Kalayil Manian Manesh

Electrochemical determination of dopamine and ascorbic acid at a novel gold nanoparticles distributed poly(4-aminothiophenol) modified electrode

A modified electrode is fabricated by embedding gold nanoparticles into a layer of electroactive polymer, poly(4-aminothiophenol) (PAT) on the surface of glassy carbon (GC) electrode. Cyclic voltammetry (CV) is performed to deposit PAT and concomitantly deposit Au nanoparticles. Field emission transmission electron microscopic image of the modified electrode, PAT-Au(nano)-ME, indicates the presence of uniformly distributed Au nanoparticles having the sizes of 8-10nm. Electrochemical behavior of the PAT-Au(nano)-ME towards detection of ascorbic acid (AA) and dopamine (DA) is studied using CV. Electrocatalytic determination of DA in the presence of fixed concentration of AA and vice versa, are studied using differential pulse voltammetry (DPV). PAT-Au(nano)-ME exhibits two well defined anodic peaks at the potential of 75 and 400mV for the oxidation of AA and DA, respectively with a potential difference of 325mV. Further, the simultaneous determination of AA and DA is studied by varying the concentration of AA and DA. PAT-Au(nano)-ME exhibits selectivity and sensitivity for the simultaneous determination of AA and DA without fouling by the oxidation products of AA or DA. PAT and Au nanoparticles provide synergic influence on the accurate electrochemical determination of AA or DA from a mixture having any one of the component (AA or DA) in excess. The practical analytical utilities of the PAT-Au(nano)-ME are demonstrated by the determination of DA and AA in dopamine hydrochloride injection and human blood serum samples.

Electrocatalytic oxidation of NADH at gold nanoparticles loaded poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) film modified electrode and integration of alcohol dehydrogenase for alcohol sensing.

A new modified electrode is fabricated by dispersing gold nanoparticles onto the matrix of poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid), PEDOT-PSS. The electrocatalytic activity of the PEDOT-PSS-Au(nano) electrode towards the oxidation of beta-nicotinamide adenine dinucleotide (NADH) is investigated. A substantial decrease in the overpotential (>0.7 V) has been observed for the oxidation of NADH at the PEDOT-PSS-Au(nano) electrode in comparison to the potential at PEDOT-PSS electrode. The Au nanoparticles dispersed in the PEDOT-PSS matrix prevents the fouling of electrode surface by the oxidation products of NADH and augments the oxidation of NADH at a less positive potential (+0.04V vs. SCE). The electrode shows high sensitivity to the electrocatalytic oxidation of NADH. Further, the presence of ascorbic acid and uric acid does not interfere during the detection of NADH. Important practical advantages such as stability of the electrode (retains approximately 95% of its original activity after 20 days), reproducibility of the measurements (R.S.D.: 2.8%; n=5), selectivity and wide linear dynamic range (1-80 microM; R(2)=0.996) are achieved at PEDOT-PSS-Au(nano) electrode. The ability of PEDOT-PSS-Au(nano) electrode to promote the electron transfer between NADH and the electrode makes us to fabricate a biocompatible dehydrogenase-based biosensor for the measurement of ethanol. The biosensor showed high sensitivity to ethanol with rapid detection, good reproducibility and excellent stability.

Fabrication of enzymatic glucose biosensor based on palladium nanoparticles dispersed onto poly(3,4-ethylenedioxythiophene) nanofibers.

A new methodology involving the combination of a soft template (surfactant) and an ionic liquid (co-surfactant) is used to electrodeposit poly(3,4-ethylenedioxythiophene) (PEDOT) nanofibers. Electrochemical deposition of palladium nanoparticles and glucose oxidase (GOx) immobilization are done sequentially into nanofibrous PEDOT to fabricate the modified electrode (ME) (denoted as PEDOT-Pd/GOx-ME). The PEDOT-Pd/GOx-ME displays excellent performances for glucose at +0.4 V (vs. Ag/AgCl) with a high sensitivity (1.6 mA M(-)(1) cm(-2)) in a wider linear concentration range, 0.5 to 30 mM (correlation coefficient of 0.9985). Further, the electrode is insusceptible to the electroactive interfering species.

One-pot construction of mediatorless bi-enzymatic glucose biosensor based on organic-inorganic hybrid

A new methodology for the fabrication of bienzymatic amperometric glucose biosensor based on the use of an organic-inorganic hybrid is presented. The fabrication involves a self-assembly directed one-pot electrochemical process. Bi-enzymes, horseradish peroxidase (HRP) and glucose oxidase (GOx) are immobilized into the porous and electroactive silica-polyaniline hybrid composite through electrochemical polymerization of N[3-(trimethoxysilyl)propyl]aniline in the presence of enzymes. The modified electrode is designated as PTMSPA/HRP-GOx. The direct electron transfer of HRP is achieved at the modified electrode. Also, the electrode exhibits excellent bio-electro-catalytic activity for the reduction of hydrogen peroxide. The response current at PTMSPA/HRP-GOx modified electrode revealed a good linear relationship with concentration of glucose range between 1 and 20mM with a response time of 7s. Thus, the modified electrode shows the combined advantages of polyaniline and silica networks through synergistic influence from the individual components. The PTMSPA assembly has shown the potential for a third generation amperometric biosensor.

Electrochemical detection of celecoxib at a polyaniline grafted multiwall carbon nanotubes modified electrode

A modified electrode is fabricated by grafting polyaniline (PANI) chains onto multiwall carbon nanotubes (MWNTs) and utilized for the adsorptive reduction of celecoxib (CEL). PANI-g-MWNTs modified electrode appreciably enhances the sensitive detection of CEL in extremely lower concentrations (1x10(-11)M). Square wave stripping voltammogram (SWSV) shows a reduction peak at -1.08V with a high peak current for SW frequency of 100Hz, amplitude of 25mV and step height of 6mV. The high surface area of PANI-g-MWNTs is effectively utilized for the adsorption of CEL to preconcentrate at the electrode. The PANI chains covalently linked to MWNTs mediate the electron transfer processes. The present finding open-up the scope for extending on the use of other conducting polymers grafted MWNTs modified electrodes for the detection of compounds that do not have surface-active properties at conventional electrodes.

Hollow spherical nanostructured polydiphenylamine for direct electrochemistry and glucose biosensor

Nanostructured, hollow spheres of polydiphenylamine (HS-PDPA) are prepared through a soft template assisted self-assembly approach. An enzymatic glucose biosensor is fabricated through immobilizing glucose oxidase (GOx) into HS-PDPA matrix. The HS-PDPA-GOx electrode exhibits a pair of well-defined reversible redox peaks with a fast heterogeneous electron transfer rate. At an applied potential of +0.65V, HS-PDPA-GOx electrode possesses high sensitivity (1.77 microAmM(-1)cm(-2)), stability and reproducibility towards glucose. The amperometric current response of HS-PDPA-GOx to glucose is linear in the concentration range between 1 and 28 mM with a detection limit of 0.05 mM (S/N=3). Also, HS-PDPA-GOx electrode shows high selectivity towards glucose in the presence of ascorbic acid, uric acid and acetaminophen at their maximum physiological concentrations.

Fabrication of Functional Nanofibrous Ammonia Sensor

A nanofibrous sensor for ammonia gas is fabricated by electrospinning the composite of poly(diphenylamine) (PDPA) with poly(methyl methacrylate) (PMMA) onto the patterned interdigit electrode. The composite electrospun membrane shows interconnected fibrous morphology. Functional groups in PDPA and the high active surface area of the fibrous membrane make the device detect a lower concentration of ammonia with a good reproducibility. The sensing capability of the device is studied by monitoring the changes in resistance of the membrane with different concentrations of ammonia. The changes in resistance of the membrane shows linearity with the concentration of ammonia in the limit of 10 and 300 ppm. UV-visible spectroscopy reveals the mechanism of sensing ammonia by the membrane.

Pd (core)–Au (shell) nanoparticles catalyzed conversion of NADH to NAD+ by UV–vis spectroscopy—A kinetic analysis

Kinetics of Pd (core)-Au (shell) nanoparticles (NPs) catalyzed transformation of dihydronicotinamide adenine dinucleotide (NADH) to NAD(+) was monitored by UV-vis spectroscopy. Pd (core)-Au (shell) NPs were prepared by microwave irradiation method. High resolution transmission electron microscopy image reveals the core-shell morphology. X-ray diffraction pattern shows the presence of distinct crystalline domains for Pd and Au. The changes in absorbances at 340 nm were followed for various time intervals. Rates of conversion of NADH to NAD(+) were determined for different conditions. The conversion of NADH to NAD(+) was to be first order with respect to NADH at lower concentrations (upto 0.04 mM) and pseudo-first-order beyond 0.04 mM. Rate constants for the Pd (core) Au-(shell) NPs catalyzed transformation of NADH to NAD(+) were deduced.

Influence of Finely Dispersed Carbon Nanotubes on the Performance Characteristics of Polymer Electrolytes for Lithium Batteries

Electrospun membranes of poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP)/multiwall carbon nanotube (MWCNT) composite are prepared and loaded with lithium salts from electrolyte solution. Field emission transmission electron microscopy provides evidence for the uniform distribution of MWCNTs into the matrix of PVdF-HFP. The interconnected morphology as evident from field emission scanning electron micrograph forms the path for the lithium ion conduction. Results from electrochemical impedance spectroscopy inform that the presence of MWCNTs in PVdF-HFP matrix improves interfacial stability between lithium electrode and membrane and augment conduction path in the polymer electrolyte membrane. Further results from impedance measurement reveal the contribution of MWCNTs toward conductivity. A prototype cell is fabricated with PVdF-HFP/MWCNT as polymer electrolyte. The electrospun PVdF-HFP electrolyte membrane with 2% MWCNTs content shows an ionic conductivity of about 5.85 mSmiddotcm-1 at 25 degC. Also, PVdF-HFP/MWCNT electrolyte membrane exhibits good electrochemical and interfacial stability and can be potentially suitable as electrolyte in lithium ion secondary battery