A novel hydrogen peroxide sensor based on the redox of ferrocene on room temperature ionic liquid film

A novel sensor was constructed based on the catalytic activity of ferrocene (Fc) that was immobilized on a room temperature ionic liquids (RTILs), 1-ethyl-3-methyl imidazolium tetrafluoroborate ([EMIM][BF₄]), film. Electrochemical behavior of ferrocene was investigated by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). A pair of stable, well-defined and quasi-reversible redox peak of ferrocene could be obtained at pH 7.0 phosphate buffer. Further investigations reveal that both anodic and cathodic peak currents of ferrocene vary linearly with the concentration of hydrogen peroxide (H₂O₂). Based on this, a new sensor for the measurement of H₂O₂ can be fabricated facilely. This sensor allowed us to measure H₂O₂ by polarizing the electrode under ether anodic or cathodic potential with an excellent stability and anti-interfering ability.     

Nonenzymatic hydrogen peroxide sensor based on a glassy carbon electrode modified with electrospun PdO-NiO composite nanofibers

A glassy carbon electrode was modified with PdO-NiO composite nanofibers (PdO-NiO-NFs) and applied to the electrocatalytic reduction of hydrogen peroxide (H₂O₂). The PdO-NiO-NFs were synthesized by electrospinning and subsequent thermal treatment, and then characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. Factors such as the composition and fraction of nanofibers, and of the applied potential were also studied. The sensor exhibits high sensitivity for H₂O₂ (583.43 μA?·?mM^?1?·?cm^?2), a wide linear range (from 5.0 μM to 19 mM), a low detection limit (2.94 μM at an SNR of 3), good long term stability, and is resistant to fouling.

Nonenzymatic glucose voltammetric sensor based on gold nanoparticles/carbon nanotubes/ionic liquid nanocomposite

In this paper, a novel nonenzymatic glucose voltammetric sensor based on a kind of nanocomposite of gold nanoparticles (GNPs) embedded in multi-walled carbon nanotubes (MWCNTs)/ionic liquid (IL) gel was reported. The surface morphology of this nanocomposite was characterized using X-ray photoelectron spectrometer (XPS), scanning electron microscope (SEM) and transmission electron microscope (TEM), respectively. It can be found that most of GNPs lie close to the ektexine of MWCNTs and the others have obviously inserted the inner of MWCNTs through the defects or ends of MWCNTs, due to the attraction between GNPs and MWCNTs as well as the repulsion between GNPs and IL. Voltammetry was used to evaluate the electrocatalytic activities of the nanocomposite biosensor toward nonenzymatic glucose oxidation in alkaline media. The GNPs embedded in MWCNTs/IL gel have strong and sensitive voltammetric responses to glucose, owing to a possible synergistic effect among GNPs, MWCNTs and IL. Under the optimal condition, the linear range for the detection of the glucose is 5.0-120 μM with the correlation coefficient of 0.998, based on the oxidation peak observed during cathodic direction of the potential sweep. The kinetics and mechanism of glucose electro-oxidation were intensively investigated in this system. This kind of nanocomposite biosensor is also highly resistant toward poisoning by chloride ions and capable of sensing glucose oxidation in the presence of 20 μM uric acid and 70 μM ascorbic acid. This work provides a simple and easy approach to the detection of glucose in body fluid with high sensitivity and excellent selectivity.     

基于室温离子液体的电导型气体传感器

本文利用室温离子液体对水或有机蒸气吸收后其离子导电性的改变,研制了以离子液体BmimPF6为敏感材料的电导型气体传感器.考查了BmimPF6用量对传感器响应的影响,测定了传感器对不同浓度的水蒸汽及乙醇、二氯甲烷等饱和有机蒸气的响应.实验结果显示,该传感器具有制作方便、结构简单、稳定性高及线性范围宽等优点,可被用于不同浓度的水或有机蒸气/氮气混合气氛中,水蒸汽或有机蒸气浓度的测定.此外,还针对该传感器对乙醇等不同饱和有机蒸气响应信号与这些有机溶剂的理化性质参数间的定量关系,采用化学计量学方法进行了建模分析.     

Nonenzymatic sensor for hydrogen peroxide based on the electrodeposition of silver nanoparticles on poly(ionic liquid)-stabilized graphene sheets

We have developed a nonenzymatic sensor for hydrogen peroxide (HP) that is based on a new kind of nanocomposite consisting of silver nanoparticles (AgNPs) electrodeposited on a basic film of a poly(ionic liquid) containing graphene. The nanocomposite was characterized by scanning electron microscopy, energy dispersive X-ray studies, cyclic voltammetry, and chronoamperometry. The AgNPs on the basic composite film provide the electrode with enhanced sensitivity in that the signal obtained for HP is 10-fold improved in the best case. The sensor exhibits good linear response in the 0.1 μM to 2.2 mM HP concentration range, and the detection limit is 0.05 μM (at S/N?=?3).      

Direct electron transfer of cytochrome c and its biosensor based on gold nanoparticles/room temperature ionic liquid/carbon nanotubes composite film

A robust and effective composite film based on gold nanoparticles (GNPs)/room temperature ionic liquid (RTIL)/multi-wall carbon nanotubes (MWNTs) modified glassy carbon (GC) electrode was prepared by a layer-by-layer self-assembly technique. Cytochrome c (Cyt c) was successfully immobilized on the RTIL-nanohybrid film modified GC electrode by electrostatic adsorption. Direct electrochemistry and electrocatalysis of Cyt c were investigated. The results suggested that Cyt c could be tightly adsorbed on the modified electrode. A pair of well-defined quasi-reversible redox peaks of Cyt c was obtained in 0.10 M, pH 7.0 phosphate buffer solution (PBS). RTIL-nanohybrid film showed an obvious promotion for the direct electron transfer between Cyt c and the underlying electrode. The immobilized Cyt c exhibited an excellent electrocatalytic activity towards the reduction of H₂O₂. The catalysis currents increased linearly to the H₂O₂ concentration in a wide range of 5.0 × 10⁻⁵– 1.15 × 10⁻³ M. Based on the multilayer film, the third-generation biosensor could be constructed for the determination of H₂O₂.     

Nonenzymatic amperometric sensor of hydrogen peroxide and glucose based on Pt nanoparticles/ordered mesoporous carbon nanocomposite

A simple and facile synthetic method to incorporate Pt nanoparticles inside the mesopores of ordered mesoporous carbons (OMCs) is reported. The Pt/OMCs nanocomposite was characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and nitrogen adsorption-desorption. The results show that the incorporation of Pt nanoparticles inside the pores of OMCs does not change the highly ordered two-dimensional hexagonal mesostructure of OMCs matrix. Nonenzymatic amperometric sensor of hydrogen peroxide and glucose based on the Pt/OMCs nanocomposite-modified glassy carbon (GC) electrode is developed. Compared with the original OMCs-modified electrode, the Pt/OMCs-modified electrode displays improved current response towards hydrogen peroxide and gives linear range from 2 to 4212 μM. At an applied potential of −0.08 V, the Pt/OMCs nanocomposite gives linearity in the range of 0.5-4.5 mM glucose in neutral buffered saline solution. This glucose sensor also exhibits good ability of anti-interference to electroactive molecules. The combination the unique properties of Pt nanoparticles and the ordered mesostructure of OMCs matrix guarantees the enhanced response for hydrogen peroxide and glucose.     

Voltammetric myoglobin sensor based on a glassy carbon electrode modified with a composite film consisting of carbon nanotubes and a molecularly imprinted polymerized ionic liquid

The ionic liquid 1-{3-[(2-aminoethyl)amino]propyl}-3-vinylimidazole bromide was synthesized and used to fabricate a molecularly imprinted film for electrochemical sensing of myoglobin (Myo). This film was deposited on a glassy carbon electrode modified with multi-walled carbon nanotubes by using the ionic liquid as the functional monomer, Myo as the template, N,N′-methylenebisacrylamide as the crosslinker, and a redox system containing ammonium persulfate and N,N,N′,N′-tetramethylethylenediamine as the initiator. The sensing performance of the modified electrode was investigated by using the hexacyanoferrate system as an electrochemical redox probe. The results demonstrated that the sensor possesses good selectivity and high sensitivity. The oxidation peak current at the potential of ~0.3 V (vs. SCE) was found linearly related to the myoglobin concentration in the range from 60.0 nM to 6.0 μM, with a 9.7 nM detection limit at an S/N ratio of 3. The sensor was applied to the determination of Myo in spiked serum samples where it showed average recoveries (for n = 5) of 96.5 %.

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Graphical abstract By using a polymerizable ionic liquid as the functional monomer, a myoglobin imprinted polymer was fabricated on a multi-walled carbon nanotube modified glassy carbon electrode. The sensing performances of the molecularly imprinted sensor towards myoglobin demonstrated good selectivity, sensitivity and accuracy.

     

Formic acid electro-synthesis from carbon dioxide in a room temperature ionic liquid

The novel synthesis of formic acid has been achieved in a room temperature ionic liquid via the reaction of electro-activated carbon dioxide and protons on pre-anodised platinum. Only mild reaction conditions of room temperature and 1 atm CO(2) were used. This work highlights the effect of pre-anodisation on Pt surfaces.     

Synthesis of copolyimides based on room temperature ionic liquid diamines

Block copolyimides based on aromatic dianhydrides and diamines copolymerized with diamino room temperature ionic liquid (RTIL) monomers were synthesized over a range of compositions. Specifically, two diamino RTILs, 1,3‐di(3‐aminopropyl) imidazolium bis[(trifluoromethyl)sulfonyl] imide ([DAPIM] [NTf₂]) and 1,12‐di[3‐(3‐aminopropyl) imidazolium] dodecane bis[(trifluoromethyl) sulfonyl] imide ([C₁₂ (DAPIM)₂] [NTf₂]₂) were synthesized using a Boc protection method. The two RTILs were reacted with 2,2‐bis(3,4‐carboxylphenyl) hexafluoropropane dianhydride (6FDA) to produce 6FDA‐RTILs oligomers that formed the RTIL component for the block copolyimides. The oligomers were reacted with 6FDA and m‐phenylenediamine (MDA) at oligomer concentration from 6.5 to 25.8 mol % to form block copolyimides. Increasing the concentration of the 6FDA‐RTIL oligomer in the block copolyimides resulted in a decrease in the thermal degradation temperature, glass transition temperature and an increase in the density. The gas permeability of the RTIL based block copolyimide decreased but the ideal permeability selectivity for CO₂/CH₄ gas pair increased relative to the pure 6FDA‐MDA. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4036–4046, 2010     

基于室温离子液体的有序多孔金膜葡萄糖传感器

将1-丁基-3-甲基咪唑四氟硼酸盐（[BMIm][BF4]）、N,N-二甲基甲酰胺（DMF）与葡萄糖氧化酶（GOD）的混合物修饰于三维有序大孔（3DOM）金膜电极上,构建了一种新型的葡萄糖传感器．固定的GOD在pH7．0的磷酸缓冲液（PBS）中展现出一对可逆性好的氧化还原峰,这归因于GOD的活性中心黄素腺嘌呤二核苷酸（FAD）的直接电化学行为．研究表明,离子液体（IL）、DMF以及3DOM金膜对GOD的直接电化学都起到了重要的作用．3DOM金膜修饰电极作为基底提高了酶的负载量,加速了GOD与电极表面的电子传递;IL的应用增加了固定GOD的电化学活性;DMF与IL、GOD的协同作用更好地保持了GOD的生物活性．固定在电极表面的GOD对葡萄糖显示出良好的催化性能,其检测线性范围为10～125nmol／L,检测限为3．3nmol／L（S／N=3）,酶催化反应的表观米氏常数Km为0．018mmol／L．     

A sensor based on polyaniline nanofibers/ionic liquid-functionalized carbon nanotubes composite for electrocatalytic oxidation of guanine

In this paper, a novel polyaniline (PANI) nanofibers/ionic liquid-functionalized carbon nanotubes (IL-CNTs) composite-modified electrode was prepared, and its application on electrocatalytic oxidation of guanine of sequence-specific DNA was investigated. The surface morphology and the related electrochemical behaviors of the PANI/IL-CNTs composite film were characterized with scanning electron microscopy, electrochemical impedance spectroscopy and cyclic voltammetry, respectively. The PANI/IL-CNTs composite showed a good response current toward the direct electrooxidation of ssDNA due to the synergistic effect between PANI nanofibers and IL-CNTs. Based on this, it was adopted as an excellent sensing platform for highly sensitive determination of guanine. The detection limit was 3.1 × 10^?9 mol/L.     

Preparation of the glucose sensor based on three-dimensional ordered macroporous gold film and room temperature ionic liquid

A novel type of glucose sensor was fabricated based on a glucose oxidase (GOD)-N,N-dimethtylformamide (DMF)-[BMIm][BF₄] composites modified three-dimensional ordered macroporous (3DOM) gold film electrode. The immobilized GOD exhibits a pair of well-defined reversible peaks in 50 mM pH 7.0 phosphate buffer solutions (PBS), which could be attributed to the redox of flavin adenine dinucleotide (FAD) in GOD. The research results show that ionic liquid ([BMIm][BF₄]), DMF and 3DOM gold film are crucial for GOD to exhibit a pair of stable and reversible peaks. It is believed that the large active area of 3DOM gold film can increase the amount of immobilized GOD. Simultaneously, the application of IL enhances the stability of GOD and facilitates the electron transfer between GOD and the electrode. The synergetic effect of DMF can help the GOD to maintain its bioactivity better. GOD immobilized on the electrode exhibits the favorable electrocatalytic property to glucose, and the prepared sensor has a linear range from 10 to 125 nM with a detection limit of 3.3 nM at a signal-to-noise ratio of 3σ. The apparent K _m (Michaelis- Menten constant) for the enzymatic reaction is 0.018 mM.     

An electrochemical gas sensor based on paper supported room temperature ionic liquids

A sensitive and fast-responding membrane-free amperometric gas sensor is described, consisting of a small filter paper foil soaked with a room temperature ionic liquid (RTIL), upon which three electrodes are screen printed with carbon ink, using a suitable mask. It takes advantage of the high electrical conductivity and negligible vapour pressure of RTILs as well as their easy immobilization into a porous and inexpensive supporting material such as paper. Moreover, thanks to a careful control of the preparation procedure, a very close contact between the RTIL and electrode material can be achieved so as to allow gaseous analytes to undergo charge transfer just as soon as they reach the three-phase sites where the electrode material, paper supported RTIL and gas phase meet. Thus, the adverse effect on recorded currents of slow steps such as analyte diffusion and dissolution in a solvent is avoided. To evaluate the performance of this device, it was used as a wall-jet amperometric detector for flow injection analysis of 1-butanethiol vapours, adopted as the model gaseous analyte, present in headspace samples in equilibrium with aqueous solutions at controlled concentrations. With this purpose, the RTIL soaked paper electrochemical detector (RTIL-PED) was assembled by using 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide as the wicking RTIL and printing the working electrode with carbon ink doped with cobalt(II) phthalocyanine, to profit from its ability to electrocatalyze thiol oxidation. The results obtained were quite satisfactory (detection limit: 0.5 μM; dynamic range: 2-200 μM, both referring to solution concentrations; correlation coefficient: 0.998; repeatability: ±7% RSD; long-term stability: 9%), thus suggesting the possible use of this device for manifold applications.     

Electrosynthesis of hydrogen peroxide in room temperature ionic liquids and in situ epoxidation of alkenes

Hydrogen peroxide can be electrosynthesized from oxygen in [bmim][BF(4)]-water and used in situ for the epoxidation of alkenes.     

The hydrogen evolution reaction in a room temperature ionic liquid: mechanism and electrocatalyst trends

The kinetics and mechanism of the proton reduction reaction in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C(2)mim][NTf(2)]) was studied at gold, molybdenum, nickel, titanium and platinum electrodes. Significant differences in electrochemical rate constants were observed between the different metals and with the corresponding processes in aqueous solution. The hydrogen evolution mechanism was consistent at all five metals in the ionic liquid, in stark contrast to the known behaviour in aqueous systems.     

A non-enzymatic sensor for hydrogen peroxide based on polyaniline, multiwalled carbon nanotubes and gold nanoparticles modified Au electrode

We describe the construction of a polyaniline (PANI), multiwalled carbon nanotubes (MWCNTs) and gold nanoparticles (AuNPs) modified Au electrode for determination of hydrogen peroxide without using peroxidase (HRP). The AuNPs/MWCNT/PANI composite film deposited on Au electrode was characterized by Scanning Electron Microscopy (SEM) and electrochemical methods. Cyclic voltammetric (CV) studies of the electrode at different stages of construction demonstrated that the modified electrode had enhanced electrochemical oxidation of H(2)O(2), which offers a number of attractive features to develop amperometric sensors based on split of H(2)O(2). The amperometric response to H(2)O(2) showed a linear relationship in the range from 3.0 μM to 600.0 μM with a detection limit of 0.3 μM (S/N = 3) and with high sensitivity of 3.3 mA μM(-1). The sensor gave accurate and satisfactory results, when employed for determination of H(2)O(2) in milk and urine.     

Amperometric sensor for hydrogen peroxide based on electric wire composed of horseradish peroxidase and toluidine blue-multiwalled carbon nanotubes nanocomposite

A kind of nanocomposites with good dispersion in water was prepared through noncovalent adsorption of toluidine blue (Tb) on multiwalled carbon nanotubes (MWCNT) for electric communication between horseradish peroxidase (HRP) and electrode. The nanocomposites could be conveniently cast on electrode surface. With the aid of chitosan, HRP was then immobilized on the nanostructure to form a reagentless amperometric sensor for hydrogen peroxide. UV-vis spectroscopy and electrochemical impedance spectroscopy were used to characterize the adsorption of Tb on MWCNT. The presence of both Tb as mediator of electron transfer and MWCNT as conductor enhanced greatly the enzymatic response to the reduction of hydrogen peroxide. The novel biosensor exhibited fast response towards hydrogen peroxide with a detection limit of 1.7x10(-6)M and the linear range extended up to 4x10(-4)M without the interference of ascorbic acid and uric acid. The Michaelis-Menten constant (K'(m)) of the immobilized HRP was evaluated to be 0.16mM.     

A highly sensitive hydrogen peroxide amperometric sensor based on MnO2-modified vertically aligned multiwalled carbon nanotubes

In this report, a highly sensitive amperometric sensor based on MnO₂-modified vertically aligned multiwalled carbon nanotubes (MnO₂/VACNTs) for determination of hydrogen peroxide (H₂O₂) was fabricated by electrodeposition. The morphology of the nanocomposite was characterized by scanning electron microscopy, energy-dispersive X-ray spectrometer and X-ray diffraction. Cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy were applied to investigate the electrochemical properties of the MnO₂/VACNTs nanocomposite electrode. The mechanism for the electrochemical reaction of H₂O₂ at the MnO₂/VACNTs nanocomposite electrode was also discussed. In borate buffer (pH 7.8, 0.20 M), the MnO₂/VACNTs nanocomposite electrode exhibits a linear dependence (R = 0.998) on the concentration of H₂O₂ from 1.2 × 10⁻⁶ M to 1.8 × 10⁻³ M, a high sensitivity of 1.08 × 10⁶ μA M⁻¹ cm⁻² and a detection limit of 8.0 × 10⁻⁷ M (signal/noise = 3). Meanwhile, the MnO₂/VACNTs nanocomposite electrode is also highly resistant towards typical inorganic salts and some biomolecules such as acetic acid, citric acid, uric acid and d-(+)-glucose, etc. In addition, the sensor based on the MnO₂/VACNTs nanocomposite electrode was applied for the determination of trace of H₂O₂ in milk with high accuracy, demonstrating its potential for practical application.     

Amperometric hydrogen peroxide sensor based on a sol-gel-derived ceramic carbon composite electrode with toluidine blue covalently immobilized using 3-aminopropyltrimethoxysilane

A carbon composite amperometric hydrogen peroxide sensor has been developed using a sol-gel technique. Toluidine blue (TB), which acts as the redox mediator, was covalently immobilized via glutaraldehyde crosslinking with an organically modified silane, namely 3-aminopropyltrimethoxysilane (APTMOS). Methyltrimethoxysilane (MTMOS) was used as the additional monomer; this controls the hydrophobicity of the electrode surface, thus limiting the wettability. The immobilization of TB within the sol-gel matrix was confirmed with FTIR studies. The sol-gel mixture containing TB immobilized in APTMOS and MTMOS was mixed with graphite powder in order to prepare the carbon composite electrode. The electrode was characterized using voltammetric techniques and its electrocatalytic activity for the reduction of hydrogen peroxide was also studied. The carbon composite electrode has the advantage of sensing H₂O₂ at a lower potential and with a higher sensitivity, and interferences due to ascorbic acid, uric acid and acetaminophen were greatly minimized. The linear range for the determination of H₂O₂ extends from 5.37 × 10⁻⁶ to 6.15 × 10⁻³ M, with a correlation coefficient of 0.9981. The detection limit was found to be 2.15 × 10⁻⁶ M. The covalent immobilization of TB effectively prevents the leakage of the water-soluble mediator during measurements. The modified electrode, aside from electrocatalyzing the reduction of H₂O₂, exhibits distinct advantages in terms of surface renewal in the event of surface fouling, as well as simple preparation, good chemical and mechanical stability, and good reproducibility. Figure Amperometric hydrogen peroxide sensor based on sol-gel-derived ceramic carbon composite electrode with toluidine blue covalently immobilized using 3-aminopropyltrimethoxysilane Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.