packing in the CER3 acyl chains. Moreover, the CH and CS induced an increase of the order in the CER3 acyl chains over the physiological temperatures while a disordering was seen above 60 degrees C. In addition, the thermal phase behaviors observed for the CER3/PA-d(31) dispersion at pH 5.2 and 7.4, suggested a phase separation between the CER3 and PA-d(31) molecules in this mixture. Nevertheless, the miscibility between the CER3 and PA-d(31) was raised in the presence of CH or CS at pH 5.2. In particular, the incorporation of these sterols into the CER3/PA-d(31) dispersion at pH 5.2 appeared to result in an increase of the order in the acyl chains of CER3 and PA-d(31) at about 37 degrees C. In contrast, a phase separation was observed between the CER3 and PA-d(31) in the CER3/PAd(31)/CH and CER3/PA-d(31)/CS dispersions at pH 7.4. Interestingly, the pH change from 5.2 to 7.4 in these tertiary dispersions was also accompanied by a substantial deprotonation of the PA-d(31) molecules which seemed more pronounced in the presence of CH as compared with CS. Altogether, the results suggested that the ceramides, fatty acids and sterols could play an important structural role in the SC cohesion.