Ronald J. Mascarenhas

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.

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.

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.

Iron nanoparticles decorated multi-wall carbon nanotubes modified carbon paste electrode as an electrochemical sensor for the simultaneous determination of uric acid in the presence of ascorbic acid, dopamine and L-tyrosine.

Iron nanoparticles decorated multi-wall carbon nanotubes modified carbon paste electrode (Fe-MWCNTs/MCPE) was prepared by bulk-modification method. The electrochemical impedance spectroscopy (EIS) suggests least charge transfer resistance at the modified electrode. The electrochemical behavior of UA was studied in 0.1M phosphate buffer solution (PBS) of pH3.0 using cyclic voltammetry (CV) while differential pulse voltammetry (DPV) was used for quantification. The spectroelectrochemial study of oxidation of UA at Fe-MWCNTs/MCPE showed a decrease in the absorbance of two peaks with time, which are ascribed to π to π(⁎) and n to π(⁎) transitions. Under optimum condition, the DPV response offered two linear dynamic ranges for UA in the concentration range 7.0×10(-8)M-1.0×10(-6)M and 2.0×10(-6)M-1.0×10(-5)M with detection limit (4.80±0.35)×10(-8)M (S/N=3). The practical analytical application of this sensor was successfully evaluated by determination of spiked UA in clinical samples, such as human blood serum and urine with good percentage recovery. The proposed electrochemical sensor offers a simple, reliable, rapid, reproducible and cost effective analysis of a quaternary mixture of biomolecules containing AA, DA, UA and Tyr which was free from mutual interferences.

Pristine multi-walled carbon nanotubes/SDS modified carbon paste electrode as an amperometric sensor for epinephrine

An amperometric sensor for the determination of epinephrine (EP) was fabricated by modifying the carbon paste electrode (CPE) with pristine multi-walled carbon nanotubes (pMWCNTs) using bulk modification followed by drop casting of sodium dodecyl sulfate (SDS) onto the surface for its optimal potential application. The modified electrode showed an excellent electrocatalytic activity towards EP by decreasing the overpotential and greatly enhancing the current sensitivity. FE-SEM images confirmed the dispersion of pMWCNTs in the CPE matrix. EDX analysis ensured the surface coverage of SDS. A comparative study of pMWCNTs with those of oxidized MWCNTs (MWCNTsOX) modified electrodes reveals that the former is the best base material for the construction of the sensor with advantages of lower oxidation overpotential and the least background current. The performance of the modified electrode was impressive in terms of the least charge transfer resistance (Rct), highest values for diffusion coefficient (DEP) and standard heterogeneous electron transfer rate constant (k°). Analytical characterization of the modified electrode exhibited two linear dynamic ranges from 1.0×10(-7) to 1.0×10(-6)M and 1.0×10(-6) to 1.0×10(-4)M with a detection limit of (4.5±0.18)×10(-8)M. A 100-fold excess of serotonin, acetaminophen, folic acid, uric acid, tryptophan, tyrosine and cysteine, 10-fold excess of ascorbic acid and twofold excess of dopamine do not interfere in the quantification of EP at this electrode. The analytical applications of the modified electrode were demonstrated by determining EP in spiked blood serum and adrenaline tartrate injection. The modified electrode involves a simple fabrication procedure, minimum usage of the modifier, quick response, excellent stability, reproducibility and anti-fouling effects.

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.

Facile preparation of poly(methylene blue) modified carbon paste electrode for the detection and quantification of catechin

Free radicals are formed as byproducts of metabolism, and are highly unstable due to the presence of unpaired electrons. They readily react with other important cellular components such as DNA causing them damage. Antioxidants such as (+)-catechin (CAT), neutralize free radicals in the blood stream. Hence there is a need for detection and quantification of catechin concentration in various food sources and beverages. Electro-oxidative properties of catechin were investigated using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). A carbon paste working electrode modified by electropolymerizing methylene blue (MB) was fabricated. Field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) techniques were used to study the surface morphology of the electrode. Quasi-reversible electron transfer reaction occurred at +0.260V through a diffusion controlled process. In comparison to the bare carbon paste electrode (CPE), there was a significant 5.3 times increment in anodic current sensitivity at the modified electrode at physiological pH. Our findings indicate that for the electro-oxidation of CAT, CPE is a better base material for electropolymerization of MB compared to glassy carbon electrode (GCE). Nyquist plot followed the theoretical shape, indicating low interfacial charge transfer resistance of 0.095kΩ at the modified electrode. Calibration plots obtained by DPV were linear in two ranges of 1.0×10-3 to 1.0×10-6 and 1.0×10-7 to 0.1×10-8M. The limit of detection (LOD) and limit of quantification (LOQ) was 4.9nM and 14nM respectively. Application of the developed electrode was demonstrated by detecting catechin in green tea and spiked fruit juice with satisfactory recoveries. The sensor was stable, sensitive, selective and reproducible.

A multi-walled carbon nanotube/poly-2,6-dichlorophenolindophenol film modified carbon paste electrode for the amperometric determination of L-tyrosine

A novel multi-walled carbon nanotube/poly-2,6-dichlorophenolindophenol (DCPIP) film modified carbon paste electrode (MCPE/MWCNTs/p-DCPIP) was constructed using drop casting and electropolymerization methods. Cyclic voltammetry and amperometric techniques were employed for the determination of L-tyrosine (Tyr). An electrochemically induced oxa–Michael addition reaction has been proposed as a possible mechanism of the electropolymerization of DCPIP on the surface of the modified electrode. The surface morphology and interface properties of the electrodes were investigated by FE-SEM images and the electrochemical impedance spectroscopy (EIS), respectively. The AFM images confirm the formation of nano fibrous deposits of DCPIP. The spectroelectrochemical study performed reveals the structural changes in Tyr during oxidation. This sensor was used for the selective detection of Tyr at physiological pH in the presence of some common interfering biomolecules. Chronoamperometic technique was employed for the determination of the diffusion coefficient and the standard heterogeneous electron transfer rate constant (k0) of Tyr at the modified electrode. The sensor exhibited a linear response to Tyr over a wide concentration range of 0.3 μM–8.0 μM and 10.0 μM–110.0 μM with a detection limit (70.5 ± 2.35) nM (S/N = 3). The practical utility of the sensor was demonstrated by determining Tyr in spiked human blood serum and soya sauce.

A novel and sensitive hexadecyltrimethylammoniumbromide functionalized Fe decorated MWCNTs modified carbon paste electrode for the selective determination of Quercetin

The fabrication of differential pulse voltametry (DPV) sensor for the effective detection of Quercetin (QR) was achieved by modifying carbon paste electrode (CPE) with Iron decorated multi walled carbon nano tubes (Fe-MWCNTs) followed by drop casting of hexadecyltrimethylammonium bromide onto the surface for optimal results. Cyclic voltammetry and DPV techniques were used for qualitative and quantitative analysis of QR (Quercetin) respectively. The sensor revealed impressive electro-catalytic behavior towards oxidation of QR with almost 6.4 times increase in current compared to bare carbon paste electrode CPE and also decrease in the energetics. Under optimum conditions, a wide linear dynamic range of 0.06 to 3000μM, with a lower limit of detection, 1.20nM with S/N=3 was observed. Absence of peak for the interfering molecules such as Folic acid and Ascorbic acid makes it a unique sensor with significant analytical advantage. The quantification of QR at this sensor was not affected by the presence of 1000 fold Uric Acid implying that the sensor is capable of specifically identifying QR in a mixture of interfering molecules. In this paper, we demonstrate that with minimal use of modifiers and simple procedures of fabrication, the fabricated sensor exhibits excellent stability, reproducibility and swift responses. Application of the developed electrode was demonstrated by detecting QR in wine and coconut water samples with satisfactory recoveries.

Multi-wall Carbon Nanotubes Decorated with Barium Oxide Nanoparticles

A simple, reproducible and efficient technique to decorate multi-wall carbon nanotubes (MWCNTs) with barium oxide nanoparticles (BaO NPs) using infrared (IR) irradiation is developed. NaOH treatment leads to the purification of MWCNTs (p-MWCNTs). Functionalizing p-MWCNTs with tricarboxylic aryl diazonium salts generated in-situ and then reacting it with barium acetate in the presence of IR irradiation is the key step in efficiently impregnating p-MWCNTs-D3 with barium acetate (p-MWCNTs-D3/BA). Materials are characterized using XPS, TEM and PXRD. Homogeneous distribution of BaO NPs on MWCNTs is evidenced, with a Gaussian mean diameter of 5.1 nm. This method is also applicable to large scale preparation which opens interesting perspectives for nanotechnology applications.