Multi-residue analysis and ultra-trace quantification of 36 priority substances from the European Water Framework Directive by GC-MS and LC-FLD-MS/MS in surface waters

A multi residue analysis was developed for screening, quantification and confirmation of 36 priority organic compounds included in the 2000/60/EC European Water Framework Directive. The compounds analyzed included 19 pesticides, 8 PAH, 5 endocrine-disruptors and 4 organochlorine compounds. The method was developed in three steps. First, automated off-line solid-phase extraction using Strata X cartridges was optimized to trap simultaneously the 36 studied compounds. Second, the more volatile compounds were analysed by gas chromatography coupled to mass spectrometry with electron impact ionisation in selected ion monitoring mode (SIM). Third, the last 20 compounds were detected and quantified, in one run, by liquid chromatography coupled to fluorescence detector and tandem mass spectrometry. The excellent selectivity and sensitivity allowed us satisfactory quantification and confirmation at levels as low as 0.2-67 ng L⁻¹ with recoveries between 59 and 105%. Such methodology was then applied to French surface waters: all the waters present organic contaminants, and their concentration varied according to the origin and nature of substances.     

Faceting and stability of smectic A droplets on a solid substrate

It is shown that a smectic A droplet deposited on a solid substrate treated for strong homeotropic anchoring is faceted at the top in spite of the fact that there are no steps at the free surface, but instead edge dislocations in the bulk. The radius of the facet and the full profile of the curved part of the droplet are determined as a function of the temperature in the vicinity of a nematic-smectic A phase transition. It is shown that the observed profiles do not correspond to the actual equilibrium shape, but to metastable configurations close to their point of marginal stability. In addition, we predict that the profiles must be different for a given temperature depending on whether the droplet has been heated or cooled down to reach this temperature. Finally, we discuss the problem of the formation of giant dislocations in big droplets (Grandjean terraces).     

微生物胞外聚合物对重金属镉的解毒作用及红外光谱分析

为探索微生物胞外物在微生物对重金属的抗性和去除过程中的作用,比较分析了对重金属镉具有不同抗性和去除率的菌株SCSE425-7和SCSE709-6胞外物的产生情况和菌株的红外光谱谱图。结果表明,在含镉条件培养时,菌株SCSE425-7表现了较高的镉抗性,分泌了相对较多的可溶性胞外多糖;而菌株SCSE709-6镉抗性较SCSE425-7低,但镉的生物去除性能较好,分泌了更多不可溶胞外聚合物。这说明,在重金属毒性胁迫下,微生物分泌的可溶性胞外多糖可能有助于提高微生物对重金属的抗性,而不可溶性胞外聚合物有助于重金属的微生物吸附。菌株红外光谱分析结果表明不可溶胞外聚合物上的酰胺基和羧基是其吸附镉离子的主要官能团。     

d(C4)相关序列形成四分子i-Motif结构的电喷雾质谱研究

设计了与富含胞嘧啶(C)的DNA序列d(C4)相关的DNA序列d(C4), d(TC4), d(AC4), d(T2C4), d(A2C4), d(C4T), d(C4A)和d(TC4T); 采用电喷雾质谱测定发现这些序列形成四分子非共价复合物离子, 根据离子的相对丰度可确定形成四链i-motif结构的数量和可能性; 同时考察了腺嘌呤(A)和胸腺嘧啶(T)在d(C4)序列的5'和3'端对其形成四分子i-motif结构的影响. 结果表明, 在d(C4)的5'端增加A碱基或T碱基更易形成四分子复合物; 5'端含T碱基比含A碱基更利于形成四分子复合物; 而在d(C4)序列中增加2个A碱基或T碱基比增加相应的单个碱基形成了更高丰度的四分子离子峰.     

双状态切换下BVP振子的复杂行为分析

非线性切换系统具有广泛的工程背景,而传统的非线性理论不能直接用来解决其中的问题,因而成为当前国内外热点和前沿课题之一. 目前相关工作大都是围绕固定时间或单状态切换开展的,而实际工程系统大都属于多状态切换问题,同时多状态切换涉及到更为丰富的动力学行为. 本文基于两广义BVP 振子,通过引入双向切换开关,构建了双状态切换下的非线性动力学模型,进而研究状态切换导致的各种运动模式及其相应的产生机制. 应用非光滑系统的Poincaré映射理论,推导了双状态切换下的Lyapunov 指数的计算公式,结合子系统的分岔分析,得到了切换系统随分岔参数变化的动力学演化过程及其相应的最大Lyapunov 指数的变化情况. 得到了双状态切换条件下系统存在着各种形式的振荡行为,分析了诸如周期突变等现象及通往混沌的倍周期分岔道路,揭示了不同运动模式的产生机制及倍周期序列的本质. 与固定时间切换和单状态切换系统不同,双临界状态切换系统存在着更为丰富的非线性现象,其主要原因在于双状态切换会产生更多的切换点,且切换点的位置更加多变. 同时切换系统的倍周期分岔序列与光滑系统中的倍周期分岔序列不同,切换系统的倍周期分岔序列只对应于切换点数目的成倍增加,而其相应的周期一般不对应于严格的周期倍化过程.      

Characterization and in vitro phase I microsomal metabolism of designer benzodiazepines — an update comprising adinazolam,cloniprazepam, fonazepam, 3‐hydroxyphenazepam,metizolam and nitrazolam

Designer benzodiazepines represent an emerging class of new psychoactive substances. While other classes of new psychoactive substances such as cannabinoid receptor agonists and designer stimulants are mainly consumed for hedonistic reasons, designer benzodiazepines may also be consumed as ‘self‐medication’ by persons suffering from anxiety or other psychiatric disorders or as stand‐by ‘antidote’ by users of stimulant and hallucinogenic drugs. In the present study, five benzodiazepines (adinazolam, cloniprazepam, fonazepam, 3‐hydroxyphenazepam and nitrazolam) and one thienodiazepine (metizolam) offered as ‘research chemicals’ on the Internet were characterized and their main in vitro phase I metabolites tentatively identified after incubation with pooled human liver microsomes. For all compounds, the structural formula declared by the vendor was confirmed by nuclear magnetic resonance spectroscopy, gas chromatography–mass spectrometry (MS), liquid chromatography MS/MS and liquid chromatography quadrupole time‐of‐flight MS analysis. The detected in vitro phase I metabolites of adinazolam were N‐desmethyladinazolam and N‐didesmethyladinazolam. Metizolam showed a similar metabolism to other thienodiazepines comprising monohydroxylations and dihydroxylation. Cloniprazepam was metabolized to numerous metabolites with the main metabolic steps being N‐dealkylation, hydroxylation and reduction of the nitro function. It has to be noted that clonazepam is a metabolite of cloniprazepam, which may lead to difficulties when interpreting analytical findings. Nitrazolam and fonazepam both underwent monohydroxylation and reduction of the nitro function. In the case of 3‐OH‐phenazepam, no in vitro phase I metabolites were detected. Formation of licensed benzodiazepines (clonazepam after uptake of cloniprazepam) and the sale of metabolites of prescribed benzodiazepines (fonazepam, identical to norflunitrazepam, and 3‐hydroxyphenazepam) present the risk of incorrect interpretation of analytical findings. Copyright © 2016 John Wiley & Sons, Ltd.     

Simultaneous analysis of small organic acids and humic acids using high performance size exclusion chromatography

An accurate and fast method for simultaneous determination of small organic acids and much larger humic acids was developed using high performance size exclusion chromatography. Two small organic acids, i.e. salicylic acid and 2,3‐dihydroxybenzoic acid, and one purified humic acid material were used in this study. Under the experimental conditions, the UV peaks of salicylic acid and 2,3‐dihydroxybenzoic acid were well separated from the peaks of humic acid in the chromatogram. Concentrations of the two small organic acids could be accurately determined from their peak areas. The concentration of humic acid in the mixture could then be derived from mass balance calculations. The measured results agreed well with the nominal concentrations. The detection limits are 0.05 mg/L and 0.01 mg/L for salicylic acid and 2,3‐dihydroxybenzoic acid, respectively. Applicability of the method to natural samples was tested using groundwater, glacier, and river water samples (both original and spiked with salicylic acid and 2,3‐dihydroxybenzoic acid) with a total organic carbon concentration ranging from 2.1 to 179.5 mg C/L. The results obtained are promising, especially for groundwater samples and river water samples with a total organic carbon concentration below 9 mg C/L.     

A Simple and Efficient Device for Treatment of Fluoride Samples in Analysis by the Selective Electrode Method.

Abstract

A simple, efficient and economic device for fluoride mass transference is presented in this study. Hexamethyldisiloxane (HMDS) is used to volatilize fluoride and, in addition to 0.05M NaOH, 0.3M citrate/phosphate/1 M KCl, pH 7.8 (buffer A) and 0.5 M citrate pH 5.5 (buffer B) are used as the trapping solution with the aim of an additional gain when concentration is a limiting condition in the use of the selective electrode. Using 0.05M NaOH, the fluoride mass transferred was in the range of 40 - 0.2 μg, and with buffer A the mass transferred was around 0.2 μg, with a total recovery in a few hours. The influence of interfering substances on fluoride volatilization was assessed. Fluoride was transferred from standard solutions in either the absence or presence of interfering substances (ethanol, propyleneglycol, glycerol, sorbitol, artificial saliva), and the respective recoveries were determined. Due to its simplicity and low cost several device units can be assembled allowing simultaneous analysis for rapid and accurate comparison of different samples. This device is useful for eliminating interfering substances, to concentrate samples as a function of the limit of method, and/or to attenuate gradative loss of the electrode sensitivity.     

Multiexciton molecules in the hexaborides

We investigate multiexciton bound states in a semiconducting phase of divalent hexaborides. Due to three degenerate valleys in both the conduction and valence bands the binding energy of a 6-exciton molecule is greatly enhanced by the shell effect. The ground state energies of multiexciton molecules are calculated using the density functional formalism. We also show that charged impurities stabilize multiexciton complexes leading to condensation of localized excitons. These complexes can act as nucleation centers of local moments. Received 24 October 2000     

SiC bonding in ( C 60 ) n Si m clusters

This paper deals with a new type of SiC bonding where silicon atom seems to bridge C₆₀ molecules. We have studied films obtained by deposition of (C₆₀)_nSi_m clusters prepared in a laser vaporization source. Prior deposition, free ionized clusters were studied in a time-of-flight mass spectrometer. Mixed clusters (C₆₀)_nSi_m were clearly observed. Abundance and photofragmentation mass spectroscopies revealed the relatively high stability of the (C₆₀)_nSi _n ⁺ , (C₆₀)_nSi _{n - 1} ⁺ and (C₆₀)_nSi _{n - 2} ⁺ species. This observation is in favor of the arrangement of these complexes as polymers where the C₆₀ cages may be bridged by a silicon atom. Free neutral clusters are then deposited onto substrate making up a nanogranular thin film (≃ 100 nm). The film is probed by Auger and X-ray photoemission spectroscopies, but above all by surface enhanced Raman scattering. The results suggest an unusual chemical bonding between silicon and carbon and the environment of the silicon atom is expected to be totally different from the sp³ lattice: ten or twelve carbon neighbors might surround silicon atom. The bonding is discussed to the light of the so-called fullerene polymerization as observed for pure fullerite upon laser irradiation. This opens a new route for bridging C₆₀ molecules together with an appreciable energy bonding, since the usual van der Waals bonding in fullerite could be replaced by an ionocovalent bond. Such an assumption must be checked in the future by XAS and EXAFS experiments. Received 15 November 2000