用于放射性卤代药物合成的高速无载体固相标记法

本文研究了一种适合于卤素标记化合物的高分子氧化剂的合成及其性能, 研究了适合于某些卤代放射性药物合成的高速、无载体产物的固相标记法和固相反应。 用于肿瘤探针的药物带电诺丹明和肾功能显像剂胆固醇在固定化后, 将这两种药物进行固相法碘标记并对产物进行了鉴定, 得到了放射化学纯度大于95%, 放射性回收率高于96%的标记化合物, 实现了5分钟内完成放射性标记药物无需分离就可得到极高放化纯产物的高速标记法。本文还对其它能生成有机汞化合物的固相标记法进行了讨论。     

Artifact formation of methyl- and ethyl-mercury compounds from inorganic mercury during derivatization using sodium tetra(n-propyl)borate

Sodium tetra(n-propyl)borate (NaBPr₄) was introduced as derivatization reagent to extend the possibility for determining ethyl-mercury compounds. This study investigated the artifact formation of methyl- and ethyl-mercury compounds during NaBPr₄ derivatization, together with the influence of this artifact on organomercury analysis in environmental samples. The artifact methyl- and ethyl-mercury compounds during NaBPr₄ derivatization were evident and depended strongly on the amount of Hg(II) present in the solution for derivatization. Some unidentified organomercury compounds were found when the amount of Hg(II) in the derivatization solution was over 1 μg. The amounts of NaBPr₄ and acetate buffer and the presence of organometallic compounds other than organomercury showed little influence on the artifact effect. The artifact monoethylmercury encompasses 0.99-2.9% of the amount of Hg(II) present and interferes strongly with the monoethylmercury analysis. The formation rate of artifact monomethylmercury is much lower and ca. 0.03-0.28% of the Hg(II) present. The artifact affects remarkably the monomethylmercury analysis for solid samples when these have a low ratio of monomethylmercury-to-total Hg concentrations (≤0.003) and the recovery of Hg from the samples is high. Mathematical correction seems to be difficult due to the low reproducibility of this artifact effect. Formation of artifact organomercury compounds caused during NaBPr₄ derivatization may lead to false Hg speciation and overestimate concentrations of organomercury compounds.     

反相液相色谱法测定化工废水中的无机汞和有机汞

用反相离子对色谱对无机汞和3种有机汞化合物进行了形态分析。以65%甲醇作流动相,加入四丁基溴化铵（TBA）做离子对试剂,用紫外检测器在230nm进行检测。对影响汞化合物吸收强度和保留时间的因素如甲醇和四丁基溴化铵的浓度进行了优化。在不同的线性范围内对无机汞和3种有机汞化合物作了工作曲线,4种化合物均成良好的线性关系。     

Gas-chromatographic determination of organomercury(II) compounds

Gas chromatography has proved to be an invaluable technique not only for the identification and determination of organomercury(II) compounds but also for differentiating inorganically bound from organically bound mercury. It also offers a possible route for determining various inorganic species through their conversion into organomercury(II) compounds. These procedures and the chemical and instrumental problems associated with them are reviewed.     

Simultaneous determination of organotin,organolead, and organomercury compounds in environmental samples using capillary gas chromatography with atomic emission detection

As part of a continuing evaluation of new analytical and sample preparation techniques conducted by the US Environmental Protection Agency (EPA), the use of capillary gas chromatography with atomic emission detection (GC-AED) for the simultaneous determination of organotin, organolead, and organomercury compounds in environmental samples was investigated. Pentylmagnesium bromide was used to pentylate ionic organotin, organolead, and organomercury compounds; the pentyl derivatives were then separated by GC and determined by AED. Several important GC-AED parameters, including the type of injector inlet, carrier gas flow rate, and helium make-up gas flow rate, were optimized for the simultaneous determination of these organometallic compounds. Their minimum detectable concentrations were approximately 1.0 to 2.5 ng/mL using a 0.5-μL on-column injection. The calibration curves exhibited good linearity between 2.5 and 2500 ng/mL for organotin and organolead compounds, and between 2.5 and 10000 ng/mL for organomercury compounds.     

Photochemical reactions of organomercury compounds in organic solvents

The quantum yields of photolysis of organomercury compounds in different organic solvents have been measured. It was shown that the quantum yields of photolysis of nitro derivatives of mercury compounds and the symmetric (methylnaphtyl)mercury compound are equal to unity. The photolysis of halo derivatives of benzylmercury proceeds with lower quantum yields as compared with photolysis of analogous dibenzylmercury derivatives. The quantum yields of photolysis of organomercury compounds are almost independent of the solvent.     

冷蒸气发生-原子荧光光谱法测定化工废水中的无机汞和总有机汞

用氢化物发生－原子荧光光谱法测定了化工废水中的无机汞和总有机汞。无机汞可以直接测定;用过硫酸钾在沸水浴中加热20min即可把有机汞转化为无机汞,实现总汞的测定,二者之差为总有机汞。对影响测定灵敏度的一些实验参数进行了优化,汞的检测限为8．2ng/L。     

Organomercury derivatives of arylazobenzoic acids

A number of organomercury derivatives of arylazobenzoic acids have been prepared and characterised by analytical, IR, PMR and electronic absorption spectral data. In the 3-coordinated organomercury complexes the N å Hg bond appears to be weak. The 4-coordinated complexes obtained from the terdentate ligands o-(2- hydroxybenzene-azo) benzoic acids show a large bathochromic shift of the π-π^* transition of the ligand indicating a much stronger N å Hg bond.     

Kinetics of the decomposition of symmetrical organomercury compounds

Summary A series of organic radicals arranged in order of their rates of removal from symmetrical organomercury compounds with hydrogen chloride in different solvents is given.     

固相微萃取技术及其在有机锡和有机汞分析中的应用

固相微萃取是近年来发展起来的一种简便便快捷的样品前处理技术,这项技术不需要有机萃取剂,是一种环境友好的萃取过程。本文在前人工作和我们自己研究的基础上,讨论了ＳＰＭＥ技术在有机锡和有机汞分析中的应用及各项参数对测定的影响。     

Speciation of organomercury compounds by capillary electrophoresis with pre-column derivatization and on-line stacking

A simple capillary electrophoresis method was developed to separate and quantify methylmercury, ethylmercury, and phenylmercury with the enhancement of pre-column derivatization and on-line stacking.     

Characterization of an unprecedented organomercury adduct via Hg(II)-mediated cyclization of N9-propargylguanine

This communication describes mercury(II)-mediated cyclization of N9-propargylguanine under hydrothermal conditions. The structural investigations reported here confirm cyclization and reveal simultaneous formation of a unique organomercury adduct of a tricyclic guanine derivative.     

Chemically-induced dynamic nuclear polarisation. Photoreactions of organomercury compounds

The photolysis of symmetric and asymmetric organomercury compounds has been studied by CIDNP. No indications of the existence of RHg· radicals have been found. Depending on the solvent, reactions occur from excited states with different spin multiplicities.     

On assistance in β-elimination reactions

It has been shown that organomercury compounds containing strongly electro-negative groups in the β-position and which are not capable of inter- and intramolecular interaction with the mercury atom, undergo symmetrization and substitution reactions rather than β-elimination in the presence of nucleophiles.     

Utilization of aminomercuration and hydroxymercuration reactions in the synthesis of heterocycles (review)

The cyclization of ethyleneamines by the action of mercury salts to give five- and six-membered nitrogen heterocycles is examined. The mechanism and stereochemistry of this reaction and the chemical and three-dimensional structures of the intermediate organomercury compounds and some chemical properties of the latter are discussed.     

The alkylation of aromatic compounds accompanying the demercuration of organomercury salts

Conclusions The possibility of using the demercuration of organomercury salts for alkylating certain aromatic hydrocarbons has been shown.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2083–2084, September, 1967.     

Formation of linear meta-oligophenyls in the decomposition of polymeric mercury derivatives of meta-substituted benzene compounds by powders of metals

Conclusions Decomposition of polymer organomercury compounds, obtained from m-diiodo-and m-dibromobenzene and sodium amalgams with powders of palladium or silver, leads to diphenyl and noncyclic m-oligophenyls.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, p. 1880, August, 1970.     

A single crystal X-ray study of the products of halogen mercury cyclization of 8-allylthioquinoline

The reaction products of 8-allylthioquinoline with mercury halides are studied by single crystal X-ray diffraction. It is shown that the products are organomercury derivatives of salts of 2,3-dihydro[1,4]-thiazino[2,3,4-ij]quinoliniuim.     

Separation of Organomercury Species Using Nonaqueous Capillary Electrophoresis Coupled with Sample Stacking and Electrokinetic Injection Techniques

A nonaqueous capillary electrophoresis (NACE) method, 30 mM ammonium acetate in methanol as background electrolyte (BGE), was developed for separation of the organomercury species without complexing reagents. The effects of different solutes and solvents in BGE were studied. Three species of organomercury, methylmercury, ethylmercury and phenylmercury, were separated well and all the number of theoretical plates were over 10⁶. The present NACE method was also coupled with sample stacking and electrokinetic injection techniques to enhance the detection sensitivity. Under the optimum conditions, the limit of detection (S/N = 3) is 18 ng mL⁻¹ and the linear relation range from 40 to 750 ng mL⁻¹ were obtained for methylmercury.     

Indirect Mercury Speciation in Biological Tissues by Closed‐Vessel Microwave‐Assisted Digestion and Flow‐Injection Cold‐Vapor Atomic Fluorescence Detection

Abstract

A simple and rapid method based on closed vessel microwave‐assisted extraction was developed to determine total, inorganic mercury and organomercury in biological tissues. Total mercury was extracted using HNO₃:H₂O₂ (4:1) mixture. In a separate subsample, extraction of mercury species was carried out with tetramethylammonium hydroxide (TMAH). The total and inorganic mercury analyses were carried out by flow‐injection cold‐vapor atomic fluorescence spectrometry (FI‐CV‐AFS). The organomercury concentration was calculated by difference. Considering a sample amount of 0.2 g, the detection limits were 4 and 26 ng/g for total and inorganic mercury, respectively. The accuracy of the procedures was checked by analyzing certified reference materials and recovery studies of spiked fish tissues.