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     

普鲁士蓝修饰电极结合硅溶胶-凝胶技术制备高灵敏葡萄糖传感器

基于普鲁士蓝修饰玻碳电极结合二氧化硅溶胶 凝胶固定化酶技术构造具有“三明治”式结构的酶电极。考察了酶电极对葡萄糖的电化学响应以及操作条件。结果表明 :所制备的传感器在pH 6 .5 ,电位为- 0 .0 5V条件下对葡萄糖在 0～ 5mmol/L呈线性响应 ,响应时间为 12s ,检出限为 0 .0 2mmol/L ,灵敏度高达1 182 μA/ (mmol·L-1)。传感器的稳定性好 ,4 5d其响应值仍保持 90 %。     

纳米金葡萄糖氧化酶修饰电极对葡萄糖的电化学行为研究

利用自组装技术固定化酶稳定的优点,及纳米金的高灵敏电催化作用制备了纳米金修饰葡萄糖氧化酶修饰金电极.结果表明,制备的修饰电极对葡萄糖具有很好的电催化氧化功能.在选择的条件下,修饰电极对葡萄糖在0～28 mmol/L浓度范围内呈线性响应,响应时间为15 s,检出限为0.27 mmol,响应电流的平均密度为33.52 nA/cm2,两周后响应值保持88%,可满足实际应用要求.     

葡萄糖氧化酶在羟基磷灰石／Nation复合膜修饰电极上的直接电化学及其对葡萄糖的生物传感

将葡萄糖氧化酶固定于羟基磷灰石（HAp）-Nation复合膜,构建了高灵敏、高选择性的葡萄糖传感器．羟基磷灰石和Nation良好的协同作用,可以有效地提高传感器的稳定性与灵敏度．实验结果表明：固定在复合膜修饰电极上的葡萄糖氧化酶呈现出一对较好的近乎可逆的氧化还原峰,并且对葡萄糖的氧化有良好的催化作用,同时消耗溶解氧,从而导致溶解氧还原峰的降低．在-0.8V处,随葡萄糖浓度的增加,葡萄糖氧化酶催化葡萄糖氧化时消耗溶解氧的量增加,溶解氧还原电流逐渐降低,因此该修饰电极可以作为葡萄糖传感器实现对葡萄糖的高灵敏检测．在0．12～2．16mmol·L^-1浓度范围内,溶解氧还原电流的降低与葡萄糖的浓度成正比,据此可以测定出溶液中葡萄糖的浓度,该传感器的检出限和灵敏度分别为0．02mmol·L^-1（SIN=3）和6．75mA·mol·L^-1．因此,HAp-Nation复合膜为酶的固定和直接电化学研究提供了一个新的有效平台,在构建新型无试剂葡萄糖传感器方面具有较大的应用前景．     

聚邻苯二胺修饰玻碳电极的制备及电催化性能

在磷酸盐缓冲溶液中研究了邻苯二胺在玻碳电极表面的聚合过程,探讨了各氧化还原峰的变化机理,用扫描电镜表征了聚邻苯二胺膜的形态结构。发现制备的聚邻苯二胺膜修饰电极对H2O2有显著的电催化还原特性,线性回归方程为:Δipa(μA)=-1.63 1.07cH2O2(mmol.L-1)(R=0.9947,n=19),线性范围为:5.89×10-2mmol.L-1~44.4 mmol.L-1,检出限为:0.02 mmol.L-1(3S/k),这对与产生H2O2的氧化酶相结合制备出响应各种底物的电化学生物传感器非常重要。考察了制备条件对膜电极电催化还原活性的影响,发现只有在弱酸条件下制备的膜电极才有较高的电催化活性。探讨了影响膜电极电催化还原灵敏度的因素,并考察了膜电极的稳定性。     

聚天青B/铜纳米复合物膜修饰电极用于葡萄糖的测定

采用电化学方法制备了聚天青B/铜纳米复合物膜修饰电极,研究了葡萄糖在该修饰电极上的氧化行为。讨论了利用该修饰电极测定葡萄糖的最佳条件。结果表明:在优化的条件下,葡萄糖浓度在10μmol/L~10 mmol/L范围内,响应电流与其浓度呈线性关系,其回归方程为:I=0.226 0.047C,(r=0.993),检出限为5μmol/L。该电极与聚天青B修饰电极相比,本法响应更为灵敏,线性范围更宽。     

聚5-磺基水杨酸修饰电极上对苯二酚的电化学行为

用循环伏安法将 5 磺基水杨酸修饰于玻碳电极表面 ,制备出对对苯二酚具有电催化作用的聚合物膜修饰电极。研究了对苯二酚 (HQ)在该聚合物薄膜修饰电极上的电化学行为。在 0 5mmol/LH2 SO4底液中 ,HQ在该电极上的线性范围为 2 0× 1 0 - 6～ 1 0× 1 0 - 4 mol/L。该修饰电极可将对苯二酚和邻苯二酚(CC)的氧化峰分开约 1 0 5mV     

基于聚锂均苯三甲酸/多壁碳纳米管复合膜的葡萄糖生物传感器的研究

利用电聚合方法在裸玻碳(GC)电极上修饰一种新型金属有机框架化合物锂均苯三甲酸(Li-BTC),并采用滴涂技术制备了Nafion/GOx/MWNTs/poly-Li-BTC/GC葡萄糖生物传感器。利用扫描电镜分析了复合膜(含MWNTs和poly-Li-BTC)的形貌,采用循环伏安和交流阻抗方法对修饰电极的电化学性能进行了研究。结果表明,此复合膜可增大裸玻碳电极的有效表面积、改善电极的电催化活性。利用循环伏安法和计时安培法研究了葡萄糖在Nafion/GOx/MWNTs/poly-Li-BTC/GC电极上的电化学特性。结果表明:葡萄糖的浓度在0.02～1.56 mmol/L范围内,此修饰电极的电流响应与葡萄糖的浓度呈线性关系,其相关系数为0.9992,检出限为5.1μmol/L(信噪比为3∶1)。修饰电极的米氏常数为0.832 mmol/L,回收率为96.3#～100.3#。本研究制备的葡萄糖生物传感器具有较好的重复性、重现性、选择性与稳定性,用于葡萄糖注射液中葡萄糖含量的检测,结果满意。     

基于多层叉指超微带电极阵列的葡萄糖传感器

采用多层工艺和光刻方法在玻璃衬底上加工了亚微米级金叉指型超微带电极阵列（IDA）,IDA电极的宽度为362nm,电极表面位于沟槽内。实验表明,所加工的IDA电极可作为生物和化学传感器的一次性超微基体电极。采用电聚合的方法将葡萄糖氧化酶（GOD）和吡咯（PPy）固定于IDA电极,该修饰电极可作为葡萄糖传感器。采用该葡萄糖传感器对磷酸钾缓冲溶液（pH7．0）中的葡萄糖浓度进行了比对测量,在2．0-7．0mmol／L的浓度范围内,传感器的响应时间为10s;灵敏度为14．6nA／（mmol／L）,相关系数为0．999。     

聚中性红修饰玻碳电极葡萄糖生物传感器

以中性红为电子媒介体,电聚合于Nafion修饰的玻碳电极表面,以戊二醛作交联剂固定葡萄糖氧化酶,最后覆盖一层Nafion膜防止酶流失,构建一种新型葡萄糖生物传感器.详细探讨了传感器的电化学性能及对葡萄糖的最佳响应条件.结果表明,30℃时,传感器在pH 7.0的PBS中对葡萄糖的线性响应范围为1.0×10-5~5.0×10-3mol.L-1.该传感器制作简单、性能优良,有潜在应用前景.     

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.     

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.     

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.     

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 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.