A hydrogen peroxide sensor based on a horseradish peroxidase/polyaniline/carboxy-functionalized multiwalled carbon nanotube modified gold electrode

We have developed a polyaniline/carboxy-functionalized multiwalled carbon nanotube (PAn/MWCNTCOOH) nanocomposite by blending the emeraldine base form of polyaniline (PAn) and carboxy-functionalized multiwalled carbon nanotubes (MWCNT) in dried dimethyl sulfoxide (DMSO) at room temperature. The conductivity of the resulting PAn/MWCNTCOOH was 3.6 × 10⁻³ S cm⁻¹, mainly as a result of the protonation of the PAn with the carboxyl group and the radical cations of the MWCNT fragments. Horseradish peroxidase (HRP) was immobilized within the PAn/MWCNTCOOH nanocomposite modified Au (PAn/MWCNTCOOH/Au) electrode to form HRP/PAn/MWCNTCOOH/Au for use as a hydrogen peroxide (H₂O₂) sensor. The adsorption between the negatively charged PAn/MWCNTCOOH nanocomposite and the positively charged HRP resulted in a very good sensitivity to H₂O₂ and an increased electrochemically catalytical current during cyclic voltammetry. The HRP/PAn/MWCNTCOOH/Au electrode exhibited a broad linear response range for H₂O₂ concentrations (86 μM–10 mM). This sensor exhibited good sensitivity (194.9 μA mM⁻¹ cm⁻²), a fast response time (2.9 s), and good reproducibility and stability at an applied potential of −0.35 V. The construction of the enzymatic sensor demonstrated the potential application of PAn/MWCNTCOOH nanocomposites for the detection of H₂O₂ with high performance and excellent stability.     

Simultaneous determination of dihydroxybenzene isomers based on thionine functionalized multiwall carbon nanotubes modified electrode

In this article, simultaneous determination of dihydroxybenzene isomers [hydroquinone (HQ), catechol (CC), and resorcinol (RC)] was investigated using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) at thionine functionalized multiwalled carbon nanotube (TH-MWCNTs) modified glass carbon electrode. CV and DPV results showed that the TH-MWCNTs modified electrode exhibited excellent recognition ability toward the three isomers of dihydroxybenzene. Their oxidize peak currents were linear over ranges from 9.0 × 10^?7 to 3.6 × 10^?4 M for HQ, from 3.3 × 10^?6 to 8.1 × 10^?4 M for CC and from 4.3 × 10^?6 to 9.0 × 10^?4 M for RC, with the detection limits of 2.7 × 10^?7, 1.0 × 10^?6, and 1.1 × 10^?6 M, respectively. The proposed method would potentially be applied to multi-component analysis in environmental control and chemical industry.     

Polyethylenimine‐functionalized multiwalled carbon nanotube for the adsorption of hydrogen sulfide

Functionalized multiwalled carbon nanotubes (MWCNTs) were synthesized with ethane diamine and polyethylenimine (PEI) with molecular weights of 1800 [MWCNT‐PEI weight‐average molecular weight (M_w) = 1800] and 70,000 (MWCNT‐PEI M_w = 70,000), respectively. The structures and properties of the ethane diamine functionalized MWCNTs and PEI‐functionalized MWCNTs were characterized by Raman spectroscopy, thermogravimetric analysis, X‐ray powder diffraction, and scanning electron microscopy. An increase with the D/G (D, Disorder band; G, Graphite) ratio of the functionalized MWCNTs in the Raman spectra proved that the ethane diamine and PEI were successfully bonded to the surface of the pristine MWCNTs. The results of TGA also confirmed this. In addition, the structure of the functionalized MWCNTs showed no significant changes compared with the pristine MWCNTs; this was confirmed by X‐ray powder diffraction. Hydrogen sulfide (H₂S) sorption on the functionalized MWCNTs was studied by UV spectroscopy. As expected, the results of UV spectroscopy shows that the MWCNTs bonded with higher molecular weight PEI had a more excellent H₂S adsorption efficiency than those bonded with low‐molecular‐weight PEI and ethane diamine, a micromolecular amine. The effects of the pH and temperature on the adsorption of H₂S were also studied. Under the conditions investigated, the maximum first‐time H₂S adsorption efficiency of 1.94 mmol/g was observed for MWCNT‐PEI (M_w = 70,000) in the 60 mg/L sodium hydrosulfide (NaHS) aqueous solution. In addition, the H₂S reversible adsorption of the functionalized MWCNTs was conducted, and the second‐time H₂S adsorption efficiency of MWCNT‐PEI (M_w = 70,000) reached 1.83 mmol/g in the 60 mg/L NaHS aqueous solution. The results demonstrate that the MWCNTs decorated with high‐molecular‐weight PEI were potentially excellent and reversible H₂S adsorbents. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44742.     

Simultaneous voltammetric determination of ascorbic acid, acetaminophen and isoniazid using thionine immobilized multi-walled carbon nanotube modified carbon paste electrode

A carbon paste electrode (CPE) modified with thionine immobilized on multi-walled carbon nanotube (MWCNT), was prepared for simultaneous determination of ascorbic acid (AA) and acetaminophen (AC) in the presence of isoniazid (INZ). The electrochemical response characteristics of the modified electrode toward AA, AC and INZ were investigated by cyclic and differential pulse voltammetry (CV and DPV). The results showed an efficient catalytic role for the electro-oxidation of AA and AC, leading to a remarkable peak resolution (∼303 mV) for two compounds. On the other hand, the presence of INZ, which is considered as important drug interference for AC, does not affect the voltammetric responses of these pharmaceuticals. The mechanism of the modified electrode was analyzed by monitoring the CVs at various potential sweep rates and pHs of the buffer solutions. Under the optimum conditions, the calibration curves for AA, AC and INZ were obtained in the range of 1 × 10⁻⁶ to 1 × 10⁻⁴ M, 1 × 10⁻⁷ to 1 × 10⁻⁴ M and 1 × 10⁻⁶ to 1 × 10⁻⁴ M, respectively. The prepared modified electrode shows several advantages such as simple preparation method, high sensitivity, long-time stability, ease of preparation and regeneration of the electrode surface by simple polishing and excellent reproducibility. The proposed method was applied to determination of AA, AC and INZ in commercial drugs and in plasma samples and the obtained results were satisfactory.     

Using multiwalled carbon nanotube modified electrodes for the adsorptive striping voltammetric determination of hesperidin

Hesperidin, a flavone glycoside found in the skins and juices of citrus fruits, can be detected using multiwalled carbon nanotube (MWCNT)-modified electrodes using the technique of adsorptive stripping voltammetry (AdSV) with accumulation at open circuit potential. This is relevant because hesperidin can be used as an indication of the citrus fruit juice's freshness. The oxidation mechanism to explain the observed voltammetry corresponds to the redox chemistry of the guaiacol sub-unit within the hesperidin molecular structure. Hesperidin could be detected over a linear range up to 30 μM, and with a detection limit of 0.61 μM and 7 nM, with less than 5% variation between different electrodes, using cyclic voltammetric or square wave adsorptive stripping techniques respectively. This methodology was extended to MWCNT-modified screen-printed electrodes (MWCNT-SPEs), allowing the development of a cheap, mass produced, disposable sensor that we show is capable of measuring the concentration of hesperidin in real orange juice samples, and be applied within the citrus fruit industry.     

多壁碳纳米管修饰电极测定诺氟沙星

运用循环伏安法、线性扫描伏安法及示差脉冲伏安法等测试技术研究了诺氟沙星在多壁碳纳米管修饰玻碳电极上的电化学行为,建立了一种直接测定诺氟沙星的电化学分析方法.结果表明,与裸玻碳电极相比,多壁碳纳米管修饰电极能显著提高诺氟沙星的氧化峰电流.在优化的实验条件下,氧化峰电流与诺氟沙星浓度在1.0×10-7～1.0×10-6mol/L和1.0×10-6～2.5×10-5 moL/L范围呈现良好的线性关系,检出限为3.0×10-8mol/L对1.0×10-5mol/L诺氟沙星溶液平行测定10次的RSD为4.1%.测定了诺氟沙星胶囊中诺氟沙星的含量,结果满意.     

A novel hydrogen peroxide sensor based on multiwalled carbon nanotubes/poly(pyrocatechol violet)‐modified glassy carbon electrode

In this work, a new hydrogen peroxide (H₂O₂) sensor was reported based on electropolymerizing pyrocatechol violet (PCV) on a glassy carbon electrode modified with multiwalled carbon nanotubes (MWCNTs). The modified electrode was characterized by cyclic voltammetry (CV) and scanning electron micrography. The result of electrochemical experiments showed a favorable catalytic activity toward the reduction of H₂O₂ at ?0.4 V with a linear response range from 2.0 μM to 2.4 mM and a detection limit of 0.7 μM (at a S/N = 3). The well catalytic activity of proposed sensor could be attributed to the poly‐PCV/MWCNTs composite film on the electrocatalytic reduction of H₂O₂. In addition, the sensor also exhibited a high sensitivity, good stability, and reproducibility. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Electrochemical determination of thiamazole at a multi-wall carbon nanotube modified glassy carbon electrode

A simple and convenient method is described for voltammetric determination of thiamazole, a commonly used anti-hyperthyroid drug, based on its electrochemical oxidation at a multi-wall carbon nanotube modified glassy carbon electrode. Under optimized conditions, the proposed method exhibited acceptable analytical performances in terms of linearity (over the concentration range from 1.0 × 10⁻⁷ to 5.0 × 10⁻⁴ mol L⁻¹, r = 0.9983), detection limit (3.0 × 10⁻⁸ mol L⁻¹) and reproducibility (RSD = 2.64%, n = 10, for 5.0 × 10⁻⁵ mol L⁻¹ thiamazole). To further validate its possible application, the method was used for the quantification of thiamazole in pharmaceutical formulations and biological fluids.     

A new modified multiwalled carbon nanotube paste electrode for quantification of tin in fruit juice and bottled water samples

In this paper, a new modified multiwalled carbon nanotube electrode is reported for anodic stripping voltammetry quantification of tin. The electrode is based on the use of N-Nitrozo-N-Phenylhydroxylamine (cupferron) and multiwalled carbon nanotube. The influence of supporting electrolytes, deposition time, and applied potential on the sensitivity of electrode were investigated. The detection limit was 0.12 ng/ml and the RSD at a concentration level of 50 ng/ml, was 1.5%. The electrode has been applied for the determination of tin in fruit juice and bottled water with the satisfactory results.     

Electrochemical determination of phloroglucinol using a carbon nanotube modified electrode enhanced by surfactant

A novel technique is utilized to detect trace amounts of phloroglucinol. In pH 5.0, 0.1 mol L⁻¹ HAc–NaAc buffer solution, phloroglucinol exhibited a stable and sensitive oxidation signal at a glassy carbon electrode modified with multi-wall carbon nanotube. By using the surfactant cetyl pyridinium chloride, the electrochemical response was greatly enhanced. The mechanism was systematically explored. In the range 9.0 × 10⁻⁷–3.0 × 10⁻⁴ mol L⁻¹, the oxidation peak currents of phloroglucinol have a linear relationship with concentration: the limit of detection was estimated to be 2.5 × 10⁻⁷ mol L⁻¹ (S/N = 3). The method was adopted to detect the content of phloroglucinol injection, and the recovery was from 97.5% to 103.0%.     

Electrical conductivity of chemically modified multiwalled carbon nanotube/epoxy composites

The electrical conductivity of oxidized multiwalled carbon nanotubes (MWNT)/epoxy composites is investigated with respect to the chemical treatment of the MWNT. The oxidation is carried out by refluxing the as-received MWNT in concentrated HNO₃ and H₂O₂/NH₄OH solutions, respectively, under several different treatment conditions. The oxidized MWNT are negatively charged and functionalized with carboxylic groups by both solutions. The MWNT oxidized under severe conditions are well purified, but their crystalline structures are partially damaged. It is recognized that the damage to the MWNT has considerable influence on the electrical properties of the MWNT composites, causing the electrical conductivity to be lowered at a low content of MWNT and the percolation threshold to be raised. The MWNT oxidized by the mixture of H₂O₂ and NH₄OH solution provides epoxy composites with a higher conductivity than those produced with the MWNT oxidized by nitric acid over the whole range of MWNT, independently of the oxidation conditions.     

A flexible graphene/multiwalled carbon nanotube film as a high performance electrode material for supercapacitors

A flexible graphene/multiwalled carbon nanotube (GN/MWCNT) film has been fabricated by flow-directed assembly from a complex dispersion of graphite oxide (GO) and pristine MWCNTs followed by the use of gas-based hydrazine to reduce the GO into GN sheets. The GN/MWCNT (16 wt.% MWCNTs) film characterized by Fourier transformation infrared spectra, X-ray diffraction and scanning electron microscope has a layered structure with MWCNTs uniformly sandwiched between the GN sheets. The MWCNTs in the obtained composite film not only efficiently increase the basal spacing but also bridge the defects for electron transfer between GN sheets, increasing electrolyte/electrode contact area and facilitating transportation of electrolyte ion and electron into the inner region of electrode. Electrochemical data demonstrate that the GN/MWCNT film possesses a specific capacitance of 265 F g⁻¹ at 0.1 A g⁻¹ and a good rate capability (49% capacity retention at 50 A g⁻¹), and displays an excellent specific capacitance retention of 97% after 2000 continuous charge/discharge cycles. The results of electrochemical measurements indicate that the freestanding GN/MWCNT film has a potential application in flexible energy storage devices.     

A simple and sensitive electroanalytical determination of anxiolytic buspirone hydrochloride drug based on multiwalled carbon nanotubes modified electrode

In the present study, a simple and sensitive buspirone hydrochloride (BPH) sensor was developed based on multiwalled carbon nanotubes (MWCNT) modified electrode. The modified electrode was characterized using transmission electron microscopy and electrochemical impedance spectroscopy. The MWCNT modified electrode showed an enhanced oxidation peak current response toward BPH than unmodified electrode. The oxidation peak potential of BPH at modified electrode was 0.85, which was quite lower than that of bare electrode (0.88 V). The BPH was successfully determined at modified electrode using different electrochemical methods, such as cyclic voltammetry (CV), differential pulse voltammetry (DPV), and amperometry. The good sensitivity and linear range response of BPH were obtained using amperometry when compared with other methods employed in this study (CV and DPV). The modified electrode displayed the electro-oxidation of BPH in the linear response from 0.5 to 99.5 μM with the sensitivity of 16.49 μA μM^?1 cm^?2. The limit of detection was calculated as 0.22 μM. In addition, the modified electrode exhibited a good repeatability and repeatability with acceptable stability.     

A novel non-enzymatic hydrogen peroxide sensor based on single walled carbon nanotubes–manganese complex modified glassy carbon electrode

A simple procedure was developed to prepare a glassy carbon (GC) electrode modified with single wall carbon nanotubes (SWCNTs) and phenazine derivative of Mn-complex. With immersing the GC/CNTs modified electrode into Mn-complex solution for a short period of time 20–100 s, a stable thin layer of the complex was immobilized onto electrode surface. Modified electrode showed a well defined redox couples at wide pH range (1–12). The surface coverages and heterogeneous electron transfer rate constants (k_s) of immobilized Mn-complex were approximately 1.58 × 10⁻¹⁰ mole cm⁻² and 48.84 s⁻¹. The modified electrode showed excellent electrocatalytic activity toward H₂O₂ reduction. Detection limit, sensitivity, linear concentration range and k_cat for H₂O₂ were, 0.2 μM and 692 nA μM⁻¹ cm⁻², 1 μM to 1.5 mM and 7.96(±0.2) × 10³ M⁻¹ s⁻¹, respectively. Compared to other modified electrodes, this electrode has many advantageous such as remarkable catalytic activity, good reproducibility, simple preparation procedure and long term stability.     

多壁碳纳米管修饰电极测定水样中痕量镉

通过多壁碳纳米管修饰玻碳电极,建立了水样中痕量镉的线性扫描阳极溶出伏安分析法。优化了支持电解质及pH、修饰剂用量、富集电位及时间等测定条件,在pH 4.0的NaAc-HAc缓冲液中,-1.10 V富集5 min后,溶出峰电流与Cd2 浓度在2.0×10-8~5.0×10-5mol/L的范围内呈良好的线性关系,检测限为8.0×10-9mol/L。该法用于实际水样中痕量镉的测定,平均回收率在98.7%~105.0%之间,结果满意。     

Highly sensitive and simultaneous determination of hydroquinone and catechol at poly(thionine) modified glassy carbon electrode

A simple and highly sensitive electrochemical method for the simultaneous and quantitative detection of hydroquinone (HQ) and catechol (CT) was developed, based on a poly(thionine)-modified glassy carbon electrode (GCE). The modified electrode showed excellent electrocatalytic activity and reversibility towards the oxidation of both HQ and CT in 0.1 M phosphate buffer solution (PBS, pH 7.0). The peak-to-peak separations (ΔE_p) between oxidation and reduction waves in CV were decreased significantly from 262 and 204 mV at the bare GCE, to 63 and 56 mV, respectively for HQ and CT at the poly(thionine) modified GCE. Furthermore, the redox responses from the mixture of HQ and CT were easily resolved in both CV and DPV due to a difference in the catalytic activity of the modified GCE to each component. The peak potential separation of ca. 0.1 V was large enough for the simultaneous determination of HQ and CT electrochemically. The oxidation peak currents of HQ and CT were linear over the range from 1 to 120 μM in the presence of 100 and 200 μM of HQ and CT, respectively. The modified electrode showed very high sensitivity of 1.8 and 1.2 μA μM⁻¹ cm⁻² for HQ and CT, respectively. The detection limits (S/N = 3) for HQ and CT were 30 and 25 nM, respectively. The developed sensor was successfully examined for real sample analysis with tap water and revealed stable and reliable recovery data.     

A disposable sensor based on immobilization of acetylcholinesterase to multiwall carbon nanotube modified screen-printed electrode for determination of carbaryl

A simple method has been devised for immobilization of acetylcholinesterase (AChE) covalent bonding to a multiwall carbon nanotube (MWNT)-cross-linked cellulose acetate composite on a screen-printed carbon electrode (SPCE) and a sensitive and disposable amperometric sensor for rapid determination of carbaryl pesticide is proposed. The immobilized enzyme was preserved on this film because of the excellent biocompatibility and non-toxicity of cellulose acetate. Based on the inherent conductive properties of the MWNT, the immobilized AChE had greater affinity for ATCl and excellent catalytic effect in the hydrolysis of ATCl. MWNT improved the interface enzymatic hydrolysis reaction and increased the amperometric response of the sensor. Under optimum conditions, the inhibition of carbaryl on AChE increased linearly with the increasing concentration of carbaryl in two ranges, from 0.01 to 0.5 μg mL⁻¹ and from 2 to 20 μg mL⁻¹, with the correlation coefficients of 0.9985 and 0.9977, respectively. The detection limit was 0.004 μg mL⁻¹ taken as the concentration equivalent to 10% decrease in signal. The sensor showed acceptable stability, accuracy and could be fabricated in batches, thus it is economic and portable. This type of disposable enzyme-based amperometric sensor has extensive application potential in environmental monitoring of pesticides.     

Dielectric properties of irradiated polymer/multiwalled carbon nanotube and its amino functionalized form

The polymer/multiwalled carbon nanotube [poly(vinyl alcohol) (PVA)/carboxyethyl acrylate (CEA)]‐multiwalled carbon nanotube (MWCNT) and its amino functionalized (PVA/CEA)‐MWCNT‐NH₂ nanocomposite samples were successfully synthesized by the chemical method in the form of films. The samples were irradiated with gamma‐ray doses of 50 and 100 kGy and with ion beam fluence of 2.5 × 10¹⁸ and 3.75 × 10¹⁸ ions cm^?2. The prepared nanocomposite samples were characterized using X‐ray diffraction and thermogravimetric analysis. The X‐ray diffraction and thermogravimetric analysis confirm the existence of the chemical crosslinking occurred in the polymer compositions. The AC electrical conductivity, electrical modulus, dielectric constant, and dielectric loss in the frequency range 10²–10⁶ Hz are measured at room temperature. The electrical conductivity is increased with MWCNT doping, gamma‐irradiation, and by ion beam irradiation. A comprehensive analysis of the results revealed that dielectric properties are improved due to the induced physicochemical changes and conductive networks induced by ion beam irradiation. The behavioral effect of these embedded nanoparticles in a PVA matrix on the microstructural, dielectric, and electric properties is analyzed for possible device applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46647.     

Electrocatalytic reduction of hydrogen peroxide at nanostructured copper modified electrode

The electrocatalytic reduction of hydrogen peroxide (H₂O₂) has been studied at nanostructured copper (Cu_nano) modified glassy carbon (GC/Cu_nano) electrode in phosphate buffer (pH 7.2). The electrical properties of GC/Cu_nano modified electrodes were studied by electrochemical impedance spectroscopy (EIS). Surface and electrochemical characterization were carried out by using atomic force microscopy (AFM) and cyclic voltammetry. A well-defined H₂O₂ reduction signal, which is due to mediation of a surface active site redox transition exhibits at the GC/Cu_nano electrode. The Cu_nano is acting as a bridge without the aid of any other electron mediator, which enables the direct electron transfer between the modified electrode and the substrate. The results are compared with bulk copper macroelectrode and emphasized the efficiency of the Cu_nano modified electrode. Systematic investigations were made to optimize the experimental parameter, such as applied potential (E_app) for copper electrodeposition. The calibration curve obtained from chronoamperometric studies was found to be linear in the range 0.5 to 8.0 μM H₂O₂ with a detection limit of ca.10 nM (S/N = 3) at the GC/Cu_nano electrode. The modified electrode is stable for 1 week in phosphate buffer after repetitive measurements.