制备方法对Fe/NCNTs催化剂结构及费托反应性能的影响

以碳氮纳米管(NCNTs)为载体, 利用氮的锚定作用, 采用三种不同的制备方法(等体积浸渍法、胶体法和沉积沉淀法)方便地构建了负载铁物种的Fe/NCNTs催化剂. 系统考察了制备方法对催化剂的结构及费托反应性能的影响. 结果表明, 制备方法影响铁纳米粒子的粒度和分布、催化剂的还原和碳化行为, 使催化剂表现出不同的催化性能. 等体积浸渍法得到分散性较好、粒径小和分布窄[(8±4) nm]、容易还原和碳化的催化剂, 反应中呈现出最高的低碳烯烃选择性、催化活性和稳定性. 胶体法得到了形貌各异的粒子, 反应中活性相易被氧化使得催化剂活性及稳定性较差. 沉积沉淀法得到了粒径过大、难以还原和碳化的粒子, 反应15 h后催化剂活性及稳定性急剧下降. 该研究为利用氮掺杂碳纳米材料作为载体设计和开发高性能的费托合成催化剂提供了有益参考.     

Microwave-Assisted Rapid Preparation of Substituted Carbazole-9-acetic and Propionic Acids and their Absorption and Fluorescence Spectra

Summary.  A rapid one-pot synthesis of substituted carbazole-9-acetic and -propionic acids under microwave irradiation is described. N-Alkylation and hydrolysis was carried out in DMF without catalyst. The absorption and fluorescence spectroscopic characteristics of the title compounds are discussed. Received January 31, 2000. Accepted (revised) March 7, 2000     

Improved Chiral Synthesis of Ravuconazole

A short, elegant, and high yielding synthesis of ravoconazole is presented. The key step of this synthesis is an enantioselective palladium-catalyzed chiral zinc-allene addition reaction. The starting materials are 2-chloro-1-(2,4-difluorophenyl)-ethanone and (R)-4-phenylbutyn-2-ol obtained from enzymatic resolution of its racemate.     

Coordination of stocking decisions in an assemble-to-order environment

This paper examines an assemble-to-order environment involving a short-life-cycle product that is sold in two different configurations, each requiring a unique component that must be stocked in advance. Both configurations of the product are assembled on the same equipment which has limited capacity. The focus of the analysis is on the determination of the appropriate stocking quantities for each of the configuration specific components. Because the same assembly capacity is often reused for different instances of the component stocking problem, we treat assembly capacity as exogenous. This represents the fact that capacity decisions are often made less frequently than are procurement/production quantity decisions. We first solve for the first-best stocking policy when the components are produced internally. We then consider the case when the components are procured from external suppliers, and investigate how different forms of contract between the assembler and the component suppliers affect coordination of the supply chain as well as each party’s profit. One particularly interesting finding is that it is possible to coordinate the supply chain with a single-price contract between each supplier and the assembler while awarding all parties positive profit.     

A modified ODE-based algorithm for unconstrained optimization problems

This paper presents a modified ODE-based algorithm for unconstrained optimization problems. It combines the idea of IMPBOT algorithm with nonmonotone and subspace techniques. The main feature of this method is that at each iteration, a lower dimensional system of linear equations is solved to obtain a trial step. Under some standard assumptions, the method is proven to be globally convergent. Numerical results show the efficiency of this proposed method in practical computation.     

Synthesis of 2,2-difluoro-2H-chromenes through the tandem reaction of ethyl 3-bromo-3,3-difluoropropionate with salicylaldehyde derivatives

A series of 2,2-difluoro-2H-chromenes were synthesized from the tandem reactions of ethyl 3-bromo-3,3-difluoropropionate with salicylaldehyde derivatives in good yields under basic conditions. In acidic environment defluorination took place during the reaction. A plausible mechanism was proposed based on the experimental results.     

A three-process quantum engine cycle consisting of a two-level system

Based on the thermodynamic properties of isoenergetic,adiabatic and isothermal quantum processes,it is shown that it is possible to combine the three processes into a quantum engine cycle.The efficiency of the three-process cycle can be derived and is dependent on the highest and lowest temperatures.The efficiency in some operation regions does not demonstrate a monotonically increasing function of the temperature difference.When the highest temperature of the cycle is larger than the critical temperature,which can be determined by the characteristics of the three-process cycle,a unique region where the efficiency decreased with the increase of the temperature difference exists.     

Additional ent‐Kaurane Diterpenoids from Rubus corchorifolius L. f.

A further chemical investigation of the plant Rubus corchorifolius L. f., collected in Hunan Province, afforded three new ent‐kauranoids 3 – 5 . Their structures were elucidated by various spectroscopic methods.     

A facile synthesis of a complex type N-glycan thiazoline as an effective inhibitor against the antibody-deactivating endo-β-N-acetylglucosaminidases

Endo-β-N-acetylglucosaminidases are a class of endoglycosidases that deglycosylate N-glycans from glycoproteins. We describe here a facile synthesis of a complex type N-glycan thiazoline as a new mechanism-based inhibitor for this class of enzymes. The synthesis started with the readily available sialoglycopeptide (SGP) and its conversion into the glycan thiazoline through several enzymatic and chemical reactions. The synthetic glycan thiazoline showed potent inhibitory activity against several endoglycosidases including the two antibody-deactivating enzymes, Endo-S and Endo-S2, from human pathogen Streptococcus pyogenes, which would be useful as tools for structural and functional studies of these enzymes.     

Synthesis and physicochemical characterization of two gadolinium(III) TTDA-like complexes and their interaction with human serum albumin

Two novel derivatives of TTDA (3,6,10-tri(carboxymethyl)-3,6,10-triazadodecanedioic acid), TTDA-BOM and TTDA-N'-BOM, each having a benzyloxymethyl group, were synthesized. (17)O NMR longitudinal and transverse relaxation rates and chemical shifts of aqueous solutions of their Gd(III) complexes were measured at variable temperature with a magnetic field strength of 9.4 T. The water exchange rate (k(ex)(298)) values for [Gd(TTDA-BOM)(H(2)O)](2-) (117 x 10(6) s(-1)) and [Gd(TTDA-N'-BOM)(H(2)O)](2-) (131 x 10(6) s(-1)) are significantly higher than those of [Gd(DTPA)(H(2)O)](2-) (4.1 x 10(6) s(-1)) and [Gd(BOPTA)(H(2)O)](2-) (3.45 x 10(6) s(-1)). The rotational correlation time (tau) values for [Gd(TTDA-BOM)(H(2)O)](2-) (119 ps) and [Gd(TTDA-N'-BOM)(H(2)O)](2-) (125 ps) are higher than those of [Gd(DTPA)(H(2)O)](2-) (103 ps) and [Gd(TTDA)(H(2)O)](2-) (104 ps). The stepwise stoichiometric binding constants of [Gd(TTDA-BOM)(H(2)O)](2)(-) and [Gd(TTDA-N'-BOM)(H(2)O)](2)(-) bound to HSA are obtained by ultrafiltration studies. Fluorescent probe displacement studies exhibit that [Gd(TTDA-BOM)(H(2)O)](2-) and [Gd(TTDA-N'-BOM)(H(2)O)](2-) can displace dansylsarcosine from HSA with inhibition constants (K(i)) of 1900 and 1600 microM, respectively; however, they are not able to displace warfarin. These results indicate that [Gd(TTDA-BOM)(H(2)O)](2-) and [Gd(TTDA-N'-BOM)(H(2)O)](2-) have a weak binding to site II on HSA. In addition, the mean bound relaxivity (r(1b)) and bound relaxivity (r(1)(b)) values for the [Gd(TTDA-BOM)(H(2)O)](2-)/HSA and [Gd(TTDA-N'-BOM)(H(2)O)](2-)/HSA adducts are obtained by ultrafiltration and relaxivity studies, respectively. The bound relaxivity of these adducts values are significantly higher than those of [Gd(BOPTA)(H(2)O)](2-)/HSA and [Gd(DTPA-BOM(3))(H(2)O)](2-)/HSA. These results also suggest that bound relaxivity is site dependent. In binding sites studies of Gd(III) chelates to HSA, a significant decrease of the relaxation rates (R(1obs)) was observed for the [Eu(TTDA-BOM)(H(2)O)](2-) complex which was added to the [Gd(TTDA-N'-BOM)(H(2)O)](2-)/HSA solution, and this indicated that these Gd(III) complexes share the same HSA binding site. Finally, as measured by the Zn(II) transmetalation process, the kinetic stability of these Gd(III) complexes are significantly higher than that of [Gd(DTPA-BMA)(H(2)O)].