生命科学中的分析化学--蛋白质组分析

概述了分析化学在生命科学中的重要作用和蛋白质组分析的现状与展望。介绍了生物试样的制备、双向凝胶电泳分离蛋白质以及生物质谱鉴定蛋白质等蛋白质组分析的主要技术平台。     

蛋白质直接电化学研究及其应用

蛋白质直接电化学研究在生物电化学中具有重要地位,对于蛋白质结构-功能研究、蛋白质电子传递过程的热力学和动力学研究都有着重要意义,而且是研制第三代电化学生物传感器的基础。本文对在裸电极、分子自组装修饰电极和模拟生物膜修饰电极上进行蛋白质直接电化学的研究及相关应用进行简要综述。     

蛋白质直接电化学研究及其应用

蛋白质直接电化学研究在生物电化学中具有重要地位,对于蛋白质结构-功能研究、蛋白质电子传递过程的热力学和动力学研究都有着重要意义,而且是研制第三代电化学生物传感器的基础.本文对在裸电极、分子自组装修饰电极和模拟生物膜修饰电极上进行蛋白质直接电化学的研究及相关应用进行简要综述.     

RNA-蛋白质相互作用位点的预测

蛋白质与RNA的相互作用在很多生物过程中起到了非常重要的作用.例如,蛋白质的合成,基因融合,mRNA的加工等生物过程.RNA在蛋白质上的结合位点的识别,主要是通过生物物理学方法在体外研究和分析RNA蛋白质复合物.这些方法需要实验过程繁琐、耗费大量人力和财力.     

蛋白质直接电化学研究及其应用

蛋白质直接电化学研究在生物电化学中具有重要地位，对于蛋白质结构．功能研究、蛋白质电子传递过程的热力学和动力学研究都有着重要意义，而且是研制第三代电化学生物传感器的基础。本文对在裸电极、分子自组装修饰电极和模拟生物膜修饰电极上进行蛋白质直接电化学的研究及相关应用进行简要综述。     

界面电场对血红蛋白在多孔金电极上的吸附和生物活性的影响(英文)

蛋白质的界面吸附及其生物活性因它在构建生物传感、生物电子器件和生物燃料电池等方面具有重要的作用而倍受关注.对此,界面电场是吸附的一个重要影响因素,它能明显地影响蛋白质分子在材料界面的吸附量、分子构象以及分子定向.本文应用电化学方法和红外光谱技术研究了血红蛋白在三维多孔金膜电极上的吸附动力学及其生物活性随界面电场的变化关系.结果表明,由界面电场产生的过量表面电荷可借助与蛋白质分子之间的静电作用加速蛋白质分子在电极表面的吸附,提高其吸附量;但是,过高的界面电场将破坏吸附蛋白质的构象以及降低它还原过氧化氢的催化活性;只有在零电荷电位下,吸附在电极表面的血红蛋白才能保持其天然的构象和生物催化活性.本研究将为生物传感器、生物电子器件和生物燃料电池的构建提供理论依据,加深对荷电生物界面上生物分子界面行为的认识.     

定量蛋白质组学分析方法

精确测量多个不同生理或病理条件下生物样本中蛋白质表达量的变化是定量蛋白质组学(quantitative proteomics)研究的重要内容。与传统的蛋白质定量方法(见表1)相比,组学规模的蛋白质定量可以实现在一次实验中对成百上千个蛋白质的定量测定和比较分析,为规模化发现和验证疾病诊断的生物标志物以及发展新的药物靶标提供了重要手段。     

导电原子力显微镜对蛋白质在分子水平上的电学表征

蛋白质电子传递的研究不仅对阐述生物能量传递具有重要的意义,而且有助于促进生物分子在分子电子器件中的应用．金属蛋白以其固有的电化学和电学特性,在光合作用和呼吸作用中起到重要作用．其中铜蓝蛋白具有良好的电化学性质和明确的分子结构,常常用作研究蛋白质电子传递的模型分子。很多具有微观尺度表征能力的分析仪器可用于研究表面吸附的蛋白质分子。     

血红蛋白在自组装单层修饰电极上的直接电化学研究

对于氧化还原蛋白质在电极界面上的直接电子转移的研究对于生物传感器的构建,生物材料的发展和生物系统的认识有很重要的作用~([1]).虽然许多方法已经实现了蛋白质的直接电子传递,这些方法多数侧重于生物传感器的构建,对如何通过控制蛋白质的吸附状态来实现直接电子传递并没有系统的报道.蛋白质在吸附到电极表面的过程中,许多因素都能影响蛋白质的电子传递,如蛋白质的取向,蛋白质的活性中心与电极的距离等.     

单分子荧光共振能量转移用于生物大分子构象动态变化过程研究进展

生物大分子参与生命活动的各个过程,在单分子水平上实时观测和分析生物大分子自身的结构动态以及生物大分子相互作用的动态过程,对于深入理解生物大分子的作用机制具有重要意义。自提出以来,单分子荧光共振能量转移技术逐渐展现出其在研究生物大分子构象变化和相互作用过程等方面的巨大潜力,一系列新的作用机理陆续被提出。本文对单分子荧光共振能量转移技术在蛋白质与核酸分子构象动态变化、蛋白质-蛋白质相互作用以及蛋白质-核酸相互作用等方面取得的研究进展进行了综述。     

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.