亲水金和憎水二氧化硅纳米颗粒对葡萄糖生物传感器响应灵敏度的增强作用

用亲水金、憎水二氧化硅纳米颗粒固定葡萄糖氧化酶(GOD),采用聚乙烯醇缩丁醛(PVB)为辅助固酶膜基质来制备葡萄糖生物传感器,并考察了亲水金、憎水二氧化硅纳米颗粒对酶电极电流响应的影响.实验表明,引入纳米粒子可显著增强电极响应灵敏度.并对两种不同性质纳米颗粒所起作用的可能机理进行讨论,从理论和实验上证明了纳米颗粒对固定酶的作用.为制备有实用价值的葡萄糖生物传感器提供了可供参考的实验和理论依据.     

碳纳米管负载铂颗粒酶电极葡萄糖传感器

以碳纳米管负载纳米铂颗粒修饰玻碳电极 (CNT Pt/GCE)为基底 ,用明胶固定葡萄糖氧化酶(GOD) ,构建了电流型葡萄糖生物传感器 (GOD/CNT Pt/GCE)。在实验中 ,GOD/CNT Pt/GCE显示了良好的分析性能 ,与常规铂电极葡萄糖传感器 (GOD/Pt)相比较 ,测定葡萄糖的检出限从 6 .7× 10 -3 mol/L下降到8.3× 10 -4mol/L ;工作电位从 0 .6 5V下降至 0 .4 5V ;响应时间从 30s下降至 5s左右。实验结果表明 ,具有高度电催化活性的CNT Pt/GCE可作为酶传感器的一种新型基体电极。     

亲水金和憎水二氧化硅纳米颗粒对葡萄糖生物传感器响应灵 …

用亲水金、憎水二氧化硅纳米颗粒固定葡萄糖氧化酶（ＧＯＤ）,采有聚乙烯醇缩丁醛（ＰＶＢ）为辅助固酶膜基质来制备葡萄糖生物传感器,并考察了亲水金、憎水二氧化硅纳米颗粒对酶电极电流响应的影响。实验表明,引入纳米粒子可显著增强电极响应灵敏度,并对两种不同性质纳米所起作用的可能机理进行讨论,从理论和实验上辛 明了纳米颗粒对固定酶的作用。为制备有实用价值的葡萄糖生物传感器提供了可供参考的实验和理论依据。     

光照纳米银颗粒对葡萄糖生物传感器响应电流的抑制

采用纳米银-壳聚糖复合膜固定葡萄糖氧化酶,构建葡萄糖生物传感器.利用计时电流法对不同光照时间纳米银颗粒组装的酶电极响应电流进行了表征.实验结果表明,光照纳米银颗粒可以抑制葡萄糖生物传感器的响应电流;随着光照时间的延长,纳米银颗粒的抑制作用逐渐增强,当光照时间达到120min时,葡萄糖生物传感器的响应电流最小(-3.953μA/cm²).葡萄糖生物传感器响应电流的抑制可能是由纳米银颗粒表面的Ag⁺离子浓度及表面性能的变化引起的.     

基于“Click”反应耦合酶的高灵敏葡萄糖生物传感器的研究

采用葡萄糖氧化酶（GOD）为模板,利用"Click"反应固定,构建了新型葡萄糖生物传感器。首先,将碳纳米管叠氮化,并将GOD炔基化;在Cu⁺的催化作用下,两者发生"Click"反应;在Nafion的作用下固定在玻碳电极表面,制得葡萄糖生物传感器。采用傅里叶红外光谱（FTIR）法对碳纳米管"Click"反应前后的性质进行了表征。采用循环伏安法和计时电流法考察了电极的电化学行为,并对传感器的性能进行了详细研究。结果表明:在优化的实验条件下,此电极对葡萄糖有明显的催化作用,电流与葡萄糖的浓度在6.0×10-7～1.4×10-3 mol/L范围内呈现良好的线性关系,检出限达2.0×10^-7mol/L。此传感器具有良好的灵敏度、稳定性和重现性。对血清样品中的葡萄糖进行检测,结果令人满意。     

基于钯纳米颗粒修饰直立碳纳米管电极的电化学葡萄糖生物传感器

将电化学氧化生成的Pd(Ⅳ)离子配合到直立碳纳米管(ACNTs)上, 使其还原为纳米颗粒(Pb nps), 从而制得Pd nps-ACNTs纳米复合物电极, 经过葡萄糖氧化酶(GOD)进一步修饰后, 制成GOD/Pds nps/ACNTs酶电极, 通过测量GOD和葡萄糖酶促反应中产生的H₂O₂含量, 进而监测葡萄糖浓度. 实验结果表明, 电极表面大量Pd纳米颗粒的存在显著提高了传感器的检测灵敏度, 使酶电极具有响应时间短(<5 s)及检测电位低(<0.4 V)等优点.     

聚亚甲基蓝和纳米金修饰玻碳电极的葡萄糖生物传感器

用循环伏安法在玻碳电极上电聚合一层稳定的亚甲蓝聚合物膜,研究了这层膜在0.1mol/L磷酸缓冲溶液(pH7.0)中的电化学性质。用纳米金溶胶与聚乙烯醇缩丁醛(PVB)构成复合固酶基质,采用溶胶-凝胶法固定葡萄糖氧化酶(GOD)于亚甲蓝修饰的玻碳电极表面,制成了新型葡萄糖生物传感器。实验发现,加入纳米金后提高了酶电极对葡萄糖的电流响应,所制备的传感器具有响应快、灵敏度高、稳定性好,对葡萄糖的线性响应范围为1×10-6~3×10-3mol/L,检出限为5×10-7mol/L。并具有抗尿酸、抗坏血酸干扰的特点。     

纳米聚苯胺修饰石墨电极的葡萄糖双酶传感器

用循环伏安法在石墨电极上制得纳米纤维聚苯胺, 并在其上固定葡萄糖氧化酶(GOD)和辣根过氧化物酶(HRP)制备葡萄糖双酶传感器. 用交流阻抗、SEM等技术对其进行表征; 考察了各种因素对双酶电极响应电流的影响以及双酶电极的稳定性. 该传感器对葡萄糖响应电流的测定在0.05 V(vs SCE)下进行, 有效避免了电活性物质的影响, 线性响应范围为0.05-2.0 mmol·L-1.     

纳米颗粒增强的葡萄糖生物传感器

研制的纳米增强葡萄糖传感器是用纳米憎水Ａｕ颗粒。亲水Ａｕ颗粒、憎水ＳｉＯ_２颗粒以及Ａｕ和－ＳｉＯ_2颗粒混合与聚乙烯醇缩丁醛（ＰＶＢ）构成复合固酶膜基质,用溶胶－凝胶法固定葡萄糖氧化酶（ＧＯＤ）,组成葡萄糖生物传感器．实验表明,纳米颗粒可以大幅度提高固定化酶的催化活性,响应电流从相应浓度的几十纳安增强到几千纳安,电极响应迅速, １ｍｉｎ达到稳态,探讨了纳米颗粒效应在固定化酶中所起的作用,开辟了制备直接电子传递第三代生物传感器的新途径和纳米颗粒应用的新领域。     

纳米金-生物酶膜在葡萄糖生物传感器上的应用

把金纳米颗粒加入到生物酶膜中制备葡萄糖生物传感器,分析了电极的反应机理和金纳米颗粒对电极电流响应的影响,并进行了电极的性能测定。试验表明,引入金纳米粒子可显著提高电极的响应灵敏度．制备的传感器抗干扰性强,稳定性高,成本较低,操作简便.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

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.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

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%).     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.     

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.