Factors controlling the regioselectivity of additions to α-enones—III: Reactions of 3-aryl α-enones with phosphorylated anions

Reaction of phosphonoester 2 and phosphononitrile 3 with chalcone and p-methoxychaleone in THF-t-BuOK at room temperature gives only the product resulting from CC double bond attack. The same reagents with benzalacetone lead to mixture of products resulting from CC double bond and carbonyl attack, though phosphine oxide 4 gives only the products of CC attack. Dypnone gives products of carbonyl attack with 3 and does not react with 2.These results are discussed in terms of perturbation theory: C₄ attack increases with delocalization of the reagent's negative charge and lowering of the α-enone LUMO level.     

A liquid chromatography/electrospray ionization-tandem mass spectrometry method for quantification of specific organophosphorus pesticide biomarkers in human urine

Organophosphorus pesticides are commonly used in both agricultural and residential settings. The widespread use of these chemicals makes it almost impossible for humans to avoid exposure. In order to determine background human exposure, there is a need for fast, reliable, and sensitive analytical methods. We have developed a sensitive method to quantify specific biomarkers of the organophosphorus pesticides acephate, azinphos, chlorpyrifos, coumaphos, diazinon, isazofos, malathion, methamidophos, parathion and pirimiphos or their O,O-dimethyl analogues in human urine, as their selective metabolites or as the intact pesticide. Isotopically labeled internal standards were used for eight of the analytes. The use of labeled internal standards in combination with high-performance liquid chromatography electrospray ionization–tandem mass spectrometry provided a high degree of specificity. Repeated analysis of urine samples fortified with high and low concentrations of the analytes gave relative standard deviations (RSD) of less than 10% for the analytes with an isotopically labeled standard. Analytes without isotopically labeled standards had higher RSD. For all compounds except methamidophos and acephate, the recoveries were greater than 70%. The limits of quantification for most of the analytes were in the range of 0.1 to 1 ng/mL. We detected concentrations of most of these pesticides and/or their metabolites in urine samples from non-occupationally exposed persons using our method. Our frequencies of detection for the analytes measured ranged from 1% to 98%.     

Synthesis, characterization and crystal structures of two polyphilic mesogenic compounds

Three homologous series of semi-perfluorinated liquid crystals: 4-(2,2,3,3,4,4,4-heptafluoro-butyloxycarbonyl)phenyl, 4-(2,2,3,3,4,4,5,5-octafluoropentyloxycarbonyl)phenyl and 4-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyloxycarbonyl)phenyl 4-[(n-perfluoroalkyl)alkyloxy]benzoates have been synthesized. Their mesomorphic properties were studied by DSC, microscopic observation and X-ray diffraction. Their layer spacings are smaller than the molecular length (L). The ratio d_SA/L is about 0.7. The crystal structure of two derivatives of the first family have also been investigated. In both structures the molecules pack in smectic C-like sheets where neighbouring molecules are antiparallel, interacting through dipolar and van der Waals forces. The interactions between contiguous sheets, through the ends of perfluorinated chains are very weak. The X-ray diffraction results on the mesophases and on the crystalline structures of two compounds of the first family are compared. From this, we propose a model of the smectic phases with a zig-zag structure.     

EFFICACY OF PHOTODYNAMIC THERAPY ON ORIGINAL AND RECURRENT RAT MAMMARY TUMORS

Abstract— Photodynamic therapy has demonstrated efficacy toward primary, metastatic and recurrent human tumors. Here, we investigated the ability of photodynamic therapy, using Photofrin, to inhibit growth of R3230AC mammary adenocarcinomas when tumors were treated as original implants and again as lesions recurring at the initial treatment site. The results demonstrate that both initial implants and lesions recurring after the first photodynamic treatment respond similarly to the same photodynamic therapy protocol, with mean tumor volume doubling times of ˜ 11 days in both cases. Cells cultured from original tumor implants or tumors that recurred after photodynamic treatment accumulate equivalent amounts of [¹⁴C]polyhematoporphyrin. Single cell suspensions prepared from either original or recurrent tumors from animals administered 5 mg/kg Photofrin and exposed to light in vitro displayed comparable phototoxicity. Additionally, examination of tumors by light microscopy revealed no morphological differences between the original tumor implants and the recurrent lesions. Taken together, these data indicate that lesions which recurred at the site of the initial photodynamic treatment were not resistant to a second identical course of photodynamic therapy.     

Methode d'analyse quantitative par spectrometrie Raman-laser associee aux fibres optiques pour le suivi d'une fermentation alcooliqueA quantitative laser Raman spectrometric method with fibre optics for monitoring an alcoholic fermentation

Laser Raman spectrometry with a fibre-optic system is used to monitor the concentrations of ethanol, glucose and fructose at various stages of an alcoholic fermentation process. For evaluation of the data, cross-correlation and multivariate least-squares procedures are compared; the latter gives the best results. Ethanol, glucose and fructose can be determined remotely with a precision of ca. 10 g l^?1 (10–15%).     

Neosappanone A, a xanthine oxidase (XO) inhibitory dimeric methanodibenzoxocinone with a new carbon skeleton from Caesalpinia sappan

A novel dimeric methanodibenzoxocinone, named neosappanone A (1), possessing a unique unprecedented novel carbon framework, has been isolated from the heartwood of Caesalpinia sappan L. of Vietnam, and its structure was elucidated on the basis of spectroscopic analysis. Neosappanone A (1) competitively inhibited xanthine oxidase in a concentration-dependent manner (IC₅₀, 29.7 μM; K_i, 16.3 μM).     

Laccase-catalyzed carbon-carbon bond formation: oxidative dimerization of salicylic esters by air in aqueous solution

The laccase catalyzed oxidative dimerization of salicylic esters, a rare example of a laccase-catalyzed carbon-carbon bond formation, was studied. This reaction allows the use of air as stoichiometric oxidant and proceeds in aqueous solution. The preparative scope and the mechanism of the method, which provides a new and convenient access to functionalized biaryls under mild conditions, were investigated.     

Ion Chromatographic determination of trace anions and cations in high-purity water

An ion chromatographic measuring system for the off-line and on-line determination of some trace anions and cations in high-purity water is presented. The ng/L level of anions and cations in 20-130 mL high-purity water can be analyzed after preconcentration on ion exchange columns. The concentrated solutes are eluted by eluents from the trap column and separated using a Dionex analytical column. The quantification of each ion is achieved using the suppressor technique and conductivity detector. The influence of various parameters on the results is discussed. The detection limits of cations and anions are between 10 and 30 ng/L for chloride, bromide, nitrate, phosphate, sulphate, sodium, ammonium, potassium, magnesium and calcium ions.     

High-performances membranes for pervaporation I. Poly(vinyl alcohol)–poly(N-vinyl pyrrolidone) blends

Dense membranes were prepared from poly(vinyl alcohol)–poly(N-vinyl pyrrolidone) (PVA–PVP) blends of different compositions and studied in swelling and dehydration by pervaporation of three organic solvents contaminated by 5 wt% water. The swelling generally increases with the PVP content. No extraction occurs in water–tetrahydrofuran (THF) and water–methyl ethyl ketone (MEK) mixtures. In ethanol containing 10 wt% of water, there is no extraction for blends containing less than 40 wt% PVP and an increasing extraction beyond this PVP content. The pervaporation flux of the water–ethanol mixture increases drastically at the same threshold whereas the water permselectivity falls to a low level. The values of the diffusion and permeability coefficients determined from transient permeation of the test water–ethanol mixture exhibit a similar sudden increase at the same PVP content threshold. This singular behavior of the blend membranes is interpreted by a strong affinity of the PVP component to ethanol, combined with a disappearance of crystallites in the blend at this threshold. Consequently the amorphous membrane can swell freely according to the affinity of the PVP component, leading to the observed behavior.     

Action des bromures de perfluoroalkylmagnésiums sur les aldéhydes α,βéthyléniques

Perfluoroalkylmagnesium bromide, C_nF_2n+1MgBr (n = 2, 6, 8), reacts with α,β-unsaturated aldehydes to give allylic alcohols as the sole products. No attack on the β-carbon atom of the carbonyl was detected, even when the reaction was carried out in the presence of CuCl. Part of the Grignard reagent decomposes to trans-R_FCFCFBr and trans-R_FCFCFI. Neither a mechanism involving dissociation into R⁺_F MgX^- nor the formation of a carbene intermediate is capable of explaining the thermal decomposition of the Grignard reagent.