核磁共振碳谱的研究:烷烃化学位移和CSS与分子距边矢量λ

系统研究了核磁共振碳谱及其化学位移规律性.提出了一种新的分子图论参数:分子距离一边数矢量(λ或MDE矢量),并发现它与烷烃的¹³C NMR有良好的相关性。     

Synthetic studies of halichondrin B, an antitumor polyether macrolide isolated from a marine sponge. 8. Synthesis of the lactone part (C1---C36) via horner-emmons coupling between C1---C15 and C16---C36 fragments and Yamaguchi lactonization

The lactone part (2) of halichondrin B (1) was synthesized by Yamaguchi macrolactonization of the seco-acid (3), which was synthesized via coupling of C1---C15(4) with C16---C36 (5), prepared through stereoselective construction of the E ring starting from C16---C26 (7) and C27---C36 (8).     

Convergence analysis of the projective scaling algorithm based on a long-step homogeneous affine scaling algorithm

In this paper we give a new convergence analysis of a projective scaling algorithm. We consider a long-step affine scaling algorithm applied to a homogeneous linear programming problem obtained from the original linear programming problem. This algorithm takes a fixed fraction λ≤2/3 of the way towards the boundary of the nonnegative orthant at each iteration. The iteration sequence for the original problem is obtained by pulling back the homogeneous iterates onto the original feasible region with a conical projection, which generates the same search direction as the original projective scaling algorithm at each iterate. The recent convergence results for the long-step affine scaling algorithm by the authors are applied to this algorithm to obtain some convergence results on the projective scaling algorithm. Specifically, we will show (i) polynomiality of the algorithm with complexities of O(nL) and O(n ² L) iterations for λ<2/3 and λ=2/3, respectively; (ii) global covnergence of the algorithm when the optimal face is unbounded; (iii) convergence of the primal iterates to a relative interior point of the optimal face; (iv) convergence of the dual estimates to the analytic center of the dual optimal face; and (v) convergence of the reduction rate of the objective function value to 1−λ.     

Synthesis of polypeptides from activated urethane derivatives of α‐amino acids

A series of activated urethane‐type derivatives of α‐amino acids were synthesized and applied to polypeptide synthesis. The urethane used herein, N‐(4‐nitrophenoxycarbonyl)‐α‐amino acids 1 , were synthesized by N‐carbamoylation of γ‐benzyl‐L ‐glutamate, β‐benzyl‐L ‐aspartate, L ‐leucine, L ‐phenylalanine, and L ‐proline, with 4‐nitrophenyl chloroformate. When 1 was dissolved in N,N‐dimethylacetamide (DMAc) and heated at 60 °C, it was smoothly converted into the corresponding polypeptides with releasing 4‐nitrophenol and carbon dioxide. Spectroscopic analyses of the obtained polypeptides revealed that they were comparable with the authentic polypeptides synthesized by the ring‐opening polymerizations of amino acid N‐carboxyanhydrides (NCAs). Besides the successful polycondensations of a series of 1 , their polycondensations of 1a and other 1 were also successfully carried out to obtain the corresponding statistic copolypeptides. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2525–2535, 2008     

Production of endohedral <Superscript>133</Superscript>Xe-higher fullerenes by ion implantation

Endohedral ¹³³Xe-higher fullerenes (¹³³Xe@C₇₆ and ¹³³Xe@C₈₄) were produced by implantation of ¹³³Xe ions using an isotope separator. A high performance liquid chromatography (HPLC) analysis showed that the peak of endohedral ¹³³Xe-higher fullerenes shifted backward from that of empty fullerenes, suggesting a possibility of the separation of endohedral ¹³³Xe-higher fullerenes from empty fullerenes. The yields of endohedral ¹³³Xe-fullerenes were in the order of ¹³³Xe@C₇₆<¹³³Xe@C₈₄<¹³³Xe@C₆₀<¹³³Xe@C₇₀.     

Convenient synthesis of poly(γ‐benzyl‐L‐glutamate) from activated urethane derivatives of γ‐benzyl‐L‐glutamate

A series of activated urethane‐type derivatives of γ‐benzyl‐L ‐glutamate were synthesized, and their potential as monomers for polypeptide synthesis was investigated. The derivatives of the focus of this work were a series of N‐aryloxycarbonyl‐γ‐benzyl‐L ‐glutamate 1 , of which aryl groups were phenyl, 4‐chlorophenyl, and 4‐nitrophenyl. These urethanes 1 were reactive in polar solvents such as dimethylsulfoxide, N,N‐dimethylformamide (DMF), and N,N‐dimethylacetamide (DMAc), and were efficiently converted into poly(γ‐benzyl‐L ‐glutamate) (poly(BLG)) under mild conditions; at 60 °C without addition of any catalyst. Among the three urethanes, that having 4‐nitrophenoxycarbonyl group 1c was the most reactive to give poly(BLG) efficiently, as was expected from the highly electron deficient nature of the nitrophenoxycarbonyl group. On the other hand, the urethane 1a having phenoxycarbonyl group was also efficiently converted into poly(BLG), in spite of the intrinsically less electrophilicity of the phenoxycarbonyl group. In addition, the successful formation of poly(BLG) by the reaction of 1a favored its diluted concentration (0.1 M) much more than 2.0 M, the optimum initial concentration for 1c . ¹H NMR spectroscopic analyses of the reactions in situ revealed that the predominant pathway from 1 to poly(BLG) involved the intramolecular cyclization of 1 into the corresponding N‐carboxyanhydride, with release of phenol and its successive ring‐opening polymerization with release of carbon dioxide. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2649–2657, 2008     

Crystallographic report: Dichloro[bis(1‐methylimidazole‐2)disulfide]zinc(II)

The Zn center in [ZnCl₂(L‐S‐S‐L)], where L‐S‐S‐L = bis(1‐methylimidazole‐2)disulfide, adopts a tetrahedral configuration defined by two Cl atoms and two N atoms from L‐S‐S‐L, which was obtained by in situ oxidation of 1‐methylimidazole‐2‐thione. Copyright © 2005 John Wiley & Sons, Ltd.     

Atmospheric concentrations of sulfur dioxide, nitrogen oxides, ammonia, hydrogen chloride, nitric acid, formic and acetic acids in the south of Vietnam measured by the passive sampling method.

A passive sampling method was applied to measure the concentrations of air pollutants, such as sulfur dioxide, nitrogen oxides, ammonia, hydrogen chloride, and nitric, formic and acetic acids, in the ambient air at four test sites in the southern region of Vietnam. The monthly averages and the average concentrations of air pollutants during the period from July 2001 to September 2002 are reported here. The concentrations of air pollutants varied widely, depending on the test sites and the sampling periods. The average concentrations of sulfur dioxide in the air during the period from July 2001 to September 2002 at the four test sites were 3.3-16.9 ppb, and those of nitrogen dioxide were 5.4-12.8 ppb. The concentrations of nitrogen monoxide and hydrogen chloride were very low at all of the test sites. The observed concentrations of all of the above-mentioned pollutants were lower than those of the Vietnamese standards of air pollutants.