DNA／聚（3-甲基噻吩）复合膜修饰电极的制备及其应用于研究8-羟基-2＇-脱氧鸟嘌呤核苷的伏安行为及测定

首先通过电聚合方法在玻碳电极表面制备了聚（3-甲基噻吩）（P3MT）修饰膜,然后在一定电位下将DNA分子电沉积到P3MT表面,制备了DNA／（P3MT）复合膜修饰玻碳电极．研究了8-羟基-2’-脱氧鸟嘌呤核苷（8-OH-dG）在该复合膜修饰电极上的伏安行为以及扫描速度、pH值和尿酸对其伏安行为和检测的影响．实验结果表明,该复合膜修饰电极结合了P3MT和DNA两者的优点,使8-OH-dG在复合膜修饰电极上的电化学行为明显改善,而且具有很好的重现性和稳定性．在0．1mol／LpH7．0的磷酸盐缓冲溶液（PBS）中,8-OH-dG的氧化峰电流与其浓度在0．28～4．2μmol／L和4．2～19．6μmol／L两个范围内成良好的线性关系,检出限为56nmol／L（S／N=3）．该研究可以为制备HPLC或毛细管电泳电化学检测器检测8-OH—dG打下一定的基础,因此在检测尿样中8-OH-dG的研究方面具有潜在的应用价值．     

NO-2的芯片毛细管电泳-修饰碳糊电极电化学检测

制备了3-巯丙基三甲氧基硅烷-铜(MPTMS-Cu)/MCM-41分子筛修饰碳糊电极,研究了该修饰电极对NO-2电化学还原的 电催化作用,分析了修饰物含量、溶液pH对电化学反应的影响。以该电极为检测电极,设计制作了芯片毛细管电泳-电化学 检测系统,探讨了NO-2的芯片毛细管电泳检测方法。以50 mmol/L醋酸钠(pH 5.8)为电泳缓冲液、分离电压为-1.6　kV时 ,检测可在40 s内完成。纯水中NO-2检测的线性浓度范围为10.0～5000.0 μmol/L,检出限为4.0 μmol/L。     

多巴胺在电沉积石墨烯修饰碳分子线电极上的电化学测定

以分子线二苯乙炔为修饰剂和粘合剂制备了一种新型的碳糊电极-碳分子线电极(CMWE),并以其为基底电极采用电化学还原法将石墨烯(GR)沉积到CMWE表面得到电沉积石墨烯修饰碳分子线电极(GR/CMWE)。考察了多巴胺(DA)在该修饰电极上的电化学行为。实验结果显示DA在GR/CMWE上出现了1对峰形良好的氧化还原峰,与裸电极相比,该氧化还原峰的电流增大,峰电位差减小,表明修饰电极对DA的电化学反应有催化作用。在最佳实验条件下峰电流与DA浓度在8.0×10-7~2.0×10-3mol/L范围内呈良好的线性关系,检出限(3σ)为2.55×10-7mol/L。将该电极用于多巴胺注射液样品的检测,结果满意。     

Nafion-离子液体-修饰碳糊电极在抗坏血酸和尿酸存在下选择性测定多巴胺

用Nafion和亲水性离子液体溴化1-辛基-3-甲基咪唑([OMIM]Br)作修饰剂制作了Nafion-离子液体-修饰碳糊电极;在0.1 mol/L磷酸盐缓冲溶液(pH 7.40)中,用循环伏安法(CV)和方波伏安法(SWV)研究了多巴胺在该修饰电极上的电化学行为,建立了抗坏血酸和尿酸存在下选择性测定多巴胺的新方法.研究表明,该修饰电极降低了多巴胺氧化、还原反应的过电位,增大了其氧化、还原反应的峰电流,而抗坏血酸和尿酸在该修饰电极上无响应;在方波伏安曲线上,多巴胺的氧化电流与其浓度在3.0×10-8～2.0×10-6 mol/L范围内呈线性关系,检出限为1.0×10-8 mol/L.该法可用于注射液和模拟生物样品中多巴胺的测定.     

纳米金/石墨烯修饰电极的制备及其对多巴胺的测定

利用电化学还原方法制备纳米金/石墨烯修饰玻碳电极,研究了多巴胺(DA)在该修饰电极上的电化学行为,建立了电化学测定多巴胺的新方法。结果表明,在磷酸盐缓冲溶液中,此修饰电极对多巴胺的电化学响应具有很好的催化作用。利用差示脉冲伏安技术对多巴胺的电化学氧化进行定量分析,多巴胺的氧化峰电流与其浓度在1.0×10-7～1.0×10-5mol/L范围内呈良好的线性关系,检测限低至4.0×10-8mol/L。该修饰电极适于多巴胺的分析检测。     

聚溴酚蓝修饰电极对多巴胺的电催化作用及伏安测定

在含溴酚蓝的磷酸缓冲液中,用循环伏安法在玻碳电极上制备聚合物薄膜。采用循环伏安法研究多巴胺在聚溴酚蓝修饰电极上的电化学行为,实验结果表明聚溴酚蓝修饰电极对多巴胺的氧化具有良好的电催化性能。在1．0～10μmol／L范围内,多巴胺浓度与其线性扫描伏安峰电流呈良好的线性关系,相关系数为0．9999,平均回收率为100．2％。该方法可用于盐酸多巴胺注射液中的多巴胺的测定。     

磷脂-月桂酸膜修饰玻碳电极测定多巴胺及其电化学行为

本文报道了多巴胺 (DA)在磷脂 -月桂酸修饰的玻碳电极上的电化学行为 ,在+ 0 .7～ -0 .4V(vs.Ag/ Ag Cl)电位范围内 ,于 p H 6.4的 0 .0 1 mol/ L的 KH2 PO4 -Na2 HPO4 底液中 ,多巴胺产生很灵敏的氧化峰电流。氧化峰电流与多巴胺浓度在 3 .1× 1 0 - 7～ 1 .2× 1 0 - 4mol/ L范围内呈良好线性关系。该电极可作为检测多巴胺的新型的高灵敏度电化学生物传感器     

CuNi/β-环糊精/还原氧化石墨烯修饰电极电化学检测多巴胺

建立了一种循环伏安法制备CuNi/β-环糊精/还原氧化石墨烯修饰玻碳电极(CuNi/β-CD/ERGO/GCE)的方法。通过多巴胺在该修饰电极上的电化学行为发现,该电化学传感器实现了快速、灵敏的测定多巴胺。该传感器用差分脉冲伏安法(DPV)测定多巴胺时,其电化学响应电流与多巴胺浓度在0.01~20μmol/L之间呈线性关系,检测限为8 nmol/L。该传感器用于尿液样品中的多巴胺检测,回收率在95.6%~107.2%之间。     

电还原柠嗪酸修饰电极对多巴胺和尿酸的电化学性质研究

采用循环伏安法制备了电还原柠嗪酸膜修饰碳糊电极(ECA/CPE),研究了多巴胺(DA)在该修饰电极上的电化学行为。在pH 7.0的磷酸盐缓冲溶液中,ECA/CPE对DA具有明显的电催化作用,且DA呈现出一对准可逆的氧化还原峰,其氧化峰电流与DA浓度在3.7×10-7~8.2×10-5mol/L和1.04×10-4~9.34×10-4mol/L范围内呈良好的线性关系,检出限为1×10-7mol/L(S/N=3)。使用微分脉冲伏安法,DA和尿酸(UA)在ECA/CPE上的氧化峰能完全分离,且峰电流与浓度呈良好的线性关系。该电极可用于盐酸多巴胺针剂中DA的测定以及人体尿液中UA的检测。     

氧化镍/聚苏木精修饰碳糊电极检测加替沙星

使用循环伏安法和恒电位法将聚苏木精和Ni O相继沉积至碳糊电极表面构建了Ni O/聚苏木精复合物修饰电极。运用电化学阻抗技术、循环伏安法探究了Ni O/聚苏木精复合物的表面形貌、组成及电化学性质。该修饰电极被用来检测抗菌药物加替沙星。相比裸碳糊电极,加替沙星在该修饰电极上的氧化峰电流分别提高了3倍,峰电位得到了负移。实验结果表明,加替沙星的线性范围是0.5~160μmol/L,检测限(S/N=3)为0.01μmol/L。相比其他检测技术,该修饰电极已用于实际样品中加替沙星检测。     

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.