Surface structures formed by individual adsorption and coadsorption of Mn and Bi on Cu(0 0 1), studied by LEED

We have studied the individual adsorption of Mn and Bi, and their coadsorption on Cu(0 0 1) by low-energy electron diffraction (LEED). For Mn, we have determined the c(2 × 2) structure formed at 300 K, whose structure had been determined by several methods. We reconfirmed by a tensor LEED analysis that it is a substitutional structure and that a previously reported large corrugation (0.30 Å) between substitutional Mn and remaining surface Cu atoms coincides perfectly with the present value. In the individual adsorption of Bi, we have found a c(4 × 2) structure, which is formed by cooling below ∼250 K a surface prepared by Bi deposition of ∼0.25 ML coverage at 300 K where streaky half-order LEED spots appear. The c(4 × 2) structure has been determined by the tensor LEED analysis at 130 K and it is a substitutional structure. In the coadsorption, we found a c(6 × 4) structure, which has been determined by the tensor LEED analysis. It is very similar to the previously determined structure of the c(6 × 4) formed by coadsorption of Mg and Bi, and embedded MnBi₄ clusters are arranged in the top Cu layer instead of MgBi₄. Large lateral displacements of Bi atoms in the c(6 × 4)-(Mn + Bi) suggest that the Mn atoms undergo the size-enhancement caused by their large magnetic moment.     

On the duration of the total eclipse of a satellite of a body

This paper solves the problem of the duration of the total eclipseof a satellite of a body, provided that (a) the body is sphericalin shape and the mass distribution inside the body is sphericallysymmetrical; (b) the satellite is a very small object; (c) thesatellite's orbit around a body is circular and the satellitecan pass through the centre of its shadow; (d) a source of lightis the source of the conical body's shadow (umbra) and it doesnot change its apparent position in the sky; (e) there are noperturbations on the satellite's orbit. The solution presentedrepresents the general discussion of the problem based on utilizationof some parts of the theory of contraction mappings.     

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.     

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     

Estimation of growth rate in unidirectionally solidified multicrystalline silicon by the growth-induced striation method

Multicrystalline silicon was grown by unidirectional solidification method using the accelerated crucible rotation technique. The application of the accelerated crucible rotation technique in unidirectional solidification method induced growth striations across the axial direction of the grown crystal. This striation pattern was observed from carbon concentration distribution, obtained by using Fourier transform infrared spectroscopy. The generated striation pattern was found to be weak and discontinuous. Some striations were absent, probably due to back melting, caused during each crucible rotation. From the growth striations and applied time period in crucible rotation, the growth rate was estimated by using Fourier transformation analysis.     

1H and 13C NMR spectroscopic study of oxidation of D,L‐cystine and 3,3′‐dithiobis(propionic acid) with hydrogen peroxide in aqueous solution

The oxidation of symmetrical disulfides [D ,L ‐cystine ( 1 ) and 3,3′‐dithiobis(propionic acid) ( 2 )] with hydrogen peroxide in D₂O–NaOH solution (pH 10–11) was studied by NMR spectroscopy. Assignments of the proton and carbon NMR signals of starting materials ( 1 and 2 ) and products of oxidation are based on conventional 1D NMR methods (DEPT, selective spin decoupling). Formation of C—S bond cleavage products or, in case of 2 , partially oxidized intermediates was not detected. The accelerating effect of Cu²⁺ cations, but not Fe³⁺ cations, on the oxidation rate of 1 in basic medium was demonstrated. Copyright © 2002 John Wiley & Sons, Ltd.     

一种有机电致发光共聚物的制备和性能

采用Suzuki方法合成了9，9-二辛基芴与萘并硒二唑的两种无规共聚物并研究了其紫外光谱、光致发光和电致发光性能。两种聚合物的电致发光波长为650～666nm，均为发饱和红光的LED材料，其电致发光外量子效率最高达到了1．05％。随着共聚物中萘并硒二唑含量的增加，共聚物的光致发光和电致发光的发射波长均有少量红移。证明了根据共轭高聚物链内能量转移原理，在聚芴链中引入不同含量的窄带隙杂环单元可实现对聚芴发光颜色的调节。     

Molecular dynamics and information on possible sites of interaction of intramyocellular metabolites in vivo from resolved dipolar couplings in localized H NMR spectra

Proton NMR resonances of the endogenous metabolites creatine and phosphocreatine ((P)Cr), taurine (Tau), and carnosine (Cs, β-alanyl-l-histidine) were studied with regard to residual dipolar couplings and molecular mobility. We present an analysis of the direct ¹H–¹H interaction that provides information on motional reorientation of subgroups in these molecules in vivo. For this purpose, localized ¹H NMR experiments were performed on m. gastrocnemius of healthy volunteers using a 1.5-T clinical whole-body MR scanner. We evaluated the observable dipolar coupling strength SD₀ (S = order parameter) of the (P)Cr-methyl triplet and the Tau-methylene doublet by means of the apparent line splitting. These were compared to the dipolar coupling strength of the (P)Cr-methylene doublet. In contrast to the aliphatic protons of (P)Cr and Tau, the aromatic H2 (δ = 8 ppm) and H4 (δ = 7 ppm) protons of the imidazole ring of Cs exhibit second-order spectra at 1.5 T. This effect is the consequence of incomplete transition from Zeeman to Paschen-Back regime and allows a determination of SD₀ from H2 and H4 of Cs as an alternative to evaluating the multiplet splitting which can be measured directly in high-resolution ¹H NMR spectra. Experimental data showed striking differences in the mobility of the metabolites when the dipolar coupling constant D₀ (calculated with the internuclear distance known from molecular geometry in the case of complete absence of molecular dynamics and motion) is used for comparison. The aliphatic signals involve very small order parameters S ≈ (1.4 − 3) × 10⁻⁴ indicating rapid reorientation of the corresponding subgroups in these metabolites. In contrast, analysis of the Cs resonances yielded S ≈ (113 − 137) × 10⁻⁴. Thus, the immobilization of the Cs imidazole ring owing to an anisotropic cellular substructure in human m. gastrocnemius is much more effective than for (P)Cr and Tau subgroups. Furthermore, ¹H NMR experiments on aqueous model solutions of histidine and N-acetyl-l-aspartate (NAA) enabled the assignment of an additional signal component at δ = 8 ppm of Cs in vivo to the amide group at the peptide bond. The visibility of this proton could result from hydrogen bonding which would agree with the anticipated stronger motional restriction of Cs. Referring to the observation that all dipolar-coupled multiplets resolved in localized in vivo ¹H NMR spectra of human m. gastrocnemius collapse simultaneously when the fibre structure is tilted towards the magic angle (θ ≈ 55°), a common model for molecular confinement in muscle tissue is proposed on the basis of an interaction of the studied metabolites with myocellular membrane phospholipids.     

Two‐stage copolycondensation of preformed oligomers with bisphenols by tosyl chloride/dimethylformamide/pyridine from distributions of resulting oligomers determined by a combination of gel permeation chromatography and NMR

A two‐stage co‐oligomerization of the oligomers initially formed from an equimolar mixture of isophthalic acid (IPA) and terephthalic acid (TPA) and 2,2‐bis(4‐hydroxyphenyl)propane (BPA, 50 mol %) with bisphenols (BPs, 20 mol %) was carried out using a tosyl chloride/dimethylformamide/pyridine condensing agent. The distributions of the resulting oligomers (n_x‐mers), which were quenched with methanol, were determined by a combination of gel permeation chromatography (GPC) and NMR. These distributions (presented by molar percentage) were conveniently calculated with the equation n_x (mol %) = n_x (% mol by GPC) × n₀ (mol % by NMR)/n₀ (% mol by GPC), where n_x (% mol) = n_x (wt % by GPC)/its molecular weight. The results showed the distributions of the preformed IPA/TPA‐BPA oligomers to be in fairly good accord with those obtained directly from GPC and to be supported by the NMR results. The calculation was applied to the co‐oligomers prepared up to a reaction of 0.7, at which there was an increase in the number of higher oligomers indivisible by GPC and the distributions could no longer be determined by molar percentage. The calculated distributions are discussed in relation to the results of copolycondensation. The sequence distributions in the resulting co‐oligomers, which were also examined by NMR, are compared with those in the copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 44–51, 2004     

Stability Conditions of the MMAP [ K ]/ G [ K ]/1/ LCFS Preemptive Repeat Queue

In this paper, we study the stability conditions of the MMAP[K]/G[K]/1/LCFS preemptive repeat queue. We introduce an embedded Markov chain of matrix M/G/1 type with a tree structure and identify conditions for the Markov chain to be ergodic. First, we present three conventional methods for the stability problem of the queueing system of interest. These methods are either computationally demanding or do not provide accurate information for system stability. Then we introduce a novel approach that develops two linear programs whose solutions provide sufficient conditions for stability or instability of the queueing system. The new approach is numerically efficient. The advantages and disadvantages of the methods introduced in this paper are analyzed both theoretically and numerically.