等离子体聚合沉积聚烯丙胺薄膜改性聚酯及体外血小板粘附研究

采用脉冲和连续波方式沉积等离子体聚烯丙胺薄膜改性聚酯(PET)材料表面,并进一步在等离子体聚烯丙胺薄膜表面固定肝素分子.利用衰减全反射红外光谱、X射线光电子能谱和接触角测试等离子体聚烯丙胺薄膜的元素成分、组成和表面能,采用对三氟甲基苯甲醛衍生法和甲苯胺蓝法分别检测了等离子体聚烯丙胺薄膜表面的伯胺基浓度和固定肝素分子的聚烯丙胺薄膜表面的肝素浓度.实验结果表明,脉冲等离子体聚合薄膜PPAa-P表面的伯胺基浓度为1.4%,而连续波等离子体聚合薄膜PPAa-C表面伯胺基浓度只有0.71%.等离子体聚烯丙胺薄膜改性的PET的表面能增加,其中PPAa-P改性的PET表面的表面能的极性分量增加较大.脉冲等离子体聚烯丙胺薄膜表面固定的肝素浓度为4.07μg/cm2,为连续波等离子体聚烯丙胺薄膜表面固定肝素浓度2.23μg/cm2的1.8倍.体外血小板粘附实验结果表明,表面肝素化的PET表面有较低数量的血小板粘附和激活,尤其是在固定肝素分子的脉冲等离子体聚烯丙胺薄膜改性的PET表面表现出更好的抗凝血性.     

A biosensor based on Coriolopsis gallica laccase immobilized on nitrogen-doped multiwalled carbon nanotubes and graphene oxide for polyphenol detection

The use of nanomaterials allows the design of ultrasensitive biosensors with advantages in the detection of organic molecules. Catechol and catechin are molecules that occur naturally in fruits, and their presence in products like dyes and wines affects quality standards. In this study, catechol and catechin were measured at the nanoscale by means of cyclic voltammetry. The oxidation of Coriolopsis gallica laccase immobilized on nitrogen-doped multiwalled carbon nanotubes (Lac/CN_x-MWCNT) and on graphene oxide (Lac/GO) was used to measure the concentrations of catechol and catechin. Nitrogen-doped multiwalled carbon nanotubes (CN_x-MWCNT) were synthesized by spray pyrolysis and characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and x-ray photoelectron spectroscopy (XPS). Covalently bonded hybrids with laccase (Lac/CN_x-MWCNT and Lac/GO) were generated. Catalytic activity of free enzymes determined with syringaldazine yielded 14 584 UmL⁻¹. With Lac/CN_x-MWCNT at concentrations of 6.4 mmol L⁻¹ activity was 9326 U mL⁻¹, while enzyme activity measured with Lac/GO at concentration of 6.4 mmol L⁻¹ was 9 234 U mL⁻¹. The Lac/CN_x-MWCNT hybrid showed higher stability than Lac/GO at different ethyl alcohol concentrations. The Lac/CN_x-MWCNT hybrid can measure concentrations, not previously reported, as low as 1 × 10⁻⁸ mol L⁻¹ by measuring the electric current responses.     

A biosensor based on Coriolopsis gallica laccase immobilized on nitrogen-doped multiwalled carbon nanotubes and graphene oxide for polyphenol detection

Abstract

The use of nanomaterials allows the design of ultrasensitive biosensors with advantages in the detection of organic molecules. Catechol and catechin are molecules that occur naturally in fruits, and their presence in products like dyes and wines affects quality standards. In this study, catechol and catechin were measured at the nanoscale by means of cyclic voltammetry. The oxidation of Coriolopsis gallica laccase immobilized on nitrogen-doped multiwalled carbon nanotubes (Lac/CN_x-MWCNT) and on graphene oxide (Lac/GO) was used to measure the concentrations of catechol and catechin. Nitrogen-doped multiwalled carbon nanotubes (CN_x-MWCNT) were synthesized by spray pyrolysis and characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and x-ray photoelectron spectroscopy (XPS). Covalently bonded hybrids with laccase (Lac/CN_x-MWCNT and Lac/GO) were generated. Catalytic activity of free enzymes determined with syringaldazine yielded 14 584 UmL^?1. With Lac/CN_x-MWCNT at concentrations of 6.4 mmol L^?1 activity was 9326 U mL^?1, while enzyme activity measured with Lac/GO at concentration of 6.4 mmol L^?1 was 9 234 U mL^?1. The Lac/CN_x-MWCNT hybrid showed higher stability than Lac/GO at different ethyl alcohol concentrations. The Lac/CN_x-MWCNT hybrid can measure concentrations, not previously reported, as low as 1 × 10^?8 mol L^?1 by measuring the electric current responses.     

Electrode biomaterials based on immobilized laccase. Application for enzymatic reduction of dioxygen

Three different methods of immobilization of the laccase enzyme have been studied by measuring the enzyme activity of the bioelectrode and its catalytic efficiency for dioxygen reduction in the presence of the 2,2′-azinobis (3-ethylbenzothiazoline-6-sulfonate) diammonium salt (ABTS) as a redox mediator. One approach has consisted in laccase entrapment in polypyrrole matrix electrogenerated on the electrode surface. The two other approaches have concerned the grafting of laccase on an original aminopolypyrrole film and the complexation of laccase with avidin and biotin reagents. The laccase activity and the catalytic current of dioxygen reduction have demonstrated the efficiency of covalent grafting to aminopolypyrrole film. The polymer thickness was a key parameter of the catalytic efficiency and stability of this type of biocathode.     

Characterization of enzyme immobilized carbon electrode using covalent-entrapment with polypyrrole

ABSTRACT

This study aimed to improve the enzyme immobilization of electrodes to increase electrical power and lifespan using glucose oxidase in a bioanode, laccase in a biocathode, and glucose as a fuel. Both of these enzymes were immobilized on a carbon paper through covalent entrapment. Electrodes were characterized using electrochemical measurements (cyclic voltammetry) and enzymatic biofuel cells. For continuous 16 h, the maximum power density achieved for a hydrophobic electrode was approximately 80 μW/cm² at 0.13 V. For a hydrophilic electrode, the yield was approximately 130 μW/cm² at 0.25 V, which was significantly higher than that for the hydrophobic electrode. The measurements were performed at a working temperature of 37°C with phosphate buffer solution of pH 7 as an electrolyte, and 10 mM glucose was added to the anode as a fuel. The hydrophilic electrode was superior to the hydrophobic electrode because of the covalent entrapment immobilization of glucose oxidase and laccase enzymes in enzymatic biofuel cells.     

Electrochemical detection of nitrite based on the polythionine/carbon nanotube modified electrode

In this paper, thionine was electro-polymerized onto the surface of carbon nanotube (CNT)-modified glassy carbon (GC) to fabricate the polythionine (PTH)/CNT/GC electrode. It was found that the electro-reduction current of nitrite was enhanced greatly at the PTH/CNT/GC electrode. It may be demonstrated that PTH was used as a mediator for electrocatalytic reduction of nitrite, and CNTs as an excellent nanomaterial can improve the electron transfer between the electrode and nitrite. Therefore, based on the synergic effect of PTH and CNTs, the PTH/CNT/GC electrode was employed to detect nitrite, and the high sensitivity of 5.81 μA mM^− 1, and the detection limit of 1.4 × 10^− 6 M were obtained. Besides, the modified electrode showed an inherent stability, fast response time, and good anti-interference ability. These suggested that the PTH/CNT/GC electrode was favorable and reliable for the detection of nitrite.     

Enhanced thermal stability of laccase immobilized on monolayer-modified nanoporous Au

Nanoporous Au was fabricated by the dealloying of Au-Ag alloy in nitric acid, and was modified with a self-assembled monolayer (SAM) of 4-aminothiophenol, for the enhancement of high-temperature activity of immobilized laccase. Immobilized laccase exhibited much higher activity than that of free laccase at > 45 °C. SAM surface modification greatly improved the thermal stability and reusability of immobilized laccase. For example, little degradation in laccase activity when immobilized on SAM-modified nanoporous Au was observed after 2 h incubation at 50 °C. This suggested the nanoporous structure and SAM synergistically prevented the conformational change of laccase, and resulted in the enhancement of high-temperature activity.     

基于界面相互作用构建纳米纤维素-羧基化碳纳米管-石墨/聚吡咯柔性电极复合材料

以纳米纤维素(CNF)、羧基化碳纳米管(CNTs—COOH)、铅笔石墨(PGr)、聚吡咯(PPy)为原料,通过真空抽滤、涂覆、氧化聚合等方法,同时基于氢键界面相互作用的原理,制备出具有石墨层结构的CNF-CNTs—COOH-PGr/PPy柔性电极复合材料。结果表明,CNF-CNTs—COOH-PGr/PPy柔性电极复合材料在平直、折叠和拉伸时不会断裂,展现出较强的力学性能,其拉伸强度达到28.90 MPa。亲水性CNF与CNTs—COOH构筑的多孔结构增强了离子和电子的扩散路径。PGr的加入有效增加了CNF-CNTs—COOH-PGr/PPy柔性电极复合材料的导电路径,赋予其优良的导电性能。氧化聚合后得到的CNF-CNTs—COOH-PGr/PPy柔性电极复合材料的电导率达到5.403 S·cm?1。在1 mol·L?1 H₂SO₄溶液中,0.5 A·g?1电流密度下,CNF-CNTs—COOH-PGr/PPy柔性电极复合材料具有521 F·g?1的高比电容量,且经过1 500次充放电循环后,其电容保持率高达68%。基于柔性电极优良的力学性能、电化学性能和导电性能,CNF-CNTs—COOH-PGr/PPy柔性电极复合材料具备成为柔性储能器件电极材料的基本特性。      

Determination of cyanide in wastewaters using modified glassy carbon electrode with immobilized silver hexacyanoferrate nanoparticles on multiwall carbon nanotube

The sensitive determination of cyanide in wastewaters using modified GC electrode with silver hexacyanoferrate nanoparticles (SHFNPs) immobilized on multiwall carbon nanotube (MWCNT) was reported. The immobilization of SHFNPs on MWCNT was confirmed by transmission electron microscopy (TEM). The TEM image showed that the SHFNPs retained the spherical morphology after immobilized on MWCNT. The size of SHFNPs was examined around 27 nm. The GC/MWCNT-SHFNPs was used for the determination of cyanide in borax buffer (BB) solution (pH 8.0). Using square wave voltammetry, the current response of cyanide increases linearly while increasing its concentration from 40.0 nM to 150.0 μM and a detection limit was found to be 8.3 nM (S/N=3). The present modified electrode was also successfully used for the determination of 5.0 μM cyanide in the presence of common contaminants at levels presenting in industrial wastewaters. The practical application of the present modified electrode was demonstrated by measuring the concentration of cyanide in industrial wastewater samples. Moreover, the studied sensor exhibited high sensitivity, good reproducibility and long-term stability.     

Selective determination of sucrose based on electropolymerized molecularly imprinted polymer modified multiwall carbon nanotubes/glassy carbon electrode

A novel and selective electrochemical sensor was successfully developed for the determination of sucrose by integrating electropolymerization of molecularly imprinted polymer with multiwall carbon nanotubes. The sensor was prepared by electropolymerizing of o-phenylenediamine in the presence of template, sucrose, on a multiwall carbon nanotube-modified glassy carbon electrode. The sensor preparation conditions including sucrose concentration, the number of CV cycles in the electropolymerization step, pH of incubation solution, extraction time of template from the imprinted film and the incubation time were optimized using response surface methodology (RSM). A mixture of acetonitrile/acetic acid was used to remove the template. Hexacyanoferrate(II) was used as a probe to characterize the sensor using electrochemical impedance spectroscopy, cyclic voltammetry and differential pulse voltammetry. Capturing of sucrose by the modified electrode causes decreasing the response of the electrode to hexacyanoferrate(II). Calibration curve was obtained in the sucrose concentration range of 0.01–10.0 mmol L^? 1 with a limit of detection 3 μmol L^? 1. This sensor provides an efficient way for eliminating interferences from compounds with similar structures to sucrose. The sensor was successfully used to determine sucrose in sugar beet juices with satisfactory results.     

氧化物／活性炭复合电极材料的研究

用醋酸锰和高锰酸钾制备二氧化锰粉末；用氯化钌和氢氧化钠制备水合二氧化钌粉末。以二氧化钌和二氧化锰作为电极材料的活性物质，以活性碳粉末为电极的基础原料制备复合电极，并组装超级电容器单元。用x射线衍射仪和扫描电镜对电极材料进行表征，可得复合电极具有明显的电容特征。在浓度为38％的硫酸电解质溶液中，对复合电极进行电化学性能测试，循环伏安曲线、充放电曲线和交流阻抗特性显示了复合电极材料具有良好的电化学性能。碳，锰复合电极的比容量为128F／g，碳/锰/钌复合电极的比容量为266F/g。当二氧化钌和二氧化锰在电极中质量比各占20％时，更能发挥活性物质的作用，由该电极材料组成的超级电容器具有理想的电容特性。     

Biosensor based on self-assembling acetylcholinesterase on carbon nanotubes for flow injection/amperometric detection of organophosphate pesticides and nerve agents

A highly sensitive flow injection amperometric biosensor for organophosphate pesticides and nerve agents based on self-assembled acetylcholinesterase (AChE) on a carbon nanotube (CNT)-modified glassy carbon (GC) electrode is described. AChE is immobilized on the negatively charged CNT surface by alternatively assembling a cationic poly(diallyldimethylammonium chloride) (PDDA) layer and an AChE layer. Transmission electron microscopy images confirm the formation of layer-by-layer nanostructures on carboxyl-functionalized CNTs. Fourier transform infrared reflectance spectrum indicates the AChE was immobilized successfully on the CNT/PDDA surface. The unique sandwich-like structure (PDDA/AChE/PDDA) on the CNT surface formed by self-assembling provides a favorable microenvironment to keep the bioactivity of AChE. The electrocatalytic activity of CNT leads to a greatly improved electrochemical detection of the enzymatically generated thiocholine product, including a low oxidation overvoltage (+150 mV), higher sensitivity, and stability. The developed PDDA/AChE/PDDA/CNT/GC biosensor integrated into a flow injection system was used to monitor organophosphate pesticides and nerve agents, such as paraoxon. The sensor performance, including inhibition time and regeneration conditions, was optimized with respect to operating conditions. Under the optimal conditions, the biosensor was used to measure as low as 0.4 pM paraoxon with a 6-min inhibition time. The biosensor had excellent operational lifetime stability with no decrease in the activity of enzymes for more than 20 repeated measurements over a 1-week period. The developed biosensor system is an ideal tool for online monitoring of organophosphate pesticides and nerve agents.     

石墨/TiO2共混碳薄膜对电极的电学与电化学性能研究

本文将石墨、TiO2纳米晶以及TiO2胶体共混,采用旋涂法制备了碳薄膜对电极,并用于组装染料敏化太阳能电池。采用场发射扫描电子显微镜观察薄膜的表面形貌,采用四探针电阻率测试仪、电化学交流阻抗图谱及太阳能电池综合测试仪对碳对电极的电学、电化学性质以及电池的光电性能分别进行测试;研究了薄膜厚度对碳对电极导电性能与电化学催化性能的影响。结果表明随着厚度增加,碳对电极的方块电阻和界面电荷传输电阻均变小,分别可达到26.6Ω.sp-1和11.8Ω.cm-2,而电池的填充因子及光电转换效率增大。当碳薄膜厚度为19.5μm时,光电转换效率可达到Pt对电极的70%。     

活性炭/炭黑复合电极性能研究

活性炭/炭黑复合电极通过水浴中破乳制得。采用循环伏安、恒流充放电等研究方法对复合电极的电化学性能进行研究。结果表明，在0．5mol/L的硫酸溶液中复合电极呈现良好的电化牵陛能。通过SEM、接触角的研究测定，可知复合电极与有机电解液接触性能较好．     

Electrocatalysis for the oxidation of NADH based on beta-cyclodextrin/multi-walled carbon nanotubes modified ITO electrode

In this study, the new nanocomposites of beta-cyclodextrin (beta-CD) and multi-walled carbon nanotubes (MWNTs) have been prepared and deposited on the indium tin oxide (ITO) electrodes to form the beta-CD/MWNTs modified ITO electrodes. These novel modified electrodes exhibited the abilities to lower the electrooxidation potentials of NADH substantially (ca. 600 mV) in comparison with bare ITO electrodes. Furthermore, a linear response to NADH in the concentration range of 4.0 x 10(-6) to 3.2 x 10(-3) mol/L was observed, with a detection limit of 8.0 x 10(-7) mol/L. Such ability of the novel nanocomposites to promote the electron-transfer reaction of NADH suggests great promise for dehydrogenase-based amperometric biosensors.     

基于碳纤维的新型自支撑电极制备方法

借鉴自支撑电极的制备原理,利用电化学沉积结合(NH₄)₂S₂O₈和NaOH沉积液进行表面处理等手段制备了基于碳纤维表面Cu(OH)₂纳米结构的自支撑电极,分析测试了碳纤维表面的微观形貌、表面元素组成及其分布和表面物质的晶型以及利用水热反应在其表面附着电化学物质MnO₂后的电化学性能。结果发现,当(NH₄)₂S₂O₈的浓度为0.43 g/L、NaOH浓度为30.48 g/L、处理时间为12 min时,由SEM观察发现碳纤维表面的Cu(OH)₂纳米纤维的直径、长度、数量都较适宜;XPS、XRD和EDS的测试结果,沉积液处理后碳纤维表面部分单质铜转化为Cu(OH)₂,此结构非常有利于电化学物质的负载而由此构成开放、具有核壳结构的高性能电极材料;恒电流充放电(GCD)测试结果表明此电极材料具有极快的充放电速度。因此本文首次成功地在碳纤维表面的铜层表面原位生长出Cu(OH)₂纳米纤维,为未来以超级电容器为代表的能源设备的性能提升和商业化应用开拓了一种新的电极制备方法。      

Disposable planar reference electrode based on carbon nanotubes and polyacrylate membrane

In this technical note, we report a new all-solid-state planar reference electrode based on single-walled carbon nanotubes and photocured poly(n-butylacrylate) (poly(nBA)) membrane containing the Ag/AgCl/Cl(-) ion system. Single-walled carbon nanotubes functionalized with octadecylamide (SWCNT-ODA) and deposited by drop-casting onto a disposable screen-printed electrode are an excellent all-solid-state transducer. The novel potentiometric planar reference electrode shows low potential variability (calibration slopes inferior to 2 mV/dec) for a wide range of chemical species (i.e., ions, small molecules, proteins) in a wide calibration range, redox pairs, changes in pH, and changes in ambient light. Potentiometric medium-term signal stability (-0.9 ± 0.2 mV/h) and electrochemical impedance characterization confirm the correct solid contact between the SWCNT-ODA layer and photocured poly(nBA) membrane. Overall, the materials used and the simple fabrication by screen-printing and drop-casting enable a high throughput and highly parallel and cost-effective mass manufacture of the new disposable reference electrode. Moreover, the reference electrode has a long shelf life, a characteristic that can be of special interest in decentralized and multiplexing potentiometric analysis.     

Direct electron transfer and biosensing of glucose oxidase immobilized at multiwalled carbon nanotube-alumina-coated silica modified electrode

Investigations are reported regarding the direct electrochemical performance of glucose oxidase (GOD) immobilized on a film of multiwalled carbon nanotube-alumina-coated silica (MWCNT-ACS). The surface morphology of the GOD/MWCNT-ACS nanobiocomposite is characterized by scanning electron microscopy. In cyclic voltammetric response, the immobilized GOD displays a pair of well-defined redox peaks, with a formal potential (E°′) of ? 0.466 V versus Ag/AgCl in a 0.1 M phosphate buffer solution (pH 7.5) at a scan rate of 0.05 V s^? 1; also the electrochemical response indicates a surface-controlled electrode process. The dependence of formal potential on solution pH indicates that the direct electron transfer reaction of GOD is a reversible two-electron coupled with a two-proton electrochemical reaction process. The glucose biosensor based on the GOD/MWCNT-ACS nanobiocomposite shows a sensitivity of 0.127 A M^? 1 cm^? 2 and an apparent Michaelis–Menten constant of 0.5 mM. Furthermore, the prepared biosensor exhibits excellent anti-interference ability to the commonly co-existed uric acid and ascorbic acid.