Co-P非晶态合金电子性质和局域结构的理论研究

根据Co P非晶态合金结构的短程有序和结构中可能存在P -P相互作用的实验事实 ,选择了单磷原子簇模型ConP(n =1～ 5 )和双磷原子簇模型ConP2 (n =1～ 4 ) ,用密度泛函理论方法对其进行计算 .结果表明 ,在单磷Co2 P( 2 ) 、Co3 P( 1) 及Co4P( 2 ) 模型体系中 ,Co原子供给P原子电子 ,与电负性规则一致 ,同时Co和P之间具较强化学作用 ,可以形成稳定的原子簇 ;而在双磷和单磷原子簇Co5P( 1) 模型体系中 ,形成的原子簇不稳定 ,采用单磷Co2 P( 2 ) 、Co3 P( 1) 及Co4P( 2 ) 模型能较好地反映Co P非晶态合金的结构特点 .     

Preparation of rhodium–phyllosilicate catalysts without leaching in liquid-phase 1-hexene hydrogenation

Rhodium catalysts have been prepared on palygorskite and montmorillonite (clay) supports by reduction with hydrogen (1 atmosphere) at room temperature of a cationic organometallic rhodium compound anchored to the support. The activity of these catalysts for the hydrogenation of liquid-phase 1-hexene remains constant with increase of prehydrogenation time and with re-use for several runs. No rhodium leaching is observed.     

T 1 theorem for Besov spaces on nonhomogeneous spaces

Suppose μ is a Radon measure on ℝ ^d , which may be non doubling. The only condition assumed on μ is a growth condition, namely, there is a constant C₀>0 such that for all x∈supp(μ) and r>0, μ(B(x, r))⪯C₀rⁿ, where 0<n⪯d. We prove T1 theorem for non doubling measures with weak kernel conditions. Our approach yields new results for kernels satisfying weakened regularity conditions, while recovering previously known Tolsa’s results. We also prove T1 theorem for Besov spaces on nonhomogeneous spaces with weak kernel conditions given in [7].     

Structure and electrochemical behaviour of 4,7-diazaheptyl-trimethoxy-silane and vinyl-trialkoxy-silane adsorbed at silver surface

Novel self-assembled monolayers were obtained on silver using 4,7-diazaheptyl-trimethoxy-silane (SiN) and vinyl-trialkoxy-silane (SiVA, where the alkyl group is 3,6,9,12,15,18,21,24,27,30,33,36,39,42,45,48,51,54,57,60-eicozaoxa- hexaheptaconan). It was shown that thus modified metal surface was protected against electrooxidation. A densely packed monolayer remained stable and did not desorb from the Ag electrode on the potential cycling. The structure of SiN and SiVA as well as their complexes with Li⁺ cations were calculated and visualised by the AM1d and PM5 semi-empirical methods.     

Non-isothermal short-range-order kinetics of binary alloys as influenced by solute-vacancy complexes

A model describing the roles of bound and unbound vacancies is proposed in order to predict defect decay and short-range-order kinetics of quenched binary alloys during linear heating experiments. This is an alternative treatment of a previous approach. The model has been applied to the differential scanning calorimetry (DSC) curves of Cu-5 at.% Zn quenched from different temperatures. An expression to calculate the activation energy for migration of solute-vacancy complexes was also developed which make use of DSC trace data. A value of 89.12±0.32 kJ mol^-1 was obtained for the above alloy. The relative contribution of bound and unbound vacancies to partition of effective activation energy corresponding to the ordering process as influenced by quenching temperature was also assessed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Local Feasible QP-Free Algorithms for the Constrained Minimization of SC1 Functions

We consider the problem of minimizing an SC¹ function subject to inequality constraints. We propose a local algorithm whose distinguishing features are that: (a) a fast convergence rate is achieved under reasonable assumptions that do not include strict complementarity at the solution; (b) the solution of only linear systems is required at each iteration; (c) all the points generated are feasible. After analyzing a basic Newton algorithm, we propose some variants aimed at reducing the computational costs and, in particular, we consider a quasi-Newton version of the algorithm.     

2-乙酰氨基-3,4,6-三乙酰葡萄糖的合成

细菌内毒素(ＬＰＳ)是革兰氏阳性阴性菌细胞外膜层的主要成分,由其引起的革兰氏阴性杆菌脓度症和休克是导致战创伤病人死亡的主要原因之一。而从类脂Ａ(ＬｉｐｉｄＡ)的结构出发,以非肽类物质拮抗内毒素受体ＣＤ-14为治疗手段的研究在国外刚刚起步。2-乙酰氨基-3,4,6-三乙酰葡萄糖是合成ＬｉｐｉｄＡ结构类似物的重要中间体[1,2]。它的合成一般是通过氨基葡萄糖五乙酸酯的选择性水解[3-6]脱去一个乙酰基得到。氨基葡萄糖五乙酸酯是通过氨基葡萄糖的乙酰化反应得到的,由于氨基葡萄糖不稳定,一般是用氨基葡萄糖的盐酸盐作为起始原料。由于…     

A novel tridentate nitrogen donor as ligand in copper catalyzed ATRP of methyl methacrylate

A tridentate ligand, BPIEP: 2,6‐bis[1‐(2,6‐diisopropyl phenylimino) ethyl] pyridine, having central pyridine unit and two peripheral imine coordination sites was effectively employed in controlled/“living” radical polymerization of MMA at 90°C in toluene as solvent, Cu^IBr as catalyst, and ethyl‐2‐bromoisobutyrate (EBiB) as initiator resulting in well‐defined polymers with polydispersities M_w/M_n ≤ 1.23. The rate of polymerization follows first‐order kinetics, k_app = 3.4 × 10^?5 s^?1, indicating the presence of low radical concentration ([P*] ≤ 10^?8) throughout the reaction. The polymerization rate attains a maximum at a ligand‐to‐metal ratio of 2:1 in toluene at 90°C. The solvent concentration (v/v, with respect to monomer) has a significant effect on the polymerization kinetics. The polymerization is faster in polar solvents like, diphenylether, and anisole, as compared to toluene. Increasing the monomer concentration in toluene resulted in a better control of polymerization. The molecular weights (M_n,SEC) increased linearly with conversion and were found to be higher than predicted molecular (M_n,Cal). However, the polydispersity remained narrow, i.e., ≤1.23. The initiator efficiency at lower monomer concentration approaches a value of 0.7 in 110 min as compared to 0.5 in 330 min at higher monomer concentration. The aging of the copper salt complexed with BPIEP had a beneficial effect and resulted in polymers with narrow polydispersitities and higher conversion. PMMA obtained at room temperature in toluene (33%, v/v) gave PDI of 1.22 (M_n = 8500) in 48 h whereas, at 50°C the PDI is 1.18 (M_n = 10,300), which is achieved in 23 h. The plot of lnk_app versus 1/T gave an apparent activation energy of polymerization as (ΔE^≠_app) 58.29 KJ/mol and enthalpy of equilibrium (ΔH⁰_eq) to 28.8 KJ/mol. Reverse ATRP of MMA was successfully performed using AIBN in bulk as well as solution. The controlled nature of the polymerization reaction was established through kinetic studies and chain extension experiments. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4996–5008, 2005     

Compositionally modulated Fermi surfaces, structured diffuse scattering and ternary derivatives of 1T-TaS2

Ternary derivatives of 1T-TaS₂ have been synthesized and the variation in the highly structured diffuse intensity distributions characteristic of such materials carefully monitored to investigate the effect that such substitution has upon the band structures and Fermi surfaces (FSs) of the materials. Removal of d electrons via the replacement of Ta ions with lower valent transition metal ions leads to a systematic increase in the radii of the characteristic structured diffuse intensity distribution. Extended Hückel tight binding calculations of the FSs of the doped samples are carried out and used to predict possible nesting wave-vectors. The results are in reasonably good agreement with the radii of the experimentally observed diffuse intensity distributions.