Electrochemical behavior of novel bis (aliphatic amine) ruthenium (II) and osmium (II) porphyrins

Bis (aliphatic amine) ruthenium (II) and osmium (II) porphyrins, M (Por)-(H₂NR)₂ and M(Por)(HNR′₂)₂, [M=Ru and Os; Por=meso-tetrakis (p-tolyl) porphyrinato (TTP), meso-tetrakis (4-chlorophenyl) porphyrinato (4-Cl-TPP), meso-tetrakis (3, 5-dichlorophenyl) porphyrinato (3, 5-Cl-TPP) and meso—tetraphenyl porphyrinato(TPP); R=methyl, ethyl, iso-propyl and t-butyl; R′=methyl and ethyl] were synthesized by us. The electrochemical behavior of these complexes in 1, 2-dichloroethane with TBABF₄ as supporting electrolyte, has been studied by cyclic voltammetry and controlled potential electrolysis. Bis (aliphatic amine) ruthenium (II) porphyrins under go reversible one-electron oxidation and one-electron reduction processes in 1,2-dichloroethane solution. The osmium (II) analogues is shown two oxidation couples III and V, an additional small wave IV. The redox potentials of these complexes are markedly dependent on the nature of the substituent bound to the phenyl group of the porphyrin ring. It is obvious that redox potentials increases the electron-withdrawing power of the substituents increases. The couple I was found at −0.34, −0.23 and −0.15 V vs Cp₂ Fe^+/0 (Cp₂Fe=ferrocene) for Ru(TPP)(H₂NBu-t)₂, Ru(4-Cl-TPP) (H₂NBu-t)₂ and Ru(3,5-Cl-TPP)(H₂NBu-t)₂ respectively. Supported by the foundation of the Chinese Education Commission Li Zaoying: born in 1949, Associate Professor     

Electrochemical behavior of novel bis (aliphatic amine) ruthenium (II) and osmium (II) porphyrins

Bis (aliphatic amine) ruthenium (II) and osmium (II) porphyrins, M (Por)-(H₂NR)₂ and M(Por)(HNR′₂)₂, [M=Ru and Os; Por=meso-tetrakis (p-tolyl) porphyrinato (TTP), meso-tetrakis (4-chlorophenyl) porphyrinato (4-Cl-TPP), meso-tetrakis (3, 5-dichlorophenyl) porphyrinato (3, 5-Cl-TPP) and meso—tetraphenyl porphyrinato(TPP); R=methyl, ethyl, iso-propyl and t-butyl; R′=methyl and ethyl] were synthesized by us. The electrochemical behavior of these complexes in 1, 2-dichloroethane with TBABF₄ as supporting electrolyte, has been studied by cyclic voltammetry and controlled potential electrolysis. Bis (aliphatic amine) ruthenium (II) porphyrins under go reversible one-electron oxidation and one-electron reduction processes in 1,2-dichloroethane solution. The osmium (II) analogues is shown two oxidation couples III and V, an additional small wave IV. The redox potentials of these complexes are markedly dependent on the nature of the substituent bound to the phenyl group of the porphyrin ring. It is obvious that redox potentials increases the electron-withdrawing power of the substituents increases. The couple I was found at −0.34, −0.23 and −0.15 V vs Cp₂ Fe^+/0 (Cp₂Fe=ferrocene) for Ru(TPP)(H₂NBu-t)₂, Ru(4-Cl-TPP) (H₂NBu-t)₂ and Ru(3,5-Cl-TPP)(H₂NBu-t)₂ respectively. Supported by the foundation of the Chinese Education Commission Li Zaoying: born in 1949, Associate Professor     

Synthesis and structure determination of ruthenium and osmium complexes with 2,6-bis-(diphenylphosphinomethyl) pyridine

2,6-Bis (diphenylphosphinomethyl) pyridine (PNP) reaction with Na₂OsCl₆ · 6H₂O to give the five coordinated, sixteen-electron complex Os (PNP)Cl₂. In the presence of formaldehyde, the reaction between Na₂OsCl₆· 6H₂O and PNP proceeds rapidly in boiling ethanol to give the coordinately saturated Os(PNP)Cl₂(CO). The IR spectrum of Os(PNP)Cl₂(CO) shows a strong absorption band at 1 970 cm⁻¹ assignable tov _∞ stretch. PNP reacts with RuCl₂(PPh₃)₃ and RuCl₂(DMSO)₄ (DMSO=dimethyl sulfoxide) to give Ru(PNP)Cl₂ (PPh₃) and Ru(PNP)Cl₂ (DMSO) respectively. The average Ru−Cl, Ru−P and Ru−N bond distance in Ru(PNP)Cl₂(PPh₃) determineby X-ray crystallography are 0.242, 0.236 and 0.216 nm, respectively. Li Zhaoying: born in July 1949, associate professor     

One-step disposal of Cr (Ⅵ)-bearing wastewater by natural pyrrhotite

Cr(VI)-bearing wastewater can be treated by natural pyrrhotite which is used for reductant to reduce Cr(VI) and precipitant to precipitate Cr(III) simultaneously. The disposal products can be divided into three parts in the beakers, namely supernatant in the upper part, the yellowish colloidal precipitates in the middle part and the pyrrhotite in the lower part. The content of total Cr=Cr(VI)+Cr(III) in the supernatant liquid is 0.06 mg/L, which is lower than 1.5 mg/L of the discharge standard of China and near to 0.05 mg/L of the standard of potable water. This one-step disposal composing of both reduction and precipitation which is traditionally divided into two independent steps called reducing technology and precipitating technology respectively. The new method is of obvious economic advantage and favourable to decreasing surplus mud derived from adding Ca(OH)₂ to precipitate Cr(III) traditionally so as to avoid recontamination. In fact, sodium sulfite (Na₂SO₃) used in disposal of Cr(VI) was traditionally produced from natural mineral of pyrrhotite (FeS). One molecule of FeS is 4 times more than that of Na₂SO₃ from a view point of rational use of mineral resources. Therefore the prospective of application of the one-step disposal of Cr(VI) method is full of promise.     

Photoelectrical performance of nanocrystalline TiO2 film electrode sensitized by Ru(II)-bipyridine complexes

Two kinds of Ru(II)-bipyridine complexes,cis-di(thiocyanate)bis(2,2′-bipyridyl-4,4′-dicarboxylate) ruthenium(II) andcis-di(thiocyanate)bis(2, 2′-bipyridyl-3, 3′-dicarboxylate) ruthenium(II), were utilized as the sensitizers to the nanocrystalline TiO₂ film electrodes. Study shows that the two dyes have quite different sensitization properties due to the strong steric effect of carboxyl groups. In addition, the pretreatment to nanocrystalline TiO₂ film electrodes with TiCl₄ was investigated, which is an effective way to improve the photoelectric conversion performances of sensitized TiO₂ electrodes.     

Flow-injection microcolumn on-line preconcentration for the determination of chromium (VI)

A rapid and sensitive on-line preconcentration method for spectrophotometric determination of chromium (VI) in nature water is described. Preconcentration and determination are based on (i) the quantitative and fast adsorption of chromium (VI) on the high surface area nanometer-size TiO₂ (anatase) powders, which prepared by a sol-gel method from hydrolysis of TiCl₄ and (ii) the quantitative and reproducible elution of Cr (VI) by 2.0 mol·L⁻¹ HCl. A mini-column system for preconcentration is developed, Cr(VI) on the mini-column is eluted and merged with a stream water and DPCB (1,5-diphenylcarbazide) as the chromogenic reagent. The proposed system permits throughputs of 6 sample h⁻¹ (0.001 μg·mL⁻¹ Cr(VI)) or 20 sample h⁻¹ (0.1 μg·mL⁻¹ Cr(VI)). The preconcentration factor is 55. The detection limit is 0.8 ng · mL⁻¹ Cr(VI). The reproducibility is satisfactory with a relative standard deviation of less than 3.35% (0.01 μg·mL⁻¹ Cr(VI),n=5). Supported by the National Natural Science Foundation of China Ma Wanhong: born in 1961, Ph. D. Graduate student, Associate professor     

Study on synthesis and biological activities of novel water-soluble metalloporphyrins

The synthesis and characterization of a series of metal porphyrins, M^II(Por), {Por=dianionic of 5, 10, 15, 20-tetrakis [4-(4′-bromobutyloxy) phenyl]porphyrinato and 5, 10, 15, 20-tetrakis [4-(4′-butyloxypyridine bromide)phenyl]porphyrinato, M=Zn, Cu, Mn, Co, Ni, Ru-CO} were described. The complexes 3a-3e were prepared from the reactions of compound 2 with metal acetates in chloroform, and the treatment of 3a-3f with excess of pyridine gave corresponding complexes 4a-4f. These new compounds were identified by absorption spectroscopies,¹H-NMR and elemental analyses. The results of biological activity testing for 4a-4f revealed that 4a and 4c had stronger inhibiting action on the growth metabolism ofEsche richia coli. Foundation item: Supported by the National Natural Science Foundation of China (No: 29972035) and the Zi-Qiang Science Foundation of Wuhan University, 2000 Biography: Li Zao-ying (1949-), famale, Professor, research interests, study on synthesis and biological activities of metalloprphrins.     

Cellular prion protein imaging analysis with aptamer-labeled Ru（bpy）32＋-doped silica nanoparticles

A new type of highly selective aptamer-labeled fluorescent silica nanoparticles [Apt-tris（2,2＇-bipyri- dyl）ruthenium（II）@SiO2 NPs] were prepared through the reverse microemulsion method by using prolonged fluorescence lifetime ruthenium complexes of tris（2,2＇-bipyri- dyl）ruthenium（II） （Ru（bpy）2＋） as the source of the fluorescence for cellular prion protein imaging. Investigations showed that the newly prepared Ru（bpy）32＋@Si02 NPs possessed superior advantages of strong fluorescence, low toxicity, and easy surface modification for bioconjugation. Cell imaging experiments indicated that Apt- Ru（bpy）32＋@SiO2 NPs had great tendency to human bone marrow neuroblastoma cells （SK-N-SH cells）, since they can express large amount of prion protein on the surface of the cell, while in HeLa cells this phenomenon disappeared for the reason that HeLa cells cannot express prion proteins.     

二氧化硅胶体聚合体吸附铀的研究

采用自制的二氧化硅胶体聚合体,进行了pH值、接触时间和铀初始浓度对二氧化硅胶体聚合体吸附铀效果影响试验,结果表明,溶液的pH对二氧化硅胶体聚合体吸附铀的效果影响较大,并且在pH为4时吸附铀的效果达到最佳;二氧化硅胶体聚合体吸附铀的速度快,30 min即可达到吸附平衡;该材料去除铀的效率高,当溶液中铀初始浓度低于10 mg/L时,该材料对铀的去除率大于98%;随着初始铀浓度增加,吸附容量增加,铀的去除率降低;扫描电镜分析结果表明,二氧化硅胶体聚合体表面形貌吸附铀前后变化不大;能谱分析结果表明,1 g吸附剂所吸附铀的质量分数为4.32%,与二氧化硅胶体聚合体从溶液中吸附铀43.0 mg相吻合.     

Study on synthesis and deplete harmful radical of cobalt prophyrins as the mimic of enzyme

The four cobalt porphyrins [Co (3, 4, 5-MeO-TPP) (1); Co (TTP) (2); Co (4-Cl-TPP) (3); Co (4-HSO₃-TPP) (4)] were synthesized and considered as two mimic of superoxide dismutaes (SOD) and catalase (CAT). The catalytic efficiency of them on deplete the harmful radical have been proved using riboflavin-methionine photoreduction method in the concentration range of 10⁻⁶∼10⁻⁵ mol/L. The catalytic efficiency of them at decomposing H₂O₂ has been performed by spectrophotometer. The percentage of decomposing H₂O₂ while the increasing the concentration of the imitating compounds. The lipid peroxidation produced in liver homogenated of mice was determined by spectrophotometer detecting the content of MDA.     

Os isotopic composition of the earth’s primitive upper mantle

The osmium isotopic ratio of¹⁸⁷Os/¹⁸⁸Os ranging from 0.126 to 0.127 for the primitive upper mantle (PUM) is obtained according to the correlation between¹⁸⁷Os/¹⁸⁸Os and Al₂O₃ of mantle-derived xenoliths and orogenic peridotites, which consists with Allegre and Luck’s ALM value and similar to Yin’s nuggets uniform reservoir (NUR) value. It shows that the Os isotope ratio is lower than enstatite or ondinary chondrites, similar to carbonaceous chondrites (CV3).     

In situ time-resolved FTIR investigation on the reaction mechanism of partial oxidation of methane to syngas over supported Rh and Ru catalysts

In situ time-resolved FTIR spectroscopy was used to study the reaction mechanism of partial oxidation of methane (POM) to synthesis gas and the reaction of CH₄/O₂/He (2/1/45, molar ratio) gas mixture with adsorbed CO species over Rh/SiO₂, Ru/γ-Al₂O₃ and Ru/SiO₂ catalysts at 500—600℃. It was found that CO is the primary product of POM reaction over reduced and working state Rh/SiO₂ catalysts. Direct oxidation of CH₄ is the main pathway of synthesis gas formation over Rh/SiO₂ catalyst. CO₂ is the primary product of POM over Ru/γ-Al₂O₃ and Ru/SiO₂ catalysts. The dominant reaction pathway for synthesis gas formation over Ru/γ-Al₂O₃ catalyst is via the reforming reactions of CH₄ with CO₂ and H₂O. For the POM reaction over Rh/SiO₂ and Ru/γ-Al₂O₃ catalysts, consecutive oxidation of surface CO species is an important pathway of CO₂ formation.     

Investigation of Ru （ phen ）3^2＋-Hydrazine-Ce（Ⅳ） Chemiluminescence System and Its Analytical Application

0 IntroductionThbiep ycroidmipnlee)xru ctahteinoinu mof(Ⅱ r)u t(he Rniuu(mbip,y m)3ai2n +ly) atrnids- t(r2is -,(21’ -,10-phenanthroline)ruthenium(Ⅱ) (Ru(phen)32 +) ,is a kindof sensitive analytical reagent for electrogenerated chemilumi-nescence(ECL) and chemiluminescence(CL) ,on which a par-ticular review has been presented[1]. The earliest publicationon the synthesis of Ru(bipy)32 +appeared in 1936[2], andduringthefollowing30 years ,theinvestigations relatedtothissubstance were only in…     

高铁酸盐的化学合成及高铁电极的电化学性质研究

通过NaClO化学氧化Fe(OH)₃来制备高纯度的K₂FeO₄和BaFeO₄，并在此基础上研究了BaFeO₄和K₂FeO₄电极的恒流放电性能以及用BaFeO₄和K₂FeO₄制成的锌铁碱性电池的重负荷放电性能。结果表明，BaFeO₄和K₂FeO₄电极在轻、中、重负荷放电下，其放电容量比电解MnO2 的电极提高了56%～116%。AA型锌铁碱性电池的重负荷放电时间比标准碱锰电池提高了95%以上。     

Synthesis and assembly with mesoporous silica of platinum(II) porphyrin complexes bearing carbazyl groups:Luminescent and oxygen sensing properties

Determination of oxygen is very important in vari- ous fields such as analytical chemistry, medical chem- istry and environmental and industrial applications[1]. The optical oxygen sensors are based upon the princi- ple that oxygen is a powerful quencher …     

A study of bacterial linear growth using a microcalorimetric method

By using an LKB-2277 bioactivity monitor, we have determined the thermogenesis curves of four kinds of anaerobes linear growth. From the thermogenesis curves, we established the growth thermokinetic equation: dP/dt=k _m·P ⁿ , the order of growth metabolismn=0, and calculated the mean specific rate constant of multiplication {ie95-1}. It is a new kind of bacterial growth, it was compared with exponential growth. Liu Yi: born Nov. 1970. Ph. D. Curent research interest is in biothermochemistry research Supported by the National Natural Science Foundation of China     

Synthesis and characterization of spinel Li_(1.05)Cr_(0.1)Mn_(1.9)O_(4-z)F_z as cathode materials for lithium-ion batteries

Samples with the nominal stoichiometry Li_1.05Cr_0.1Mn_1.9O_4−z F _z (z=0, 0.05, 0.1, 0.15, and 0.2) were synthesized via the solid-state reaction method and characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), galvanostatic charge/discharge, and slow rate cyclic voltammetry (SSCV) techniques. The results show that the pure spinel phase indexed to Fd3m can be obtained when z=0, 0.05, and 0.1. The substitution of F for O with z≤0.1 contributes to the increase of initial capacity compared with Li_1.05Cr_0.1Mn_1.9O₄ spinels. However, when the F-dopant content is designed to be 0.15 and 0.2, the Li_1.05Cr_0.1Mn_1.9O_4−z F _z samples deliver relatively low capacity and poor cycling properties at 55°C.     

Inorganic-organic hybrids constructed of bis（undecatungstogerma- nate）lanthanates polyoxoanions and oxalate-bridged dinuclear copper complexes and their magnetic properties

A series of inorganic-organic hybrids K₂Na _m H_9−m [{Ln(GeW₁₁O₃₉)₂}{Cu₂(bpy)₂(μ-ox)}]·nH₂O (bpy = 2,2-bipyridine and ox = oxalate; Ln = La, Nd, Sm, Eu, Gd; n = 19, 17, 22, 20, 19; m = 4, 4, 4, 9, 2) were isolated after reacting in a potassium acetate buffer. X-ray structural analyses show that compounds 1–5 are isomorphic and consist of [Ln(GeW₁₁O₃₉)₂]¹³⁻ polyoxoanion building blocks and oxalate-bridged dinuclear copper metalorganic complex with a 1D chain structure. The 1D chain further connects into the 3D framework by π-π interactions with neighboring bpy groups. The magnetic susceptibility data indicate that antiferromagnetic coupling between the neighboring Cu²⁺ ions in the structure and the rare earth ions affects magnetic property of the structure.     

Effects of Complexes and pH Buffer Solution in Electrokinetic Oxidation Treatment on Sediments Chromium Removal

Three electrokinetic(EK) experiments were designed to study the remediation efficiency of Cr(Ⅲ) by EK-oxidation method and to investigate the influence of complexes and p H buffer solution in EK-oxidation process. Sediments Cr(Ⅲ) can be oxidized into Cr(Ⅵ) effectively by KMn O4, but the oxidation efficiency is not proportional to the dose of oxidant, and chemical oxidation process leads to a bit lower buffering capacity of the sediment. Compared with the simple EK remediation, the removal efficiency of total Cr in the sediments increased 32.6% by EK-oxidation method, and the concentrations of total chromium in the sediment showed increasing trend from the cathode to the anode after EK-oxidation treatment. The p H control and KMn O4 improved the removal of Cr(Ⅵ) and total Cr from the sediments. Due to stronger complexation action of citric acid with Cr(Ⅲ) in sediments, citric acid in the catholyte obviously increased the removal rate of total Cr in sediments. Finally, the removal rate of total Cr from sediments reached 60.9% by adding complex and controlling the p H of cathode and anode pond solution on EK-oxidation processes.     

Chemiluminescence determination of thiourea using tris (1,10-phenanthroline)-ruthenium (II) KMnO4 system

The light emission produced by thiourea in oxidation process by permanganate in acidic solution in the presence of Ru(phen) ₂ ^{3 +} is used to determine 1.0×10⁻⁵ −1.0×10⁻⁵ mol/L thiourea. The limit of detection is 9.8×10⁻⁹ mol/L and the relative standard deviation is 1.1% for a 1.0×10⁻⁵ mol/L thiourea solution (n=10). The method was applied satisfactorily to the determination of thiourea. Foundation item, Support by Ministry of Education, Wuhan University and Alumni Association of it Biography: Wu Feng-wu(1963-), Male, Ph. D, research direction: analytical chemistry.