以新亚甲蓝为介体的过氧化氢传感器的电化学行为研究

利用共价键合法,将新亚甲蓝(NMB)与辣根过氧化酶(HRP)修饰于玻碳电极表面,制成一种新型的电流型H2O2传感器。探讨了该传感器在0·1mol/L磷酸缓冲溶液(pH=7·0)中的电化学性质。结果表明,NMB作为介体能够有效地在辣根过氧化酶和电极之间传递电子。测得电子转移系数为0·861,表观反应速率常数为1·27s-1。研究了传感器对H2O2的响应及动力学性质,米氏常数为8·27μmol/L,线性响应范围为2·5~100μmol/L。同时研究了pH、缓冲容量及温度等因素对H2O2传感器的影响。     

The electrochemical behavior of hydrogen peroxide sensor based on new methylene blue as mediator

利用共价键合法,将新亚甲蓝(NMB)与辣根过氧化酶(HRP)修饰于玻碳电极表面,制成一种新型的电流型H2O2传感器。探讨了该传感器在0·1mol/L磷酸缓冲溶液(pH=7·0)中的电化学性质。结果表明,NMB作为介体能够有效地在辣根过氧化酶和电极之间传递电子。测得电子转移系数为0·861,表观反应速率常数为1·27s-1。研究了传感器对H2O2的响应及动力学性质,米氏常数为8·27μmol/L,线性响应范围为2·5~100μmol/L。同时研究了pH、缓冲容量及温度等因素对H2O2传感器的影响。     

电化学免疫传感器测定牛奶中的青霉素

利用共价键合法,将新亚甲蓝(NMB)与辣根过氧化酶(HRP)标记的青霉素多克隆抗体(Ab*)修饰于玻碳电极表面,制成电流型免疫传感器;考察了该传感器的电化学行为和对H2O2的电化学响应.结果表明,NMB作为介体能有效地传递电子,传感器对H2O2具有很好的催化作用.用此传感器对牛奶中的青霉素进行检测,其线性范围为0.25～3.00ng/mL (R=0.984),检出限为0.298ng/mL.     

磁性无机-生物复合粒子敏感膜新型电流型免疫传感器的研究

合成了磁性Fe3O4纳米粒子,利用3-氨基丙基三乙氧基硅烷(APS)进行硅烷化,形成表面带有氨基的磁性Fe3O4纳米复合粒子,再用戊二醛将羊抗人免疫球蛋白G抗体(anti-IgG)固定在该磁性粒子表面,通过磁力将其修饰于固体石蜡碳糊电极表面制作成免疫传感器。与标记HRP的二抗体anti-IgG结合,以对苯二酚作为电子媒介体,实现对人免疫球蛋白G(IgG)的定量检测。IgG测定线性范围为2.5~400μg/L,检出限为0.75μg/L。该免疫传感器制作简单,成本低,表面更新方便,可用于临床血清检测。     

基于多壁碳纳米管-硫堇/Nafion纳米复合物修饰的人IgG免疫传感器的研究

制备了基于多壁碳纳米管-硫堇/Nafion纳米复合物的人IgG免疫传感器.阻抗谱、循环伏安研究表明,该免疫传感器对人IgG的检测具有优异的性能,其对人免疫球蛋白G(IgG)浓度的定量测定线性范围为1.0 ～ 200μg/L,检出限为0.25 μg/L,线性相关系数R=0.9950.该免疫传感器可用于对人血清中IgG的检...     

基于透明质酸及硫堇层层自组装的前列腺特异性抗原免疫传感器的研究

将带负电荷的透明质酸(HA)和带正电荷的电子媒介体硫堇(Thi)层层自组装到壳聚糖修饰的玻碳电极表面,利用硫堇上的氨基固定纳米金(nano-Au)并固载前列腺特异性抗体(anti-PSA),制得新型前列腺特异性抗原电流型免疫传感器。通过循环伏安法(CV)、微分脉冲伏安法(DPV)考察了该免疫传感器的电化学特性,并对影响该免疫传感器性能的各种因素进行详细研究。在优化实验条件下,此免疫传感器的线性范围为0.5~4μg/L和4~25μg/L,检出限为0.2μg/L。该免疫传感器具有制备简单、灵敏度高、稳定性好等优点。     

以新亚甲基蓝为电子媒介体的大肠杆菌微生物燃料电池的研究

以新亚甲基蓝(NMB) 为电子媒介体, 大肠杆菌为微生物催化剂, 设计了微生物燃料电池(MFC). 该MFC的开路电压为0.760 V, 短路电流为1.108 mA, 最大输出功率为116 mW/m2, 此时所对应的电流密度为390 mA/m2. 比较了中性红(NR)和NMB作为电子媒介体对MFC性能的影响. 实验结果表明, 以NMB为电子媒介体的MFC的开路电压比以NR为电子媒介体的MFC的开路电压低, 但其开路电压达到稳定所需要的时间更短, 而且其短路电流比后者高. 当放电电流大于114 mA/m2时, 前者比后者的输出功率高, 在负载1000 Ω放电时, 前者比后者有更好的稳定性.     

新型杂环查尔酮衍生物的合成及其杀虫活性研究

以含杂环的醛和氨基苯乙酮以及酰氯为原料,通过Claisen-Schmidt缩合反应和酰氯的氨解反应合成了21个新的杂环查尔酮衍生物.以蚕豆蚜(Aphis craccivora)和菜青虫(Pieris rapae)为靶标,对合成化合物的杀虫活性进行了实验室生测.结果显示,大部分化合物都对这两种害虫有一定的毒杀活性.其中,化合物2l对蚕豆蚜的半致死浓度(LC_(50))为1.6μg/m L,毒杀效果优于吡虫啉(LC_(50)为1.8μg/m L),1b、1f、2j、2n对蚕豆蚜的毒杀效果也和吡虫啉接近;化合物1f和2m对菜青虫的LC_(50)分别为6.6μg/m L和8.5μg/m L,毒杀效果比高效氯氰菊酯(LC50为9.2μg/m L)更好.     

基于丝网印刷工艺的安培型酶免疫传感器的研究

研究了一种一次性安培型免疫传感器,检测辣根过氧化物酶(HRP)。用丝网印刷工艺制备三电极结构的传感器,工作电极是碳电极,银电极是伪参比电极。采用电荷传递系数、评估厚膜电极的一致性。通过戊二醛交联法,把抗HRP酶抗体固定在电极表面。加入底物H2O2和电子介体邻苯二胺,分别用安培法和比色法进行检测和比较分析。安培法测定HRP的测量范围10μg/L~10 mg/L,检出限10μg/L;比色法测定范围为2~40 mg/L,检出限2 mg/L。同时分析了湿度对传感器寿命的影响。     

应用双槽电化学腐蚀法制备用于蛋白质芯片构建的多孔硅基底

通过双槽电化学腐蚀法制备大面积(12 mm×58 mm)均匀的多孔硅片,以小鼠免疫球蛋白G(IgG)与兔抗小鼠IgG抗体的相互作用为模型,证明其表面修饰环氧基团后能作为一种基底材料用于蛋白质微阵列芯片的构建。结果表明,兔抗小鼠IgG抗体检测的灵敏度与多孔硅基底制备时所采用的腐蚀电流密度、腐蚀时间、氢氟酸浓度有关。当电流密度为500 mA/cm2,腐蚀时间为450 s,HF浓度为25%时,IgG在多孔硅基底上的固定量最大,IgG芯片对兔抗小鼠IgG抗体的检出限为10μg/L,检测线性范围为0.32～10.0 mg/L。本方法制备的大面积均匀的多孔硅基底能够应用于蛋白质芯片的制作,并具有制备工艺简单,蛋白质固定量大等优点。     

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.