环境介质中铂族金属形态分析方法的研究进展

环境中铂族金属(PGMs)的赋存形态多样,形态分析对识别其生态风险具有十分重要的意义。本文综述了环境中3种主要铂族金属(铂、钯、铑)的形态分析方法,包括化学顺序提取、仪器联用技术及计算机模拟等,概述了这些方法的类型、特点及应用,同时阐述了它们存在的不足,并对未来发展方向进行了展望。化学顺序提取法普遍用于固相样品形态分析,当前研究中提出的提取条件和步骤多样,但不能很好地标准化;仪器联用技术在溶液元素形态分析上具有显著优势,毛细管电泳联用系统能够分离具有相同电泳能力的相似物质,但在分离能力和检出限方面不如液相色谱联用系统;计算机模拟则进一步拓展了形态分析的途径,能够实现复杂的形态计算。建议今后将多个方法进行结合,通过相互补充与完善,不断提高分析技术准确性。     

Synthesis and spectral luminescent characteristics of the porphyrin complexes with the platinum group metals

The syntheses of complexes of natural and synthetic porphyrins with Pt, Pd, Rh, and Ru are reported. Their electronic absorption spectra, phosphorescence spectra, and lifetimes at room temperature both in the presence and in the absence of oxygen were studied. Variations in the nature of the central metal atom and in the substituents in pyrrol and phenyl rings allow the obtaining of metalloporphyrins phosphorescing at room temperature with various phosphorescence excitation and emission spectra.     

Synthesis and luminescent spectral characteristics of porphyrin complexes with platinum group metals

The synthesis of natural and synthetic porphyrin complexes with Pt, Pd, Rh, and Ru is reported. Their electronic absorption spectra, phosphorescence spectra, and lifetimes at room temperature both in the presence and in the absence of oxygen were studied. It has been shown that the variation of the nature of the central metal atom and of the substituents in pyrrole and phenyl rings allows the obtaining of metalloporphyrins with various phosphorescence excitation and phosphorescing emission spectra at room temperature. The English version of the paper: Russian Journal of Bioorganic Chemistry, 2008, vol. 34, no. 2; see also http://www.maik.ru.     

The behavioral toxicology of metals.

Many metals express their toxic actions through behavioral disturbances. Such disturbances most often reflect impairment of central nervous system function, but also may arise from deleterious effects in other systems. Numerous factors influence behavioral toxicity. Uptake into brain obviously is important; the chemical form of the metal (e.g., inorganic versus organic) and route of exposure are key determinants of brain penetration. Species differences in toxicity may arise from differences in kinetics (e.g., blood-brain ratio) and affinity to target brain structures. Developmental stage is still another crucial variable, but the young organism is not necessarily the most susceptible, and nutritional considerations confound the standard paradigms. Furthermore, parametric variations of behavioral functions can no more be ignored than dose-effect functions, a principle exemplified in research on methylmercury. Unwarranted loyalties to traditional psychological tests may be one source of the current dispute about safe levels of lead simply because parametric variations of clearly specified functions are beyond the scope of such instruments.     

Biorefining of platinum group metals from model waste solutions into catalytically active bimetallic nanoparticles

Bacteria can fabricate platinum group metal (PGM) catalysts cheaply, a key consideration of industrial processes and waste decontaminations. Biorecovery of PGMs from wastes is promising but PGM leachates made from metallic scraps are acidic. A two‐step biosynthesis ‘pre‐seeds’ metallic deposits onto bacterial cells benignly; chemical reduction of subsequent metal from acidic solution via the seeds makes bioscaffolded nanoparticles (NPs). Cells of Escherichia coli were seeded using Pd(II) or Pt(IV) and exposed to a mixed Pd(II)/Pt(IV) model solution under H₂ to make bimetallic catalyst. Its catalytic activity was assessed in the reduction of Cr(VI), with 2 wt% or 5 wt% preloading of Pd giving the best catalytic activity, while 1 wt% seeds gave a poorer catalyst. Use of Pt seeds gave less effective catalyst in the final bimetallic catalyst, attributed to fewer and larger initial seeds as shown by electron microscopy, which also showed a different pattern of Pd and Pt deposition. Bimetallic catalyst (using cells preloaded with 2 wt% Pd) was used in the hydrogenation of soybean oil which was enhanced by ~fourfold using the bimetallic catalyst made from a model waste solution as compared to 2 wt% Pd preloaded cells alone, with a similar selectivity to cis C18:1 product as found using a Pd‐Al₂O₃ commercial catalyst.     

Fate of platinum metals in the environment

For many years now automotive exhaust catalysts have been used to reduce the significant amounts of harmful chemical substances generated by car engines, such as carbon monoxide, nitrogen oxides, and aromatic hydrocarbons. Although they considerably decrease environmental contamination with the above-mentioned compounds, it is known that catalysts contribute to the environmental load of platinum metals (essential components of catalysts), which are released with exhaust fumes. Contamination with platinum metals stems mainly from automotive exhaust converters, but other major sources also exist. Since platinum group elements (PGEs): platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru) and iridium (Ir) seem to spread in the environment and accumulate in living organisms, they may pose a threat to animals and humans. This paper discusses the modes and forms of PGE emission as well as their impact on the environment and living organisms.     

Microcalorimetric studies of the effects of platinum group metal complexes on bacterial growth

A range of platinum group metal complexes (PGMC) were screened for antibacterial activity against Klebsiella aerogenes and Staphylococcus aureus. The effects of the complexes were monitored by changes in the thermal and growth properties of the organisms. Active complexes caused an immediate cessation of power and biomass production which did not recover whilst the complex was present in the medium. Removal of the complex by washing the cells allowed the growth of the small viable proportion of the cells; the majority of the cells had been killed. Changes which occurred in aqueous solutions of active complexes rendered them less bactericidal; this was a possible cause of regrowth observed at sub-bactericidal levels of some complexes. Resistance to active complexes could not be achieved by serial subculture. Three palladium complexes active against K. aerogenes all had similar square planar structures, but in general it was not possible to correlate activity with structure. The unique effects of the PGMCs at low concentrations, combined with the apparent inability of the bacteria to develop resistance to them, makes the complexes a valuable addition to the antibacterial arsenal.     

环境中人为来源的铂族元素及其迁移转化研究进展

铂族元素(PGEs)在汽车尾气催化转换器(VECs)、工业催化剂和制药学领域的广泛应用,致使PGEs尤其是铂(Pt)、钯(Pd)和铑(Rh)在某些区域已经成为新型环境污染物.由于环境样品中Pt/Pd、Pt/Rh与VECs中活性成分比例有较好的相关性,因此PGEs污染主要来源于应用了铂族金属的VECs.研究显示,过去的30年里,气溶胶、永生态系统(河水、雨水、地下水、海水、沉积物)、土壤、路尘和生物有机体等不同环境介质中PGEs浓度均显著增加.人们普遍认为铂族元素是惰性的,暴露于环境中的PGEs的健康风险很小,但PGEs毒性和生物可利用性的研究表明,在多种生物地球化学过程作用下,人为排放的PGEs易发生迁移,转化为毒性更大的形态,增加生物可利用性,通过食物链传递对人类产生潜在的健康风险.本文对不同环境介质中PGEs来源、分布及生物地球化学行为的最新成果进行了总结,认为PGEs人体健康风险标准制定、PGEs标准物质的研制、近海沉积物中PGEs的研究、PGEs对滩涂贝类的毒性、食物中PGEs的污染现状及人体健康风险评估等是今后PGEs研究的重要领域.     

Industrial practice and the biology of leaching of metals from ores The 1997 Pan Labs Lecture

Biomining processes have been used successfully on a commercial scale for the recovery of metals, the most important of which are copper, uranium and gold. These processes are based on the activity of chemoautolithotrophic bacteria which are able to use either iron or sulfur as their energy source and which grow in highly acid conditions. In general, low-rate dump and heap leaching processes are used for copper recovery while the biooxidation of difficult-to-treat gold-bearing arsenopyrite ores is carried out commercially in highly aerated stirred tank reactors. Because of the high levels of bacterial activity required, limitations in the growth rate of the microorganisms which were not apparent in low-rate processes have become an important factor. A key to the commercialization of the gold-bearing arsenopyrite biooxidation process was the development of a rapidly-growing, arsenic-resistant bacterial consortium. The empirical technique of mutation and selection in a continuous-flow system was used to improve the ability of the bacteria to decompose the ore. This approach resulted in a dramatic initial enhancement in growth rate but a plateau in improvement of performance has been reached. Further advances will require a more direct approach based on an understanding of the underlying physiological mechanisms and an application of the tools of molecular biology. Considerable advances have been made in our understanding of the molecular biology of Thiobacillus ferrooxidans. However much less is known about the other biomining bacteria. Recent studies using 16S rRNA analysis techniques have indicated that T. ferrooxidans may play a smaller role in continuous flow stirred tank biomining processes than was previously thought. Received 20 November 1997/ Accepted in revised form 2 March 1998     

海水中痕量铂族元素的赋存形态及螯合树脂富集研究进展

海水中铂族元素(PGEs)的含量和赋存形态与其生物地球化学行为及生态风险密切相关,但如何确定海水中PGEs的含量和形态一直是研究的难点.螯合树脂对特定元素和特定配体结构的识别特性为突破这一瓶颈提供了可能.因此,本文综述了海水中铂族元素赋存形态的研究现状,讨论了螯合树脂吸附铂族元素的机理,并对比了不同类型螯合树脂对铂族元素的富集.结果表明: 海水中PGEs的无机络合形态主要由[MCl₃OH^2-]/[MCl4^2-](M=Pt、Pd)及M(OH)₃^{3-n(n=3～6)(M=Rh)组成;螯合树脂对PGEs的不同络合形态有一定的识别性;氮-硫型螯合树脂是研究实际条件下海水中PGEs的理想树脂.}     

Ring folding in cyclopentadienyl diazabutadiene complexes of group 4 and 5 transition metals

The syntheses of CpM(i-PrDAB)₂ (M = Nb, Ta; Cp = (C₅H₅); i-PrDAB = bis-isopropyl-1,4-diazabuta-1,3-diene) are reported. Both show fluxional NMR spectra indicating that the two DAB rings differ. The X-ray crystal structure of CpNb(i-PrDAB)₂ shows one ring to be more folded than the other. Density functional calculations have been used to investigate the degree of folding of the chelate ring in the compounds Cp₂M(R-DAB), (M = Ti, Zr, Hf, Nb, Ta; R = H, i-Pr; DAB = 1,4-diazabuta-1,3-diene) and CpM(R-DAB)₂ (M = Nb and Ta). For Cp₂M(R-DAB) the group 4 compounds all have folded rings whereas the Nb and Ta compounds have planar rings. In all compounds the rings are reduced and the folding is driven by the electron number requirements of the metal centre.