Thermal degradation behavior of poly(4-hydroxybutyric acid)

Thermal degradation behavior of poly(4-hydroxybutyric acid) (P(4HB)) was investigated by thermogravimetric and pyrolysis-gas chromatography mass spectrometric analyses under both isothermal and non-isothermal conditions. Based on the thermogravimetric analysis, it was found that two distinct processes occurred at temperatures below and above 350 °C during the non-isothermal degradation of P(4HB) samples depending on both the molecular weight and the heating rate. From ¹H NMR analysis of the residual P(4HB) molecules after isothermal degradations at different temperatures, it was confirmed that the ω-hydroxyl chain-end was remained unchanged in the residual P(4HB) molecules at temperatures below 300 °C, while the ω-chain-end of P(4HB) molecules was converted to 3-butenoyl units at temperatures above 300 °C. In contrast, the majority of the volatile products evolved during thermal degradation of P(4HB) was γ-butyrolactone regardless of the degradation temperature. From these results, it is concluded that during the thermal degradation of P(4HB), the selective formation of γ-butyrolactone via unzipping reaction from the ω-hydroxyl chain-end predominantly occurs at temperatures below 300 °C. At temperatures above 300 °C, both the cis-elimination reaction of 4HB unit and the formation of cyclic macromolecules of P(4HB) via intramolecular transesterification take place in addition to unzipping reaction from the ω-hydroxyl chain-end. Finally, the primary reaction of thermal degradation of P(4HB) at temperatures above 350 °C progresses by the cyclic rupture via intramolecular transesterification of P(4HB) molecules with a release of γ-butyrolactone as volatile product. Moreover, we carried out the thermal degradation tests for copolymer of 93 mol% of 4HB with 7 mol% of 3-hydroxybutyric acid (3HB) to examine the effect of 3HB units on thermal stability of P(4HB).     

Synthesis and Structure of MnCl2(HDpyF) (HDpyF = N,N′‐di(2‐pyridyl)formamidine): New Crystallographic Disorder and Bonding Mode of the HDpyF Ligand

The reaction of N,N′‐di(2‐pyridyl)formamidine (HDpyF) with MnCl₂‐4H₂O afforded the complex MnCl₂(HDpyF), which was characterized by X‐ray crystallography. The HDpyF ligand chelates to the Mn(II) center through the first and the third nitrogen atoms to form a six‐membered ring, leaving the second and the fourth nitrogen atoms uncoordinated. The HDpyF ligand is crystallographically disordered such that two different molecules can be solved. The neutral HDpyF ligand adopts the new s‐cis‐syn‐s‐trans conformation.     

Substituent effects on heats of formation, group interactions, and detonation properties of polyazidocubanes

We have calculated the heats of formation (HOFs) for a series of polyazidocubanes by using the density functional theory (DFT), Hartree-Fock, and MP2 methods with 6-31G* basis set as well as semiempirical methods. The cubane skeleton was chosen for a reference compound, that is, the cubane skeleton was not broken in the process of designing isodesmic reactions. There exists group additivity for the HOF with respect to the azido group. The semiempirical AM1 method also produced reliable results for the HOFs of the title compounds, but the semiempirical MINDO3 did not. The relationship between HOFs and molecular structures was discussed. It was found that the HOF increases 330-360 kJ/mol for each additional number of the azido group being added to the cubane skeleton. The distance between azido groups slightly influences the values of HOFs. The interacting energies of neighbor azido groups in polyazidocubanes are in the range of 2.3 approximately 6.6 kJ/mol, which are so small and less related to the substituent numbers. The average interaction energy between nearest neighbor --N3 groups in the most stable conformer of octaazidocubane is 2.29 kJ/mol at the B3LYP/6-31G* level. The relative stability related to the number of azido groups of the title compounds was assessed based on the calculated HOFs, the energy gaps between the frontier orbitals, and the bond orders of the C--N3 and C--C bonds. The predicted detonation velocity of hepta- and octa-derivatives is over 9 km/s, and the detonation pressure of them is ca. 40 GPa or over.     

β微管蛋白中紫杉醇(Taxol)结合腔的性质分析

采用多拷贝同时搜寻法(MCSS), 并结合现有微管抑制剂的SAR及3D-QSAR对β微管蛋白中Taxol(紫杉醇)结合腔的性质进行了分析. 结构研究结果表明, Taxol结合腔以疏水性质为主, 并指出官能团分布的具体位置: 在Phe270上方(Leu361-Pro272-Leu273-Leu228之间)的弧形区域、Asp26羧基下方及其与Glu22羧基之间、M-loop的中部, 以及Asp224内侧且靠近Arg276的胍基的位置. 而Asp224的内侧又是新提出的结合位点. 研究结果符合现有微管抑制剂的SAR, 为现有抗肿瘤药物的结构改造以及小分子微管抑制剂设计提供了理论依据.     

三辛基氧化膦(TOPO)萃取铟的研究

本文研究了三辛基氧化膦(TOPO)自盐酸溶液中萃取铟的性能,其萃取率是随酸度的增加而增加。与P_(350)和TBP相比较,萃取能力大小顺序为:TOPO>P_(350)>TBP经斜率法和化学分析法研究确定,TOPO白盐酸溶液中萃取铟的反应为:In_((a))~(3+)+H_((a))~++4Cl_((a))~-+2TOPO_((o))F(?)HInCl_4·2TOPO_((o))IR和NMR研究证明:铟是以H[InCl_4]形式被萃入TOPO有机相中的。     

Chemical Constituents from the Root of Antidesma Pentandrum var. Barbatum

Investigation of the root extract of Antidesma pentandrum var. barbatum led to the isolation of seven new compounds, antidesmol ( 1 ), antidesmanins E ( 2 ) and F ( 3 ), antidesnone ( 4 ), antidesnol ( 5 ), barbatumols A ( 6 ) and B ( 7 ), together with 14 known compounds including sodium aristolochate‐I ( 10 ) and aristolochic acid‐I methyl ester ( 11 ).     

Preparation of poly(methyl methacrylate) and copolymers having enhanced thermal stabilities using sucrose-based comonomers and additives

A series of methyl methacrylate polymers have been prepared containing sucrose-based crosslinkers and additives. Thermogravimetry and long-term aging studies at 200°C show that sucrose-based alkyl and allyl ethers provide unprecedented thermal stability to linear, as well as crosslinked, poly (methyl methacrylate) or PMMA. Linear PMMA and PMMA crosslinked with trimethylolpropane trimethacrylate (TMPTMA) both degrade at 284°C. PMMA containing octa-O-crotylsucrose (1 mol %) degraded at 322°C. Depending on concentration, PMMA containing octa-O-allylsucrose (0.1-1.0 mol % and higher) degraded between 334 and 354°C, and PMMA containing 1′,6,6′-trimethacryloyl-2,3,3′,4,4′-penta-O-methylsucrose (0.1-1.0 mol %) degraded between 309 and 320°C. PMMA containing (1 mol % each) sucrose-based esters, ester-ether derivatives, all degraded at or below the degradation temperature of pure PMMA. Long-term air aging studies revealed that PMMA containing penta-O-methylsucrose trimethacrylate, octa-O-allylsucrose, and octa-O-crotylsucrose did not flow or sag after heating for 24 h at 200°C, but the polymers did show yellowing. While linear and crosslinked samples of PMMA containing compounds other than sucrose ethers lost more than 50% of their original weight within 15 h at 200°C, PMMA containing sucrose-based ethers lost about 8 and 20% of their original weight after 1 and 8.5 days, respectively. Herein we propose a unique mechanism by which saccharide ethers may be imparting this unprecedented thermal stabilization to PMMA. While tertiary hydrogens alpha to oxygens in saccharide ethers are stable to chain transfer during normal polymerization temperatures, they readily chain transfer at 200°C where PMMA is unstable. Chain transfer of these hydrogens is followed by fragmentation to produce alkyl, allyl or crotyl radicals, which combine with the macroradicals and terminate depropagation. © 1995 John Wiley & Sons, Inc.     

锆基纤维素手性固定相直接拆分萘普生衍生物

萘普生是一种消炎镇痛药 ,其 S对映体的抗炎作用是 R构型的 2 8倍 ,萘普生及其衍生物的拆分具有重要意义 .手性固定相 HPLC直接拆分 [1～ 4 ] 是最简便的分析方法 .氧化锆是近年来备受关注的色谱载体 [5,6 ] .Carr等 [7] 对碱性药物快速拆分表明氧化锆在手性分离Scheme1　 Structuresof chiral naproxen and its derivatives中的独特选择性 .萘普生及其衍生物在锆基手性固定相上的分离未见文献报道 .本组利用自制的球形氧化锆制备了涂敷型纤维素 -三 ( 3,5 -二甲基苯基氨基甲酸酯 ) -Zr O2 手性固定相 ( CDMPC- Zr O2 - CSP) ,在正…     

Synthesis and properties of novel polyurethanes containing 3,4‐dioxybenzylidenecyanoacetate group as a nonlinear optical chromophore

Methyl 3,4‐di‐(2′‐hydroxyethoxy)benzylidenecyanoacetate ( 3 ) was prepared by hydrolysis of methyl 3,4‐di‐(2′‐vinyloxyethoxy)benzylidenecyanoacetate ( 2 ). Diol 3 was condensed with 2,4‐toluenediisocyanate, 3,3′‐dimethoxy‐4,4′‐biphenylenediisocyanate, and 1,6‐hexamethylenediisocyanate to yield polyurethanes 4 – 6 containing the nonlinear optical chromophore 3,4‐dioxybenzylidenecyanoacetate. The resulting polyurethanes 4 – 6 were soluble in common organic solvents such as acetone and dimethylformamide. Polymers 4 – 6 indicated thermal stability up to 300 °C in thermogravimetric thermograms with glass‐transition temperature values obtained from differential scanning calorimetric thermograms in the range of 78–102 °C. The second‐harmonic generation coefficients (d₃₃) of the poled polymer films were around 6.9 × 10^?9 esu. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1742–1748, 2002     

High levels of soluble herpes virus entry mediator in sera of patients with allergic and autoimmune diseases

Herpes virus entry mediator (HVEM) is a newly discovered member of the tumor necrosis factor receptor (TNFR) superfamily that has a role in herpes simplex virus entry, in T cell activation and in tumor immunity. We generated mAb against HVEM and detected soluble HVEM (SHVEM) in the sera of patients with various autoimmune diseases. HVEM was constitutively expressed on CD4(+) and CD8(+) T cells, CD19(+) B cells, CD14(+) monocytes, neutrophils and dendritic cells. In three-way MLR, mAb 122 and 139 were agonists and mAb 108 had blocking activity. An ELISA was developed to detect sHVEM in patient sera. sHVEM levels were elevated in sera of patients with allergic asthma, atopic dermatitis and rheumatoid arthritis. The mAbs discussed here may be useful for studies of the role of HVEM in immune responses. Detection of soluble HVEM might have diagnostic and prognostic value in certain immunological disorders.