基于银纳米粒子/氧化石墨烯复合薄膜制备TNP电化学传感器

利用改进的Hummers法制备了氧化石墨烯(GO), 以葡萄糖为还原剂直接在GO表面沉积银纳米粒子(AgNPs)得到性能稳定的AgNPs/GO纳米复合材料;基于该纳米复合材料修饰电极构建了一种新型的2, 4, 6-三硝基苯酚(TNP)电化学传感器。采用原子力显微镜(AFM)、扫描电镜(SEM)、透射电镜(TEM)、紫外可见光谱(UV-Vis)和交流阻抗(EIS)等多种方法对纳米复合薄膜进行了表征;并研究了TNP在复合薄膜修饰电极上的电化学行为和动力学性质。结果表明, AgNPs/GO对TNP有较强的电催化活性, 在复合薄膜修饰电极出现一灵敏的氧化峰和3个还原峰;利用氧化峰可对TNP进行定量分析。同时整个电极过程明显不可逆, 电极反应受到吸附步骤控制;复合膜电极表面覆盖度为5.617×10^-8 mol·cm^-2, 在所研究电位下的速率常数为9.745×10^-5 cm·s^-1。在pH 6.8的磷酸缓冲液中, 当富集电位为-0.70 V, 富集时间为60 s;TNP氧化峰电流与其浓度在5.0×10^-9~1.0×10^-7 mol·L^-1范围内成良好线性关系, 相关系数为0.995 8, 检出限可达1.0×10^-9 mol·L^-1。所制备的电化学传感器稳定性和选择性较好;用于实际水样中TNP的现场快速检测, 加标回收率在 97.6%~103.9%之间。     

Synthesis and characterization of dithienobenzothiadiazole-based donor–acceptor conjugated polymers for organic solar cell applications

New donor–acceptor conjugated polymers (P1 and P2) containing a fused-ring dithienobenzothiadiazole (DT-BTD building block) were synthesized by using the Stille copolymerization method. The synthesized polymers were characterized by ¹H NMR, GPC, and elemental analysis. The optical band gaps of the polymers were found to be 1.86 and 1.9 eV, respectively, as calculated from their film onset absorption edge. Upon annealing both produced a distinct shoulder peak in their film absorption spectra. The electrochemical studies of P1 and P2 revealed that the HOMO and LUMO energy levels of the polymer were −5.3, −5.1 eV, and −3.4, −3.2 eV, respectively. The polymers are thermally stable up to 250–350 °C.     

Synthesis and performance of electroless Ni–P–TiCN composite coatings on Al substrate

Electroless Ni–P and Ni–P–TiCN composite coatings have been deposited successfully on Al substrates. Scanning electron microscopy (SEM) and energy dispersive X‐ray (EDX) techniques were applied to study the surface morphology and the chemical composition of the deposited films. Moreover, X‐ray diffraction (XRD) proved that Ni–P and Ni–P–TiCN deposits have amorphous structures. The properties of Ni–P–TiCN/Al composite films such as hardness, corrosion resistance and electrocatalytic activity were examined and compared with that of Ni–P/Al film. The results of hardness measurements reveal that the presence of TiCN particles with Ni–P matrix improves its hardness. Additionally, the performance against corrosion was examined using Tafel lines and electrochemical impedance spectroscopy techniques in both of 0.6 M NaCl and a mixture of 0.5 M H₂SO₄ with 2 ppm HF solutions. The results indicate that the incorporation of high dispersed TiCN particles into Ni–P matrix led to a positive shift of the corrosion potential and an increase in the corrosion resistance for all aluminum substrates after their coating with Ni–P–TiCN. In addition, Ni–P–TiCN/Al electrodes showed a higher electrochemical catalytic activity and stability toward methanol oxidation in 0.5 M NaOH solution compared with that of Ni–P/Al. Copyright © 2014 John Wiley & Sons, Ltd.     

Influence of surface properties on the interfacial adhesion in carbon fiber/epoxy composites

A polyacrylonitrile‐based carbon fiber was electrochemically oxidized in an aqueous ammonium bicarbonate solution with current density of up to 2.76 A/m² at room temperature. X‐ray photoelectron spectroscopy revealed that the oxygen content increased with increasing current density before approaching saturation. The increase can be divided into two regions, the rapid increase region (0–1.78 A/m²) and a plateau region (1.78–2.76 A/m²). The surface chemistry analysis showed that the interlaminar shear strength (ILSS) value of the carbon fiber/epoxy composite could be improved by 24.7%. The carbon structure was examined using Raman spectroscopy in terms of order/disorder in the graphite structure and the results indicated that the relative percentage of graphite carbon in the form of sp² hybridization increased above a current density of 1.39 A/m². The increasing non‐polar graphite carbon on the carbon fiber surface decreased the surface energy. As a result, both the surface free energy () and its polar component () decreased when current density increased above 1.78 A/m². The ILSS value had no direct relationship with the nature and surface density of the oxygen‐containing functional groups nor with the carbon structure. It is the surface free energy (), especially the polar component (), which played a critical role in affecting the interfacial adhesion of carbon fiber/epoxy composites. The ILSS value changed with increasing current density and could be divided into three distinct regions, as chemical interaction region (I), anchor force region (II) and matrix damage region (III). Copyright © 2013 John Wiley & Sons, Ltd.     

Nano-crystalline FeOOH mixed with SWNT matrix as a superior anode material for lithium batteries

Nano-crystalline FeOOH particles(5～10 nm) have been uniformly mixed with electric matrix of single-walled carbon nanotubes(SWNTs)for forming FeOOH/SWNT composite via a facile ultrasonication method. Directly using the FeOOH/SWNT composite(containing 15 wt%SWNTs) as anode material for lithium battery enhances kinetics of the Li+insertion/extraction processes, thereby effectively improving reversible capacity and cycle performance, which delivers a high reversible capacity of 758 mAh g-1under a current density of 400 mA g-1even after 180 cycles, being comparable with previous reports in terms of electrochemical performance for FeOOH anode. The good electrochemical performance should be ascribed to the small particle size and nano-crystalline of FeOOH, as well as the good electronic conductivity of SWNT matrix.     

A Ti3C2TX/Pt–Pd based amperometric biosensor for sensitive cancer biomarker detection

The detection of cancer biomarkers is of great significance for the early screening of cancer. Detecting the content of sarcosine in blood or urine has been considered to provide a basis for the diagnosis of prostate cancer. However, it still lacks simple, high-precision and wide-ranging sarcosine detection methods. In this work, a Ti₃C₂T_X/Pt–Pd nanocomposite with high stability and excellent electrochemical performance has been synthesized by a facile one-step alcohol reduction and then used on a glassy carbon electrode (GCE) with sarcosine oxidase (SO_x) to form a sarcosine biosensor (GCE/Ti₃C₂T_X/Pt–Pd/SO_x). The prominent electrocatalytic activity and biocompatibility of Ti₃C₂T_X/Pt–Pd enable the SO_x to be highly active and sensitive to sarcosine. Under the optimized conditions, the prepared biosensor has a wide linear detection range to sarcosine from 1 to 1000 µM with a low limit of detection of 0.16 µM (S/N = 3) and a sensitivity of 84.1 µA/mM cm². Besides, the reliable response in serum samples shows its potential in the early diagnosis of prostate cancer. More importantly, the successful construction and application of the amperometric biosensor based on Ti₃C₂T_X/Pt–Pd will provide a meaningful reference for detecting other cancer biomarkers.     

Vitamin D Inhibits the Early Aggregation of α-Synuclein and Modulates Exocytosis Revealed by Electrochemical Measurements

Alpha-synuclein (α-Syn) localizes at presynaptic terminal and modulates synaptic functions. Increasing evidence demonstrate that α-Syn oligomers, forming at the early of aggregation, are cytotoxic and is thus related to brain neurodegenerative diseases. Herein, we find that vitamin D (VD) can reduce neurocytotoxicity. The reduced neurocytotoxicity might be attributed to the less amount of large-sized α-Syn oligomers inhibited by VD, measured by electrochemical collision at single particle level, which are not observable with traditionally ensembled method. Single-cell amperometry (SCA) results show that VD can recover the amount of neurotransmitter release during exocytosis induced by α-Syn oligomers, further verifying the neuroprotection of VD. Our study reveals the neuroprotective role of VD through inhibiting α-Syn aggregation, which is envisioned to be of great importance in treatment and prevention of the neurodegenerative diseases.     

A Happy Get-Together – Probing Electrochemical Interfaces by Non-Linear Vibrational Spectroscopy

Electrochemical interfaces are key structures in energy storage and catalysis. Hence, a molecular understanding of the active sites at these interfaces, their solvation, the structure of adsorbates, and the formation of solid-electrolyte interfaces are crucial for an in-depth mechanistic understanding of their function. Vibrational sum-frequency generation (VSFG) spectroscopy has emerged as an operando spectroscopic technique to monitor complex electrochemical interfaces due to its intrinsic interface sensitivity and chemical specificity. Thus, this review discusses the happy get-together between VSFG spectroscopy and electrochemical interfaces. Methodological approaches for answering core issues associated with the behavior of adsorbates on electrodes, the structure of solvent adlayers, the transient formation of reaction intermediates, and the emergence of solid electrolyte interphase in battery research are assessed to provide a critical inventory of highly promising avenues to bring optical spectroscopy to use in modern material research in energy conversion and storage.     

Electrochemical Dehydrogenative C−H Aminomethylation of Imidazopyridines and Related Heterocycles

A facile and environmentally friendly electrochemical protocol is herein reported for the C(sp²)−C(sp³) cross dehydrogenative coupling between imidazopyridines and N,N-dimethylanilines. The broad functional group compatibility includes halogens, ester, alcohol, sulfone as well as thiophene. This methodology is also suitable for benzo[d]imidazo[2,1-b]thiazole, thiazoimidazole and tetrahydroisoquinoline, and can be scaled up to 5 mmol. Mechanistic insights are discussed.