模糊聚类-偏最小二乘光度法同时测定锇和钌

将模糊聚类分析与偏最小二乘相结合，对锇、钌双组份重叠光谱进行解析；较好地解决了校正分析中校准模型的优化问题，提高了分析结果的准确度；研究了锇、钌－ＳｎＣｌ２－乳化剂ＯＰ－阿拉伯树胶（ＡＧ）－丁基罗丹明Ｂ（ＢＲＢ）高灵敏多元离子缔合物显色体系。锇、钌的检出限分别为 ０，６３２ μｇ／Ｌ和 ０．３６８ μｇ／Ｌ，模拟地质样品分析结果的相对误差小于±１０％。     

稳健偏最小二乘光度法同时测定贵金属元素锇和钌

本文将稳健偏最小二乘法用于贵金属元素锇、钌的光度法同时测定，较好地解决了实际校准模型由于实验误差偏离正态分布使计算结果的精度遭到破坏的问题。     

Phosphonium-Ring-Fused Bicyclic Metallafuran Complexes of Ruthenium and Osmium

Metallafuran complexes with a fused five-membered phosphonium ring were synthesized from reactions between terminal ynones HC≡C(C=O)R and cis-[Ru/Os(dppm)₂Cl₂] (dppm=1,1-bis(diphenylphosphino)methane). A metal–vinylidene-involving pathway was found to be an energetically feasible formation mechanism for these complexes. These phosphonium-containing metallafurans, like many phosphonium-functionalized drugs, have the ability to induce mitochondrial dysfunction. They also exhibit stronger cytotoxicity against several human cancer cell lines in comparison with their metal precursors and the classic anticancer drug cisplatin. Overall, this work provides structural and mechanistic insights for the rational design of functional metallacycles via activation of alkynes by Ru^II and Os^II centers.     

催化动力学分光光度法测定痕量锇

在磷酸介质及加热条件下 ,锇 对KBrO3氧化二氨替比林基 对二甲氨基苯基甲烷 (DAMAM)显色反应有强烈的催化作用 ,由此建立了测定痕量锇的催化动力学分光光度分析法。体系催化反应 (吸光度为A)和非催化反应 (吸光度为A0 )的最大吸收波长均为 5 4 0nm ,锇含量在 0～ 14 μg L范围内与 (A -A0 )呈线性关系 ,检出限为 1.82× 10 - 9g mL ,方法用于冶金产品和贵金属精矿中痕量锇的测定 ,结果满意     

Rapid Spectrophotometric Determination Of Osmium With Cyclohezane 1,3-Dione Bisthiosemicarbazone Monohydrochloride: Simultaneous Determination of Osmium and Platinum

Abstract

A simple, sensitive and rapid spectrophotometric method has been developed for the determination of osmium using cyclohexane 1,3-dione bisthiosemicarbazone mono-hydrochloride (1,3-CHDT.HCl). The method is based on the instantaneous colour reaction between 1,3-CHDT. HCl and osmium(VIII) in sodium acetate—acetic acid buffer medium (pH range 3–6). The osmium complex shows maximum absorbance at 375 nm and considerable absorbance at 510 nm. Although the complex formed between platinum(IV) and reagent (1,3-CHDT.HCl) shows maximum absorbance at 375 nm, it does not show any absorbance at 510 nm. Simultaneous determination of osmium and platinum is carried out when present alone and in presence of other foreign (associated) ions. Some physico-chemical and analytical characteristics of osmium and platinum complex are described. Interference of various foreign ions have studied and osmium is estimated selectively in the presence of constituents of platinum ores.     

催化动力学光度法测定钌

在磷酸介质中,痕量钌（Ⅲ）对溴酸钾氧化二安替比林对氨基苯基甲烷（DApAM）的显色反应具有明显的催化作用,研究了反应的最佳条件,并测定了一些动力学参数,据此建立了一种测定痕量钌（Ⅲ）的新方法,其检测限为2．10×10－9g／mL,针含量在0－20μg／L内符合比尔定律,方法用于贵金属精矿中痕量钌的测定,结果满意。     

Simple Selective Spectrophotometric Method for the Determination of Ruthenium in Carbon Supported Pt-Ru-Ge Catalyst

ABSTRACT

A simple spectrophotometric method for the determination of ruthenium in the presence of platinum in Pt-Ru-Ge catalyst applied in fuel cells has been developed. Platinum catalyst (20% Pt) with carbon support containing 0.5% Ru and 5% Ge was digested in the mixture of HCl+HNO₃ (6+1). Carbon was separated from the examined sample by filtration after dissolution of the metals. Ruthenium was converted into a complex with thiourea (λ_max=640 nm, ε = 2.9·10³ 1 mol^?1 cm^?1) in the medium of 5 M in HCl and 1% in thiourea after 15 min heating at 70 °C. Platinum does not interfere with the determination of ruthenium. Germanium is converted into volatile GeCl₄ and escapes from the examined sample during the digestion step. The content of ruthenium determined in the examined samples of catalyst amounted to 0.49% (RSD = 0.14%).     

活性炭负载钌系氨合成催化剂中钌含量的分析

采用分光光度法测定活性炭负载钌系氨合成催化剂中的钌含量．在强酸和乙醇体系中,Ru（Ⅲ）与硫脲生成蓝色物,于最大吸收波长λ=620am处测定催化剂中的钌含量．测试结果表明,该方法操作简单、干扰小,相对标准偏差为1％～3％,加标回收率在97．5％～102．0％之间,适用于活性炭负载钌系氨合成催化剂中钌含量的准确测定．     

锇(Ⅳ)催化抗坏血酸还原三溴偶氮胂的褪色反应特性及痕量锇的测定

研究了在盐酸介质中,在活化剂磷酸存在下,Os(Ⅳ)催化抗坏血酸还原三溴偶氮胂的褪色反应特性;测定了反应级数和表观活化能;拟定了反应的最佳条件,建立了测定痕量锇的新方法.在85±0.05℃水浴中加热8 min,测定的检出限为3.65×10-8 g/L,线性范围为0～4.0 μg/L,相对标准偏差为2.8%～2.9%.用于合金和催化剂样品中锇的测定,结果满意.     

Spectral Investigation on Ruthenium(III)-allyl Thiourea System

Abstract

Ruthenium(III) forms a 1:2 complex with allyl thiourea. Conformity to Beer's law was observed for up to 12 pg/ml of ruthenium, in acidic medium.

The molar absorptivity of the complex is 1.66E+04 1 mol^?1 cm^?1, at 270 nm; the Sandell's sensitivity of the reaction for ruthenium is 0.0061 μg cm^?2 per 0.001 absorbance unit.

The tolerance to diverse ions is quite satisfactory.

The infrared spectra of allyl thiourea and of its ruthenium complex, recorded in the 2.5 - 50 μ region, reveal that only sulphur-to-ruthenium bonds are present in the complex.

A comparison with the main, most recent, spectrophotometric reagents for ruthenium is reported. The present method has the advantages of simplicity and reasonable sensitivity.     

Ruthenium and Osmium Complexes That Bear Functional Azolate Chelates for Dye‐Sensitized Solar Cells

The preparation of sensitizers for dye‐sensitized solar cells (DSSCs) represents an active area of research for both sustainability and renewable energy. Both Ru^II and Os^II metal sensitizers offer unique photophysical and electrochemical properties that arise from the intrinsic electronic properties, that is, the higher propensity to form the lower‐energy metal‐to‐ligand charge‐transfer (MLCT) transition, and their capability to support chelates with multiple carboxy groups, which serve as a bridge to the metal oxide and enable efficient injection of the photoelectron. Here we present an overview of the synthesis and testing of these metal sensitizers that bear functional azolate chelates (both pyrazolate and triazolate), which are capable of modifying the metal sensitizers in a systematic and beneficial manner. Basic principles of the molecular designs, the structural relationship to the photophysical and electrochemical properties, and performances of the as‐fabricated DSSCs are highlighted. The success in the breakthrough of the synthetic protocols and potential applications might provide strong stimulus for the future development of technologies such as DSSCs, organic light‐emitting diodes, solar water splitting, and so forth.     

Coordination Booster‐Catalyst Assembly: Remote Osmium Outperforming Ruthenium in Boosting Catalytic Activity

Presented herein is a set of bimetallic and trimetallic “coordination booster‐catalyst” assemblies in which the coordination complexes [Ru^II(terpy)₂] and [Os^II(terpy)₂] acted as boosters for enhancement of the catalytic activity of [Ru^II(NHC)(para‐cymene)]‐based catalytic site. The boosters accelerated the oxidative loss of para‐cymene from the catalytic site to generate the active catalyst during the oxidation of alkenes and alkynes into corresponding aldehydes, ketones and diketones. It was found that the boosting efficiency of the [Os^II(terpy)₂] units was considerably higher than its congener [Ru^II(terpy)₂] unit in these assemblies. Mechanistic studies were conducted to understand this unique improvement.     

The Simultaneous Determination of Ruthenium and Osmium by A Radiochemical Method

Abstract

A simple radiometric procedure is proposed for the determination of raicrogram amounts of ruthenium and osmium by the use of neutron activation. Alter irradiation, the tetroxides of both metals were collectively distilled and then determined directly by measuring the photopeak areas of osmium-191 and ruthenium-103 at 45 and 498 Kev respectively. The effect of Compton continua was negligible.     

双波长分光光度法同时测定贵金属钯和锇

本文提出了在对羟基苯基荧光酮和溴化十六烷基三甲烷基甲胺存在下，双波长分光光度法同时测定微量和锇的新方法，在ｐＨ＝７．６～８．０的磷酸盐介质中，钯和锇的对羟基苯基荧光酮－ＣＴＭＡＢ配合物吸收光谱相互重叠，选择测定钯配合物的波长对为５８０．５ｎｍ与５３０．５ｎｍ，测定锇配合物的波长对为５５３．５ｎｍ与６０４．５ｎｍ，钯含量在０～７．０μｇ／１０ｍＬ范围内，锇含量在０～９．０μｇ／ｍＬ范围内，与ΔＡ值呈     

乙基罗丹明B-高碘酸盐催化光度法测定锇

在０．００８ｍｏｌ／Ｌ硫酸介质和热水浴中,Ｏｓ（Ⅳ）催化高碘酸盐氧化乙基罗丹明Ｂ（ＥＲＢ）褪色,建立了灵敏催化光度法测定锇,Ｏｓ（Ⅳ）浓度在０￣８．８ｎｇ／ｍＬ范围成线性关系,检出限为０．０２６ｎｇ／ｍＬ,对６．０ｎｇ／ｍＬ Ｏｓ（Ⅳ）测定的相对标准偏差为１．８８％（ｎ＝１１）,催化反应对Ｏｓ（Ⅳ）、ＥＲＢ、ＫＩＯ和Ｈ２ＳＯ４分别为一级反应,表观活化能为２０５．７ｋＪ／ｍｏｌ。探讨了反应机理,研究     

在PVA存在下Os-SnCl_2-亮绿离子缔合体系的研究高纯镍中微量Os的测定

本文研究了Os-SnCl_2-PVA-亮绿离子缔合体系的显色反应,摩尔吸光系数ε_(434)为5.6×10~6L·mol~(-1)·cm~(-1),锇含量在0.1～0.7μg/25mL范围内遵守比耳定律,室温下显色后,吸光度在110min内稳定。研究了30种外来离子的影响,并进行了高纯镍中微量锇的测定。     

锇胺分子氢配合物的研究进展

由于锇胺分子氢配合物中有特殊的键M(η2 H2 )和特殊的配体 分子氢的存在 ,故而具有丰富的取代化学和特殊的光谱性质。在无机化学、配位化学、生物、医药等方面都有极为广阔的应用前景。本文就此进行了简要的回顾与展望     

Ruthenium(II) and Osmium(II) Vinyl Complexes as Highly Sensitive and Selective Chromogenic and Fluorogenic Probes for the Sensing of Carbon Monoxide in Air

The detection of carbon monoxide in solution and air has been achieved using simple, inexpensive systems based on the vinyl complexes [M(CH?CHR)Cl(CO)(BTD)(PPh₃)₂] (R=aryl, BTD=2,1,3‐benzothiadiazole). Depending on the nature of the vinyl group, chromogenic and fluorogenic responses signalled the presence of this odourless, tasteless, invisible, and toxic gas. Solutions of the complexes in CHCl₃ underwent rapid change between easily differentiated colours when exposed to air samples containing CO. More significantly, the adsorption of the complexes on silica produced colorimetric probes for the naked‐eye detection of CO in the gas phase. Structural data for key species before and after the addition of CO were obtained by means of single X‐ray diffraction studies. In all cases, the ruthenium and osmium vinyl complexes studied showed a highly selective response to CO with exceptionally low detection limits. Naked‐eye detection of CO at concentrations as low as 5 ppb in air was achieved with the onset of toxic levels (i.e., 100 ppm), thus resulting in a remarkably clear colour change. Moreover, complexes bearing pyrenyl, naphthyl, and phenanthrenyl moieties were fluorescent, and greater sensitivities were achieved (through turn‐on emission fluorescence) in the presence of CO both in solution and air. This behaviour was explored computationally using time‐dependent density functional theory (TDDFT) experiments. In addition, the systems were shown to be selective for CO over all other gases tested, including water vapour and common organic solvents. Supporting the metal complexes on cellulose strips for use in an existing optoelectronic device allows numerical readings for the CO concentration to be obtained and provision of an alarm system.     

流动注射催化分光光度法测定钌的研究

利用钌（Ⅲ）对过氧化氢氧化还原型百里酚酞显色反应的显著催化作用，建立了钌的新流动注射催化分光光度分析法，该法快速灵敏、简便，用于实际样品分析，结果良好。