Kinetics and mechanism of the reactions of hexaaqua rhodium (III) with sulphur (IV) in aqueous medium

An O-bonded sulphito complex, Rh(OH₂)₅(OSO₂H)²⁺, is reversibly formed in the stoppedflow time scale when Rh(OH₂) ₆ ³⁺ and SO₂/HSO ₃ ⁻ buffer (1 <pH< 3) are allowed to react. For Rh(OH₂)₅OH₂₊+ SO₂ □ Rh(OH₂)₅(OSO₂H)²⁺ (k₁/k_-1), k₁ = (2.2 ±0.2) × 10³ dm³ mol⁻¹ s⁻¹, k₋1 = 0.58 ±0.16 s⁻¹ (25°C,I = 0.5 mol dm⁻³). The protonated O-sulphito complex is a moderate acid (K _d = 3 × 10⁻⁴ mol dm⁻³, 25°C, I= 0.5 mol dm⁻³). This complex undergoes (O, O) chelation by the bound bisulphite withk= 1.4 × 10⁻³ s⁻¹ (31°C) to Rh(OH₂)₄(O₂SO)⁺ and the chelated sulphito complex takes up another HSO ₃ ⁻ in a fast equilibrium step to yield Rh(OH₂)₃(O₂SO)(OSO₂H) which further undergoes intramolecular ligand isomerisation to the S-bonded sulphito complex: Rh(OH₂)₃(O₂SO)(OSO₂)^- → Rh(OH₂)₃(O₂SO)(SO₃)⁻ (k _iso = 3 × 10⁻⁴ s⁻¹, 31°C). A dinuclear (μ-O, O) sulphite-bridged complex, Na₄[Rh₂(μ-OH)₂(OH)₂(μ-OS(O)O)(O₂SO)(SO₃) (OH₂)]5H₂O with (O, O) chelated and S-bonded sulphites has been isolated and characterized. This complex is sparingly soluble in water and most organic solvents and very stable to acid-catalysed decomposition     

定常的热传导-对流问题的Galerkin/Petrov最小二乘混合元方法

1.引言 热传导-对流问题是大气动力学中的一个重要的方程,这个方程组也称为强迫耗散的非线性系统方程组,其较Navier-Stokes方程多了一个未知函数温度场,且温度与速度和压力之间存在着复杂的非线性关系.从热动力学可知,任何运动都会产生热量即有温度,而且温度与速度和压力之间必定互相转化,因此对该非线性系统的研究更具有实际意义.[1]先对     

Synthesis of a hairpin pyrrole-imidazole polyamide conjugate containing a quinone methide precursor and vinyl linking group

Standard procedures for elaborating a quinone methide precursor for conjugation to a DNA ligand was not compatible with the presence of a vinyl group. Instead, an acrylate linker was attached by Heck coupling subsequent to o-substitution of the phenolic precursor. This transformation required protection of the phenolic group and use of ethyl acrylate rather than acrylic acid. The presence of the vinyl group also rendered the quinone methide precursor more labile to alkaline conditions than its equivalent saturated derivative and required mild conditions for coupling to the pyrrole-imidazole polyamide.     

多周期公用工程系统运行的模型,优化方法与应用

针对多周期公用工程系统的运行优化问题，考虑了设备的启停费用的情况下。建立了混合整数非线性规划模型并证明了最优解的存在性。针对该运行优化问题本将其分解成若干子问题，然后利用改进的Hooke-Jeeves优化算法求解每个子问题。应用于具体实例，其数值结果与其它方法得到的相比。运行时间短，且更适合多周期公用工程问题的求解。     

A method and program for mass quantum chemical calculations of protein—ligand docking complexes

A new fast computational method for mass calculations of docking complexes by the AM1/PM3 semiempirical methods is proposed. The computation time is shortened by at least an order of magnitude compared to alternative schemes of quantum chemical calculations. The root-mean-square deviation of the AM1 calculated energies of formation of complexes from the results obtained by conventional diagonalization procedure is at most 0.4 kcal mol⁻¹. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 418–420, February, 2008.     

A Hybrid Approach to Scheduling with Earliness and Tardiness Costs

A hybrid technique using constraint programming and linear programming is applied to the problem of scheduling with earliness and tardiness costs. The linear model maintains a set of relaxed optimal start times which are used to guide the constraint programming search heuristic. In addition, the constraint programming problem model employs the strong constraint propagation techniques responsible for many of the advances in constraint programming for scheduling in the past few years. Empirical results validate our approach and show, in particular, that creating and solving a subproblem containing only the activities with direct impact on the cost function and then using this solution in the main search, significantly increases the number of problems that can be solved to optimality while significantly decreasing the search time.     

Banach空间中拟-似变分包含解的存在与逼近问题

研究了Banach空间中拟-似变分包含解的存在与逼近问题.给出了一种寻求解的新的迭代算法,建立了具混合误差的Ishikawa型迭代序列强收敛到解的充要条件.所得结果推广了一些相关的结果.     

双（十二烷基亚磺酰）乙烷溶剂萃取钯及其机理的研究

本文研究用双（十二烷基亚磺酰）乙烷萃取钯的性能，在ＫＩ存在下从７ｍｏｌ／Ｌ盐酸介质中用含有ＢＤＳＥ的氯仿能定量萃取钯，有机的钯可被硫脲或氨溶液反萃继之用ＴＭＫ－ＴｒｉｔｏｎＸ－１００光度法测定，研究了萃取的最佳条件及干扰情况，斜率法测得萃合物组成为Ｐｄ：Ｉ：ＢＤＳＥ＝１：２：１，红外光谱证实萃合物中ＢＤＳＥ的二个亚砜以硫原子与钯配位，萃合物为异位体络合物，提出了选择性萃取分离钯的新方法。     

Synthesis of poly-yne polymers containing transition metals,disilane, disiloxane and phosphine groups in the main chain

The synthesis and characterization of metal poly-yne polymers containing disilane, disiloxane and phosphine groups in the main chain are described. The platinum and palladium poly-yne polymers were synthesized by polycondensation reactions between a metal chloride and an α, ω-bisethynyl complex in amines in the presence of cuprous iodide as a catalyst. The nickel poly-yne polymers were synthesized by an alkynyl ligand exchange reaction between a nickel acetylide and an α, ω-bisethynyl complex in diethylamine in the presence of cuprous iodide as a catalyst. The reaction of the platinum poly-yne polymer, containing disiloxane groups in the main chain, with copper (I) salts afforded adducts of η-²-bonded σ-acetylide polymer complexes. The reactions of the palladium poly-yne polymer, containing phosphine groups in the main chain, with transition-metal carbonyl complexes afforded polymer complexes which have phosphorus in the main chain-transition-metal bonds. A concentrated solution of the platinum poly-yne polymer containing disiloxane groups in the main chain forms a lyotropic liquid crystal in dichloromethane or 1, 2-dichloroethane.