芳基汞化合物的性质研究——Ⅶ.邻位取代苯基氯化汞的质子分解反应

本文研究了邻位取代苯基氯化汞o-XC_6H_4HgCl(X=CH_3、H、Cl、Br、COOC_2H_5、NO_2)与HCl(NaI)在85％对氧陆圜水溶液中的质子分解反应,证明反应按S_El历程进行。视取代基不同,反应速度次序如下:CH_3>H>Cl>COOC_2H_5～Br>NO_2。从化学反应与紫外光谱的研究以及理论计算结果表明,p或π电子的邻位取代基对水原子有分子内配位,它对反应速度有重要影响。测定了15种p-、m-、o-取代苯基氯化汞在80％对氧陆圜水溶液中在40.0℃的质子分解反应的速度常数k_1,表明给电性取代基加速反应,吸电性取代基使反应减慢,这可以看作是反应中心在芳环上的芳基汞化合物的S_E1反应所具有的一个特点。     

The influence of the mercury and thallium atoms in organomercury and organothallium nitroxyl radicals on their reactivity

An increase is found in the reactivity of organomercury and organothallium nitroxyl mono- and biradicals of the imidazoline type in comparison with the analogous compounds without organometallic fragments. This is explained by the formation of coordination bonds NHg, NTl, and NOHg.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 224–226, January, 1993.     

GC-MIP-PED as an element-specific system for the determination of organomercury compounds

The application of the combination of gas chromatography and a self-developed plasma emission detector for organomercury speciation is presented. The system, basing on interference filter technology, is described briefly. The plasma and the optical system have to be optimized to reach highest sensitivity for mercury detection. Dimethyl-, methyl- and inorganic mercury as selected compounds have been separated on a GC column and calibrated to obtain the analytical performance data of the system used. Finally, the analysis of some real samples has been performed.     

Determination of organometallic compounds in surface water and sediment samples with SPME-CGC-ICPMS

Organometal compounds of tin, mercury and lead were simultaneously determined in environmental water and sediment samples by CGC-ICPMS. Instead of classical liquid/liquid extractions, solid phase microextraction was used as sampling technique. In this method, the organometallic compounds arein situ derivatised in the aqueous phase and simultaneously extracted onto a polydimethylsiloxane fiber, so that organic solvents are no longer necessary. The sorbed organometals are subsequently released from the fiber in the GC injection liner by thermal desorption. By sampling from the headspace, only the species of interest are sampled and no interfering matrix components are coextracted. With this new method, derivatisation, extraction, preconcentration and injection into the GC takes only 10 min with a minimum of handling steps. Owing to the very low detection limits (0.13–3.7 ng/1 as metal) only small sample amounts (25 ml of water, 0.5 g of sediment) are needed for one analysis. Finally, SPME is an inexpensive sampling technique that can be used with standard split/splitless injection systems.     

The analysis of organic mercury compounds using liquid chromatography with on-line atomic fluorescence spectrometric detection

A new method for the analysis of organic mercury compounds is reported. The organomercurials are separated by high-performance liquid chromatography (HPLC). The compounds are converted to mercury(0) in a continuous-flow system by means of an oxidizing and a subsequent reducing solution. The elemental mercury generated is swept into the cell of an atomic fluorescence spectrometer (AFS) by a stream of argon. The compositions of the oxidizing solution, which contains peroxodisulphate and copper(II) in dilute sulphuric acid, and the reducing solution, which contains alkaline tin(II) chloride, were optimized, as were the gas–liquid separator (GLS), the condensing system and the geometry of the reaction coils. The method is applied to extracts of certified reference material (CRM) and to river sediments. High concentrations of methylmercury were found in the sediment samples. At one location, the presence of ethylmercury is derived from the sample chromatogram.     

Symmetrization of organomercury(II) chlorides using basic alumina

The symmetrization reaction of organomercury(II) chlorides (RHgCl) to R₂Hg and HgCl₂ in toluene solution under identical conditions using a basic alumina column has been studied­in order to compare the effect of the nature of the R groups on the extent of symmetrization. The efficiency of symmetrization depends markedly on the electron-withdrawing nature of­R, varying from 90–94% for R = trichlorovinyl or phenyl to 11% for R = 2,6-dimethylphenyl.© 1998 John Wiley & Sons, Ltd.     

Simple oxidative pretreatment for determination of organomercury by cold vapour atomic fluorescence spectrometry

A simple and rapid method has been developed for the direct determination of organomercury in toluene extracts. The oxidative pretreatment, intended for cold vapour-atomic absorption/fluorescence spectrometry, involves the use of bromide/bromate reagent under strong acid conditions. The pretreatment is performed directly in a volumetric flask and avoids the need for back extraction and phase separation. Recoveries for methyl mercury additions to toluene, at the 2 g/1 level, ranged from 100–106%.On leave Xianjiang Environmental Research Institute, Urumqui, Xianjiang Province, Peoples Republic of China     

The crystal and molecular structure of mercury(II) bis(isopropyl)dithiophosphate, Hg[S2P(OPri)2]2, revisited: new comments about its supramolecular self-organization

The crystal structure of the title compound, Hg[S₂P(OPrⁱ)₂]₂, has been determined by single-crystal X-ray diffraction. The compound crystallizes in the centrosymmetric P2₁/c space group with a = 11.800(1), b = 8.925(2), c = 22.167(2) Å, = 94.988(7)°, and Z = 4. The same compound has been previously reported but the structure is described there in the space group C2/c. In both cases, one phosphorodithioate moiety acts as a chelating group and the other as a bridging group between neighboring mercury atoms (related to one another by the twofold screw axis), giving rise to an infinite polymer along the direction of the b axis. It turns out that in spite of the difference in space group symmetry, the structures are remarkable similar in that they are formed from infinite polymers of similar geometry. The coordination around the Hg ion shows, however, significant differences, mainly for the bridging Hg—S(4) bond length, which is 0.16 Å smaller than that previously reported.     

电磁感应加热与原子荧光光谱联用测定海产品中的无机汞和有机汞

研制了电磁感应加热装置和磁感应加热柱,并将其应用于有机汞的在线氧化。与冷蒸汽发生-原子荧光光谱法联用,在线测定了海产品中的无机汞和有机汞。样品溶液与K2S2O8在线混合后流经磁感应加热柱,在较低功率(15W)时快速升温将有机汞氧化为无机汞,测定总汞含量;加热柱为室温时,测定无机汞含量,二者之差为有机汞。对各种实验参数和干扰情况进行了详细研究。无机汞的检出限为0.036μg/L;样品分析精密度(RSD)为2.4%(n=11);有机汞的检出限为0.043μg/L,样品分析精密度(RSD)为3.6%(n=11)。     

The toxic effects of organometals on the lands cycle in HL-60 cells

The concentration of free fatty acids within cells is mainly dependent upon the following enzyme activities: liberation by phospholipase A₂ (PLA₂), activation of free acids by acyl-CoA-synthetase and re-esterification by lysophospholipid acyltransferase (LAT). In many cell types, especially those of the haematopeotic system, this deacylation-reacylation cycle (‘Lands cycle’) plays an important role in the regulation of free fatty acid concentration, above all that of arachidonic acid. We have shown here that heavy-metal compounds affect this cycle mainly at two points and thereby lead to an increase of free fatty acids. On the one hand, organometals cause an inhibition of the reacylation of lysophospholipids; and on the other, the induction of PLA₂ activity produces the same result. All compounds investigated such as methylmercury chloride (MeHgCl), diethyltriethyl-, and trimethyl-lead chloride (Et₂PbCl₂, Et₃PbCl, Me₃PbCl) as well as trimethyltin chloride (Et₃SnCl) and di-t-butyltin dichloride (t-Bu₂SnCl₂) show at least one of these effects. In the case of Et₃PbCl, the use of PLA₂-inhibitors or pertussis toxin causes a drastic decrease in the amount of arachidonic acid liberated. These experiments demonstrate that the organometallic compounds inhibit the reacylation and/or stimulate the deacylation of fatty acids that are involved in many important biological or pathological mechanisms. The results suggest that in differentiated HL-60 cells the organometal compounds stimulate the Lands cycle by increasing the activity of the PLA₂, possibly via a signal-transduction mechanism, and this effect is intensified via an inhibition of reesterification.