Molecularly imprinted conducting polymer based electrochemical sensor for detection of atrazine

An original electrochemical sensor based on molecularly imprinted conducting polymer (MICP) is developed, which enables the recognition of a small pesticide target molecule, atrazine. The conjugated MICP, poly(3,4-ethylenedioxythiophene-co-thiophene-acetic acid), has been electrochemically synthesized onto a platinum electrode following two steps: (i) polymerization of comonomers in the presence of atrazine, already associated to the acetic acid substituent through hydrogen bonding, and (ii) removal of atrazine from the resulting polymer, which leaves the acetic acid substituents open for association with atrazine. The obtained sensing MICP is highly specific towards newly added atrazine and the recognition can be quantitatively analyzed by the variation of the cyclic voltammogram of MICP. The developed sensor shows remarkable properties: selectivity towards triazinic family, large range of detection (10⁻⁹ mol L⁻¹ to 1.5 × 10⁻² mol L⁻¹ in atrazine) and low detection threshold (10⁻⁷ mol L⁻¹).     

Synthesis and characterization of hybrid materials based on 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid and Dawson-type tungstophosphate K7[H4PW18O62]·18H2O and K6[P2W18O62]·13H2O

In this study, we synthesized hybrid materials using well-Dawson polyoxometalates (POMs), K₇[H₄PW₁₈O₆₂]·18H₂O or K₆[P₂W₁₈O₆₂]·13H₂O and a room temperature ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF₄]). K, W, P and CHN elemental analysis showed that one mole of [H₄PW₁₈O₆₂]⁷⁻ reacts with 6 moles of BMIM⁺ and one mole of [P₂W₁₈O₆₂]⁶⁻ reacts with 4 moles of BMIM⁺ to form, respectively, K[BMIM]₆H₄PW₁₈O₆₂ and K₂[BMIM]₄P₂W₁₈O₆₂. X-ray diffraction illustrated amorphous structure of the hybrid materials. FT-IR spectra showed the presence of both 1-butyl-3-methylimidazolium cation and the Dawson anion. TG analysis displayed a relative thermal stability of the hybrid materials compared to the parents Dawson POMs. Cyclic voltammetry showed that the reduction peak potentials of the Dawson anion in the hybrid materials shift towards negative values and the shift is more pronounced for K[BMIM]₆H₄PW₁₈O₆₂ compared to K₂[BMIM]₄P₂W₁₈O₆₂. This was attributed to a decrease in the acidity of the Dawson POM anion in the hybrid material.     

Graphene Oxide Doped Poly（hydroxymethylated-3,4- ethylenedioxythiophene）： Enhanced Sensitivity for Electrochemical Determination of Rutin and Ascorbic Acid

A novel graphene oxide doped poly(hydroxymethylated-3,4-ethylenedioxythiophene)(PEDOT-MeOH/GO) composite film was synthesized and utilized as an efficient electrode material for simultaneous detection of rutin and ascorbic acid(AA). PEDOT-MeOH/GO films were synthesized on glassy carbon electrode(GCE) by a facile one-step electrochemical approach and were characterized by scanning electron microscopy, UV-Vis spectroscopy, FTIR spectra and electrochemical methods. Then the PEDOT-MeOH/GO/GCE was applied successfully in the simultaneous detection of rutin and AA. The results showed that the oxidation peak currents of rutin and AA obtained at the PEDOT-MeOH/GO/GCE were much higher than those at the traditional conducting polymer PEDOT/GO/GCE, PEDOT-MeOH/GCE, PEDOT/GCE and bare GCE. Under optimized conditions, the linear ranges for rutin and AA are 20 nmol/L-10 μmol/L and 8 μmol/L-1 mmol/L, respectively. The detection limit is 6 nmol/L for rutin and 2 μmol/L for AA(S/N = 3), which are lower than those of the reported electrochemical sensors.     

An Effective Approach for the Silylation of Hydroxyl Compounds in Room Temperature Ionic Liquids

Abstract

The room temperature ionic liquid (RTIL) 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMImPF₆) is used as a “green” recyclable alternative to conventional solvents for the silylation of a series of hydroxyl compounds (alcohols and phenols) with t-butyldimethylchlorosilane (TBDMCS), which has some advantages such as simplicity of the synthetic procedure, the potential for recycling of the ionic liquid and the environmentally benign.     

室温离子液体电化学稳定性的研究

随着绿色化学的发展,人们对室温离子液体(RTIL)的研究已日益备受重视,较早发现的如由二烷基咪唑正离子(EMI^ )和氯化铝负配离子(A1Cl4^-)组成的离子液体(氯化铝类离子液体),具有许多优良的物理化学性质,如电导率高,在高温下仍有很低的蒸汽压,电化学稳定性好(即有宽阔的电化学窗口),     

Electrochemical polymerization of 1-(4-nitrophenyl)-2,5-di(2-thienyl)-1 H-pyrrole as a novel immobilization platform for microbial sensing

Two types of bacterial biosensor were constructed by immobilization of Gluconobacter oxydans and Pseudomonas fluorescens cells on graphite electrodes modified with the conducting polymer; poly(1-(4-nitrophenyl)-2,5-di(2-thienyl)-1 H-pyrrole) [SNS(NO₂)]. The measurement was based on the respiratory activity of cells estimated by the oxygen consumption at − 0.7 V due to the metabolic activity in the presence of substrate. As well as analytical characterization, the linear detection ranges, effects of electropolymerization time, pH and cell amount were examined by using glucose as the substrate. The linear relationships were observed in the range of 0.25–4.0 mM and 0.2–1.0 mM for G. oxydans and P. fluorescens based sensors, respectively.     

室温离子液体电解液中尖晶石LiMn_2O_4的电化学性质

应用循环伏安、恒电流充放电和电化学阻抗技术研究了尖晶石L iMn2O4于室温离子液体电解液中的电化学性质.实验表明,以室温离子液体作电解液,L iMn2O4的首次放电容量可达108.2 mAh/g、循环效率高于90%,温度和电流密度显著影响电极的电化学性能.交流阻抗测定了L i+在电极/电解液相界面迁移的活化能,为55 kJ/mol.根据界面反应的高活化能解释了L iMn2O4在该离子液体电解液中低温性能和倍率充放电性能不佳的原因.     

离子液基萃取金属离子的研究进展

室温离子液体作为一种新型绿色溶剂,因其具有不挥发、不易燃等重要特性,故近年来在各种金属离子液/液萃取领域的应用日益受到关注。本文系统评述了离子液基萃取金属离子的分配规律、萃取机理、缺陷和克服方法,并展望了该分离方法在环境分析化学领域的应用前景。     

Study of electrochemical stability of conducting polymers by bidimensional spectroelectrochemistry: p- and n-doping of poly(4,4′-bis(butylthio)-2,2′-bithiophene) films

UV-vis bidimensional spectroelectrochemistry has been applied to the study of the electrochemical stability of conducting polymer films during p- and n-doping processes. Specifically, poly(4,4′-bis(butylthio)-2,2′-bithiophene) has been chosen as example to prove the usefulness and suitability of this multi-response technique to characterize polymer stability during p- and n-doping. It was found that oxidative doping and corresponding de-doping alone did not result in noticeable polymer film degradation. However, in experiments involving both p- and n-doping of this conducting polymer, soluble species arising from the polymer film were detected in solution for the first time, indicating a lower electrochemical stability of the film under these experimental conditions. Moreover, bidimensional spectroelectrochemistry has enabled us not only to detect the soluble degradation products, but also the potential range in which the degradation takes place.     

基于室温离子液体的活化石墨烯粉末超级电容储能性能

室温离子液体(RTILs)具有电压窗口高等优点,被认为是实现超级电容高性能储能的绿色电解液。但是,离子液体的电导率低、粘度高,使得其储能性能不佳。本文探究了溶剂效应对离子液体超级电容储能性能的影响。以石墨烯粉末为活性材料,选取1-丁基-3-甲基咪唑四氟硼酸盐为离子液体,通过添加乙腈溶剂配置了具有不同摩尔分数ρIL的电解液(从0.25到1.0)。结果表明,溶剂效应对超级电容性能的影响与电压扫描速率或电流密度密切相关。低扫描速率下,溶剂对储能基本没有影响,而高扫描速率下,添加溶剂可显著提升比电容(在ρIL=0.25时,增加~2倍)。这是由于溶剂削弱了离子-离子间交互作用,从而降低了电解液粘度(~29倍),内阻(~5.5倍)和介电弛豫时间(~6.3倍)。在ρIL=0.25时,超级电容最大能量和功率密度分别为65.2 Wh·kg~(-1)和18066.6 W·kg~(-1),显著优于近期文献报道结果。特别地,当工作温度提升到50°C时,其能量密度将达到85.5 Wh·kg~(-1),显著高于传统水系、有机电解液超级电容和铅酸电池,与镍金属氢化物和锂离子电池性能相当。     

Effective and Functional Surface Design for Biosensing Applications Based on a Novel Conducting Polymer and PMMA/Clay Nanocomposite

Surface functionalization plays a crucial role in the design of biosensors. For this purpose, a novel functional monomer, 6‐(4,7‐bis(2,3‐dihydrothieno[3,4‐b][1,4]dioxin‐5‐yl)‐2H‐benzo[d][1,2,3]triazol‐2‐yl)hexan‐1‐amine (BEDOA‐6), was designed and synthesized. Poly(BEDOA‐6) was utilized as an immobilization matrix for glucose oxidase biosensor construction. Moreover, polymethylmethacrylate (PMMA) layered silicate nanocomposites were prepared by in situ suspension polymerization. Conducting polymer surface was modified with PMMA/clay nanocomposite material and a glucose biosensor was developed. In addition, XPS and SEM were utilized to characterize the surface properties. The biosensor shows a wide linear range between 2.8 µM and 1.2 mM to glucose with a low detection limit of 1.99 µM. Finally, the biosensor was tested on serum samples containing actual human blood. The results were in well‐agreement with a reference method.     

Room temperature imidazolium ionic liquid: a solvent for extraction of carbamates prior to liquid chromatographic analysis

A simple and rapid method for preconcentration of carbamate insecticides, including methomyl, propoxur, carbofuran, carbaryl, isoprocarb, methiocarb and promecarb, has been developed. It was based on a liquid-liquid microextraction using a [C₄MIM][PF₆] room temperature ionic liquid as an extraction solvent prior to analysis by high performance liquid chromatography with UV detection. Experimental parameters affecting the extraction performance, such as the volumes of sample, extractant and dissolving solvent, and extraction time, were studied. Under the selected conditions, the enrichment factors in the range between 10 and 25 could be achieved with the limit of detection in the range of 2-40 μg L⁻¹, and with the relative standard deviations of lower than 0.6 and 10.2% for retention time and peak area, respectively. The proposed method offers advantages in reduction of the exposure danger to toxic solvents used in the conventional liquid-liquid extraction, simplicity of the extraction processes, rapidity, and sensitivity enhancement. The method was demonstrated to apply to the analysis of fruit and natural surface water samples.     

Ti3C2Tx MXene compounds for electrochemical energy storage

Since their discovery in 2011, MXene compounds, and in particular the Ti₃C₂-based phases, have gained increasing interest from researchers leading to over 2000 scientific works in 2020. The peculiar morphological, charge transport, and surface properties make the MXenes ideal materials for energy storage applications such as active material in alkaline ion batteries and supercapacitors, as conductive or buffer agent in composite electrodes for high energy applications, and as electrocatalytic materials for oxygen evolution or redox flow batteries. Among this almost endless literature, this work focuses on 5 recent articles (2019/2020) that summarize the potential of MXenes in different energy storage applications, also resuming the most promising preparatory routes regarding industrial scalability.     

Side-chain liquid crystalline polyesters for optical information storage

Azobenzene side-chain liquid crystalline polyester structures suitable for permanent optical storage are described. The synthesis and characterization of the polyesters together with differential scanning calorimetry and X-ray investigations are discussed. Optical anisotropic investigations and holographic storage in one particular polyester are described in detail and polarized Fourier transform infrared spectroscopic data complementing the optical data are presented. Optical and atomic force microscope investigations point to a laser-induced aggregation as responsible for permanent optical storage.     

Facile ordered ZnCo2O4@MnO2 nanosheet arrays for superior-performance supercapacitor electrode

Constructing ZnCo₂O₄ nanosheet arrays (NSAs)@MnO₂ nanosheets core-shell nanostructures directly on the current collector (Ni foam) was successfully realized via hydrothermal process and heat treatment. The whole surfaces of uniform ZnCo₂O₄ NSAs were covered with well-ordered MnO₂ nanosheets, which make the whole system have a large specific surface area. At a low current density of 2 mA cm⁻², supercapacitor electrode made of ZnCo₂O₄@MnO₂ composite gave rise to a superior specific capacity about 929.2 C g⁻¹. Although at an ultrahigh current density of 40 mA cm⁻², it still kept a satisfactory specific capacity about 751.1 C g⁻¹, and retained ∼95.75% of the capacity even after 5000 cycles. Because of the synergistic effect between ZnCo₂O₄ and MnO₂ and the great surface area of the system with the special core-shell structure, ZnCo₂O₄@MnO₂ composite has the excellent rate performance, considerable capacity, and quite good cycle performance, which make it a candidate for a new generation of superior-performance electrochemical supercapacitors.     

电化学方法研究贮氢电极合金的P—C—T曲线

根据电化学和热力学的基础理论,考虑了氢气的逸度、碱液中水的活度以及碱液中水蒸汽的分压等影响因素,精确计算了金属氢化物电极反应的能斯特方程。结合三电极测试体系,建立了一套贮氢电极合金的P-C-T曲线电化学测定方法,并给出实验操作及相关参数确定的细节。该方法适用于涉及到大量实验工作的贮氢电极合金的成分优化及工艺研究。     

Determination of Gold(III) by Simplified Room-Temperature Ionic Liquid Extraction with Flame Atomic Absorption Spectrometry

A new simplified extraction of gold(III) using a room-temperature ionic liquid prior to determination by flame atomic absorption spectrometry has been developed. The extraction method uses 1-butyl-3-methylimidazolium hexafluorophosphate without a chelating agent. The parameters of the extraction system were investigated in detail. Under the optimized conditions, a linear range of 0.19 to 38.20 µg · mL^?1, a limit of detection of 0.072 µg · mL^?1, an enrichment factor of 10.0, and an extraction capacity of 6.6 mg · g^?1 were obtained. The extraction mechanism and the selectivity of 1-butyl-3-methylimidazolium hexafluorophosphate for gold(III) were also investigated. The method was applied for the determination of gold(III) in water samples with satisfactory results.     

Research on electrochemical properties of nonaqueous ionic liquid microemulsions

The nonaqueous ionic liquid (IL) microemulsions composed of 1-butyl-3-methylimidazolium tetrafluoroborate, Triton X-100, and toluene were prepared and the electrochemical properties of the nonaqueous IL microemulsions were investigated in this paper. It is shown that characteristics of the nonaqueous IL microemulsions such as electrical conductivity, electrochemical window, and solubility are good, which indicate that the nonaqueous IL microemulsions can be used as electrolyte for electrochemical research. The electrochemical properties of the nonaqueous IL microemulsions were researched by cyclic voltammetry (CV) and electrochemical impedance spectroscopy methods using potassium ferricyanide as electroactive probe. It was found that the reversibility was better and the peak current densities of CV were higher for the [Fe(CN)₆]³⁻/[Fe(CN)₆]⁴⁻ electrode reaction in the nonaqueous IL microemulsions than those in IL. However, the electrochemical behavior of the probe in the nonaqueous IL microemulsions with different microenvironments (oil-in-IL, IL-in-oil, and bicontinuous) was different. The electrochemical property of the probe in the oil-in-IL microemulsion was the best, which was studied in detail.     

Porous SnO2/layered titanate nanohybrid with enhanced electrochemical performance for reversible lithium storage

A porous hybrid of titanate nanosheets with SnO(2) nanoparticles has been realized by an exfoliation and reassembling route. The present nanohybrid shows a large reversible capacity of 860 mA h g(-1) with a good capacity retention (about 60% retention of the initial capacity after 50 cycles).     

Effect of LiH on electrochemical hydrogen storage properties of Ti55V10Ni35 quasicrystal

The electrochemical hydrogen storage properties and mechanisms of the Ti₅₅V₁₀Ni₃₅ quasicrystal + xLiH(x = 3, 6 and 9 wt.%) system are investigated and discussed in this paper. A composite material in the Ti₅₅V₁₀Ni₃₅ quasicrystal and system has been synthesized moderately by means of mechanical milling under an argon atmosphere, which can avoid reaction of releasing of hydrogen during the process of milling. The results indicate that the addition of LiH significantly improves the electrochemical characteristics of composite material. The maximum discharge capacity increases from 220.1 mAh/g to 292.3 mAh/g on Ti₅₅V₁₀Ni₃₅ + 6 wt.% LiH, and the cycling stability is also enhanced too. In addition, the high rate dischargeability (HRD) is ameliorated remarkably, and the value of HRD value at 240 mA/g rises by 78.1%–87.8% for Ti₅₅V₁₀Ni₃₅ + 6 wt.% LiH alloy electrodes. The improvement of characteristics of the electrochemical hydrogen storage characteristics may be attributed to LiH, which has excellent electrochemical activity.