电化学聚合法制备聚中性红膜修饰电极及其应用

以正交试验法研究了影响电聚合中性红制备膜修饰电极的具体条件 ,通过较少次数的试验得到了最佳条件 ,并依此制得了聚中性红膜修饰电极。用抗坏血酸对其电化学性能进行了表征 ,该修饰电极对抗坏血酸有较强的催化氧化作用 ,氧化电流与抗坏血酸的浓度在 1 .0× 1 0 - 5mol/L～ 2 .5× 1 0 - 2 mol/L之间呈线性关系 ,相关系数r=0 .9994,氧化电位为 3 3 0mV ,比裸玻碳电极负移 2 3 0mV左右 ,而且电极重现性良好。     

壳聚糖修饰电极上的铁氰根离子对抗坏血酸的电催化氧化作用

在玻碳电极表面滴涂一层壳聚糖膜 ,壳聚糖分子中 -NH2 在酸性溶液中发生质子化 ,靠静电引力作用吸附富集荷负电的电子介体Fe(CN) 63 -,使其固定在电极表面 ,研究了此Fe(CN) 63 - 壳聚糖 GC修饰电极对抗坏血酸的催化氧化作用。抗坏血酸的浓度在 3.0× 1 0 -6～ 5 .0× 1 0 -3 mol L范围内呈很好的线性关系 ,相关系数为 0 .998,检测限达 1 .0× 1 0 -6mol L。该法已用于测定蔬菜中抗坏血酸的含量。     

钛钼氧化物负载硅钨酸盐聚苯胺膜修饰电极制备及对抗坏血酸的电催化

用循环伏安法研究了金属氧化物(TiO2-MoO3)负载硅钨酸盐聚苯胺膜电极的制备,优化了聚合条件,并对该化学修饰电极的电化学行为,包括溶液的pH的影响等进行了研究,同时研究了抗坏血酸在此修饰电极上的电化学行为。该修饰膜对抗坏血酸有良好的电催化氧化作用。用计时电流法及伏安法研究了抗坏血酸在此修饰电极上的电化学行为,计算出抗坏血酸在修饰电极膜内的表观扩散系数为1.88×10-7cm2/s;抗坏血酸浓度在5.0×10-5-6.9×10-3mol/L范围内呈线性关系,相关系数为0.9961,检出限为1.2×10-6mol/L。可用于测定西红柿、橙汁中的抗坏血酸,结果令人满意。     

碘在玻碳汞膜电极上的伏安行为及应用

研究了碘化合物在玻碳汞膜电极上的伏安行为，碘酸根分别于-1220mV，-1162mV和-1270mV（vs．SCE）出现0～二阶伏安峰，并得到了扩散系数D0和电子传递速率常数ks。食品烹调中碘的存在形式受到溶液pH和共存物影响。无抗坏血酸存在且pH≥2．40时，加入的IO3^-在食品中转化为I^-，当pH〈2．40时，则以I2形式存在，当抗坏血酸共存时，则以I^-形式存在。     

聚色氨酸／镍复合膜修饰电极测定抗坏血酸的研究

采用电化学聚合法制备了聚色氨酸／镍复合膜修饰玻碳电极,研究了抗坏血酸在该修饰电极上的电化学行为,建立了测定痕量抗坏血酸的新方法。在pH6．2的磷酸盐缓冲溶液中,抗坏血酸在修饰电极上产生一个灵敏的氧化峰,采用线性扫描伏安法测定,其氧化峰电流与抗坏血酸浓度在2．0×10^-6 -1．0×10^-3mol／L范围内呈良好的线性关系,检出限为5．0×10^-7mol／L。对1．0×10^-4mol／L抗坏血酸溶液平行测定6次,测定结果的相对标准偏差为1．9％。该法用于片剂中抗坏血酸含量的测定,加标回收率为97．8％～101．2％。     

普鲁士蓝修饰铂盘电极的胆固醇传感器的研制

在制备普鲁士蓝膜修饰铂盘电极的基础上 ,利用修饰电极对过氧化氢的电催化还原特性 ,制得了性能优良的胆固醇传感器。作者系统地考察了有关修饰膜制备和测试实验条件对传感器性能的影响 ,结果表明 :传感器的最佳工作电位是 0 .0 5V ,测试溶液的最适pH值为 7.0。在选定的工作条件下 ,传感器的灵敏度为 15 0nA mmol·L- 1 ,线性范围为 0 .2～ 2mmol/L ,响应时间为 1min ,寿命在 1个月以上。本方法制得的传感器能有效消除抗坏血酸、尿酸的干扰 ,有望用于血液中胆固醇的测定     

锰C-抗坏血酸甲醛-化学发光体系的研究

实验观察到锰 氧化抗坏血酸可以产生弱的化学发光 ,甲醛对这一化学发光反应有较强的增敏作用 ,据此建立了测定抗坏血酸的流动注射化学发光分析法。方法的检出限为 2× 1 0 -8mol/L抗坏血酸 ;线性响应范围为 6 .0× 1 0 -8～ 2 .0× 1 0 -5mol/L。对 1 .0× 1 0 -6mol/L的抗坏血酸进行 1 1次测定 ,相对标准偏差为 2 3%。该方法已成功应用于维生素C针剂和片剂中抗坏血酸含量的测定 ,结果与药典方法测得值一致     

除锈剂对莲藕铁膜的去除效果研究

分别以采摘后的莲藕和水泥微池中种植的莲藕为材料,比较不同除锈剂对根状茎铁膜的去除效果,以期为莲藕根状茎铁膜的田间防除提供依据。在莲藕采后除铁膜实验中,抗坏血酸在较短时间内将莲藕根状茎上的铁膜完全去除干净,除锈效果好,其次是草酸和柠檬酸。抗坏血酸和柠檬酸混合除锈可提高除锈效率,0.000 87 mol/L柠檬酸和0.012 5 mol/L抗坏血酸共混合处理3 h、0.000 43 mol/L柠檬酸和0.012 5 mol/L抗坏血酸混合处理3 h,可提高除锈效率,减少除锈剂使用。可见将抗坏血酸和柠檬酸按一定比例混合施用对铁膜的去除效果更好,其成本较单独使用抗坏血酸或柠檬酸低。     

多巴胺在聚中性红修饰碳纤维微电极上的电化学行为

利用电聚合方法制备了聚中性红(PNR)修饰碳纤维微电极.根据循环伏安(CV)、电位阶跃实验结果,得出了多巴胺(DA)在PNR膜中的表观扩散系数D0=7.0×10-9cm2/s、膜表面表观标准电子转移速率常数κ=0.55 cm/s;该电极对DA响应灵敏,对抗坏血酸具有良好的抗干扰能力,可望用于活体中DA的测定.     

铁氰酸镍膜修饰金电极的研制及应用

通过层层组装的方法,将Ni^2＋和[Fe（CN）6]^3-交替沉积在巯基乙酸功能化的金电极表面．首次成功制备了铁氰酸镍多层膜修饰电极,用循环伏安法研究了该多层膜的电化学行为,实验表明峰电流随膜层数的增加而增加,膜均匀增长．该修饰电极对一价金属离子Na^＋,K^＋,NH4^＋具有选择性响应,尤其对K^＋存在准能斯特响应,响应范围0．01～1．0mol／L;而且该电极对抗坏血酸（AA）和S2O3^2-体系的氧化具有良好的电催化作用,线性范围分别为：1．14×10^-4～1．14×10^-3mol／L和5．0×10^-4～3．1×10^-3mol／L．     

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.