Fabrication and Electrochemical Behavior of Hemoglobin Modified Carbon Ionic Liquid Electrode

A new hemoglobin (Hb) and room temperature ionic liquid modified carbon paste electrode was constructed by mixing Hb with 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIMPF₆) and graphite powder together. The Hb modified carbon ionic liquid electrode (Hb‐CILE) was further characterized by FT‐IR spectra, scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). Hb in the carbon ionic liquid electrode remained its natural structure and showed good direct electrochemical behaviors. A pair of well‐defined quasireversible redox peaks appeared with the apparent standard potential (E′) as ?0.334 (vs. SCE) in pH 7.0 phosphate buffer solution (PBS). The electrochemical parameters such as the electron transfer number (n), the electron transfer coefficient (α) and the heterogeneous electron transfer kinetic constant (k_s) of the electrode reaction were calculated with the results as 1.2, 0.465 and 0.434 s^?1, respectively. The fabricated Hb‐CILE exhibited excellent electrocatalytic activity to the reduction of H₂O₂. The calibration range for H₂O₂ quantitation was between 8.0×10^?6 mol/L and 2.8×10^?4 mol/L with the linear regression equation as I_ss (μA)=0.12 C (μmol/L)+0.73 (n=18, γ=0.997) and the detection limit as 1.0×10^?6 mol/L (3σ). The apparent Michaelis–Menten constant (K_M^app) of Hb in the modified electrode was estimated to be 1.103 mmol/L. The surface of this electrochemical sensor can be renewed by a simple polishing step and showed good reproducibility.     

Direct Electrochemistry of Myoglobin in a Nafion‐Ionic Liquid Composite Film Modified Carbon Ionic Liquid Electrode

In this paper two kinds of ionic liquids (ILs) were used for the construction of a myoglobin (Mb) electrochemical biosensor. Firstly a hydrophilic ionic liquid of 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIMBF₄) was used as binder to prepare a carbon ionic liquid electrode (CILE), then a Nafion and hydrophobic ionic liquid of 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIMPF₆) composite film was applied on the surface of the CILE. The direct electrochemistry of Mb in the Nafion‐BMIMPF₆/CILE was achieved with the cathodic and anodic peak potentials located at ?0.345 V and ?0.213 V (vs. SCE). The formal potential (E°′) was located at ?0.279 V, which was the characteristic of Mb Fe^III/Fe^II redox couples. The electrochemical behaviors of Mb in the Nafion‐ionic liquid composite film modified CILE were carefully investigated. The Mb modified electrode showed good electrocatalytic behaviors to the reduction of trichloroacetic acid (TCA) and NaNO₂. Based on the Nafion‐BMIMPF₆/Mb/CILE, a new third generation reagentless biosensor was constructed.     

Electrochemistry and Electrocatalysis of a Nafion/Nano‐CaCO3/Hb Film Modified Carbon Ionic Liquid Electrode Using BMIMPF6 as Binder

In this paper a room temperature ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIMPF₆) was used as binder for the construction of carbon ionic liquid electrode (CILE) and a new electrochemical biosensor was developed for determination of H₂O₂ by immobilization of hemoglobin (Hb) in the composite film of Nafion/nano‐CaCO₃ on the surface of CILE. The Hb modified electrode showed a pair of well‐defined, quasi‐reversible redox peaks with E_pa and E_pc as ?0.265 V and ?0.470 V (vs. SCE). The formal potential (E°′) was got by the midpoint of E_pa and E_pc as ?0.368 V, which was the characteristic of Hb Fe(III)/Fe(II) redox couples. The peak to peak separation was 205 mV in pH 7.0 Britton–Robinson (B–R) buffer solution at the scan rate of 100 mV/s. The direct electrochemistry of Hb in the film was carefully investigated and the electrochemical parameters of Hb on the modified electrode were calculated as α=0.487 and k_s=0.128 s^?1. The Nafion/nano‐CaCO₃/Hb film electrode showed good electrocatalysis to the reduction of H₂O₂ in the linear range from 8.0 to 240.0 μmol/L and the detection limit as 5.0 μmol/L (3σ). The apparent Michaelis–Menten constant (K_M^app) was estimated to be 65.7 μmol/L. UV‐vis absorption spectroscopy and FT‐IR spectroscopy showed that Hb in the Nafion/nano‐CaCO₃ composite film could retain its native structure.     

Studies on Liquid/liquid Extraction of Copper Ion with Room Temperature Ionic Liquid

Room temperature ionic liquids are regarded as “Green solvents” for their nonvolatile and thermally stable properties. They are employed to replace traditional volatile organic solvents in organic synthesis, solvent extraction, and electrochemistry. In this work, a water immiscible room temperature ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate [C₄mim][PF₆], was used as an alternative solvent for liquid/liquid extraction of copper ions. Metal chelators, including dithizone, 8‐hydroxyquinoline, and 1‐(2‐pyridylazo)‐2‐naphthol, were employed to form neutral metal‐chelate complexes with copper ions so that copper ions were extracted from aqueous solution into [C₄mim][PF₆]. The parameters that affect the extraction of copper ions with this biphasic system were investigated. The extraction behavior in this novel biphasic system is shown to be consistent with that of traditional solvents. For example, the extraction with this biphasic system is strongly pH dependent. So, the extraction efficiency of coppers ion from an aqueous phase can be manipulated by tailoring the pH value of the extraction system. Hence, the extraction, separation and preconcentraction of copper ions can be accomplished by controlling the pH value of the extraction system. It appears that the use of ionic liquid as an alternate solvent system in liquid/liquid extraction of copper ions is very promising.     

Direct Electrochemistry of Hemoglobin on Single‐Walled Carbon Nanotubes Modified Carbon Ionic Liquid Electrode and Its Electrocatalysis

In this article we report on the fabrication of a carbon ionic liquid electrode (CILE) by using a room temperature ionic liquid of 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIMPF₆) as binder. It was further modified by single‐walled carbon nanotubes (SWCNTs) to get a SWCNTs modified CILE denoted as SWCNTs/CILE. The redox protein of hemoglobin (Hb) was further immobilized on the surface of SWCNTs/CILE with the help of Nafion film. UV‐vis and FT‐IR spectra indicated that the immobilized Hb retained its native conformation in the composite film. The direct electrochemistry of Hb on the SWCNTs/CILE was carefully studied in pH 7.0 phosphate buffer solution (PBS). Cyclic voltammetric results indicated that a pair of well‐defined and quasireversible voltammetric peaks of Hb heme Fe(III)/Fe(II) was obtained with the formal potential (E°') at ?0.306 V (vs. SCE). The electrochemical parameters such as the electron transfer coefficient (α), the electron transfer number (n) and the apparent heterogeneous electron transfer rate constant (k_s) were calculated as 0.34, 0.989 and 0.538 s^?1, respectively. The fabricated Hb modified electrode showed good electrocatalytic ability to the reduction of trichloroacetic acid (TCA) in the concentration range from 20.0 to 150.0 mmol/L with the detection limit of 10.0 mmol/L (3σ).     

A Cryptate Reference Electrode for Ionic Liquids

The cryptate electrode (Ag/Ag⁺222), prepared by immersing silver wire in a solution of silver(I) salt and the cryptand 222 (4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane) in ionic liquids have been studied. The potential of the electrode is stabilized by the equilibrium of the Ag⁺ ion complexation by the cryptand, similarly to the potential stabilization by the ionic product of slightly soluble salts, used in aqueous electrodes of the second kind. The Ag/Ag⁺222 cryptate electrode (concentration of the cryptate was much higher than the silver(I) cation concentration, [222]>[Ag⁺]) may be used as a reference electrode in room temperature ionic liquids. The potential of the Ag/Ag⁺222 electrode is less sensitive to the presence of impurities, such as halides or water, in comparison to the Ag/Ag⁺ electrode. After anodic or cathodic polarization, the potential of the Ag/Ag⁺222 electrode comes back to the initial open circuit potential quickly. Preparation of the Ag/Ag⁺222 reference electrode is very easy: a silver wire is immersed in a solution of Ag⁺ salt and cryptand 222 (both available commercially) in the ionic liquid under study.     

Optical and Bioelectrochemical Characterization of Water‐Miscible Ionic Liquids Based Composites of Multiwalled Carbon Nanotubes

Acidic treated multiwalled carbon nanotubes (AMWNTs) were ground with water‐miscible room temperature ionic liquids, 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([bmim]BF₄), and resulted in AMWNTs‐[bmim]BF₄ composite. Its electrical‐ionic conductivity and optical properties were compared with the other two types of carbon materials‐[bmim]BF₄ composites: pyrolytic graphite powder (PGP), pristine multiwalled carbon nanotubes (PMWNTs), through the ac impedance technology and Raman spectroscopy. The impedance data show that AMWNTs‐[bmim]BF₄ composite exhibits the highest conductivity. Raman spectra study exhibits that the [bmim]BF₄ can form gel with PMWNTs and AMWNTs but only form a viscous liquid with PGP. AMWNTs‐[bmim]BF₄ gel modified GC electrode was applied in direct electrochemistry of heme proteins (Hb and HRP) and it catalysis to the reduction of H₂O₂ was investigated.     

Electrocatalysis of Hemoglobin in ZnO Nanoparticle/Ionic Liquid Composite Film Modified Glassy Carbon Electrode

A nanobiocompatible composite containing hemoglobin (Hb), ZnO nanoparticles (nano‐ZnO) and ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIMPF₆) was fabricated and further modified on the glassy carbon electrode (GCE). The electrochemical behaviours of Hb in the composite film were carefully studied and a pair of quasi‐reversible redox peaks appeared in pH 7.0 phosphate buffer solution, which was attributed to the electrode reaction of Hb heme Fe(III)/Fe(II) redox couple. The presences of nano‐ZnO and BMIMPF₆ in the film can retain the bioactivity of Hb and greatly enhance the direct electron transfer of Hb. The immobilized Hb showed high stability and good electrocatalytic ability to the reduction of hydrogen peroxide and O₂.     

血红蛋白在离子液体[BMIM]PF6碳糊电极上的直接电化学

制备了离子液体[BMIM]PF6修饰碳糊电极(CILE), 并对其形貌和电化学行为进行了表征. 采用涂布法利用壳聚糖-皂土有机-无机复合膜将血红蛋白(Hb)固定于CILE电极表面, 利用紫外可见光谱、红外光谱和电化学方法等手段对包埋于膜内的Hb的性质进行了表征. 结果表明, Hb在薄膜内保持了其原始构象与生物活性, 循环伏安实验表明, 在pH=7.0的Britton-Robinson (B-R)缓冲液中, Hb表现出一对峰形良好的准可逆氧化还原峰, 为Hb Fe(III)/Fe(II)电对的特征峰, 对其直接电化学行为进行了研究, 求出式电位为-0.352 V(vs SCE), 电子转移数为0.885, 电荷传递系数为0.578, 表观异相电子转移速率常数为0.149 s-1.     

A Detailed Study of the (Electro)chemical Behavior of Bis(trifluoromethanesulfonyl)imide Based Ionic Liquids at Different Purification Steps

A systematic investigation of the major impurities content as well as of their effect on the electrochemical behavior of synthesized N‐butyl‐N‐methylpyrrolidinium (Py_1.4), N‐(2‐methoxyethyl)‐N‐methylpyrrolidinium (Py_1.102) and 1‐butyl‐3‐methylimidazolium (bmim) bis(trifluoromethanesulfonyl)imide has been carried out and the efficacy of an optimized multistep purification protocol for obtaining ILs suitable for electrochemical applications has been verified.     

A Fast and Highly Efficient Protocol for Reductive Amination of Aromatic Aldehydes Using NaBH4 and Isoxazole Amines in an Ionic Liquid Medium

Reductive amination of aromatic aldehydes using NaBH₄ and isoxazole amines is carried out in a Brønsted acidic ionic liquid 1‐methylimidazolium tetrafluoroborate [(HMIm)BF₄]. The ionic liquid plays dual roles of solvent as well as catalyst for the efficient transformation of aromatic aldehydes to heterocyclic substituted amines in excellent yields without any undesired side product formation. The newly synthesized compounds ( 3 , 6 and 7 ) were characterized by IR, ¹H NMR and mass spectral techniques.     

离子液体中硫氰根在铂电极上吸附行为的SERS研究

利用表面增强拉曼光谱(SERS)研究了室温离子液体1-丁基-3-甲基咪唑氟硼酸盐([BMIM]BF4)中SCN-在Pt电极表面的吸附行为. 研究结果表明, 离子液体中SCN-在较宽的电位范围内吸附在Pt电极上, 且SCN-的吸附方式随着电位区间的变化而变化, 在不同的电位区间内检测到了不同的Stark位移: -0.9~0.4 V约为34 cm-1/V, 对应于S端吸附; -1.6~-1.2 V约为40 cm-1/V, 该区间以N端吸附为主, 中间电位区间为吸附方式的转变区, 且Pt电极在离子液体[BMIM]BF4中的零电荷电位约为-1.1 V(vs. Pt ).     

Direct Electrochemistry and Electrocatalysis of Myoglobin with Ionic Liquid through Multilayers Film on Carbon Ionic Liquid Electrode

Multilayers of myoglobin (Mb) with ionic liquid 1‐ethyl‐3‐methylimidazolium tetrafluoroborate ([EMIM]BF₄) was assembled on carbon ionic liquid electrode (CILE) based on the electrostatic attraction between the negatively charged Mb and the positively charged imidazolium ion of IL. The CILE was fabricated with 1‐ethyl‐3‐methylimidazolium ethylsulfate ([EMIM]EtOSO₃) as the modifier, which exhibited imidazolium ion on the electrode surface. Then Mb molecules were assembled on the surface of CILE step‐by‐step to get a {IL/Mb}_n multilayer film modified electrode. UV‐Vis adsorption and FT‐IR spectra indicated that Mb remained its native structure in the IL matrix. In deaerated phosphate buffer solution (pH 7.0) a pair of well‐defined quasi‐reversible redox peaks appeared with the apparent formal potential (E^0′) as ‐0.212 V (vs. SCE), which was the characteristic of Mb heme Fe(III)/Fe(II) redox couples. The results indicated that the direct electron transfer of Mb was realized on the modified electrode. The {IL/Mb}_n/CILE displayed excellent electrocatalytic ability to the trichloroacetic acid reduction in the concentration range from 2.0 to 22.0 mmol/L with the detection limit of 0.6 mmol/L (3σ). The proposed method provides a new platform to fabricate the third generation biosensor based on the self‐assembly of redox protein with ILs.     

Electrochemical Determination of Ascorbic Acid in Room Temperature Ionic Liquid BPPF6 Modified Carbon Paste Electrode

A room temperature ionic liquid N‐butylpyridinium hexafluorophosphate (BPPF₆) was used as a binder to make an ionic liquid modified carbon paste electrode (IL‐CPE), which showed good characteristics such as simple preparation procedure, fast electrochemical response and good conductivity. The electrochemical oxidation of ascorbic acid (AA) on the new IL‐CPE was carefully studied. The oxidation peak potential of AA on the IL‐CPE appeared at 109 mV (vs. SCE), which was about 338 mV decrease of the overpotential compared to that obtained on the traditional carbon paste electrode (CPE) and the oxidation peak current was increased for about four times. The electrochemical parameters of AA on the IL‐CPE were calculated with the charge transfer coefficient (α) and the electrode reaction rate constant (k_s) as 0.87 and 0.800 s^?1, respectively. Based on the relationship of the oxidation peak current and the concentration of AA a sensitive analytical method was established with cyclic voltammetry. The linear range for AA determination was in the range from 1.0×10^?5 to 3.0×10^?3 mol/L with the linear regression equation as I_p (μA)=?2.52–0.064C (μmol/L) (n=13, γ=0.9942) and the detection limit was calculated as 8.0×10^?6 mol/L (3σ). The proposed method was free of the interferences of coexisting substances such as dopamine (DA) and amino acids etc., and successfully applied to the vitamin C tablets determination.     

The Electrochemistry of Vitamin B12 in Ionic Liquids and Its Use in the Electrocatalytic Reduction of Vicinal Dibromoalkanes

We present the first electrochemical study in ionic liquid media of cyanocobalamin (vitamin B₁₂), a biologically important molecule, and show its suitability as catalyst in the electroreduction of dibromoalkanes.     

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.     

季铵盐型离子液体中全氟烷基磺酰亚胺盐催化的芳烃硝化反应

全氟烷基磺酰亚胺盐与季铵型离子液体（Cu(N(C4F9SO2)2)2/[N4446][NTf2] 或 In(NTf2)3/[N4446][NTf2]）组成的新催化体系,可以很好的催化芳香族化合物的硝化反应。以氯苯的硝化为例,用硝酸和醋酸酐混合物为硝化试剂,在2mol%的Cu(N(C4F9SO2)2)2或In(NTf2)3催化剂催化下,室温下反应10分钟,氯苯的转化率就可分别达到87.6% 和 90.6%,反应产物的邻/对位比为4.3和4.8。并且这种催化剂与离子液体组成的催化体系很容易被回收,并可以连续使用5次以上。     

Ionic liquid as extraction agent for detection of volatile phenols in wastewater and its regeneration

Volatile phenols in the wastewater provide a basic parameter of the pollution. Spectrophotometric method based on the reactions of the individual phenols with 4‐aminoantipyrine in the presence of an oxidizing agent is the current official analytical method in many countries. In this paper, we propose a method for extracting the resultant colored dye with ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate instead of chloroform. The results revealed excellent extraction efficiency, and the used ionic liquid could be regenerated easily. The method with small volume green reagent could be potentially applied in portable devices for in situ environmental analysis.     

Determination of phenols in environmental water samples by ionic liquid-based headspace liquid-phase microextraction coupled with high-performance liquid chromatography

Headspace liquid-phase microextraction (HS-LPME) has been applied to efficient enrichment of phenols such as 2-nitrophenol, 4-chlorophenol, 2,4-dichlorophenol, and 2-naphthol from water samples based on 1-butyl-3-methylimidazolium hexafluorophosphate ([C4MIM][PF6]) as an extractant. Some parameters that may influence HS-LPME were investigated. The linear range was in the range of 0.5-100 microg/L, and the enrichment factors and repeatability (RSD, n = 6) of the proposed method were in the range of 17.2-160.7 and 5.4-8.9%, respectively. The detection limit for each analyte ranged from 0.3 to 0.5 microg/L. Complex matrices of environmental water samples had a small effect on the enrichment, and this problem could be resolved by the addition of sodium ethylene diamine tetraacetate (EDTA) into the samples. The spiked recoveries were in the range of 89.4-114.2%. All these facts demonstrated that the proposed method, with merits of low cost, simplicity, and easy operation, would be a competitive alternative procedure for the determination of such compounds at trace level.