酶法合成的葡萄糖氧化酶-纳米金复合物的直接电化学与生物传感

将NaAuCl₄、葡萄糖氧化酶（GOx）和葡萄糖混合,借一步酶促反应制得吸附GOx的金纳米颗粒（AuNPs）,再通过滴干修饰法研制了Nafion/GOx-AuNPs修饰的玻碳（GC）电极,并考察了该酶电极上GOx的直接电化学和生物传感性能. 这种酶法合成的GOx-AuNPs复合物有良好的酶直接电化学活性,也保持了GOx的生物活性,似可归因于酶法合成的纳米金更接近酶氧化还原活性中心的缘故. 该酶电极在-0.4 V（vs. SCE）电位下,其稳态电流下降与葡萄糖浓度（0.5 4 mmol·L^-1）成正比,检测下限0.2 mol·L^-1.     

基于叶片状氧化铜纳米材料的无酶葡萄糖传感电极

将Nafion交联剂与纳米材料修饰至玻碳电极基底制备一种无酶葡萄糖传感器,通过循环伏安曲线、时间-电流曲线检测该电极电化学特性. 氧化铜纳米复合膜具有高比表面积和多活性点位的优点. 实验结果表明,氧化铜纳米电极对葡萄糖的检测线性响应范围0.01 ~ 0.3 mmol·L^-1,灵敏度1783.58 μA·L·mmol^-1·cm^-2,检测限0.80 μmol·L^-1 (S/N=3),稳定性较好,能抵抗抗坏血酸、多巴胺和尿酸干扰.     

柯尔克孜族和维吾尔族ACE基因多态性与2型糖尿病的关联研究

探讨新疆柯尔克孜族和维吾尔族人群血管紧张素转化酶（ACE）基因rs1799752位点插入或缺失（I/D）多态性及其与2型糖尿病（TypeⅡdiabetes mellitus,T2DM）的关系．方法采用病例-对照的研究设计．采集无血缘关系、年龄性别匹配的新疆柯尔克孜族样本117例、维吾尔族样本127例,分为2型糖尿病组（T2DM）、糖耐量异常组（impaired glucose tolerance, IGT）和糖耐量正常组（normal glucose tolerance, NGT）,以Hardy-Weinberg平衡检验确认研究样本的群体代表性,采用PCR技术检测ACE基因I/D多态性．结果（1）病例组与对照组ACE基因多态性的分布符合Hardy-Weinberg平衡定律,所选人群具有代表性;（2）柯尔克孜族DD型42.74%,ID型31.58%,II型26.50%,D和I 等位基因频率分别为58.115%和41.876%;维吾尔族DD型35.43%,ID型28.35%,II型36.22%,D和I 等位基因频率分别为49.626%和50.387%．（3）ACE基因频率差异在柯尔克孜族（χ2=70.11,P 〈0.01）,维吾尔族（χ^2=35.11,P〈0.01）的糖调节异常组与糖耐量正常组间,分别具有统计学意义．在维吾尔族T2DM组中携带DD、ID、ID＋DD基因型的个体较携带II基因型的个体发生糖代谢异常（T2DM＋IGT）的危险性增加（OR=7.812,95%CI=3.135-19.607;OR=4.854,95%CI=1.835-12.821;OR=6.410,95%CI=2.865-14.286,携带D等位基因的个体较携带I等位基因的个体发生糖代谢异常（T2DM＋IGT）的危险性增加（OR=4.444,95%CI=2.617-7.576）,而柯尔克孜族DD、ID＋DD基因型和D等位基因性对糖代谢异常（T2DM＋IGT）的发病风险降低．结论ACE基因I/D多态性与新疆两个少数民族T2DM相关,ACE基因I/D多态性可能是维吾尔族T2DM的危险因素,柯尔克孜族的保护因素．     

光电微损法检测血糖

介绍了一种新型的光电微损法血糖检测技术 ,以此技术为基础研制的血糖仪以TI公司新推出的低功耗微处理器MSP4 30F4 13为核心。该仪器有 3个特点 :(1)在光电接受部分采用了类似分光计的单波长双检测管结构 ,以避免因发光二极管LED工作状态不稳定而带来的误差 ;(2 )通过多次比较法自动判断反应终止时间 ,即开始计算处理的时间 ;(3)可存储 5 0次测量结果。将其测量血糖浓度的结果与Prestige公司血糖仪的测量结果进行了对比。数据表明 ,其测量结果是准确可信的。光电式微损血糖仪具有操作简便 ,测定时间短 ,结果准确可靠 ,对器件一致性要求不高 ,低功耗等优点 ,是一种供糖尿病患者在家庭中监测控制自身血糖浓度的理想仪器。     

Electronics and Structural Properties of Single-Walled Carbon Nanotubes Interacting with a Glucose Molecule：ab initio Calculations

The adsorption of glucose molecule on single-walled carbon nanotubes (SWCNTs) is investigated by density functional theory calculations. Adsorption energies and equilibrium distances are evaluated, and glucose binding to the typical semiconducting and metallic nanotubes with various diameters and chirality are compared. We also investigated the role of the structural defects on the adsorption capability of the SWCNTs. We could observe larger adsorption energies for the larger diameters semiconducting CNTs, while the story is paradoxical for the metallic CNTs. The obtained results reveal that the adsorption energy is significantly higher for nanotubes with higher chiral angles. Finally, the adsorption energies are calculated for defected nanotubes for various configurations such as glucose molecule approaching to the pentagon, hexagon, and heptagon sites in the tube surface. We find that the respected defects have a minor contribution to the adsorption mechanism of the glucose on SWNTs. The calculation of electron transfers and the density of states supports that the electronic properties of SWCNTs do not change significantly after the gluycose molecular adsorption. Consequently, one can predict that presence of glucose would neither modify the electronic structure of the SWCNTs nor direct to a change in the conductivity of the intrinsic nanotubes.     

烷基-β-D-吡喃葡萄糖苷的合成与性能

以葡萄糖为原料,经乙酰化、选择性脱C1位乙酰基、转化成三氯乙酰亚胺酯、与受体醇偶联和脱保护5步反应合成了11种不同碳链长度的烷基β-D-吡喃葡萄糖苷。 利用核磁共振、偏光显微镜和热失重分析法对其进行结构表征和性能测试。 结果表明,当烷基β-D-吡喃葡萄糖苷疏水烷基链长n为 6~10时,均具有发泡和乳化性能,特别是正壬基β-D-吡喃葡萄糖苷(n=9)具有更加优异的发泡和乳化性能;当烷基β-D-吡喃葡萄糖苷疏水链的长度n≥7时,均具有热致液晶行为,特别是正十二烷基β-D-吡喃葡萄糖苷(n=12)和十四烷基β-D-吡喃葡萄糖苷(n=14)能够形成更加稳定的液晶态。     

离子液体中CNT/nanoTiO_2-Pt膜电极电催化氧化葡萄糖

循环伏安法研究葡萄糖在离子液体[EMI]BF4中于碳纳米管/纳米TiO2膜载Pt(CNT/nanoTiO2-Pt)复合膜电极上的电催化氧化.结果表明,CNT/nanoTiO2-Pt电极对葡萄糖氧化具有高催化活性,氧化电位为-0.46V;在组成为离子液体与水的体积比为3∶1的电解液中,葡萄糖的氧化效果最好.电极反应过程受浓差极化控制.     

基于Ni12P5纳米粒子的电化学传感器用于灵敏测定葡萄糖

通过改进的热溶剂胶体合成法制备了单分散的Ni₁₂P₅纳米粒子,并利用X射线衍射、透射电子显微镜、X射线光电子能谱、X射线能谱对Ni₁₂P₅纳米粒子的晶体结构、化学组成和形貌等进行了表征。基于单分散Ni₁₂P₅纳米粒子研制出的非酶葡萄糖传感器具有出色的性能,其快速响应时间小于3 s,检测范围广（0.002~4.2 mmol·L^-1）,灵敏度高达1 572 mA·L·mol^-1·cm^-2,检测限低至0.8 μmol·L^-1。此外,该传感器在用于人体血液中葡萄糖的实际检测中取得了满意的效果。     

Detection of Adrenaline in Blood Plasma as Biomarker for Adrenal Venous Sampling

An amperometric bi‐enzyme biosensor based on substrate recycling principle for the amplification of the sensor signal has been developed for the detection of adrenaline in blood. Adrenaline can be used as biomarker verifying successful adrenal venous sampling procedure. The adrenaline biosensor has been realized via modification of a galvanic oxygen sensor with a bi‐enzyme membrane combining a genetically modified laccase and a pyrroloquinoline quinone‐dependent glucose dehydrogenase. The measurement conditions such as pH value and temperature were optimized to enhance the sensor performance. A high sensitivity and a low detection limit of about 0.5–1 nM adrenaline have been achieved in phosphate buffer at pH 7.4, relevant for measurements in blood samples. The sensitivity of the biosensor to other catecholamines such as noradrenaline, dopamine and dobutamine has been studied. Finally, the sensor has been successfully applied for the detection of adrenaline in human blood plasma.     

Applying Co3O4@nanoporous Carbon to Nonenzymatic Glucose Biofuel Cell and Biosensor

A novel hierarchically nanoporous carbon (NPC) derived from Al‐based porous coordination polymer is prepared by two‐step carbonization method for immobilization of the Co₃O₄ in the application of the nonenzymatic biofuel cells and biosensors. The structure and morphology are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high‐resolution transmission electron microscopy (HRTEM), and X‐ray diffraction (XRD). Brunauer‐Emmett‐Teller (BET) is to characterize the porous nature of the NPC, and X‐ray photoelectron spectroscopy (XPS) is to characterize the composition of Co₃O₄@nanoporous carbon (Co₃O₄@NPC). Without collapse in the high carbonization temperature (above 1600 °C), the NPC maintains the nanoporous structure and high specific surface area of 1551.2 m² g⁻¹. In addition, the NPC is composited with Co₃O₄ by hydrothermal method to form the Co₃O₄@NPC. When tested as the nonenzymatic electrocatalyst for glucose oxidation reaction (GOR), the Co₃O₄@NPC exhibits higher response to glucose, in which the current shifts up by 64 %, than pure Co₃O₄ in 0.1 M KOH. The limit of detection is 0.005 mM (S/N=3) and response time is within 3 s. The detection range can be divided into two sections of 0.02–1.4 mM and 1.4–10.7 mM with the sensitivity of 249.1 μA mM⁻¹ cm⁻² and 66.6 μA mM⁻¹ cm⁻², respectively. A glucose fuel cell is constructed with the Co₃O₄@NPC as the anode and Pt/C catalyst as the cathode. The open‐circuit potential of the nonenzymatic glucose/O₂ fuel cell was 0.68 V, with a maximum power density of 0.52 mW cm⁻² at 0.27 V. This work may contribute to exploring other nanoporous carbons for application in glucose fuel cells and biosensors.