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Chinese Journal of Structural chemistry 1999年第4期18卷 54-59页

作者： XU JiaXi\ ZHANG ZeYing\= (college of chemistry and molecular engineering, peking university, beijing 100871, china) Coll. of Chem. and Molec. Eng. Peking University Beijing 100871 China

１ＩＮＴＲＯＤＵＣＴＩＯＮＰａｌａｄｉｕｍｃｏｍｐｌｅｘｅｓｓｕｃｈａｓｔｅｔｒａｋｉｓ（ｔｒｉｐｈｅｎｙｌｐｈｏｓｐｈｉｎｅ）ｐａｌａｄｉｕｍａｒｅａｋｉｎｄｏｆｉｍｐｏｒｔａｎｔｃａｔａｌｙｓｔｓｉｎｔｈｅｒｅａ... 详细信息

１ＩＮＴＲＯＤＵＣＴＩＯＮＰａｌａｄｉｕｍｃｏｍｐｌｅｘｅｓｓｕｃｈａｓｔｅｔｒａｋｉｓ（ｔｒｉｐｈｅｎｙｌｐｈｏｓｐｈｉｎｅ）ｐａｌａｄｉｕｍａｒｅａｋｉｎｄｏｆｉｍｐｏｒｔａｎｔｃａｔａｌｙｓｔｓｉｎｔｈｅｒｅａｃｔｉｏｎｏｆｃａｒｂｏｎｃａｒ...

关键词： palladium complex synthesis molecular structure crystal structure

Inhibitory effect of picroside Ⅱ on hepatocyte apoptosis

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Acta Pharmacologica Sinica 2005年第6期26卷 729-736页

作者： Hua GAO, Ya-wei ZHOU~2 college of chemistry and molecular engineering, peking university, beijing 100871, china college of chemistry and molecular engineering Peking University Beijing China

Aim: To investigate the influence of picroside on hepatocyte apoptosis and its mechanism. Methods: Morphological changes and quantification of apoptotic cells were determined under transmission electron microscopy and flow cytometry respectively. DNA fragmentation was visualized by agarose gel electrophoresis. Semi-quantitative reverse transcription-PCR (RT-PCR) was used to analyze the expression of bcl-2 and bax genes. The content of manganese-superoxide dismutase (SOD) in liver mitochondria was detected by the Marland method. The content of malonic aldehyde (MDA) and the protein level in liver tissue were determined by thiobarbituric acid colorimetry and Lowry method. Results: Picroside decreased the levels of alanine aminotransferase and aspartate aminotransferase in the serum resulting from acute-liver injured mice induced with D-GalN and LPS; it also reduced the content of MDA, and thus, enhanced the activity of SOD. Picroside 0 mg/kg was found to protect hepatocytes against apoptosis in a dose-dependent manner; it up-regulated the expression of bcl-2 genes, thus increased the bcl-2/bax ratio. Conclusion: Picroside 鈪an protect hepatocytes against injury and prevent hepatocytes from apoptosis. It might by upregulating the bcl-2 gene expression and antioxidation.

关键词： picroside Ⅱ hepatocytes apoptosis oxidative stress bcl-2 genes bax genes

STABILITY OF POLY(N,N'-METHYLENEBISACRYLAMIDE-co-4-VINYLPYRIDINE)MICROGEL DISPERSION AND ADJUSTMENT OF THE HYDROPHOBICITY IN THE MICROGELS

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Chinese Journal of Polymer Science 2005年第6期23卷 635-642页

作者： Qing-de Chen Xing-hai Shen and Hong-cheng Gao Department of Applied chemistry,college of chemistry and molecular engineering,peking university,beijing 100871,china Department of Applied chemistry College of Chemistry and Molecular Engineering Peking University Beijing 100871 China

In the UV-Vis spectra of pure light-scattering systems, there is an exponential relationship between absorbance and wavelength （A = Kλ^-n）. Here, the exponent n is named as flocculation-coagulation parameter. In the present paper, the effects of different additives on the stability of poly（N,N＇-methylenebisacrylamide-co-4-vinylpyridine）（poly（Bis-co-4-VP）） microgel dispersion were studied in detail via this parameter. The results showed that the stability of the dispersion mainly comes from the ionization of pyridine groups, making the microgel positively charged on its surface. This was confirmed by the measurement of Zeta potential and the result of conductometric titration. The result of fluorescence analysis indicated that the hydrophobicity in the microgels is enhanced with the increase in total 4-VP unit content.

关键词： Microgel dispersion(s) 4-Vinylpyridine Flocculation-coagulation parameter Zeta potential

EFFECTS OF L-PHENYLALANINE ON THE RADIATION SYNTHESIS OF POLY(N,N'-METHYLENEBISACRYLAMIDE-co-4-VINYLPYRIDINE)(MICRO)GELS

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Chinese Journal of Polymer Science 2005年第6期23卷 643-650页

The effects of L-phenylalanine （L-Phe） on the synthesis ofpoly（N,N＇-methylenebisacrylamide-co-4-vinylpyridine）（poly（Bis-co-4-VP））（micro）gels by γ-ray irradiation were studied. The addition of L-Phe could not only decrease the gelation dose （Dg） of the synthesis obviously, but also transform the morphology of copolymer from microgel to gel. In addition, the swelling ability of the （micro）gels was also affected in the presence of L-Phe. The decrease of Dg was ascribed to the effect of pH, while the transformation of the morphology was ascribed to the effect of L-Phe on the stability of the poly（Bis-co-4-VP） microgel. Such an effect was confirmed further as compared with the effects of L-alanine, L-glutamic acid, L-arginine, sulfuric acid and aqueous ammonia.

关键词： L-Phenylalanine γ-Ray irradiation Gelation dose Morphology transformation (Micro)gel

PROPERTIES OF POLYURETHANE ELASTOMERS BASED ON POLY (OXYETHYLENE-co-OXYTETRAMETHYLENE) DIOL

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Chinese Journal of Polymer Science 2001年第4期19卷 371-376页

作者： Chen-yu Su Guang-li Zhang Hong-zhi Zhang Department of Polymer Science and engineering college of chemistry and molecular engineering peking university beijing 100871, china 北京大学北京

Polyurethane elastomers derived from 4,4 ' -methylene bis(phenyl isocyanate), butylene glycol and the low oxyethylene moiety content copolyether of tetrahydrofuran and ethylene oxide, obtained by copolymerization using heteropolyacid-ethylene oxide initiator system, were prepared. The polyurethanes exhibited an increased water absorption and much better low temperature resilience, which remained high even at a temperature of -3 degreesC, while that of polyurethane based upon poly(tetramethylene ether) glycol of the 'same molecular weight, i.e. being 2000, and molecular weight distribution, i.e, in the range of 1.4-1.5, starts to decrease dramatically at 5 degreesC.

关键词： polyurethane poly(oxyethylene-co-oxytetramethylene) diol low temperature resilience heteropolyacid-ethylene oxide initiator system

Antiviral compounds and one new iridoid glycoside from Cornus officinalis

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Progress in Natural Science:Materials International 2006年第2期16卷 142-146页

作者： WANG Yue, LI Zhengquan, CHEN Lirong and XU Xiaojie (college of chemistry and molecular engineering, peking university, beijing 100871, china) college of chemistry and molecular engineering Peking University Beijing 100871 China

From Cornus officinalis Sieb. et Zucc., bioassay-guided fractionation led to the isolation of four active tannin compounds with high effectiveness of inhibiting Hepatitis C virus NS3 serine protease in vitro. The compounds are: 1,2,3, 6-tetragalloyl-β-D-glucopyranose (1), 1,2,3,4,6- pentagalloyl-β-D-glucopyranose (2), Tellimagrandin I (3) and Tellimagrandin II(4). The four compounds could inhibit HCV NS3 protease in vitro with IC50 values of 6.98, 5.11, 7.0 and 4.8μmol/L respectively. In addition, a new iridoid glycoside (5) was also isolated from Cornus officinalis Sieb. et Zucc., which was assigned to be 7-O-butyl morroniside by spec-troscopic analysis.

关键词： inhibitor HCV NS3 protease iridoid glycoside Cornus officinalis Sieb. et Zucc.

A NOVEL PHOTO-INITIATING SYSTEM FOR ATOM TRANSFER RADICAL POLYMERIZATION OF STYRENE

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Chinese Journal of Polymer Science 2001年第5期19卷 441-445页

作者： Shu-hui Qin Dong-qi Qin Kun-yuan Qiu Department of Polymer Science and engineering college of chemistry and molecular engineering peking university beijing 100871, china 北京大学北京

A novel photo-induced initiating system, 2,2-dimethoxy-2-phenylacetophenone (DMPA)/ferric tri(NN-diethyldithiocarbamate) [Fe(DC)(3)], was developed and used for the atom transfer radical polymerization (ATRP) of styrene in toluene. The polymerization proceeds with DMPA as photo-initiator, Fe(DC)(3) as catalyst and DC as a reversible transfer group, while the halogen and ligands are free. Well-defined PSt was prepared and the polymerization mechanism revealed by end group analysis belongs to a reverse ATRP. Block copolymer was prepared by using thus obtained PSt as macroinitiator and Fe(DC)(2) as catalyst under UV light irradiation via a conventional ATRP process.

关键词： photo atom transfer radical polymerization living radical polymerization well-defined polystyrene block copolymer

SYNTHESIS AND CHARACTERIZATION OF A NOVEL BLUE LIGHT EMITTING ROD-COIL DIBLOCK OLIGOMER

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Chinese Journal of Polymer Science 2002年第5期20卷 401-407页

作者： Lifang Yang Haifeng He Hongqing Cao Xinhua Wan Qi-feng Zhou Department of Polymer Science & engineering college of chemistry & molecular engineering peking university beijing 100871, china Department of Polymer Science & engineering College of Chemistry & Molecular Engineering Peking University 北京 100871 Department of Polymer Science & engineering College of Chemistry & Molecular Engineering Peking University 北京 100871

Four new rod-coil diblock molecules, which had well-defined para-phenylene oligomers (PPP, from biphenyl to quinquephenyl) as rigid segments and poly(ethylene oxide) (PEO, M-w ca. 750) as flexible segments, were synthesized. The chemical structure and the number of repeating unit in PEO coil and PPP rod were characterized by H-1-NMR and MALDI-TOF mass spectrometry. The diblock oligomers showed good solubility in common organic solvents and aggregated in water as characterized by a blue shift in UV-vis absorption spectra, a red shift in emission spectra, quenching of the fluorescence and formation of the microfibrilla and fractal-like structures. The formation of different supramolecular structures meant that this effort might lead to commercial important highly organized functional materials.

关键词： rod-coil diblock oligomer MALDI-TOF mass spectrometry microfibrilla aggregate fractal-like pattern

Systematic study of the transfer of amino acids across the water/1,2-dichloroethane interface facilitated by dibenzo-18-crown-6

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Science china chemistry 2004年第1期47卷 24-33页

作者： CHEN Yong, YUAN Yi, ZHANG Meiqin, LI Fei, SUN Peng, GAO Zhao & SHAO YuanhuaState Key Laboratory of Electroanalytical chemistry, Changchun Institute of Applied chemistry, Chinese Academy of Sciences, Changchun 130022, china college of chemistry and molecular engineering, peking university, beijing 100871, china Lab. of Electroanalytical Chem. Changchun Inst. of Appl. Chem. Chinese Acad. of Sci. Changchun 130022 China Coll. of Chem. and molecular Eng. Peking Univ. Beijing 100871 China

Facilitated ion transfer reactions of 20 amino acids with dibenzo-18-crown-6 (DB18C6) at the water/1,2-dichloroethane (W/DCE) interfaces supported at the tips of micro- and nano-pipets were investigated systematically using cyclic voltammetry. It was found that there were only 10 amino acids, that is, Leu, Val, lie, Phe, Trp, Met, Ala, Gly, Cys, Gin (in brief), whose protonated forms as cations can give well-defined facilitated ion transfer voltammograms within the potential window, and the reaction pathway was proven to be consistent with the transfer by interfacial complexation/dissociation (TIC/TID) mechanisms. The association constants of DB 18C6 with different amino acids in the DCE (β0), and the kinetic parameters of reaction were evaluated based on the steady-state voltammetry of micro- or nano-pipets, respectively. The experimental results demonstrated that the selectivity of complexation of protonated amino acid by DB18C6 compared with that of alkali metal cations was low, which can be attributed to the vicinal effect arising from steric hindrance introduced by their side group and the steric bulk effect by lipophilic stabilization. Moreover, the association constants and the standard rate constants for different amino acids showed good correlations with their hydrophobicity (π), except Gly and Met, which inferred that the selectivity of such heterogeneous complex reaction for different amino acids with DB18C6, was not only affected by discrimination in binding these ions to the crown ether macro-cycle, but also significantly modified by the ion transfer Gibbs energy which was closely related to the structure of the transferred ions, protonated amino acids.

关键词： micro-/nano-pipet, water/1,2-dichloroethane interface, facilitated ion transfer, cyclic voltammetry, amino acid.

Reinvestigation on the Reaction of Salicylic Chloride with Salicylic Amide and X-ray Crystal Structure of a New Macrocyclic Polyester

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Chinese Journal of Structural chemistry 2003年第5期22卷 512-516页

作者： DU Da-Ming② CHEN Xiao HUA Wen-Ting JIN Xiang-Lin (Key Laboratory of Bioorganic chemistry and molecular engineering of Ministry of Education, college of chemistry and molecular engineering, peking university, beijing 100871, china) college of chemistry and molecular engineering Peking University Key Laboratory of Bioorganic Chemistry and Molecular Engineering Ministry of Education 北京 100871

The reaction of salicylic chloride and salicylic amide at 170 ℃ gave benzoxazine and a new macrocyclic polyester 3, whose crystal structure has been determined by single-crystal X-ray diffraction analysis. Compound 3: C28H16O8, Mr = 480.41, monoclinic, space group P21/n, a = 15.353(3), b = 14.196(3), c = 21.147(4) ? b = 103.32(3), V = 4485(2) ?, Z = 8, F(000) = 1984, Dc = 1.423 g/cm3 and m = 0.106 mm-1. The final R = 0.0535 and wR = 0.1275 for 7903 observed reflections (I ≥ 2(I)). In the asymmetric unit of the compound there exist two independent molecules which are connected by weak aromatic CH…O hydrogen bonding between C(47)?H(47) and atom O(7) of the carbonyl group.

关键词： salicylic chloride salicylic amide polyester macrocycle crystal structure