生物功能电极（Ⅴ）：—葡萄糖氧化酶在环糊精聚合物中的固…

将葡萄糖氧化酶固定在α－环糊精聚合物中，而电子传递体分子被包含在环糊精腔穴中，固定化酶膜的ＦＴＩＲ测定表明，ＧＯＤ与环糊精聚合物发生共价连接，制备了含电子传递体的不同ＧＯＤ酶电极并比较了它们的性能，含四硫代富瓦烯的酶电极具有良好的电流响应特性，可望成为第二代葡萄糖酶电极的新构型。     

β-环糊精聚合物-二茂铁安培型葡萄糖氧化酶电极

利用 β-环糊精的空穴结构 ,通过主客体化学反应将二茂铁包络在 β-环糊精聚合物的空穴中 ,同时将葡萄糖氧化酶交联在 β-环糊精聚合物上 ,制成对葡萄糖有灵敏响应的生物传感器。循环伏安和安培检测表明包络在 β-环糊精聚合物空穴中的二茂铁更加接近酶的氧化还原中心 ,可以有效地作为葡萄糖氧化酶和玻碳电极之间的电子媒介体 ,葡萄糖浓度在1.0×10-2 ～8.0mmol/L范围内 ,其浓度与电流响应值呈良好的线性关系 ,方法的检出限为2.0×10-3 mmol/L(S/N=3) ,在10s之内达到最大响应的95 %。用该法测定了血清中的葡萄糖含量 ,结果与传统方法吻合。     

生物功能电极(Ⅴ)─葡萄糖氧化酶在环糊精聚合物中的固定化

将葡萄糖氧化酶(GOD)固定在α-环糊精聚合物中,而电子传递体分子被包含在环糊精腔穴中。固定化酶膜的FTIR测定表明,GOD与环糊精聚合物发生共价连接。制备了含电子传递体的不同GOD酶电极并比较了它们的性能。含四硫代富瓦烯的酶电极具有良好的电流响应特性,可望成为第二代葡萄糖酶电极的新构型。     

非均相环糊精在水相有机合成反应中的应用

本文详细综述了非均相环糊精在水相有机合成反应中的应用,包括非均相环糊精在水相氧化反应、还原反应、取代反应、加成反应和光催化反应中的应用。同时,全面阐述了在催化或促进水相有机合成反应中环糊精非均相化的策略,包括形成水不溶性交联聚合物和将环糊精固载在水不溶性载体上两种途径。目前非均相环糊精在水相有机合成反应中的应用还基本局限在简单的相转移催化剂领域,相关报道也较少,处于起步阶段;基于非均相环糊精构筑超分子仿酶是今后该领域的发展趋势和必然归属,应在发挥非均相优势的同时,保留环糊精单元在超分子仿酶构筑中的优良功用。     

环糊精聚合物的分子包合作用及在酶电极中的应用

伏安法用于研究环糊精预聚合物的分子包合作用．红外光谱实验表明环糊精预聚合物与戊二醛缩聚生成的聚合物带有悬挂的羰基,后者能使葡萄糖氧化酶共价固定化．由于分子包合作用,电子受体可存储在含酶的环糊精聚合物膜中,从而提高了酶膜中电子受体的浓度又减少了电子受体的用量．用ＴＴＦ等作电子受体,可实现酶和电子受体在环糊精聚合物中的同时固定化．环糊精聚合物膜中的组成和膜厚度可以控制,为酶电极的基础研究工作提供了方便．     

环糊精聚合物与苯醌的分子包合作用及其在酶电极中的应用

研究了水溶性环糊精预聚合物的存在对苯醌/氢醌体系在铂电极上氧化还原行为的影响, 根据伏安曲线讨论了该预聚合物与苯醌的分子包合作用。环糊精预聚合物与戊二醛缩聚反应而形成的不溶性聚合物膜用于葡萄糖氧化酶的固定化, 以制得新型的第二代葡萄糖电极。由于分子包合作用, 作为电子受体的苯醌在含酶的环糊精聚合物膜中具有较高的浓度, 从而加速了固定化酶的电子传递。测定了酶电极上BQ反应的动力学参数。     

以β—环糊精聚合物的超分子包结物为固定化介质的安培型？…

阐述了一种新的生物传感器的固定化方法。利用β－环糊精聚合物与亚甲基蓝间的超分子作用及β－ＣＤＰ与戊二醛间的缩聚作用,将介体和酶代同固定在电极上,制成的过氧化氢传感器有良好的稳定性和充分的电子流动性,对１．０μｍｏｌ／Ｌ￣１．１ｍｍｏｌ／ＬＨ２Ｏ２呈线性响应,检出限为０．５μｍｏｌ／Ｌ。     

环糊精葡萄糖基转移酶的固定化及其应用──Ⅲ．固定化环糊精葡萄糖基转移酶制备环糊精的研究

用固定化环糊精葡萄糖基转移酶催化淀粉环化反应,考察了反应时间、乙醇浓度和淀粉液化程度对环糊精产率的影响。环糊精产率最高达54%,固定化酶经多次重复使用或长时间连续操作,酶活力降低较少,产品经纸色谱分离后用碘显色,发现产品主要为β-环糊精。     

玻璃纳米孔洞电极的制备及对环糊精单分子的检测

采用玻璃毛细管融封后打磨,直接得到了纳米孔洞玻璃电极。此电极洞壁厚实坚固,容易操作,电流噪声低,可实现对β-环糊精单个分子的检测。发现单个环糊精分子可以产生清晰分辨的两种幅度的电流脉冲,提出是环糊精在孔洞内的两种取向造成的。脉冲幅度与孔洞尺寸密切相关。在(10±5)nm的孔洞电极上可以得到2～5pA的响应脉冲。研究了电压大小与方向的影响,结果表明,电渗流对检测影响显著。在电渗流方向与环糊精扩散方向相反的条件下,100～600mV电极电位即可产生良好的脉冲信号,但平均脉冲宽度随电极电位的增大呈线先增大后减小的趋势,约在300mV电位下脉冲宽度最大。     

基于环糊精包结络合作用的大分子自组装

本文综述了基于环糊精包结络合作用的大分子自组装的研究进展,包括：（1) 线型、梳型、多臂星型或超支化聚合物与环糊精或其二聚体自组装形成多聚轮烷（分子项链）、多聚准轮烷、双多聚（准）轮烷、分子管、双分子管、超分子凝胶及其应用;（2）桥联环糊精与桥联客体分子自组装制备线型或超支化超分子聚合物;（3）温度、pH值、光及客体分子刺激响应智能体系; （4) 通过亲水性的环糊精线型均聚物与含金刚烷的疏水性聚合物之间的包结络合作用来制备高分子胶束及其空心球等。     

Dopamine Oxidation at Per(6‐deoxy‐6‐thio)‐α‐Cyclodextrin Monolayer Modified Gold Electrodes

The gold electrode is functionalized by sequential self‐assembly of a monolayer of the title thiolated cyclodextrin with and without dopamine included in the cavities. The structure of α‐cyclodextrin modified gold electrode is carefully characterized using STM and AFM. Surface complexation of dopamine is examined and its association constant is evaluated. Chemical reactions accompanying the electrode process of dopamine, which interfere in the electrochemical dopamine determination, are described and the conditions to avoid them are proposed. Dopamine incorporated in the α‐cyclodextrin sites anchored to the electrode surface was found to provide electrochemical contact of the electrode with the solution‐resident dopamine. Dopamine present in the α‐cyclodextrin cavities has different properties compared to dopamine in the bulk buffer solution and can act as a mediator for the dopamine molecules diffusing to the electrode. This unique mediation effect leads to improvement of the sensitivity of dopamine determination using the α‐cyclodextrin modified electrode and a procedure for the determination of dopamine in large excess of ascorbate is proposed.     

Gold Nanoparticles‐β‐Cyclodextrin‐Chitosan‐Graphene Modified Glassy Carbon Electrode for Ultrasensitive Detection of Dopamine and Uric Acid

The nanocomposite (denoted as GR‐AuNPs‐CD‐CS) of graphene (GR), gold nanoparticles (AuNPs), chitosan (CS) and β‐cyclodextrin (β‐CD) was prepared to modify a glassy carbon electrode. The as‐modified electrode was explored for the ultrasensitive detection of dopamine (DA) and uric acid (UA). The modified electrode demonstrated linearly increased current response in the concentration range of 0.1–120 µm for DA and 0.05–70 µm for UA, with so far the best detection limit for DA and UA. Good stability and repeatability were further demonstrated for the as‐made sensor.     

Supramolecular Amperometric Immunosensor for Detection of Human Chorionic Gonadotropin

Human chorionic gonadotropin (hCG) is a hormone produced in high concentrations through the placental trophoblasts and is used for the detection of pregnancy and certain diseases. Here we explored a supramolecular strategy for the potentially substrateless amperometric detection of hCG. A carboxymethylcellulose (CMC) carrier was synthesised and trifunctionalised with anti‐βhCG antibody, horse radish peroxidase (HRP) and ferrocene (Fc) moieties. The ferrocene was used to house the functionalised CMC within the cavities of electrode surface immobilised cyclodextrin, via host‐guest interactions. hCG was detected via a sandwich format, forming an immunocomplex between the surface immobilised antibody and a glucose oxidase/lactate oxidase labelled secondary antibody. Following formation of the immunocomplex, lactate/glucose, which would typically be present in serum/urine samples, was added and the hydrogen peroxide formed detected at the electrode surface via the HRP‐Fc enzyme‐mediator couple. The work reported demonstrates a potential supramolecular platform for the detection of targets in blood/urine samples using endogenous substrates.     

Nonenzymatic Electrochemical Biosensor Based on Novel Hydrophilic Ferrocene‐terminated Hyperbranched Polymer and its Application in Glucose Detection

We designed a novel water soluble topological structure polymer‐ferrocene‐ terminated hyperbranched polyurethane (HPU‐Fc) with good water solubility. The redox behaviors and the electrochemical kinetics parameters of HPU‐Fcs were explored by cyclic voltammetry (CV) according to electrochemical principle. The topological structure polymer was applied for the design and engineering of non‐enzymatic glucose sensor. The designed sensor showed good response to glucose concentration with good stability, favorable accuracy and high selectivity. The electrode was also used to detect glucose in blood samples, and the glucose contents detected by the electrode were in good agreement with those from the hospital where a common automatic biochemical analyzer (HF240–300) was used. This finding makes HPU‐Fc a promising biosensor for directly sensing glucose.     

A biosensor prepared by co-entrapment of a glucose oxidase and a carbon nanotube within an electrochemically deposited redox polymer multilayer

A glucose biosensor based on a nanocomposite made by layer-by-layer electrodeposition of the redox polymer into a multilayer containing glucose oxidase (GOx) and single-walled carbon nanotubes (SWCNT) on a screen-printed carbon electrode (SPCE) surface was developed. The objectives of the electrodeposition of redox polymer are to stabilize further the multilayer using a coordinative cross-linked redox polymer and to wire the GOx. The electrochemistry of the layer-by-layer assembly of the GOx/SWCNT/redox polymer nanocomposite was followed by cyclic voltammetry. The resultant biosensor provided stable and reproducible electrocatalytic responses to glucose, and the electrocatalytic current for glucose oxidation was enhanced with an increase in the number of layers. The biosensor displayed a linear range from 0.5 to 6.0mM, a sensitivity of 16.4μA/(mMcm(2)), and a response time of about 5s. It shows no response to 0.05mM of ascorbic acid, 0.32mM of uric acid and 0.20mM of acetaminophen using a Nafion membrane covering the nanocomposite-modified electrode surface.     

Feasibility Study of Introducing Redox Property by Modification of PMBN Polymer for Biofuel Cell Applications

In this study, the feasibility of introducing redox property to an amphiphilic phospholipid polymer (PMBN) was investigated. The active ester group in the side chain of the polymer was used to react with pyrroloquinoline quinine (PQQ). Redox peaks that corresponded to PQQ redox potentials were observed after the modification. Glucose oxidase was immobilized to the modified polymer. Electrochemical oxidation of glucose was carried out with the polymer electrode. The oxidation current increased with elevating glucose concentration indicating electron transfer established between the electrode and enzyme. It suggests that by modification, PMBN is possible to use for enzyme electrode for bioelectronics.     

A glucose electrode based on carbon paste chemically modified with a ferrocene-containing siloxane polymer and glucose oxidase,coated with a poly(ester-sulfonic acid) cation-exchanger

A carbon-paste chemically modified with glucose oxidase and a ferrocene-containing siloxane polymer was further modified by coating the electrode surface with a poly(ester-sulfonic acid) cation-exchanger, Eastman AQ-29D. The polymer is obtained as a homogeneous aqueous dispersion at pH 5–6; when dried, the polymer coating is not water-soluble. The coating was shown not to be detrimental to the enzyme activity but to prevent electrochemically active anionic interferents such as ascorbate and urate from reaching the electrode surface. The polymer coating also prevented glucose oxidase from leaking out of the carbon paste into the contacting solution and protected the electrode surface from fouling agents present in urine and bovine serum albumin. Uncoated electrodes lost some 10-2-15% of their original response to glucose after storage in buffer for three weeks whereas the response of the coated electrodes remained constant. Calibration curves for glucose were strictly linear up to about 5 mM for uncoated and up to 20 mM for coated electrodes. The response current to glucose was not decreased after coating.     

硅溶胶-凝胶包埋纳米金和酶的葡萄糖生物传感器

采用溶胶-凝胶技术将金纳米粒子和葡萄糖氧化酶一次性固定于硅溶胶-凝胶的网络结构中,制备了葡萄糖生物电化学传感器并优化了传感器的制备条件。酶电极对葡萄糖具有良好的电化学响应,葡萄糖浓度在0.02~2.0 mmol/L范围内和催化电流呈线性关系,检出限为0.005 mmol/L。酶电极在4 ℃下贮存100 d后对葡萄糖的响应仅下降8%。该酶电极灵敏度高、响应快、稳定性好。     

Development of amperometric glucose biosensor through immobilizing enzyme in a Pt nanoparticles/mesoporous carbon matrix

Pt nanoparticles were deposited on mesoporous carbon material CMK-3. Glucose oxidase (GOx) was immobilized in the resulting Pt nanoparticles/mesoporous carbon (Pt/CMK-3) matrix, and then the mixture was cast on a glassy carbon electrode (GCE) using gelatin as a binder. The glucose biosensor exhibited excellent current response to glucose after cross-linking with glutaraldehyde. At 0.6V (vs. SCE) the response current was linear to glucose concentration in the range of 0.04-12.2mM. The response time (time for achieving 95% of the maximum current) was 15s and the detection limit (S/N=3) was 1 microM. The Michaelis-Menten constant (K(m)(app)) and the maximum current density (i(max)) were 10.8 mM and 908 microAcm(-2), respectively. The activation energy of the enzymatic reaction was estimated to be 22.54 kJ mol(-1). The biosensor showed good stability. It achieved the maximum response current at about 52 degrees C and retained 95.1% of its initial response current after being stored for 30 days. In addition, some fabrication and operation parameters for the biosensor were optimized in this work. The biosensor was used to monitor the glucose levels of serum samples after being covered with an extra Nafion film to improve its anti-interferent ability and satisfied results were obtained.