Computational NMR spectroscopy of organoarsenicals and the natural polyarsenic compound arsenicin A

The (1)H and (13)C NMR chemical shifts and coupling constants of a series of organoarsenic compounds were calculated with DFT methods and compared with available experimental spectra. We show that non-relativistic methods successfully model the NMR spectra of these molecules; relativistic spin-orbit effects are small but appreciable for (13)C shifts, and their inclusion is beneficial. Application of the same methods of calculation to the intriguing natural polyarsenic compound arsenicin A allowed several viable alternative structures to be ruled out and thereby confirmed the previously suggested adamantane-like structure of arsenicin A. These results not only reinforce the known predictive power of DFT NMR calculations, but also open the way for the investigation of other naturally occurring molecules with unusual structures outside the scope of empirical methods.     

Is solar UV frying fish?

A personal selection of 39 recent papers is presented covering various aspects of current developments in bioorganic chemistry and novel natural products such as the first natural polyarsenic organic natural product, arsenicin A, from the sponge Echinochalina bargibanti.     

银盐法测定饮用水中砷的含量

为测定饮用水中砷的含量并探讨其最佳测定条件,用银盐法测定了饮用水中砷的含量,并改变温度、酸度、锌粒大小和加入量进行了实验.结果表明,测定饮用水中砷的含量的最佳条件是:最佳温度25℃,在50 mL测量液中加入1:1的硫酸4mL,5g锌粒.该法操作快速、简便,结果准确、可靠,加标回收率为98%-103%.     

Metabolism of arsenic compounds by the blue mussel mytilus edulis after accumulation from seawater spiked with arsenic compounds

Blue mussels (Mytilus edulis) were exposed to 100 μg As dm^?3 in the form of arsenite, arsenate, methylarsonic acid, dimethylarsinic acid, arsenobetaine, arsenocholine, trimethylarsine oxide, tetramethylarsonium iodide or dimethyl-(2-hydroxyethyl)arsine oxide in seawater for 10 days. The seawater was renewed and spiked with the arsenic compounds daily. Analyses of water samples taken 24 h after spiking showed that arsenobetaine and arsenocholine had been converted to trimethylarsine oxide, whereas trimethylarsine oxide and tetramethylarsonium iodide were unchanged. Arsenobetaine was accumulated by mussels most efficienty, followed in efficiency by arsenocholine and tetramethylarsonium iodide. None of the other arsenic compounds was significantly accumulated by the mussels. Extraction of mussel tissues with methanol revealed that control mussels contained arsenobetaine, a dimethyl-(5-ribosyl)arsine oxide and an additional arsenic compound, possibly dimethylarsinic acid. Mussels exposed to arsenobetaine contained almost all their experimentally accumulated arsenic as arsenobetaine, and mussels exposed to tetramethylarsonium iodide contained it as the tetramethylarsonium compound. Mussels exposed to arsenocholine had arsenobetaine as the major arsenic compound and glycerylphosphorylarsenocholine as a minor arsenic compound in their tissues. The results show that arsenobetaine and arsenocholine are efficiently accumulated from seawater by blue mussels and that in both cases the accumulated arsenic is present in the tissues as arsenobetaine. Consequently arsenobetaine and/or arsenocholine present at very low concentrations in seawater may be responsible for the presence of arsenobetaine in M. edulis and probably also among other marine animals. The quantity of arsenobetaine accumulated by the mussels decreases with increasing concentrations of betaine. HPLC-ICP-MS was found to be very powerful for the investigation of the metabolism of arsenic compounds in biological systems.     

The chemical form and acute toxicity of arsenic compounds in marine organisms

A method for the separation and identification of inorganic and methylated arsenic compounds in marine organisms was constructed by using a hydride generation/cold trap/gas chromatography mass spectrometry (HG/CT/GC MS) measurement system. The chemical form of arsenic compounds in marine organisms was examined by the HG/CT/GC MS system after alkaline digestion. It was observed that trimethylarsenic compounds were distributed mainly in the water-soluble fraction of muscle of carnivorous gastropods, crustaceans and fish. Also, dimethylated arsenic compounds were distributed in the water-soluble fraction of Phaeophyceae. It is thought that most of the trimethylated arsenic is likely to be arsenobetaine since this compound released trimethylarsine by alkaline digestion and subsequent reduction with sodium borohydride. The major arsenic compound isolated from the water-soluble fraction in the muscle and liver of sharks was identified as arsenobetaine from IR, FAB Ms data, NMR spectra and TLC behaviour. The acute toxicity of arsenobetaine was studied in male mice. The LD₅₀ value was higher than 10 g kg⁻¹. This compound was found in urine in the non-metabolized form. No particular toxic symptoms were observed following administration. These results suggest that arsenobetaine has low toxicity and is not metabolized in mice. The LD₅₀ values of other minor arsenicals in marine organisms, trimethylarsine oxide, arsenocholine and tetramethylarsonium salt, were also examined in mice.     

Desorption electrospray ionization mass spectrometry (DESI-MS) applied to the speciation of arsenic compounds from fern leaves

The different chemical forms of arsenic compounds, including inorganic and organic species, present distinct environmental impacts and toxicities. Desorption electrospray ionization mass spectrometry (DESI-MS) is an excellent technique for in situ analysis, as it operates under atmospheric pressure and room temperature and is conducted with no/minimal sample pretreatment. Aimed at expanding its scope, DESI-MS is applied herein for the quick and reliable detection of inorganic (arsenate—As(V): AsO₄ ^3? and arsenite—As(III): AsO₂ ^?) and organic (dimethylarsinic acid—DMA: (CH₃)₂AsO(OH) and disodium methyl arsonate hexahydrate: CH₃AsO₃·2Na·6H₂O) arsenic compounds in fern leaves. Operational conditions of DESI-MS were optimized with DMA standard deposited on paper surfaces to improve ionization efficiency and detection limits. Mass spectra data for all arsenic species were acquired in both the positive and negative ion modes. The positive ion mode was shown to be useful in detecting both the organic and inorganic arsenic compounds. The negative ion mode was shown only to be useful in detecting As(V) species. Moreover, MS/MS spectra were recorded to confirm the identity of each arsenic compound by the characteristic fragmentation profiles. Optimized conditions of DESI-MS were applied to the analysis of fern leaves. LC-ICP-MS was employed to confirm the results obtained by DESI-MS and to quantify the arsenic species in fern leaves. The results confirmed the applicability of DESI-MS in detecting arsenic compounds in complex matrices.     

氢化物发生-银盐分光光度法测定中草药中砷的含量

采用氢化物发生-银盐分光光度法对中草药中溶解态砷的含量进行了测定。结果表明,砷标准曲线的回归方程为C=1．4474 A-0．0087,r=0．99,在0～0．4μg/mL的范围内,线性关系良好。对5种样品进行了回收实验,回收率为92．4％-102．6％,相对标准偏差为1．26％-2．43％。该法简单、快速、灵敏、准确。     

Arsenic compounds in marine and terrestrial organisms: Analytical,chemical and biochemical aspects

Arsenic has a reputation as a poison, because arsenic trioxide was used during medieval times as an agent for murder. Lingering memories of these events make any arsenic-containing material suspect. Toxicity is a property of a specific compound and varies with the composition and structure of compounds. Developments in analytical methodology made it possible not only to determine total arsenic in a variety of matrices but also arsenic compounds. Knowledge about the arsenic cycle in marine systems has expanded considerably during the past decade. The marine arsenic cycle appears to be more complex than the cycle in the terrestrial environment. More attention must be given to the minor arsenic-containing compounds detected in organisms and experiments should be undertaken that provide information about the biochemical pathways used for the transformation of arsenic compounds.     

高效液相色谱-原子荧光光谱 (HPLC-AFS)法测定水产动植物样品中无机砷

采用液相色谱-蒸气发生-原子荧光光谱联用技术(HPLC-HG-AFS,以下简称LC-AFS)对水产动植物样品中无机砷进行测定。藻类中以紫菜、海带、羊栖菜为研究对象,水产动物中以贝类、鱼类、虾类为研究对象,实验中研究了流动相的种类和浓度、提取剂的种类和浓度,并通过正交实验法确定了最佳提取温度、提取时间、氧化时间。在最优的实验条件下运用等度洗脱的方式测定了样品中无机砷的含量,并对方法的有效性进行了验证,结果表明,三价砷、五价砷、一甲基砷和二甲基砷在5~100μg/L范围内线性关系良好;同时对不同海产品进行加标回收实验,结果表明,各组分的加标回收率在80%~105%。平行样品测定结果的相对标准偏差在2%~6%。说明液相色谱-原子荧光光谱联用法很好地解决了水产品中砷形态测定的问题,尤其对无机砷的测定提供了非常有效的方法。方法简便、准确、设备价格低廉,完全可用于水产动植物产品中无机砷的测定。     

Speciation of Arsenic Compounds in the Urine of Rats Orally Exposed to Dimethylarsinic Acid Ion Chromatography with ICP–MS as an Element-Selective Detector

A combined ion chromatography (IC) with inductively coupled plasma mass spectrometry (ICP—MS) system as an element-selective detector has been used for the determination of arsenic compounds. Seven arsenic compounds were separated by cation-exchange chromatography. Subsequently, the separated arsenic compounds were directly introduced into the ICP—MS and were detected at m/z =75. Detection limits for the seven arsenic compounds ranged from 0.8 to 3.8 μg As/l. The IC–ICP–MS system was applied to the determination of arsenic compounds in the urine of dimethylarsinic acid (DMAA)-exposed rats. DMAA was the most abundant arsenic compound detected. Arsenous acid, monomethylarsonic acid and trimethylarsine oxide were also detected.     

Arsenic solubility, mobility and speciation in the deposits from a copper production waste storage

The sediments in large pond for discharge of waste products of metallurgical activity were studied with respect to the valence forms of arsenic and its mobility. A sequential extraction procedure for arsenic compounds was applied and optimized according to the nature of analyzed products. During the first stage, the content of water-soluble arsenic compounds was determined, during the second—HCl-soluble forms and during the third—compounds soluble in sodium hydroxide. The optimum conditions for leaching arsenic from sediments (sample weight, concentration and volume of extractants, time of treatment) were established for each fraction.Speciation studies for determining As(III) and As(V) were carried out in the obtained arsenic extracts. The ability of the proposed sequential extraction procedure to specify the valence forms of inorganic arsenic was evaluated using model samples with added As(III) and As(V) and the recovery of spikes has been assessed. It was found that oxidation of As(III) and processes of sorption and sedimentation of As(V) proceed upon dissolution. A depth profiling was performed of the content of diverse forms of Às in two sites. The content of water-soluble As does not exceed 7.4% of total As in the sediments, As(III) being lower than 7.4% of that of the extracted As. The bulk of arsenic compounds (above 78% As) is dissolved in 2M HCl, and As(V) was found to be more than 94% of extracted arsenic. The analytical features of the procedure are as follow: precision, evaluated through the repeatability w > 0.96 and accuracy, estimated by the recovery above 93%, calculated on the basis of a twice repeated analysis of a series of 9 samples.     

A novel method for the estimation of arsenic(V) in organic compounds

A novel method for the determination of arsenic(V) in organic compounds has been developed by reducing combined arsenic(V) to arsenic(III) in aqueous acetic acid medium with zinc dust. In some cases, addition of ethyl alcohol is necessary to dissolve the compound and to keep the arsenic(III) compound in solution. The arsenic(III) is titrated with iodine and the end-point is detected visually with starch as indicator or potentiometrically.     

香兰素席夫碱的合成和光致变色性

以香兰素和邻苯二胺为原料合成了席夫碱,以质谱和核磁等手段进行了结构表征。该化合物有较好的光致变色性,其分子结构在紫外-热或者酸-碱作用下,可发生可逆循环变化过程。文中探讨了紫外、热、酸碱度对化合物结构的影响,及其引起的光谱性质的变化,结果表明,它有望应用于信息存储材料领域。     

Separation and identification of highly fluorescent compounds derived from trans-resveratrol in the leaves of Vitis vinifera infected by Plasmopara viticola

A method for identification of highly fluorescent compounds in vine leaves infected by Plasmopara viticola was developed using reversed phase liquid chromatography with simultaneous diode array and fluorometric detection. Fluorescent compounds were extracted from leaves with a methanol-water mixture (70:30). Separation by HPLC was performed using a C(18) column and gradient elution with water-acetonitrile mixtures (20-80% of acetonitrile). The main unknown fluorescent compound was identified by line spectral comparison with a standard obtained by UV photoisomerization of trans-resveratrol glucoside, and its structure was confirmed by liquid chromatography-mass spectrometry. Identification and structural elucidation of the fluorescent compound in the leaves of Vitis vinifera allows early detection of Plasmopara viticola invasion.     

南海佳丽鹿角珊瑚化学成分的研究(一)

从中国南海的一种石珊瑚一佳丽鹿角珊瑚（Acroporapuchro）的乙酸乙酯可溶部分获得两个有机化合物：正十六碳酸（Ⅰ）和（24S）－24-甲基胆甾醇（Ⅱ）。它们的结构是通过EIMS、IR、1HNMR、13CNMR和DEPT等实验分析确定的。其中纯的（24S）-24-甲基胆甾醇是首次从自然界大量获得。本文首次提供化合物（Ⅱ）的完整波谱数据。     

Rapid access to infrared reference spectra of arbitrary organic compounds: scope and limitations of an approach to the simulation of infrared spectra by neural networks

Substance identification by infrared spectroscopy is performed by comparison of the experimental spectrum with a reference spectrum from a printed compilation or a database. If the analyzed compound can not be found in a database the corresponding reference spectrum has to be simulated. In order to achieve this, several reasonable candidates of structures for the compound at hand have to be conceived and for all these, infrared spectra have to be developed. The simulated spectrum that is most similar to the experimental suggests the correct structure. A rapid spectrum prediction method based on neural networks has been developed that supplies reference spectra for any organic compound. The scope and limitations of this method will be discussed on a test set of 16 compounds representing a broad range of organic chemistry.     

Classification of IR spectra of organic compounds by the methods of multidimensional statistics

In order to clarify the possibilities of classifying the IR spectra of organic compounds by methods of multidimensional statistics, with the object of casting further light on the relationship between the structure of a compound and noncharacteristic spectral criteria, an experiment was carried out, in which methods of factor analysis were applied to the entire set of spectra. A clusterization was obtained of the original spectra conforming with the chemical classification of the compounds studied and universal vectors for transition into a low-dimensionality space, where the spectra studied are described by 11 factors instead of the initial 65. The concept of spatial identification of the spectra is discussed.K. A. Timiryazev Agricultural Academy. Translated from Zhurnal Strukturnoi Khimii, Vol. 34, No. 1, pp. 94–100, January–February, 1993.     

Computer-Assisted Verification of Agreement Between IR Spectrum and Hypothetical Chemical Structure

A method is suggested for estimating the agreement between the IR spectrum and the hypothetical structure of an organic compound. The technique is based on coverage of the molecular graph by the structural fragments revealed for the compounds selected from the database using the maximal similarity criterion between the spectra of the compounds and the query spectrum. The efficiency of this approach is demonstrated by reference to some examples and by analyzing two data samples with correct and wrong structure assignments to spectra.     

Oxonol 染料的稳态光物理行为研究

对oxonol——一种带负电荷类菁染料化合物溶液的光谱和光物理问题进行了研究.发现它和一般分子内共轭的电荷转移化合物相比，无论在吸收光谱或荧光发射光谱上，都表现出不同的光物理和光化学行为.对出现的这种差异，特别是负的溶致变色行为和在不同pH条件下分子的互变异构等对吸收光谱的影响进行了讨论.     

Evaluation of the relationship between spectral and structural similarity in IR spectroscopy

Representation of a structural formula of a compound as a complete set of nonisomorphic k-vertex (2 ≤k≤7) connected fragments is used to evaluate the structural similarity of compounds. The spectra and structures of spectrally or structurally alike compounds are compared statistically using a database containing 32,000 IR spectra and structures. This study reveals some tendencies typical for both full IR spectra and their abbreviated versions represented by sets of most characteristic peaks. Applicability of IR databases to spectrum simulation for compounds with a specified structure is justified statistically. A method is proposed for evaluating the efficiency of a search algorithm selecting structural analogs of the compound from an IR database according to the query spectrum. Translated fromZhurnal Strukturnoi Khimii, Vol. 41, No. 2, pp. 379–390, March–April, 2000.