醇脱氢酶在反胶束溶液中的催化动力学性质

以十六烷基三甲基溴化铵(CATB)-辛烷-己醇反胶束体系对醇脱氢酶(ADH)进行固定化,试验了含水量、酶液pH值、CTAB和己醇浓度对ADH固定化的影响。对游离酶和固定化酶的催化动力学性质研究表明：酶促反应的最适pH值分别为8.2和8.8,最适温度分别是31℃和20℃,对乙醇的米氏常数Km分别为12mmol/L和7.4mmol/L。在30℃时,游离酶存放150min后失活90%,固定化酶失活50%,表明反胶束固定化ADH有较好的热稳定性。     

反胶束固定化乳酸脱氢酶的催化动力学性质研究

以十六烷基三甲基溴化铵(CATB)-辛烷-己醇反胶束体系对乳酸脱氢酶(LDH)进行固定化,试验了含水量、CTAB和己醇浓度对LDH固定化的影响。对游离酶和固定化酶的催化动力学性质研究表明:酶促反应的最适pH值分别为9.2和9.5,最适温度分别是37℃和43℃,对乳酸的米氏常数Km分别为1.4 mmol/L和2.3mmol/L。30℃时,游离酶存放2 h,约失活50%,而固定化酶仅失活10%,表明反胶束固定化LDH具有较好的热稳定性。     

游离脂肪酶NS81006催化油脂醇解制备生物柴油的酶促反应动力学

探究了游离脂肪酶NS81006催化油脂甲(乙)醇解制备生物柴油的反应历程,并对该体系进行了酶促反应动力学研究.结果表明,催化过程中油脂同时存在酯交换及先水解再酯化两种反应历程.在以甲醇或乙醇作为酰基受体的反应过程中,酯交换反应速率明显大于水解反应速率.进一步研究表明,油脂甲醇解反应速率常数大于乙醇解,揭示了以甲醇或乙醇为不同酰基受体时反应速率存在差异的主要原因在于乙醇解反应的酯交换过程较慢.     

溶胶-凝胶固定化多酶催化二氧化碳转化为甲醇反应初探

 为了探索温室气体CO2的固定和利用的新途径，以正硅酸乙酯为\r\n前驱体，用改进的溶胶－凝胶法对甲酸脱氢酶、甲醛脱氢酶和乙醇脱氢\r\n酶进行了包埋共固定化，并以包埋的三种酶为催化剂，以还原型烟酰胺\r\n腺嘌呤二核苷酸（NADH）为电子供体，在低温低压下将CO2转化为甲醇\r\n．初步研究了反应温度、pH值、酶含量及NADH用量对甲醇收率的影响．\r\n实验结果表明，在37℃和pH7．0的条件下，甲醇的收率可达92．4％．\r\n由于酶空间构型的微小变化和空间位阻效应的存在，与液相酶反应结果\r\n相比，包埋后的酶活性略有降低．     

酶促反应热动力学方程的研究

由酶促反应速率方程积分式和酶促反应中能量变化与物质参与反应量的关系推出了单底物酶促反应的热动力学方程。并用精氨酸的酶促水解反应进行了验证,求出的米氏常数K_m和最大速率Vmax与文献值相符。     

壳聚糖固定化醇脱氢酶的制备及其酶学性质研究

报道了醇脱氢酶(ADH)的固定化和酶学性质研究。以壳聚糖作为载体,戊二醛作为交联剂。固定化ADH的最适条件为:以6%戊二醛将壳聚糖交联2 h,与ADH反应2.5 h。对游离和固定化ADH酶学性质的研究表明:酶促反应的最适pH均为8.2,最适温度分别为37℃和40℃,对乙醇的表观米氏常数Km分别为33.9 mmol/L和46.2 mmol/L。与游离酶相比,固定化酶具有良好的操作稳定性。     

固定化酶扩散-反应问题的近似解

固定化酶在生物技术领域具有重要的理论和实际意义。由于固定化酶内部存在扩散传质阻力,因此固定化酶系统的化学反应速率不同于游离酶的反应速率。固定化酶反应动力学一般是基质浓度的非线性函数。通过求解固定化酶扩散 反应微分方程,可以得到固定化酶有效因子,而有效因子是固定化酶反应系统设计和模拟的重要参数,也是评定固定化酶系统性能优劣的重要因素之一。有效因子的计算通常采用将扩散 反应微分方程离散化的方法,例如正交配置法求解[1,2]。本文基于大参数的假设,在寻求固定化酶扩散 反应问题近似解的基础上,导出计算固定化酶有效…     

固定化醇脱氢酶的制备及性质

以壳聚糖为载体,通过交联结合使醇脱氢酶(ADH)得以固定化。固定化的最适条件为:交联剂戊二醛浓度0.6%,pH值6.8,酶的偶联时间2.5h。对游离酶和固定化酶的动力学性质研究表明,酶促反应的最适pH分别为8.2和8.4,最适温度为34℃和35℃。酶的米氏常数为13mmol·L-1和48mmol·L-1。与游离酶相比,固定化酶在复用性上具有优势。应用固定化酶测定了试样中铬含量。     

羧甲基纤维素水凝胶生物降解动力学研究

用氯化铝对羧甲基纤维素进行交联,制得了水凝胶.考察了底物浓度、酶浓度以及降解温度对该水凝胶降解速率的影响,探讨了酶降解动力学及“表观”活化能对酶浓度的依赖关系.结果表明,该酶促反应最佳温度为37 ℃,降解反应对底物浓度和酶浓度的反应级数分别为1级和1.2级;得到了与传统的Michaelis-Menten动力学机制不同的非均相酶促反应动力学模型,确定了“表观”活化能与酶浓度之间的定量关系.     

聚乙烯醇凝胶固定化简单节杆菌的研究

研究了以聚乙烯醇（ＰＶＡ）凝胶为载体，用包埋法固定化简单节杆菌（ＡｒｔｈｒｏｂａｃｔｅｒＳｉｍｐｌｅｘ）Ｂｙ－２－１３的制备条件及固定化菌的酶的一般性质．固定化菌的最大酶活力收率可达１００％，其ｐＨ稳定性及储存稳定性均高于游离菌．固定化菌经六次重复使用，酶活力仍不低于原始活力．     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.