Electrochemical studies of octadecanethiol and octanethiol films on variable surface area mercury sessile drops

Octadecanethiol (ODT) and octanethiol (OT) films at the mercury-electrolyte interface are examined using cyclic voltammetry and differential capacitance measurements at a single frequency. A mercury flow-system is used to alter the volume, and therefore, the surface area and surface pressure of the mercury electrode. Manipulation of the mercury electrode's volume enables the introduction and removal of defects in the insulating thiol films. OT and ODT film behavior are contrasted under conditions of expansion and contraction. ODT forms extremely impermeable layers that allow 1000 time less redox probe current than seen on uncoated drops. Expansion of the mercury electrode to increase the electrode surface area produces defects and pinholes in the thiol film. These defects are almost completely removed when the drop is compressed back to its initial surface area. OT also forms insulating films on mercury sessile drops, however these films contain more defects than ODT films. While expansion of an OT-coated mercury drop increases redox probe current, recompression of the drop does not return the film to its initial condition. Pinholes and defects in the OT and ODT films can also be produced by cycling to negative potentials, which produce abrupt stripping peaks.     

聚苯胺/二氧化硅复合薄膜的制备及其防腐性能

采用电化学辅助自组装法(Electrochemically assisted self-assembly,EASA)在304不锈钢(304SS)电极上制得二氧化硅(SiO_2)薄膜,然后以循环伏安法(CV)在其上制得了具有防腐性能的聚苯胺/二氧化硅(PANI-SiO_2)薄膜。通过透射电镜(TEM)研究了SiO_2薄膜的孔径,采用扫描电镜(SEM)研究了复合薄膜的形貌,采用Tafel极化曲线、电化学交流阻抗(EIS)研究了复合薄膜在5%氨基磺酸(SA)溶液中的耐蚀性能。结果表明:制得的SiO_2孔径约为2.5nm,相对于聚苯胺,复合薄膜排列较为规则,具有较高的腐蚀电位(-0.248 V)和较低的腐蚀电流密度(1.505×10~(-5) A·cm~(-2))。     

石墨烯/聚苯胺复合材料修饰碳糊电极测定镉(Ⅱ)离子

采用原位聚合法制备石墨烯/聚苯胺复合材料,利用透射电子显微镜(TEM)和X射线衍射(XRD)对其进行了表征;并将制得的石墨烯/聚苯胺复合材料作为化学修饰剂制成石墨烯/聚苯胺复合材料修饰碳糊电极,利用三电极体系循环伏安法,在NH3-NH4Cl缓冲溶液中测定镉离子(Cd~(2+))的电化学行为。结果表明:石墨烯/聚苯胺(GSs/PANI)复合材料提高了碳糊电极的电化学性能,使其对Cd~(2+)的电化学响应和选择性均得到提高。在石墨烯/聚苯胺复合材料质量分数为0.5%,pH=10.75的NH3-NH4Cl缓冲溶液的最佳检测条件下,Cd~(2+)的响应电流与Cd~(2+)的浓度在1.0×10-8~2.0×10-5 mol·L-1的范围内呈现出良好的线性关系,相关系数为0.9939,检出限为2.246×10-8 mol·L-1。     

石墨烯/银纳米颗粒复合材料的制备及其对双氧水的电化学检测

以氧化石墨烯(GO)和硝酸银为原材料,聚乙烯吡咯烷酮(PVP)为还原剂和稳定剂,通过水热法制备出还原氧化石墨烯/银纳米颗粒(rGO/AgNPs)复合材料。采用透射电子显微镜(TEM)、X射线衍射(XRD)及紫外-可见分光光度计(UV-Vis)对rGO/AgNPs复合材料的形貌、组成和结构进行表征。同时,将rGO/AgNPs复合材料修饰到玻碳电极表面制备出过氧化氢(H_2O_2)电化学传感器,通过循环伏安法(CV)和计时安培响应法(i-t)对传感器进行电化学性能测试。实验结果表明:制备的rGO/AgNPs传感器具有较好的电化学性能,其对H_2O_2检测的灵敏度为340.6μA·(mmol/L)~(-1)·cm~(-2),响应时间为3s,最低检测极限为7.5μmol/L(S/N=3),线性检测范围为20~4950μmol/L(线性相关系数为R=0.9973)。     

基于自组装技术的单晶硅表面镀铜工艺

本研究在单晶硅基底表面自组装制备了3-氨丙基三乙氧基硅烷(APTES)自组装薄膜,并在此基础上进行化学镀和电镀研究,最终得到了致密均匀的铜膜,镀层与单晶硅基底通过配位键连接,粘结力强。利用循环伏安(CV)法探索得到了最佳电镀工艺参数为:电流密度1.56A/dm2,电镀时间600s。借助接触角测试仪测定了不同试样表面的润湿性,通过X射线能谱仪(EDX)、扫描电子显微镜(SEM)对镀层的元素含量和表面形貌进行了表征。获得的铜镀层致密均匀并呈现金属光泽。     

Electrochemical Behavior of Single CuO Nanoparticles: Implications for the Assessment of their Environmental Fate

The electrochemical behavior of copper oxide nanoparticles is investigated at both the single particle and at the ensemble level in neutral aqueous solutions through the electrode‐particle collision method and cyclic voltammetry, respectively. The influence of Cl^? and NO₃^? anions on the electrochemical processes occurring at the nanoparticles is further evaluated. The electroactivity of CuO nanoparticles is found to differ between the two types of experiments. At the single‐particle scale, the reduction of the CuO nanoparticles proceeds to a higher extent in the presence of chloride ion than of nitrate ion containing solutions. However, at the multiparticle scale the CuO reduction proceeds to the same extent regardless of the type of anions present in solution. The implications for assessing realistically the environmental fate and therefore the toxicity of metal‐based nanoparticles in general, and copper‐based nanoparticles in particular, are discussed.     

Iterative decision feedback equalizer with cyclic detection for DFT-S OFDM system

One of the most challenging problems in high-data-rate wireless transmission is to reduce inter-symbol interference (ISI) resulted from the time dispersion caused by multi-path propagation. To solve this problem, equalization is introduced. Generally, efficient decision feedback equalizer (DFE) holds better performance than linear equalizer for the cancellation of ISI without noise enhancement. However, its inherent error propagation has some limitation for further improvement. In fact, as shown later in simulation results, conventional frequency domain DFE (FD-DFE) almost cannot be used in Discrete Fourier Transform-Spread Orthogonal Frequency Division Multiplex (DFT-S OFDM) system in Evolved-UMTS (Universal Mobile Telecommunications System) Terrestrial Radio Access (E-UTRA) uplink transmission [3GPP, TR 25.814 V1.2.3. Physical layer aspects for evolved UTRA. May 2006 [release 7]]. Unique word (UW) is proposed in the literatures, as a known symbol sequence, can make error propagation beyond one FFT-block impossible since the last symbols of every block are always decided correctly. But the UW-based scheme is not appropriate for DFT-S OFDM, so it must be modified. This paper proposes a simple DFE-based equalization algorithm for DFT-S OFDM. Through cyclic detection and iteration, the new algorithm obtains a noticeable gain than conventional DFE, and is almost as effective as the modified UW-based methods but with much higher bandwidth efficiency. Furthermore, it does not need to change the frame structure of existing protocol.     

Aptamer biosensor for label-free impedance spectroscopy detection of thrombin based on gold nanoparticles

This paper presents a simple electrochemical impedance spectroscopy (EIS) aptasensor based on an anti-thrombin-aptamer as a molecular recognition element. Improvement in sensitivity was achieved by utilizing gold nanoparticles (AuNPs), which were self-assembled on the surface of a bare electrode by using 1,6-Hexanedithiol as a medium. To quantify the amount of thrombin, changes in the interfacial electron transfer resistance (R_et) of the aptasensor were monitored using the redox couple of an [Fe(CN)₆]^3−/4− probe. The plot of (Reti−Ret₀)/Ret₀ against the logarithm of thrombin concentration is linear with over the range from 0.1 nM to 30 nM with a detection limit of 0.013 nM. Meanwhile, the packing density of aptamers was determined by cyclic voltammetric (CV) studies of redox cations (e.g., [Ru(NH₃)₆]³⁺) which were electrostatically bound to the DNA phosphate backbones. The results indicate that the total amount of aptamer probes immobilized on the gold nanoparticle surface is sixfold higher than that on the bare electrode. The aptasensor also showed good selectivity for thrombin without being affected by the presence of other proteins.     

A label-free amperometric immunosensor based on horseradish peroxidase functionalized carbon nanotubes and bilayer gold nanoparticles

In this work, a novel label-free amperometric immunosensor has been constructed for detecting α-1-fetoprotein (AFP) based on nanocomposite of horseradish peroxidase (HRP) labeled carbon nanotubes (CNTs). First, the gold nanoparticles (AuNPs) were electrodeposited on the surface of the glass carbon electrode by electrochemical reduction of gold chloride tetrahydrate (HAuCl₄) to immobilize horseradish peroxidase labeled carbon nanotubes (HRP-CNTs). Then HRP-CNTs bioconjugate was immobilized on the surface of the electrodeposited AuNPs layer by the combination of forces (coordination and electrostatic force). Subsequently, it was immersed into gold colloidal nanoparticles (GNPs) solution, which was used to immobilize antibody biomolecules (anti-AFP). Enhanced sensitivity was obtained by using bioconjugates featuring HRP labeled (HRP-CNTs), which had lager specific surface area and good electronic catalysis (current response signal) compared to carbon nanotubes. Under optimized conditions, the linear ranges were from 0.2 to 200 ng mL⁻¹ with a detection limit of 0.067 ng mL⁻¹ (at an S/N of 3). The proposed immunosenor showed good precision, acceptable stability and reproducibility and could be used for the detection AFP in normal human serum, which provided a potential alternative tool for the detection of protein in clinical diagnosis.     

Comparing sensitivities of differently oriented multi-walled carbon nanotubes integrated on silicon wafer for electrochemical biosensors

In this study, we report on multi-walled carbon nanotubes fabricated on silicon substrate with four different orientations via chemical vapor deposition. It is well-known that chemical treatments improve the nanotube electrochemical reactivity by creating edge-like defects on their exposed sidewalls. Before use, we performed an acid treatment on carbon nanotubes. To prove the effect of the treatment on these nanostructured electrodes, contact angles were measured. Then, sensitivities and detection limits were evaluated performing cyclic voltammetry. Two target molecules were used: potassium ferricyanide, an inorganic electroactive molecule, and hydrogen peroxide that is a product of reactions catalyzed by many enzymes, such as oxidases and peroxidases. Carbon nanotubes with tilted tips become hydrophilic after the treatment showing a contact angle of 22° ± 2°. This kind of electrode has shown also the best electrochemical performance. Sensitivity and detection limit values are 110.0 ± 0.5 μA/(mM cm²) and 8 μM for potassium ferricyanide solutions and 16.4 ± 0.1 μA/(mM cm²) and 24 μM using hydrogen peroxide as target compound. Considering the results of wettability and voltammetric measurements, nanotubes with tilted tips-based electrodes are found to be the most promising for future biosensing applications.