Formation of polymeric micelles with amino surfaces from amphiphilic AB‐type diblock copolymers composed of poly(glycolic acid lysine) segments and polylactide segments

Amphiphilic AB‐type diblock copolymers composed of hydrophobic poly(L ‐lactide) (PLA) segments and hydrophilic poly(glycolic acid lysine) [poly(Glc‐Lys)] segments with amino side‐chain groups self‐associated to form PLA‐based polymeric micelles with amino surfaces in an aqueous solution. The average diameter of the loose core–shell polymeric micelles for poly(Glc‐Lys) [number‐average molecular weight (M_n) = 1240]‐b‐PLA (M_n = 7000) obtained by a dimethyl sulfoxide/water dialysis method was estimated to be about 50 nm in water by dynamic light scattering measurements. The size and shape of the obtained polymeric micelles were further observed with transmission electron microscopy and atomic force microscopy. To investigate the possibility of applying the obtained PLA‐based polymeric micelles as bioabsorbable vehicles for hydrophobic drugs, we tested the entrapment of drugs in poly(Glc‐Lys) (M_n = 1240)‐b‐PLA (M_n = 7000) micelles and their release with doxorubicin as a hydrophobic drug. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1426–1432, 2002     

氟代二苯乙烯氨基酸的合成及性能

以4-碘-L-苯丙氨酸为初始原料,经羧基和氨基的保护得到化合物2;化合物2与4-氟苯乙烯进行Heck反应得化合物3;化合物3脱去保护基得氟代二苯乙烯氨基酸(4,47.4%);其结构经1H NMR,13C NMR,IR和MS(ESI-TOF)确证。光学性质研究结果表明:4的激发、发射波长分别为314 nm和355 nm,斯托克斯位移为41 nm,荧光量子产率为0.22。化合物4在甲醇溶液中存在光致顺反异构现象,反式→顺式结构转变速率常数为0.026 min^-1。     

镧系与二甘醇-二-(邻羟基苯基)醚配合物的合成与表征

本文合成14种镧系高氯酸盐及硝酸盐分别与二甘醇-二-(邻羟基苯基)醚(记为EO_2(HOP)_2,EO=ethylene oxide,HOP为邻羟基苯基)形成的新配合物,确证组成为Ln(ClO_4)_3·EO_2(HOP)_2·nH_2O(Ln:La-Eu,n=10,Ln:Gd,Dy-Tm,Y,n=7),La_3(NO_3)_9·(EO_2(HOP)_2)_2·3H_2O及La(ClO_4)_2·EO_2H(OP)_25H_2O。文中研究了配合物红外,紫外、~1HNMR谱及~(13)C纵向弛豫时间T_1等,并讨论了共存阴离子、溶剂及配体不同端基对成配的影响。     

Artificial model for cystathionine β-synthase: efficient β-replacement reaction with thiols employing a novel pyridoxal model compound having an imidazole function

As a second-generation pyridoxal model compound for cystathionine β-synthase, we designed a novel model compound having an ionophore function and an imidazole function, application of which to the β-replacement reaction with various thiols smoothly took place to give S-substituted cysteines. Peptides having a serine-O-carbonate residue at the N-terminal position were also converted to the corresponding peptides having an S-substituted cysteine residue under the catalytic conditions of the novel pyridoxal model compound.     

五氯化磷辅助下氨基酸的自组装成肽反应研究

L-α-氨基酸和D-α-氨基酸可与五氯化磷直接发生磷酰化反应，随后自组装成多肽，但β-氨基酸不能成肽，DL-α-氨基酸成肽困难；在SOCl2存在下，α-氨基酸也不能成肽，用电喷雾质谱研究了氨基酸的自组装反应，反应过程中有五元环状的氨基酸五配位磷中间体生成，使用硅烷基保护的氨基酸，在^31PNMR中可观察到五配位磷中间体。     

Catalytic Oxidation of Dimethyl Ether to Dimethoxymethane over Cs Modified HaPW12O40/SiO2 Catalysts

The attractive utilization route for one-step catalytic oxidation of dimethyl ether to dimethoxymethane was successfully carried out over the H3PW12O40（40%）/SiO2 catalyst, modified by Cs, K, Ni, and V. The Cs modification of H3PW12O40（40%）/SiO2 gave the most promising result of 20% dimethyl ether conversion and 34.8% dimethoxymethane selectivity. Dimethoxymethane could be synthe- sized via methoxy groups decomposed from dimethyl ether through the synergistic effect between the acid sites and the redox sites of Cs modified H3PW12O40（40%）/SiO2.     

有机锗氨基酸酯类系列化合物的快原子轰击质谱规律

为增强有机锗化合物的生物活性，合成了一系列有机锗氨基酸酯类倍半氧化物，并重点研究了它们的快原子轰击质谱（ＦＡＢＭＳ）。研究结果表明：该系列化合物的各碎片离子峰与其组成及结构均有很好的对应关系及很强的规律性     

Carbonyl‐Komplexe von Chrom,Molybdän und Wolfram mit Isocyanacetat. Reaktionen am koordinierten Isocyanacetat. Stabilisierung von Isocyanessigsäure und Isocyanacetylchlorid am Metall. Isocyanopeptide [1]

Carbonyl Complexes of Chromium, Molybdenum and Tungsten with Isocyano Acetate. Reactions of Coordinated Isocyanoacetate. Stabilization of Isocyanoacetic Acid and Isocyanoacetyl Chloride at the Metal Atom. Isocyanopeptides The reactions of [(OC)₅MCNCH₂CO₂Et] (M = Cr, W) with Na[N(SiMe₃)₂] or with KOH afford the isocyanoacetate complexes [(OC)₅MCNCH₂CO₂]^? ( 1,2 ). Similarly, the complex [(OC)₃Mo(CNCH₂CO₂^?Li⁺)₃] ( 4 ) was obtained from [(OC)₃Mo(CNCH₂CO₂Et)₃] ( 3 ) and LiOH. Protonation of 1 and 2 affords the sublimable isocyanoacetic acid complexes [(OC)₅MCNCH₂CO₂H] ( 5 , 6 ; M = Cr, W) in which the functional isocyanide is stabilized at the metal atom. Reactions of [(OC)₅WCNCH₂CO₂^?K⁺] and of [(OC)₃Mo(CNCH₂CO₂^?Li⁺)₃] with oxalyl dichloride give the isocyanoacetyl chloride compounds [(OC)₅WCNCH₂COCl] ( 9 ) (sublimable) and [(OC)₃Mo(CNCH₂COCl)₃] ( 10 ); the latter ( 10 ) was not isolated. Complexes 9 and 10 were reacted in situ with β‐alanine, glycine, phenylalanine and methionine esters as well as the peptide esters GlyGlyOEt, PhePheOMe, Phe‐β‐AlaOMe, and GlyGlyGlyOMe to form the isocyanoacetyl amino acid esters ( 11 ‐ 14 ) and the isocyanoacetyl peptide esters ( 15 ‐ 18 ) which are stabilized at the molybdenum atom.     

pH值对聚四氨基酞菁钴膜电化学和紫外光谱性质的影响

用循环伏安法在导电玻璃(ITO)和玻碳电极(GC)上制备了聚氨基酞菁钴(CoTAPc)修饰电极(CoTAPc/GC)。探讨了pH值对CoTAPc膜的光谱和电化学性质的影响，发现其氧化还原电位与pH值有线性关系，电催化活性也随酸度的增加而增加。CoTAPc膜的紫外吸收带变化与溶液pH值及在溶液中浸泡时间有关。     

2-氨基-4, 6-二甲基嘧啶与锌盐配合物的制备及生成焓测定

Thepyrimidinesasaclassareknowntopossessextraordinarybiologicalpropertiesthataregenerallydistinguishedqualitativelybytheirapplicationsinpesticide,herbicide,bactericide,andmedicineinter-mediates犤1犦.Asurveyoftheseapplicationsandanum-beroftherelatedvariationsthataredevelopedrecent-ly,suchastheextraordinaryeffectiveherbicideofsulfonylsulfourea,revealsthebroadbiologicalimpor-tancejustbecauseofthewideoccurrenceofpyrimi-dinesringsystemsinthesemolecules犤2犦.Ithasbeenshownthatthemedicineintermediates…