Electrosorption of Os(III)-complex at single-wall carbon nanotubes immobilized on a glassy carbon electrode: application to nanomolar detection of bromate, periodate and iodate

A simple procedure was developed to prepare a glassy carbon electrode modified with single-wall carbon nanotubes (SWCNTs) and Os(III)-complex. The glassy carbon (GC) electrode modified with CNTs was immersed into Os(III)-complex solution (direct deposition) for a short period of time (60 s). 1,4,8,12-Tetraazacyclotetradecane osmium(III) chloride, (Os(III)LCl₂)·ClO₄, irreversibly and strongly adsorbed on SWCNTs immobilized on the surface of GC electrode. Cyclic voltammograms of the Os(III)-complex-incorporated-SWCNTs indicate a pair of well defined and nearly reversible redox couple with surface confined characteristic at wide pH range (1-8). The surface coverage (Γ) and charge transfer rate constant (k_s) of the immobilized Os-complex on SWCNTs were 3.07 × 10⁻⁹ mol cm⁻², 5.5 (±0.2) s⁻¹, 2.94 × 10⁻⁹ mol cm⁻², 7.3 (±0.3) s⁻¹ at buffer solution with pH 2 and 7, respectively, indicate high loading ability of SWCNTs for Os(III) complex and great facilitation of the electron transfer between electroactive redox center and carbon nanotubes immobilized on the electrode surface. Modified electrodes showed higher electrocatalytic activity toward reduction of BrO₃⁻, IO₃⁻ and IO₄⁻ in acidic solutions. The catalytic rate constants for catalytic reduction bromate, periodate and iodate were 3.79 (±0.2) × 10³, 7.32 (±0.2) × 10³ and 1.75 (±0.2) × 10³ M⁻¹ s ⁻¹, respectively. The hydrodynamic amperometry of rotating modified electrode at constant potential (0.3 V) was used for nanomolar detection of selected analytes. Excellent electrochemical reversibility of the redox couple, good reproducibility, high stability, low detection limit, long life time, fast amperometric response time, wide linear concentration range, technical simplicity and possibility of rapid preparation are great advantage of this sensor.     

Study of purification process of single-walled carbon nanotubes by thermoanalytical techniques

The thermal behaviour of commercial Carbolex single-walled carbon nanotubes (SWCNTs) both as-received and after purification by a novel method has been studied by thermogravimetric/derivative thermogravimetric/difference thermal analysis (TG/DTG/DTA). Purification from metal catalysts (Ni and Y) has been successfully obtained using 0.1 M I₂ in iso-propanol instead of the usual concentrated HNO₃. The final residues of thermal analysis have been characterised by scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDS). The gathered results showed that the as-received SWCNTs burns out in a one-step between 573 and 923 K, whereas the SWCNTs treated with HNO₃ become highly hygroscopic. The I₂-iso-propanol-treated SWCNTs showed three overlapped exothermic peaks between 500 and 973 K in the DTA curve, which allowed separating amorphous carbon from SWCNTs by air-thermal treatment at 573 K. The graphite-like compounds, which are present in both untreated and treated SWCNTs, does not burn up to 1173 K.     

Bulk synthesis of large diameter semiconducting single-walled carbon nanotubes by oxygen-assisted floating catalyst chemical vapor deposition

Semiconducting single-walled carbon nanotubes (s-SWCNTs) with a mean diameter of 1.6 nm were synthesized on a large scale by using oxygen-assisted floating catalyst chemical vapor deposition. The oxygen introduced can selectively etch metallic SWCNTs in situ, while the sulfur growth promoter functions in promoting the growth of SWCNTs with a large diameter. The electronic properties of the SWCNTs were characterized by laser Raman spectroscopy, absorption spectroscopy, and field effect transistor measurements. It was found that the content of s-SWCNTs in the samples was highly sensitive to the amount of oxygen introduced. Under optimum synthesis conditions, enriched s-SWCNTs can be obtained in milligram quantities per batch.     

Surface and bulk properties of severely fluorinated carbon fibres

The development of ultra-inert composites using fluorinated carbon fibres as the reinforcement requires fluorinated carbon fibres with a durable surface composition. Here we report the effect of direct fluorination using an F₂/N₂ mixture at 653 K on the surface and bulk properties of two types of high strength carbon fibres. These were treated up to a surface fluorine content of ∼64 at.% and a bulk fluorine content of ∼15 mass%. A colour change was observed after fluorination caused by the changes in the graphitic band structure of the carbon fibres by the introduction of carbon sp³ hybridisation. The tensile strength and Young's modulus decrease after fluorination by up to 33 and 22%, respectively. XRD shows marginal changes in the interlayer distance but the crystallite size increases. Changes in the electrical conductivity of the fluorinated carbon fibres indicate that the modification is confined to the near surface volume. Predominantly covalent C-F bonds are formed as shown by X-ray photoelectron spectroscopy (XPS) and measured zeta (ζ)-potentials. Hence the fluorinated fibres are hydrophobic and have low surface tensions. This and the large increase in fibre surface area, as determined by nitrogen adsorption, is expected to facilitate interfacial interaction between fluorinated carbon fibres and fluoropolymers.     

Preparation of solid-phase microextraction fiber coated with single-walled carbon nanotubes by electrophoretic deposition and its application in extracting phenols from aqueous samples

A novel solid-phase microextraction (SPME) Pt fiber coated with single-walled carbon nanotubes (SWCNTs) was prepared by electrophoretic deposition (EPD) and applied to the determination of phenols in aqueous samples by direct immersion (DI)-SPME-HPLC-UV. The results revealed that EPD was a simple and reproducible technique for the preparation of SPME fibers coated with SWCNTs without the use of adhesive. The obtained SWCNT coating did not swell in organic solvents nor strip off from substrate, and possessed high mechanical strength due to the strong Van der Waals attractions between the surfaces of the SWCNTs. The prepared SPME fiber was conductive since both SWCNT coating and Pt wire were conductive. Using Pt wire as substrate, the fiber was unbreakable. Owing to the presence of oxygenated groups on SWCNTs and the high surface area of SWCNTs, the SWCNT fiber was similar to or superior to commercial PA fiber in extracting the studied phenols from aqueous sample. A durability of more than 80 analyses was achieved for one unique fiber. Under optimized conditions, the detection limits for the phenols varied between 0.9 and 3.8 ng/mL, the precisions were in the range of 0.7–3.2% (n = 3), and linear ranges were within 10 and 300 ng/mL. The method was successfully applied to the analysis of spiked seawater and tap water samples with the recoveries from 87.5 to 102.0%.     

A facile preparation of nanocrystalline Mo2C from graphite or carbon nanotubes

Nanocrystalline Mo₂C powders were successfully synthesized at 500 °C by reacting molybdenum chloride (MoCl₅) with C (graphite or carbon nanotube) in metallic sodium medium. X-ray powder diffractometer (XRD), transmission electron microscope (TEM), X-ray photoelectron spectroscope (XPS) and surface area analyzer (BET method) were used to characterize the samples. Experiments reveal that the carbon source used for the carbide synthesis has a great effect on the particle size and the surface area of the samples. When micro-sized graphite was used as C source the obtained nanocrystalline Mo₂C powder consists of particles of 30∼100 nm, with a surface area of 2.311 m²/g. When carbon nanotubes were used as C source, the as-synthesized Mo₂C sample is composed of particles of 20∼50 nm, with a surface area of 23.458 m²/g, which is an order of magnitude larger than that of the carbide prepared from the graphite.     

Evaluation of the solid-phase microextraction fiber coated with single walled carbon nanotubes for the determination of benzene,toluene, ethylbenzene,xylenes in aqueous samples

A solid-phase microextraction (SPME) fiber coated with single walled carbon nanotubes (SWCNTs) was prepared by electrophoretic deposition and treated at 500 °C in H₂ stream. In order to evaluate the characteristics of the obtained fiber, it was applied in the headspace solid-phase microextraction (HS-SPME) of benzene, toluene, ethylbenzene and xylenes (BTEX) from water sample and quantification by gas chromatography with flame ionization detection (GC-FID). The results indicated that the thermal treatment with H₂ enhanced the extraction of the SWCNTs fiber for BTEX significantly. Thermal stability and durability of the fiber were also investigated, showing excellent stability up to 350 °C and life time over 120 times. In the comparison with the commercial CAR–PDMS fiber, the SWCNTs fiber showed similar and higher extraction efficiencies for BTEX. Under the optimized conditions, the linearity, LODs (S/N = 3) and LOQs (S/N = 10) of the method based on the SWCNTs fiber were 0.5–50.0, 0.005–0.026 and 0.017–0.088 μg/L, respectively. Repeatability for one fiber (n = 3) was in the range of 1.5–5.6% and fiber-to-fiber reproducibility (n = 3) was in the range of 4.2–8.3%. The proposed method was successfully applied in the analysis of BTEX compounds in seawater, tap water and wastewater from a paint plant.     

Single-walled carbon nanotubes as stationary phase in gas chromatographic separation and determination of argon, carbon dioxide and hydrogen

A chromatographic technique is introduced based on single-walled carbon nanotubes (SWCNTs) as stationary phase for separation of Ar, CO₂ and H₂ at parts per million (ppm) levels. The efficiency of SWCNTs was compared with solid materials such as molecular sieve, charcoal, multi-walled carbon nanotubes and carbon nanofibers. The morphology of SWCNTs was optimized for maximum adsorption of H₂, CO₂ and Ar and minimum adsorption of gases such as N₂, O₂, CO and H₂O vapour. To control temperature of the gas chromatography column, peltier cooler was used. Mixtures of Ar, CO₂ and H₂ were separated according to column temperature program. Relative standard deviation for nine replicate analyses of 0.2 mL H₂ containing 10 μL of each Ar or CO₂ was 2.5% for Ar, 2.8% for CO₂ and 3.6% for H₂. The interfering effects of CO, and O₂ were investigated. Working ranges were evaluated as 40-600 ppm for Ar, 30-850 ppm for CO₂ and 10-1200 ppm for H₂. Significant sensitivity, small relative standard deviation (RSD) and acceptable limit of detection (LOD) were obtained for each analyte, showing capability of SWCNTs for gas separation and determination processes. Finally, the method was used to evaluate the contents of CO₂ in air sample.     

Determination of endocrine-disrupting compounds in water by carbon nanotubes solid-phase microextraction fiber coupled online with high performance liquid chromatography

The commercial solid phase microextraction (SPME) fibers are not stable enough in organic solvent and tend to swell and strip off from the silica fiber in the high performance liquid chromatography (HPLC) mobile phase, and therefore the application of SPME coupled online with HPLC is limited. In this study, an SPME fiber coated with single walled carbon nanotubes (SWCNTs), prepared by means of electrophoretic deposition, was coupled on line to HPLC for the determination of four endocrine-disrupting compounds, i.e. bisphenol A (BPA), estrone (E₁), 17α-ethynylestradiol (EE₂) and octylphenol (OP), in aqueous samples. The results showed that the SWCNTs coating on the prepared fiber did not swell and strip off from the platinum fiber throughout the experiment, thus indicating a high resistance to the HPLC mobile phase, the mixture of water and acetonitrile. The SWCNTs fiber had similar (for OP) or higher (for BPA, EE₂ and E₁) extraction efficiencies than the commonly used polyacrylate fiber, and had a lifetime of more than 120 operation times. Under the optimized conditions, the linearity of the proposed method was 1.0-30.0 μg/L for BPA and OP and 3.0-90.0 μg/L for E₁ and EE₂. The limits of detection (LODs; S/N = 3) and limits of quantification (LOQs; S/N = 10) of the method were 0.32-0.52 μg/L and 1.06-1.72 μg/L, respectively. Repeatability for one fiber (n = 3) was in the range of 1.3-7.1% and fiber-to-fiber reproducibility (n = 3) was in the range of 1.6-8.4%. The proposed method was successfully applied for the analysis of spiked tap water and seawater samples with recoveries from 81.8 to 97.3%.     

Sensitive detection of endocrine disrupters using ionic liquid--single walled carbon nanotubes modified screen-printed based biosensors

Simple and low cost biosensor based on screen-printed electrode for sensitive detection of some alkylphenols was developed, by entrapment of HRP in a nanocomposite gel based on single-walled carbon nanotubes (SWCNTs) and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF₆]) ionic liquid. Raman and FTIR spectroscopy, CV and EIS studies demonstrate the interaction between SWCNTs and ionic liquid. The nanocomposite gel, SWCNT-[BMIM][PF₆] provides to the modified sensor a considerable enhanced electrocatalytic activity toward hydrogen peroxide reduction. The HRP based biosensor exhibits high sensitivity and good stability, allowing a detection of the alkylphenols at an applied potential of −0.2 V vs. Ag/AgCl, in linear range from 5.5 to 97.7 μM for 4-t-octylphenol and respectively, between 5.5 and 140 μM for 4-n-nonylphenol, with a response time of about 5 s. The detection limit was 1.1 μM for 4-t-octylphenol, and respectively 0.4 μM for 4-n-nonylphenol (S/N = 3).     

Electropolymerized surface ion imprinting films on a gold nanoparticles/single-wall carbon nanotube nanohybrids modified glassy carbon electrode for electrochemical detection of trace mercury(II) in water

Electrochemical detection of Hg(II) using a electropolymerized ion imprinting poly(2-mercaptobenzothiazole) films at the surface of gold nanoparticles/single-walled carbon nanotube nanohybrids modified glassy carbon electrode (PMBT/AuNPs/SWCNTs/GCE) is described for the first time. The Hg(II)-imprinted PMBT/AuNPs/SWCNTs/GCE sensor exhibits larger binding to functionalized capacity, larger affinity, faster binding kinetics and higher selectivity to template Hg(II). The differential pulse anodic stripping voltammetry (DPASV) response of the Hg(II)-imprinted PMBT/AuNPs/SWCNTs/GCE sensor to Hg(II) is ca. 3.7- and 10.5-fold higher than that at the non-imprinted PMBT/AuNPs/SWCNTs/GCE and the imprinted PMBT/AuNPs/GCE, respectively, and the detection limit for Hg(II) is 0.08 nM (S/N = 3, which is well below the guideline value given by the World Health Organization) and a sensitivity of 0.749 μA nM⁻¹ was obtained. Excellent wide linear range (0.4–96.0 nM) and good repeatability (relative standard deviation of 2.6%) were obtained for Hg(II). The interference experiments show that Ag(I), Pb(II), Cd(II), Zn(II) and Cu(II) had little or no influence on the Hg(II) signal. These values, particularly the high sensitivity and excellent selectivity in contrast to the values reported previously in the area of electrochemical Hg(II) detection, demonstrate the analytical performance of the Hg(II)-imprinted PMBT/AuNPs/SWCNTs/GCE toward Hg(II) is superior to the existing electrodes and could be used for efficient determination of Hg(II) in natural water samples.     

Effects of acid treatment on activated carbon used as a support for Rb and K catalyst for C2F5I synthesis and its mechanism

In the present work, the activated carbon (AC) support was treated with HCl, HNO₃ and HF solution. The order of catalyst dispersion was as follows: Rb-K/AC-HNO₃ > Rb-K/AC-HF > Rb-K/AC-HCl > Rb-K/AC. The same sequence was also observed for the amount of the acid surface oxygen groups on AC, but not for the basicity of the catalyst. The key role of acid treatment on AC surface chemistry and the basic sites, which are closely related to catalyst dispersion and basicity, is examined to rationalize these findings. On the other hand, a consideration of the reaction mechanism suggests that the reaction proceeds via CF₂ carbenes formed on the catalyst surface as intermediates, followed by carbine disproportionation to CF₃ radicals and CF₃CF₂ radicals, followed by reaction with I₂ to produce CF₃CF₂I, and it was also found that the Rb-K/AC-HCl catalyst with a high dispersion and moderate basicity was helpful for the enhancement of catalytic activity for C₂F₅I synthesis.     

Surface fluorination and electrochemical behavior of petroleum cokes graphitized at medium and high temperatures for secondary lithium battery

The surface structure and electrochemical performance have been investigated of petroleum cokes heat-treated at 2100 and 2600 °C (abbreviated to PC2100 and PC2600) and those fluorinated by elemental fluorine at 200 and 300 °C. XPS study indicated that surface fluorine was covalently bonded to carbon and surface fluorine contents were in the range of 4.9-17.8 at.%. Surface oxygen was reduced by fluorination. BET surface areas were nearly the same before and after fluorination. Fluorination enhanced D-band intensity in two Raman shifts observed at 1580 cm⁻¹ (G-band) and 1360 cm⁻¹ (D-band), indicating the increase in the surface disordering. At a high current density of 150 mA/g, the capacity increase was observed for PC2100 fluorinated at 200 °C and for PC2600 fluorinated at 200 and 300 °C. The most interesting result was the increase in first coulombic efficiencies by surface fluorination. First columbic efficiencies for PC2600 fluorinated at 300 °C were increased by 12.1% at 60 mA/g and by 25.8% at 150 mA/g, respectively. The impedance measurements showed that the resistances of surface films on carbon electrodes were increased by fluorination, however, the charge transfer resistances were decreased by 12.3% for PC2100 fluorinated at 200 °C, and by 27.5 and 6.4% for PC2600 fluorinated at 200 and 300 °C, respectively. The reduction of the charge transfer resistances was consistent with increase in the charge capacities for PC2100 fluorinated at 200 °C and PC2600 fluorinated at 200 and 300 °C.     

Composite film of carbon nanotubes and chitosan for preparation of amperometric hydrogen peroxide biosensor

A new amperometric biosensor for hydrogen peroxide was developed based on cross-linking horseradish peroxidase (HRP) by glutaraldehyde with multiwall carbon nanotubes/chitosan (MWNTs/chitosan) composite film coated on a glassy carbon electrode. MWNTs were firstly dissolved in a chitosan solution. Then the morphology of MWNTs/chitosan composite film was characterized by field-emission scanning electron microscopy. The results showed that MWNTs were well soluble in chitosan and robust films could be formed on the surface. HRP was cross-linked by glutaraldehyde with MWNTs/chitosan film to prepare a hydrogen peroxide biosensor. The enzyme electrode exhibited excellent electrocatalytic activity and rapid response for H₂O₂ in the absence of a mediator. The linear range of detection towards H₂O₂ (applied potential: −0.2 V) was from 1.67 × 10⁻⁵ to 7.40 × 10⁻⁴ M with correction coefficient of 0.998. The biosensor had good repeatability and stability for the determination of H₂O₂. There were no interferences from ascorbic acid, glucose, citrate acid and lactic acid.     

Effect of nitrogen-containing groups on enhanced capacitive behaviors of multi-walled carbon nanotubes

In this work, electrochemical properties of surface treated multi-walled carbon nanotubes (MWNTs) are studied in supercapacitors. Nitrogen and oxygen functional groups containing MWNTs are prepared by urea and acidic treatments, respectively. The surface properties of the MWNTs are confirmed by X-ray photoelectron spectroscopy (XPS) and zeta-potential measurements. The textural properties are characterized by N₂ adsorption/desorption isotherm at 77 K using the BET eqaution, BJH method, and HK method. The electrochemical properties of the MWNTs are accumulated by cyclic voltammetry, impedance spectra, and charge-discharge cycling performance in 1 M H₂SO₄ at room temperature. As a result, the functionalized MWNTs lead to an increase in capacitance as compared with pristine MWNTs. It suggests that the pyridinic and pyridinic-N-oxides nitrogen species have effects on the specific capacitance due to the positive charge, and thus an improved electron transfer at high current loads results, the most important functional groups affecting capacitive behaviors.     

Amperometric detection of dopamine based on tyrosinase-SWNTs-Ppy composite electrode

A novel 3-dimensional single wall carbon nanotubes (SWNTs)-polypyrrole (Ppy) composite was prepared as an electrode by chemically polymerizing polypyrrole onto SWNTs using a LiClO₄ oxidant. This composite electrode was characterized by scanning electron microscopy (SEM) and cyclic voltammetry with 1 mM [Fe(CN)₆]⁻³/[Fe(CN)₆]⁻⁴. The SWNTs were thickly coated with chemically polymerized polypyrrole and the composite had many surface pores and crevices which could enhance mass transfer. The SWNTs-Ppy composite electrode showed a large specific surface area (30 m²/g) and a good reproducible current response, at about 100 times the peak current of a glassy carbon electrode (GCE). The diffusion coefficient was calculated to be 4.81 × 10⁻⁶ cm²/s. As a biosensor application, tyrosinase was immobilized on the functionalized SWNTs and tyrosinase-SWNTs-Ppy composite was prepared in the same manner. This tyrosinase-SWNT-Ppy composite electrode was used for amperometric detection of dopamine in the presence of ascorbic acid and showed high sensitivity (467 mA/M cm²) and lower detection limit (5 μM) compared to previous reports.     

Sensitive DNA biosensor improved by Luteolin copper(II) as indicator based on silver nanoparticles and carbon nanotubes modified electrode

A novel and sensitive electrochemical DNA biosensor has been developed for the detection of DNA hybridization. The biosensor was proposed by using copper(II) complex of Luteolin C₃₀H₁₈CuO₁₂ (CuL₂) as an electroactive indicator based on silver nanoparticles and multi-walled carbon nanotubes (Ag/MWCNTs) modified glassy carbon electrode (GCE). In this method, the 4-aminobenzoic acid (4-ABA) and Ag nanoparticles were covalently grafted on MWCNTs to form Ag/4-ABA/MWCNTs. The proposed method dramatically increased DNA attachment quantity and complementary ssDNA detection sensitivity for its large surface area and good charge-transport characteristics. DNA hybridization detection was performed using CuL₂ as an electroactive indicator. The CuL₂ was synthesized and characterized using elemental analysis (EA) and IR spectroscopy. Cyclic voltammetry (CV) and fluorescence spectroscopy were used to investigate the interaction between CuL₂ and ds-oligonucleotides (dsDNA). It was revealed that CuL₂ presented high electrochemical activity on GCE, and it could be intercalated into the double helices of dsDNA. The target ssDNA of the human hepatitis B virus (HBV) was quantified in a linear range from 3.23 × 10⁻¹² to 5.31 × 10⁻⁹ M (r = 0.9983). A detection limit of 6.46 × 10⁻¹³ M (3σ, n = 11) was achieved.     

Efficient hydrophobization and solvent microextraction for determination of trace nano-sized silver and titanium dioxide in natural waters

Hydrophobic silver and titanium (IV) oxide nanoparticles (commercial Ag and TiO₂ NPs with average particle sizes of 17 and 19 nm, respectively) were quantitatively transferred into organic phase in natural water samples. Five NP surface modification and solvent extraction agents (reagents) types, mercaptocarboxylic acid, alkylamine, mediator solvent, extraction solvent, and surfactant, were investigated and optimized with three-level orthogonal array design (OAD), an OA₂₇ (3¹³) matrix. The most favorable reagents and experimental conditions were then examined. The best extraction efficiencies of 78.6 and 73.7% were obtained for 1 mg L⁻¹ citrate-stabilized Ag and TiO₂ NPs, respectively, with 0.5 mM of 11-mercaptoundecanoic acid, 1.5 mM of octadecylamine, 1 mL of methanol, 150 μL of cyclohexane, 0.05 mM of tetra-n-octylammonium bromide, pH = 8.0, adsorption time of 2 h, sonication time of 3 min, and centrifugation time of 10 min. Enrichment factors were 97 and 83, for Ag and TiO₂ NPs, respectively. The optimum extraction conditions were successfully applied to genuine water samples at spiking levels of 2–100 μg L⁻¹ of Ag and TiO₂ NPs. The relative recoveries of (69.0–85.1)% and (61.5–78.5)% were obtained for Ag and TiO₂ NPs, respectively. The extracted surface-modified NPs were characterized with transmission electron microscopy, selected area electron diffraction, energy-dispersive X-ray, ultraviolet–visible, and Fourier transform infrared spectroscopic techniques. Based on the results, efficient ligand exchange and acid–base pair formation were observed on the NP surface without significant change in its original properties. The organic phase was microwave digested, and analyzed with inductively coupled plasma (ICP) optical emission spectroscopy and ICP mass spectrometry (ICP-MS). Detection limits of ICP-MS analyses of Ag and TiO₂ NPs were 0.02 and 0.07 μg L⁻¹, respectively.     

Selective detection of dopamine in the presence of ascorbic acid and uric acid by a carbon nanotubes-ionic liquid gel modified electrode

The electrochemistry of dopamine (DA) was studied by cyclic voltammetry at a glassy carbon electrode modified by a gel containing multi-walled carbon nanotubes (MWNTs) and room-temperature ionic liquid of 1-octyl-3-methylimidazolium hexafluorophosphate (OMIMPF₆). The thickness of gel on the surface of the electrode has to be controlled carefully because the charging currents increase with the modified layer being thicker. The anodic peaks of DA, ascorbic acid (AA) and uric acid (UA) in their mixture can be well separated since the peak potential of AA is shifted to more negative values, while that of UA is shifted to more positive values due to the modified electrode. At pH 7.08 the three peaks are separated ca. 0.20 and 0.15 V, respectively; hence DA can be determined in the presence of UA and more than 100 times excess of AA. Under optimum conditions linear calibration graphs were obtained over the DA concentration range 1.0 × 10⁻⁶ to 1.0 × 10⁻⁴ M. The detection limit of the current technique was found to be 1.0 × 10⁻⁷ M based on the signal-to-noise ratio of 3. The modified electrode has been successfully applied for the assay of DA in human blood serum. This work provides a simple and easy approach to selectively detect dopamine in the presence of ascorbic acid and uric acid.     

Sulfonated polyaniline network grafted multi-wall carbon nanotubes for enzyme immobilization, direct electrochemistry and biosensing of glucose

A new nanomaterial was prepared by grafting a layer of sulfonated polyaniline network (SPAN-NW) on to the surface of multi-walled carbon nanotube (MWNT) and effectively utilized for immobilization of an enzyme and for the fabrication of a biosensor. SPAN-NW was formed on the surface of MWNT by polymerizing a mixture of diphenyl amine 4-sulfonic acid (DPASA), 4-vinyl aniline (VA) and 2-acrylamido-2-methyl-1-propane sulfonic acid (APASA) in the presence of amine functionalized MWNT (MWNT-NH₂). The MWNT-g-SPAN-NW was immobilized with glucose oxidase (GOx) to fabricate the SPAN-NW/GOx biosensor. MWNT-g-SPAN-NW/GOx electrode showed direct electron transfer (DET) for GOx with a fast heterogeneous electron transfer rate constant (k_s) of 4.11 s^− 1. The amperometric current response of MWNT-g-SPAN-NW/GOx biosensor shows linearity up to 9 mM of glucose, with a correlation coefficient of 0.99 and a detection limit of 0.11 μM (S/N = 3). At a low applied potential of − 0.1 V, MWNT-g-SPAN-NW/GOx electrode possesses high sensitivity (4.34 μA mM^− 1) and reproducibility towards glucose.