On-line Sulfur Isotope Analysis of Organic Material by Direct Combustion: Preliminary Results and Potential Applications

Abstract

Sulfur isotopes have received little attention in ecology studies because plant and animal materials typically have low sulfur concentrations (< 1 wt.%) necessitating labor-intensive chemical extraction prior to analysis. To address the potential of direct combustion of organic material in an elemental analyzer coupled with a mass spectrometer, we compared results obtained by direct combustion to results obtained by sulfur extraction with Eschka's mixture. Direct combustion of peat and animal tissue gave reproducibility of better than 0.5‰ and on average, values are 0.8‰ higher than values obtained by Eschka extraction. Successful direct combustion of organic material appears to be a function of sample matrix and sulfur concentration. Initial results indicate that direct combustion provides fast, reliable results with minimal preparation. Pilot studies underway include defining bear diets and examining fluctuations between freshwater and brackish water in coastal environments.     

环式M(SO2)(M=Zn, Cd)分子及其阴离子的基质隔离红外光谱和密度泛函理论计算

激光溅射锌和镉原子与SO₂分子反应的低温基质隔离红外光谱实验表明,在氩和氖的惰性基质中,形成了环式M(SO₂)分子及其阴离子M(SO₂)^- (M=Zn, Cd)．相关同位素(³⁴SO₂和S¹⁸O₂)替代实验及密度泛函理论计算均证实了这一结果．此外,自然电荷布居分析表明电子从金属锌和镉的s轨道转移到了SO₂配体上形成了M⁺(SO₂)^-“离子对”复合物,且该分子中的Zn-O键以及Cd-O键均表现出强的极化共价性．而Hg原子在与SO₂反应中所表现出来的惰性可由其较强的相对论效应所致的6s价电子层收缩与高电离电位得以解     

Determination of Non-metals by High Performance Liquid Chromatography with Inductively Coupled Plasma Detection

Abstract

High performance liquid chromatography (HPLC) has often been employed in the separation and speciation of metal containing compounds. One of the most sensitive devices used for detecting those compounds after the separation is the inductively coupled plasma (ICP). The similar flow rates for these two techniques render the coupling of the devices trivial, usually involving only a short length of capillary tubing. Upon entering the plasma, species are typically determined either via atomic emission spectrometry or mass spectrometry. HPLC-ICP devices have been employed less frequently for the determination of non-metals. This review will describe the applications of HPLC-ICP techniques to the determination of compounds containing carbon, sulfur, phosphorus, and the halogens. The instrumentation used for each application will be described, and the performance of the systems will be summarized.     

硫熏中药材品质及其毒理学研究进展

硫磺熏蒸是我国传统中药材干燥的一种加工方法,该方法具有杀虫、防霉、防腐和增白等功效。近年来研究发现,硫磺熏蒸会导致中药材某些活性成分转化生成新的含硫衍生物,导致其在人体的代谢过程和药效发生改变,甚至引发毒性反应,存在安全隐患。本文在现有文献的基础上归纳总结硫元素的各种形态、硫磺熏蒸中药材化学成分的转化规律及其毒理学研究,为进一步评价硫熏工艺的合理性研究提供理论参考。     

Charge/discharge characteristics of sulfur composite electrode at different temperature and current density in rechargeable lithium batteries

The charge/discharge characteristics of the sulfur composite cathodes were investigated at different temperatures and different current densities. The composite presented the discharge capacities of 854 and 632 mAh g⁻¹ at 60 and −20 °C, respectively, while it had the discharge capacities of 792 mAh g⁻¹ at 25 °C. The composite presented the discharge capacities of 792 and 604 mAh g⁻¹ at 55.6 and 667 mA g⁻¹, respectively, at room temperature. The results showed that the sulfur composite cathodes presented good charge/discharge characteristics between 60 and −20 °C and at a high c-rate up to 667 mA g⁻¹.     

Synthesis of 4-unsubstituted 2H-1,2,3-benzothiadiazine 1,1-dioxides via ortho lithiation of protected benzaldehyde derivatives

Variously substituted 2-phenyl-1,3-dioxolanes and 2-(2-bromophenyl)-1,3-dioxolanes, prepared from the corresponding benzaldehydes, were lithiated ortho to the acetal group. Reaction of the lithio derivatives with sulfur dioxide led to the lithium sulfinate salts, which gave, upon oxidative chlorination with sulfuryl chloride, the corresponding benzenesulfonyl chlorides. Then, depending on the aromatic substitution pattern of the molecule, several protocols were elaborated for the functional group transformations leading to the target compounds. Ring closure was performed with hydrazine hydrate or acetylhydrazine, in the latter case with one-pot removal of the acetyl group. The 4-unsubstituted 2H-1,2,3-benzothiadiazine 1,1-dioxides thus obtained are potential drug candidates based on their structural similarity to biologically active phthalazinones.     

CuI-catalyzed thioarylation of active methylene compounds with in situ generated benzenethiols: Preparation of α-thioaryl-β-dicarbonyls and 4-thioaryl-5-pyrazolones

In this paper, a one-step copper-catalyzed procedure for oxidative coupling of active methylene compounds including cyclic β-diketones, cyclic β-ketoesters and 5-pyrazolone with benzenethiols is described. Benzenethiols are in situ generated in the reaction mixture from aryl halides and thiourea as sulfur transfer reagent. α-Thioaryl compounds are obtained in excellent yields and in short reaction time via the process which is free from the foul smell of thiols.     

Determination of sulfur forms in wine including free and total sulfur dioxide based on molecular absorption of carbon monosulfide in the air–acetylene flame

A new method for the determination of sulfur forms in wine, i.e., free SO₂, total SO₂, bound SO₂, total S, and sulfate, is presented. The method is based on the measurement of the carbon monosulfide (CS) molecular absorption produced in a conventional air–acetylene flame using high-resolution continuum source absorption spectrometry. Individual sulfur forms can be distinguished because of the different sensitivities of the corresponding CS molecular absorption. The sensitivity of free SO₂ is about three times higher than the value for bound SO₂ and sulfate. The method makes use of procedures similar to those used in classic reference methods. Its performance is verified by analyzing six wine samples. Relative standard deviations are between 5 and 13% for free SO₂ and between 1 and 3% for total SO₂. For the validation of the accuracy of the new method, the results are compared with those of reference methods. The agreement of the values for total SO₂ with values of the classic method is satisfactory: five out of six samples show deviations less than 16%. Due to the instability of free SO₂ in wine and the known problems of the used reference method, serious deviations of the free SO₂ results are found for three samples. The evaluation of the limits of detection focuses on the value for free SO₂, which is the sulfur form having by far the lowest concentration in wine. Here, the achievable limit of detection is 1.8 mg L⁻¹. Figure Detection of non-metal elements using continuum source flame absorption spectrometry     

Preparation, characterization, and electrocatalytic properties of hybrid coatings of hexacyanometalate-doped-cationic films

Electrochemically active hybrid coatings based on cationic films, didodecyldimethylammonium bromide (DDAB), and poly(diallyldimethylammonium chloride) (PDDAC) are prepared on electrode surface by cycling the film-covered electrode repetitively in a pH 6.5 solution containing Fe(CN)₆ ³⁻ and Ru(CN)₆ ⁴⁻ anions. Modified electrodes exhibited stable and reversible voltammetric responses corresponding to characteristics of Fe(CN)₆ ^3−/4− and Ru(CN)₆ ^4−/3− redox couples. The cyclic voltammetric features of hybrid coatings resemble that of electron transfer process of surface-confined redox couple. Electrochemical quartz crystal microbalance results show that more amounts of electroactive anionic complexes partitioned into DDAB coating than those doped into PDDAC coating from the same doping solution. Peak potentials of hybrid film-bound redox couples showed a negative shift compared to those at bare electrode and this shift was more pronounced in the case of DDAB. Finally, the advantages of hybrid coatings in electrocatalysis are demonstrated with sulfur oxoanions.     

A New Sulfur‐containing Schiff‐Base Ligand and Binding to Copper(II) and Cobalt(II)

A new Schiff‐base ligand having a potentially coordinating thioether group (2‐quinoline‐N‐(2′‐methylthiophenyl)methyleneimine, qmtpm ) has been prepared. The synthesis, structure, UV‐Vis and EPR studies of one copper(II) and two cobalt(II) complexes from this ligand is reported. The X‐ray structures of the Cu^II and Co^II chlorido complexes 1 and 2 reveal the metal atoms in highly distorted square‐pyramidal environments constituted of one tridentate ligand and two anions. On the other hand, the thiocyanato Co^II compound 3 exhibits a distorted trigonal‐bipyramidal structure. These structural variations are apparently due to the different counter‐ions which leads to distinct lattice interactions. The spectroscopic data obtained by EPR and UV‐Vis investigations are in agreement with the solid‐state structures of the coordination compounds.