一锅法合成聚乙烯吡咯烷酮修饰的铜纳米团簇用于槲皮素的检测

作为检测槲皮素的有效途径,在荧光法中如何通过简单的方法合成性能优良的荧光探针具有重要的意义。 本文以聚乙烯吡咯烷酮(PVP)为保护剂,抗坏血酸为还原剂,化学还原法合成PVP保护的分散性好、稳定性高、强荧光的铜纳米团簇(PVP-Cu NCs)。 样品表现出良好的水溶性,光稳定性和强离子稳定性。 通过紫外可见光谱(UV-Vis)、分子荧光光谱、透射电子显微镜(TEM)和X射线光电子能谱分析(XPS)对铜纳米团簇的光学性质和结构进行了分析。 结果表明:该铜纳米团簇的最大激发和发射波长分别为366和429 nm,平均粒径大小为2 nm。 基于槲皮素对该铜纳米团簇的猝灭作用,构建了一种可用于检测槲皮素的荧光传感器。 该传感体系检测槲皮素的线性范围为0.1～0.9 μmol/L和15～60 μmol/L,检测限为0.053 μmol/L(S/N=3)。 该传感器对槲皮素的检测具有很高的灵敏度和良好的选择性,可用于实际样品中槲皮素的检测。     

聚吡咯/碳纳米管分子印迹修饰电极对槲皮素的选择性测定

制备了一种新颖的可对槲皮素分子进行选择性测定的分子印迹聚合物膜修饰电极.在碳纳米管(CNT)独特的结构和力学性能作用下,以吡咯(Py)为功能单体,槲皮素为模板分子,电聚合方法制备了槲皮素的分子印迹聚合物膜修饰电极(PPy/CNT/GCEMIP).用电化学交流阻抗法研究了该修饰电极的界面性质,用循环伏安法和差分脉冲伏安法...     

合成引发方式对槲皮素-钴(Ⅱ)配位印迹聚合物结构与性能的影响

以槲皮素-钴(Ⅱ)的配合物为模板分子,在强极性甲醇溶剂中分别采用低温光引发和高温热引发聚合制备槲皮素-钴(Ⅱ)配位印迹聚合物.紫外-可见光谱分析确定了槲皮素与钴(Ⅱ)形成配合物的最佳配位比.根据印迹聚合物的平衡结合量优化功能单体丙烯酰胺用量.利用红外光谱、透射电镜和平衡结合实验,考察不同引发方式对聚合物的结构、微观形貌及结合性能的影响.进一步通过特异吸附容量和印迹指数确定,低温光引发聚合更适于配位分子印迹聚合物的制备.同时研究了不同阳、阴离子对印迹聚合物选择识别性的影响.结果表明光引发的金属配位分子印迹聚合物具有良好的吸附选择性,印迹指数可达3.919.     

Adsorption and catalysis of flavonoid quercetin on different plasmonic metal nanoparticles monitored by SERS

Raman and surface‐enhanced Raman scattering spectroscopy were used to follow the chemical modification of quercetin (QUC) on silver nanoparticles. Different metallic systems were fabricated to check the influence of the interface, in terms of electric charge or total available surface, on the catalytic change undergone by QUC. The effect of QUC surface coverage was crucial to reveal information about the different orientation and the interaction mechanism with the metal at different concentrations of this flavonoid. Surface‐enhanced Raman scattering spectra of good quality of QUC were observed at concentrations down to 10^–8 M. Chemical modifications in the presence of nanostructure metal surfaces include oxidation followed by a subsequent polymerization via a condensation of rings whereas different chemical species have been recognized under different experimental conditions. The assignment of the new species formed on the metal surface was conducted. Copyright © 2012 John Wiley & Sons, Ltd.     

Oxygenolysis reaction mechanism of copper-dependent quercetin 2,3-dioxygenase: A density functional theory study

The mechanism of the action of copper-dependent quercetin 2,3-dioxygenase(2,3QD) has been investigated by means of hybrid density functional theory.The 2,3QD enzyme cleaves the O-heterocycle of a quercetin by incorporation of both oxygen atoms into the substrate and releases carbon monoxide.The calculations show that dioxygen attack on the copper complex is energetically favorable.The adduct has a possible near-degeneracy of states between [Cu 2+-(substrate-H +)] and [Cu +-(substrate-H).],and in addition the pyramidalized C 2 atom is ideally suited for forming a dioxygen-bridged structure.In the next step,the C 3-C 4 bond is cleaved and intermediate Int 5 is formed via transition state TS 4.Finally,the O a-O b and C 2-C 3 bonds are cleaved,and CO is released in one concerted transition state(TS 5) with the barrier of 63.25 and 61.91 kJ/mol in the gas phase and protein environments,respectively.On the basis of our proposed reaction mechanism,this is the rate-limiting step of the whole catalytic cycle and is strongly driven by a relatively large exothermicity of 100.86 kJ/mol.Our work provides some valuable fundamental insights into the behavior of this enzyme.     

青钱柳叶中黄酮化合物结构及含量研究

研究青钱柳(Cydocaryap paliurus(Baud．)Iljinsk．)叶中的黄酮化合物结构及含量分布。采用溶剂萃取及多种色谱技术分离纯化,根据理化性质和光谱分析方法鉴定其结构,确定从青钱柳中分离得到山柰酚、槲皮素和异槲皮苷3个黄酮单体化合物,并用反相高效液相色谱法对其含量进行了测定,测得各自在甲醇和水提取物中的含量：山柰酚0．0387％,0．0337％;槲皮素0．0615％,0．0603％;异槲皮苷0．543％,0．464％。     

银杏叶提取物中总黄酮含量的分析方法研究

提出了一种简便、灵敏地测定银杏叶提取物中总黄酮含量的新方法。实验结果表明银杏叶提取物经酸性条件下加热水解,使黄酮苷转化为苷元再与Al3+配位,所形成的配合物具有较强的荧光,可以槲皮素为标准品,采用荧光光度法测定其总黄酮含量。在选定条件下,槲皮素的浓度与荧光强度成线性关系,线性范围:0000?75～050?μg／mL, 检测限:045?g／mL(S／N=3),回归方程: If=7799?48+63210?86ρ×107(μg／mL),相关系数R=0999?9(P<0000?1),并用标准加入法进行回收实验和银杏叶提取物(GBE)中的总黄酮含量的测定,结果令人满意。     

旋覆花化学成分研究

旋覆花是一种传统的中草药,现代研究表明旋覆花中含有多种生物活性成分。通过柱层析、HPLC等分离方法对旋覆花乙醇提取物的化学成分进行研究,分离纯化得到6种单体化合物,并通过化学方法和现代波谱学方法技术（一维及二维核磁共振谱等）进行结构鉴定。分别为：β-谷甾醇、槲皮素、α-菠甾醇、山奈酚、伊谷甾醇葡萄糖苷、α-葡萄糖。     

Beneficial Effect of Quercetin on Erythrocyte Properties in Type 2 Diabetic Rats

Diabetes mellitus is characterized by tissue oxidative damage and impaired microcirculation, as well as worsened erythrocyte properties. Measurements of erythrocyte deformability together with determination of nitric oxide (NO) production and osmotic resistance were used for the characterization of erythrocyte functionality in lean (control) and obese Zucker diabetic fatty (ZDF) rats of two age categories. Obese ZDF rats correspond to prediabetic (younger) and diabetic (older) animals. As antioxidants were suggested to protect erythrocytes, we also investigated the potential effect of quercetin (20 mg/kg/day for 6 weeks). Erythrocyte deformability was determined by the filtration method and NO production using DAF-2DA fluorescence. For erythrocyte osmotic resistance, we used hemolytic assay. Erythrocyte deformability and NO production deteriorated during aging—both were lower in older ZDF rats than in younger ones. Three-way ANOVA indicates improved erythrocyte deformability after quercetin treatment in older obese ZDF rats only, as it was not modified or deteriorated in both (lean and obese) younger and older lean animals. NO production by erythrocytes increased post treatment in all experimental groups. Our study indicates the potential benefit of quercetin treatment on erythrocyte properties in condition of diabetes mellitus. In addition, our results suggest potential age-dependency of quercetin effects in diabetes that deserve additional research.     

Advantageous/Unfavorable Effect of Quercetin on the Membranes of SK-N-SH Neuroblastoma Cells

Quercetin is a polyphenolic compound, the effects of which raise scientists’ doubts. The results of many experiments show that it has anticancer, antiinflammatory, and antioxidant properties, while other studies indicate its pro-oxidative and cytotoxic action. This compound can react with reactive oxygen species, and due to its chemical properties, it can be found in the hydrophobic-hydrophilic area of cells. These features of quercetin indicate that its action in cells will be associated with the modification of membranes and its participation in maintaining the redox balance. Therefore, this study distinguishes these two mechanisms and determines whether they are important for cell function. We check: (1) Whether the selected concentrations of quercetin are cytotoxic and destructive for SK-N-SH cell membranes (MTT, LDH, MDA tests) in situations with and without the applied oxidative stress; (2) what is the level of changes in the structural/mechanical properties of the lipid part of the membranes of these cells due to the presence of polyphenol molecules; and (3) whether the antioxidative action of quercetin protects the membrane against its modification. Our results show that changes in the stiffness/elasticity of the lipid part of the membrane constitute the decisive mechanism of action of quercetin, potentially influencing cellular processes whose initial stages are associated with membranes (e.g., reception of signals from the environment, transport).