B.E. Kumara Swamy

Multi-walled carbon nanotube modified carbon paste electrode as a sensor for the amperometric detection of l-tryptophan in biological samples

An electrochemical sensor for the amperometric determination of L-tryptophan (Trp) was fabricated by modifying the carbon paste electrode (CPE) with multi-walled carbon nanotubes (MWCNTs) using drop cast method. 4.0 μL of the dispersion containing 2.0 mg of MWCNTs in 1.0 mL of ethanol was drop cast onto the electrode surface and dried in hot air oven to form a stable layer of MWCNTs. The electro-catalytic activity of the modified electrode towards the oxidation of Trp was thoroughly investigated. The modification with MWCNTs has greatly improved the current sensitivity of CPE for the oxidation of Trp. A very minimal amount of the modifier was required to achieve such a high sensitivity. The field emission scanning electron microscopy (FESEM) images revealed a uniform coverage of the surface of CPE by MWCNTs. Nyquist plots revealed the least charge transfer resistance for the modified electrode. The analytical performance of the modified electrode was examined using amperometry under hydro-dynamic conditions. The two linear dynamic ranges observed for Trp were 0.6-9.0 μM and 10.0-100.0 μM. The amperometric determination of Trp did not suffer any interference from other biomolecules. The detection limit of Trp at modified electrode was (3.30±0.37)×10(-8)M (S/N=3). The analytical applications of the modified electrode were demonstrated by estimating Trp in the spiked milk and biological fluid such as blood serum. The modified electrode showed good reproducibility, long-term stability and anti-fouling effects.

Sol–gel immobilized biosensor for the detection of organophosphorous pesticides: A voltammetric method

Organophosphorous compounds are important neuroactive molecules whose presence exhibits significant analytical challenges. An acetylcholinesterase (AChE) based amperometric biosensor was developed by silica sol-gel film immobilization of the enzyme onto the carbon paste electrode. The mono enzyme biosensor was used for the determination of two organophosphorous compounds such as methyl parathion (MP) and acephate in 0.1M phosphate buffer (pH 7.0). The substrate used was acetylthiocholine chloride (ASChCl) confirmed the formation of thiocholine and it was electrochemically oxidized giving significant increase in anodic peak current around at 0.60 V versus calomel electrode. The influence of pH, enzyme loading and substrate concentration on the response of the biosensor was investigated. The monoenzyme biosensor provided linearity to methyl parathion and acephate in the concentration range of 0.1-0.5 ppb and 50-750 ppb with an incubation time of 20 min and 4 min. The detection limits under the optimum working conditions were found to be 0.08 ppb for methyl parathion and 87 ppb for acephate. The sensor shows good operational stability 89% of its original activity for 60 successive measurements.

Multi-walled carbon nanotube modified carbon paste electrode as an electrochemical sensor for the determination of epinephrine in the presence of ascorbic acid and uric acid

A biocompatible electrochemical sensor for selective detection of epinephrine (EP) in the presence of 1000-fold excess of ascorbic acid (AA) and uric acid (UA) was fabricated by modifying the carbon paste electrode (CPE) with multi-walled carbon nanotubes (MWCNTs) using a casting method. The electro-catalytic activity of the modified electrode for the oxidation of EP was investigated. The current sensitivity of EP was enhanced to about five times upon modification. A very minimum amount of modifier was used for modification. The voltammetric response of EP was well resolved from the responses of AA and UA. The electrochemical impedance spectroscopic (EIS) studies reveal the least charge transfer resistance for the modified electrode. The AA peak that is completely resolved from that of EP at higher concentrations of AA and the inability of the sensor to give an electrochemical response for AA below a concentration of 3.0×10(-4)M makes it a unique electrochemical sensor for the detection of EP which is 100% free from the interference of AA. Two linear dynamic ranges of 1.0×10(-4)-1.0×10(-5) and 1.0×10(-5)-5.0×10(-7)M with a detection limit of 2.9×10(-8)M were observed for EP at modified electrode. The practical utility of this modified electrode was demonstrated by detecting EP in spiked human blood serum and EP injection. The modified electrode is highly reproducible and stable with anti fouling effects.

Acetylcholinesterase based biosensor for monitoring of Malathion and Acephate in food samples: A voltammetric study

Acetylcholinesterase (AChE) biosensor was developed through silica sol-gel (SiSG) immobilisation of AChE on the carbon paste electrode (CPE) and used as working electrode. AChE catalyses the cleavage of acetylthiocholine chloride (ASChCl or substrate) to thiocholine, which was oxidised to give a disulphide compound by dimerisation at 0.60V versus saturated calomel electrode. All the experiments were carried out in 0.1M phosphate buffer solution (PBS) at pH 7.0 and 0.1M KCl solution at room temperature. The limit of detection and limit of quantification values were found to be 0.058ppm, 0.044ppm and 0.194ppm, 0.147ppm for Malathion and Acephate, respectively. The response of the biosensor showed a good linearity range with an incubation time of 4min for Malathion and Acephate, respectively. This biosensor was used for the direct determination of pesticides without any pretreatment and it requires less time for analysis.

Electropolymerisation of l-arginine at carbon paste electrode and its application to the detection of dopamine, ascorbic and uric acid

L-arginine was electropolymerised on a carbon paste electrode (CPE) to form the biopolymer by free radical formation in the electro oxidation process of the amino and carboxylic group containing compound by cyclic voltammetric technique. The modified electrode shows an excellent electrocatalytic activity towards the oxidation of both dopamine (DA) and ascorbic acid (AA). It was demonstrated that the deposited biopolymer has positive charges over the bare carbon electrode surface, which leads to the formation of electrical double layer made the fast electron transfer process could leads to the diffusion of dopamine, ascorbic acid and uric acid on their charge gradient by cyclic voltammetric technique. The response of the sensor was tested towards the different dopamine concentration. The catalytic peak current obtained was linearly related to DA concentrations in the ranges of 5×10(-5) to 1×10(-4)M L(-1) with correlation co-efficient of 0.9924 which reveals the adsorption controlled process. The detection limit for dopamine was 5×10(-7)M L(-1). The interference studies showed that the modified electrode exhibits excellent selectivity in the presence of large excess of ascorbic acid (AA) and response is fast stable, reliable, resistant to biofouling and can be applied for the real sample analysis in medical, pharmaceutical and biotechnological sectors. The adsorption-controlled process and kinetic parameters of the poly(L-arginine) were determined using electrochemical approaches.

Multi-walled carbon nanotube/poly(glycine) modified carbon paste electrode for the determination of dopamine in biological fluids and pharmaceuticals.

A modified carbon paste electrode (CPE) for the selective detection of dopamine (DA) in presence of large excess of ascorbic acid (AA) and uric acid (UA) at physiological pH has been fabricated by bulk modification of CPE with multi-walled carbon nanotubes (MWCNTs) followed by electropolymerization of glycine (Gly). The surface morphology is compared using SEM images. The presence of nitrogen was confirmed by the energy dispersion X-ray spectroscopy (EDS) indicating the polymerization of Gly on the surface of the modified electrode. The impedance study indicates a better charge transfer kinetics for DA at CPE modified with MWCNT/polyglycine electrode. The presence of MWCNTs in carbon paste matrix triggers the extent of electropolymerization of Gly and imparts more selectivity towards DA by electrochemically not sensing AA below a concentration of 3.1×10(-4)M. Due to the exclusion of the signal for AA, the interference of AA in the determination of DA is totally ruled out by DPV method which is used for its detection at lower concentrations. Large peak separation, good sensitivity, reproducibility and stability allow this modified electrode to analyze DA individually and simultaneously along with AA and UA. Detection limit of DA was determined from differential pulse voltammetric (DPV) study and found to be 1.2×10(-8)M with a linear dynamic range of 5.0×10(-7)M to 4.0×10(-5)M. The practical analytical application of this electrode was demonstrated by measurement of DA content in dopamine hydrochloride injection and human blood serum.

Poly(Patton and Reeder's reagent) modified carbon paste electrode for the sensitive detection of acetaminophen in biological fluid and pharmaceutical formulations.

An electrochemical sensor for sensitive detection of acetaminophen (AAP) was developed by electropolymerizing Patton and Reeders reagent at carbon paste electrode (CPE). Modification improves the redox kinetics of AAP with increased current sensitivity. A similar modification at multiwall carbon nanotube (MWCNT) modified CPE did not result in an impressive charge transfer. Electrochemical impedance spectroscopy (EIS) of the bare and modified electrodes investigated imply a least charge transfer resistance at Patton and Reeders reagent modified carbon paste electrode (MCPE/PR) as compared to bare CPE and MWCNT modified electrode. Differential pulse voltammetric (DPV) study at MCPE/PR electrode did not suffer any interference from its hydrolytic degradation product 4-aminophenol (4-AP) even in 1000-fold excess of its concentration and enables its detection simultaneously. A linear dynamic range of 0.7-100 μM with detection limit (S/N=3) of 0.53 μM was obtained for AAP. This modified electrode is easy to prepare, cheap, and having good reproducibility and stability. The analytical performance of the modified electrode is assessed by successfully applying it for the estimation of acetaminophen in different pharmaceutical samples and spiked biological fluid.

Simultaneous cyclic voltammetric determination of norepinephrine, ascorbic acid and uric acid using TX-100 modified carbon paste electrode

A sensitive and selective electrochemical method for the determination of norepinephrine (NE) using TX-100 modified carbon paste electrode was developed. The TX-100 modified carbon paste electrode shows excellent electrocatalytic activity towards the oxidation of NE in phosphate buffer solution (pH 7.0). The linear range of 0.5 × 10−4 to 2.0 × 10−4 M and detection limit of 5 × 10−6 M were observed at pH 7.0 phosphate buffer solution. The interference studies showed that the modified electrode exhibits excellent selectivity in the presence of large excess of ascorbic acid (AA) and uric acid (UA). The separation of the oxidation peak potentials for NE–AA and NE–UA were about 0.16 V and 0.11 V, respectively. The differences were large enough to determine AA, NE and UA individually and simultaneously. This work provides a simple and easy approach to selectively detect norepinephrine in the presence of ascorbic acid and uric acid in physiological samples.

ZnO and ZnO/polyglycine modified carbon paste electrode for electrochemical investigation of dopamine

Present work describes the characterization of commercially available ZnO and its electrochemical investigation of dopamine in the presence of ascorbic acid. ZnO was characterized by powder XRD, UV-visible absorption, fluorescence, infrared spectroscopy and scanning electron microscopy. The carbon paste electrode was modified with ZnO and ZnO/polyglycine for further electrochemical investigation of dopamine. The modified electrode shows good electrocatalytic activity towards the detection of dopamine with a reduction in overpotential. The ZnO/polyglycine modified carbon paste electrode (CPE/ZnO/Pgl) shows excellent electrochemical enhancement of peak currents for both dopamine (DA) and ascorbic acid (AA) and for simultaneous detection of DA in the presence of high concentrations of AA with 0.214 V oxidation peak potential differences between them at pH 7.4. From the scan rate variation and concentration, the oxidation of DA and AA was found to be adsorption-controlled. The use of CPE/ZnO/Pgl is demonstrated for the detection of DA in blood serum and injection samples.

Synthesis of MgFe2O4 nanoparticles and MgFe2O4 nanoparticles/CPE for electrochemical investigation of dopamine

Magnesium ferrite nanoparticles (MgFe2O4 NPs) were prepared by a solution based method using magnesium sulphate (MgSO4), ferrous sulphate (FeSO4), dl serine and NaOH as a precipitant and the obtained precipitation was calcinated under 500 °C for 4 h. The resulting material was characterized by using X-ray diffractometry (XRD) and scanning electron microscopy (SEM). The MgFe2O4 NPs were used for preparation of MgFe2O4 NPs/carbon paste electrode (MgFe2O4 NPs/CPE) and applied for electrochemical investigation of dopamine (DA) which exhibits good electrocatalytic activity for investigation of DA at physiological pH 7.4. The effect of pH range from 5.5 to 8.0 was studied and the result shows that the redox peak current was maxima at pH 7.5 and the redox peak was pH dependent with a slope of 0.061 V/pH. The scan rate effect was found to be an adsorption-controlling electrode process. The electrocatalytic currents increased linearly with an increase in DA concentration in the range 0.1–1.2 μM and the detection limit was found to be 7.7 × 10−8 M. The proposed method was successfully applied to the determination of DA in injection samples.