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。     

基于新亚甲蓝为介体的免疫传感器的研究

利用共价键合法,将新亚甲蓝(NMB)与辣根过氧化酶(HRP)标记的羊抗小鼠IgG抗体(Ab)修饰于玻碳电极表面,制成一种新型的电流型免疫传感器。研究了该传感器对H2O2的电化学响应及对小鼠IgG抗原(m IgG)的免疫检测。结果表明NMB作为介体能有效地传递电子,测得电子转移系数为0.77,表观反应速率常数为1.18 s-1。利用传感器对m IgG的检测,线性范围为0.5~3μg/L;检出限为0.028μg/L;相关系数r为0.996。     

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.     

溶胶-凝胶壳聚糖/二氧化硅杂化复合膜固定辣根过氧化酶的H2O2电化学生物传感器的研制

利用溶胶 凝胶法制备壳聚糖 二氧化硅有机无机复合杂化膜,用于对辣根过氧化酶进行固定,制得测定H2O2的电流型生物传感器。以1mmol/LK4Fe(CN)6作为电子媒介体。研究了各种因素如壳聚糖与二氧化硅的比率、pH、温度、工作电位等对传感器响应电流的影响。计时电流法测定H2O2的线性范围为2.0×10-6～6.8×10-4mol/L,检出限为8.0×10-7mol/L。测得酶催化动力学参数米氏常数Km=0 87mmol/L。用该法对实际样品进行了测定。     

新型纳米银-磷酸锆-中性红复合膜修饰电极对过氧化氢电催化还原

制备了新型纳米银 磷酸锆复合材料 ,对中性红有强烈吸附。吸附的中性红表现出更强的氧化还原性 ,氧化还原中点电位与溶液中 (pH 7)相比正移约 2 0 0mV。将辣根过氧化酶与复合材料共同修饰在电极表面制成酶电极 ,对H2 O2 有显著电催化还原作用。催化电流在 2 .5× 1 0 - 6 ～ 2 .0× 1 0 - 3mol L范围内与H2 O2 浓度成正比 ;H2 O2 检出限为 2 .0× 1 0 - 7mol L(S N =3 ) ;传感器对 1 .0× 1 0 - 5mol LH2 O2 响应时间 <1 5s;RSD为1 4% (n=1 0 )。4℃保存 6个月该电极仍有 85 %以上初始响应。传感器有效消除了抗坏血酸等共存物质的干扰 ,回收率实验结果令人满意。     

石墨烯-聚多巴胺纳米复合材料制备过氧化氢生物传感器

通过合成具有仿生功能的石墨烯-聚多巴胺纳米材料,将其与辣根过氧化酶组装到电极表面,以对苯二酚为电子媒介体制备H2O2传感器.此修饰电极对H2O2具有良好的电催化活性,检测的线性范围为5.0×10-7～3.3×10-4 mol/L;线性回归方程为Y=29.69x+ 0.04577,相关系数为R=0.9995;检出限为3.7×10-7 mol/L(S/N=3).     

基于石墨烯-壳聚糖-辣根过氧化物酶的H2O2生物传感器的研制

制备了石墨烯-壳聚糖(GR-CS)纳米复合材料,并将之与辣根过氧化物酶(HRP)混合,构建了基于石墨烯-壳聚糖-辣根过氧化物酶的生物传感器(GR-CS-HRP/GC)。探针及循环伏安研究表明,该界面具有优异的电子传导能力、较大的比表面积和良好的生物相容性,对H2O2的还原显示出较好的电催化活性,在工作电位为-0.2 V,0.05 mol/L的磷酸盐缓冲盐溶液(PBS,pH 6.8)中,该酶传感器对过氧化氢响应灵敏度高,检测范围宽,测定H2O2的线性范围为5.0×10-7～2×10-3mol/L(相关系数为0.998)。检出限为2.0×10-7mol/L(S/N=3)。并且表现出良好的稳定性和高选择性。该电极用于实际样品中H2O2的测定,结果令人满意。     

一种基于碳纳米管的安培型过氧化氢生物传感器

利用硫堇(th ion ine,Th i)作为介体结合多壁碳纳米管(MWNTs)、壳聚糖(ch itosan,CH IT)、辣根过氧化酶(HRP)的混合包埋物制作过氧化氢(H2O2)生物传感器。研究结果表明所得传感器对H2O2具有明显的增敏效应,线性范围为0.03~5.5 mmol/L,相关系数为0.9995;检出限为19μmol/L(S/N=3),具有良好的稳定性及工作寿命。     

辣根过氧化酶在磁性纳米修饰的离子注入电极上的电化学和电催化行为

辣根过氧化酶(HRP)在Co/NH2/ITO离子注入电极上有一对良好的氧化还原峰,峰电位分别为Epc=-0.2 V,Epa=-0.01 V(vsAg/AgCl)。该修饰电极对H2O2具有催化作用,可以用作H2O2的生物传感器,峰电流与H2O2的浓度分别在1.0×10-10~2.0×10-8mol/L和2.0×10-8~1.0×10-7mol/L范围内呈线性关系,线性回归方程分别为Ip(mA)=2.2986+0.06632c(nmol/L)和Ip(mA)=3.5788+7.3053E-4c(nmol/L),相关系数分别为0.9972和0.9688。检出限为1.0×10-10mol/L。     

L-半胱氨酸/辣根过氧化物酶/纳米银/辣根过氧化物酶修饰电极循环伏安法测定过氧化氢

在金电极表面自组装L-半胱氨酸,再分别吸附辣根过氧化物酶(HRP)和纳米银,制得L-半胱氨酸/辣根过氧化物酶/纳米银/辣根过氧化物酶修饰电极。采用循环伏安法研究了修饰电极的电化学特性,探讨了pH值、温度对电极响应的影响,考察了电极的重复性、稳定性及选择性。实验结果表明,HRP在修饰电极表面能进行有效和稳定的电子转移,HRP保持了其对H2O2还原的生物催化活性。该电极对H2O2检测的线性范围为8.6×10-7～1.3×10-3mol/L,r=0.9985,检出限(S/N=3)为1.6×10-7mol/L。该电极具有稳定性好、线性范围宽、检出限低等优点,同时具有一定的抗干扰能力。     

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.