Ammonia-treated activated carbon as support of Ru-Ba catalyst for ammonia synthesis

Ammonia-treated activated carbon has been studied as a support of Ru-Ba catalyst for ammonia synthesis. It is shown that the introduction of nitrogen leads to a decrease of ammonia synthesis activity for the catalysts with a low Ba/Ru molar ratio, while no significant changes are obtained for the catalysts with a high Ba/Ru molar ratio, confirming that electronegative impurities suppress the activity in ammonia synthesis and consume part of the promoters. This revised version was published online in June 2006 with corrections to the Cover Date.     

Synthesis and characterization of second-order nonlinear optical polyurethane with high thermal stability

A second-order nonlinear optical polyurethane was formed with an X-type multi-dimensional charge-transfer (CT) chromophore (DNPIPDHPI) and 3,3^′-dimethoxy-4,4^′-diphenyl diisocyanate. Simultaneous poling and polymerization and in situ second harmonic generation (SHG) measurement technique was carried on to evaluate the thermal stability of the poling induced orientation. The SHG signal of the poled polymer film was not decay below 150 °C and remains 90% of relative d₃₃ value at 200 °C, which is better than the results reported in literature. Comparison of thermal stability indicates that the X-type chromophores possess better property in controlling the decay of the SHG activity than classic chromophores.     

Synthesis, structural characterization and ferrimagnetic property of MnPS3 intercalated with nickel(II) cyclopolyamine complex cations

Two new intercalation compounds were prepared by the reactions of Ni(II) cyclopolyamine complex cations with a preintercalate Mn_1−xPS₃K_2x(H₂O)_y, respectively, through “ion exchange” process. Their structures were characterized by elemental analysis, X-ray powder diffraction and infrared spectroscopy. The lattice spacing increased 0.567 and 1.093 nm with respect to the pristine MnPS₃. Ferrimagnetism of the intercalates was confirmed by SQUID experiment with T_c at 40 and 33 K, respectively.     

Facile solid-phase synthesis of cyclic decapeptide antibiotic streptocidins A-D

Total synthesis of decapeptide antibiotics streptocidins A-D from Streptomyces sp. Tü 6071 was accomplished for the first time by solid-phase peptide synthesis followed by traceless cyclization of the activated linear precursors, without protection of nucleophilic side chain. Synthetic products were equally active as the natural products isolated from the bacterial source and found to possess similar bacterial selectivity as other members in the amphipathic antimicrobial cyclic decapeptide family.     

Different catalysis role of in‐loop and out‐of‐loop waters in assisting HNS/HSN proton transfer isomerizations: Bridging vs. surrounding effect

In this work, a density function theory (DFT) study is presented for the HNS/HSN isomerization assisted by 1–4 water molecules on the singlet state potential energy surface (PES). Two modes are considered to model the catalytic effect of these water molecules: (i) water molecule(s) participate directly in forming a proton transfer loop with HNS/HSN species, and (ii) water molecules are out of loop (referred to as out‐of‐loop waters) to assist the proton transfer. In the first mode, for the monohydration mechanism, the heat of reaction is 21.55 kcal · mol^?1 at the B3LYP/6‐311++G** level. The corresponding forward/backward barrier lowerings are obtained as 24.41/24.32 kcal · mol^?1 compared with the no‐water‐assisting isomerization barrier T (65.52/43.87 kcal · mol^?1). But when adding one water molecule on the HNS, there is another special proton‐transfer isomerization pathway with a transition state 10T′ in which the water is out of the proton transfer loop. The corresponding forward/backward barriers are 65.89/65.89 kcal · mol^?1. Clearly, this process is more difficult to follow than the R–T–P process. For the two‐water‐assisting mechanism, the heat of reaction is 19.61 kcal · mol^?1, and the forward/backward barriers are 32.27/12.66 kcal · mol^?1, decreased by 33.25/31.21 kcal · mol^?1 compared with T. For trihydration and tetrahydration, the forward/backward barriers decrease as 32.00/12.60 (30T) and 37.38/17.26 (40T) kcal · mol^?1, and the heat of reaction decreases by 19.39 and 19.23 kcal · mol^?1, compared with T, respectively. But, when four water molecules are involved in the reactant loop, the corresponding energy aspects increase compared with those of the trihydration. The forward/backward barriers are increased by 5.38 and 4.66 kcal · mol^?1 than the trihydration situation. In the second mode, the outer‐sphere water effect from the other water molecules directly H‐bonded to the loop is considered. When one to three water molecules attach to the looped water in one‐water in‐loop‐assisting proton transfer isomerization, their effects on the three energies are small, and the deviations are not more than 3 kcal · mol^?1 compared with the original monohydration‐assisting case. When adding one or two water molecules on the dihydration‐assisting mechanism, and increasing one water molecule on the trihydration, the corresponding energies also are not obviously changed. The results indicate that the forward/backward barriers for the three in‐loop water‐assisting case are the lowest, and the surrounding water molecules (out‐of‐loop) yield only a small effect. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Monolithic enantiomer-selective stationary phases for capillary electrochromatography

Monolithic materials have become a well-established format for stationary phases in the field of capillary electrochromatography. Four types of monoliths, namely particle-fixed, silica-based, polymer-based, and molecularly imprinted monoliths, have been utilized as enantiomer-selective stationary phases in CEC. This review summarizes recent developments in the area of monolithic enantiomer-selective stationary phases for CEC. The preparative procedure and the characterization of these columns are highlighted. In addition, the disadvantages and limitations of different monolithic enantiomer-selective stationary phases in CEC are briefly discussed.     

Comprehensive two-dimensional HPLC to study the interaction of multiple components in Rheum palmatum L. with HSA by coupling a silica-bonded HSA column to a silica monolithic ODS column

A mode of comprehensive 2-D LC was developed by coupling a silica-bonded HSA column to a silica monolithic ODS column. This system combined the affinity property of the HSA column and the high-speed separation ability of the monolithic ODS column. The affinity chromatography with HSA-immobilized stationary phase was applied to study the interaction of multiple components in traditional Chinese medicines (TCMs) with HSA according to their affinity to protein in the first dimension. Then the unresolved components retained on the HSA column were further separated on the silica monolithic ODS column in the second dimension. By hyphenating the 2-D separation system to diode array detector and MS detectors, the UV and molecular weight information of the separated compounds can also be obtained. The developed separation system was applied to analysis of the extract of Rheum palmatum L., a number of low-abundant components can be separated on a single peak from the HSA column after normalization of peak heights. Six compounds were preliminarily identified according to their UV and MS spectra. It showed that this system was very useful for biological fingerprinting analysis of the components in TCMs and natural products.     

Highly enantioselective hydrogenation of N-phthaloyl enamides

Rh- or Ru-catalyzed highly enantioselective hydrogenation of N-phthaloyl enamides is presented. Electron-rich TangPhos and DuanPhos are found to be effective ligands for Rh-catalyzed hydrogenation of α-aryl enamides and up to 99% ee has been achieved. In contrast, for the hydrogenation of α-alkyl enamide, the Ru-C₃-TunePhos complex is more effective and up to 69% ee can be observed. This work is the first report of the hydrogenation of N-phthaloyl enamides.     

OJ手性柱分离芳基烷酸类非甾体解热镇痛药的色谱保留特性和拆分机理

使用纤维素类手性柱OJ柱, 分离布洛芬、依托度酸、非诺洛芬钙、酮洛芬、洛索洛芬等5个芳基烷酸类非甾体解热镇痛药对映体, 并通过溶质计量置换保留模型和热力学研究对OJ手性柱手性分离机理进行探讨. 结果表明, OJ手性柱可在正相条件下分离系列芳基烷酸类非甾体解热镇痛药, 对映体的色谱保留和分离度可以通过改变流动相中醇类置换剂和浓度、有机酸性改性剂和浓度、柱温等因素调节.     

A pure blue light emitting binaphthyl derivative：Synthesis and properties

A binaphthyl derivative with pyrene on 3 and 3＇ positions was synthesized and characterized via Suzuki coupling reaction. Emission maximum in solution was located at 390 nm with a quantum efficiency of 68% by taking 9,10-diphenyl anthracene as reference,while it is shifted to 450 nm with FWHM of 104 nm resulting from aggregation state in solid film.Glass transition temperature（Tg）and decomposition temperature were measured to be 184 and 447℃,respectively,by DSC and TGA.Unlike its photoluminescence spectrum,electroluminescent spectrum peaked at about 460 nm and shows a FWHM of 69 nm corresponding to a pure blue emission.The turn-on voltage,luminance and efficiency maximum were 5 V,2953 cd/m^2 and 1.37cd/A with CIE color coordinate of（0.16,0.15）,in the device structure of ITO/NPB（40nm）/PY-BN-PY（15nm）/BPhen（40nm）/Mg：Ag.