Edge plane pyrolytic graphite as a sensing surface for the determination of fluvoxamine in urine samples of obsessive-compulsive disorder patients.

There is an increasing demand for fast and sensitive determination of antidepressants in human body fluids because of the present scenario of rising depression cases at the global level. A simple and sensitive voltammetric method using edge plane pyrolytic graphite electrode (EPPGE) as a novel sensor is presented for the determination of antidepressant fluvoxamine in urine and blood plasma samples of obsessive-compulsive disorder (OCD) patients. EPPGE is delineated the first time for this determination. EPPGE exhibited strong electrocatalytic activity and enhanced reduction signal towards the sensing of fluvoxamine. Fluvoxamine gave a well-defined reduction peak at ~ - 670 mV using EPPGE. The fluvoxamine reduction peak current was linear to its concentration in the range 5.00 × 10-9 - 0.1 × 10-6 mol L-1 and the limit of detection was found to be 3.5 × 10-9 mol L-1. The pre-eminence of EPPGE over mercury electrodes has been proved in terms of sensitivity and imperative analytical parameters. The pH study reveals the involvement of an equal number of electrons and protons in the reduction reaction mechanism. The frequency study indicated the adsorption controlled irreversible reaction mechanism. The stability and reproducibility of the offered sensor were also found most favorable. The interference study confirmed the optimum selectivity of the proposed sensor. The edge plane pyrolytic graphite sensing platform is recommended as a potential contender for the accurate and fast determination of fluvoxamine in depression medications as well as biological specimens of OCD patients.

Simultaneous detection of ATP metabolites in human plasma and urine based on palladium nanoparticle and poly(bromocresol green) composite sensor.

A sensitive voltammetric sensor based on palladium nanoparticles (PdNPs) and poly-bromocresol green (pBG) composite layer immobilized on amide functionalized single-walled carbon nanotubes (AmSWCNTs) modified pyrolytic graphite (PdNPs:pBG/AmSWCNTs/PG) has been prepared for the simultaneous determination of adenosine triphosphate (ATP) catabolites, inosine (INO), hypoxanthine (HX), xanthine (XT), and uric acid (UA). The modified PdNPs:pBG/AmSWCNTs/PG was characterized by electrochemical experiments and surface analysis, which exhibited exceptional electrocatalytic effects towards the oxidation of INO, HX, XT, and UA with a significant enhanced peak current and well resolved peaks separation for all the analytes. The linear calibration curves were obtained in the concentration range of 0.001-175 µM, 0.001-200 µM, 0.001-150 µM, and 0.001-200 µM and limits of detection were found as 0.95 nM, 1.04 nM, 1.07 nM, and 0.43 nM corresponding to INO, HX, XT, and UA, respectively. The common metabolites present in the biological fluids did not interfere in the determination. The applicability of the proposed sensor was successfully demonstrated by determining INO, HX, XT, and UA in the human plasma and urine and the obtained results were validated by using HPLC.

Conducting polymer-based electrochemical biosensors for neurotransmitters: A review.

Neurotransmitters are important biochemical molecules that control behavioral and physiological functions in central and peripheral nervous system. Therefore, the analysis of neurotransmitters in biological samples has a great clinical and pharmaceutical importance. To date, various methods have been developed for their assay. Of the various methods, the electrochemical sensors demonstrated the potential of being robust, selective, sensitive, and real time measurements. Recently, conducting polymers (CPs) and their composites have been widely employed in the fabrication of various electrochemical sensors for the determination of neurotransmitters. Hence, this review presents a brief introduction to the electrochemical biosensors, with the detailed discussion on recent trends in the development and applications of electrochemical neurotransmitter sensors based on CPs and their composites. The review covers the sensing principle of prime neurotransmitters, including glutamate, aspartate, tyrosine, epinephrine, norepinephrine, dopamine, serotonin, histamine, choline, acetylcholine, nitrogen monoxide, and hydrogen sulfide. In addition, the combination with other analytical techniques was also highlighted. Detection challenges and future prospective of the neurotransmitter sensors were discussed for the development of biomedical and healthcare applications.

A melamine based molecularly imprinted sensor for the determination of 8-hydroxydeoxyguanosine in human urine.

A sensitive and facile molecular imprinted sensor has been fabricated using edge plane pyrolytic graphite (EPPG) for the determination of an important oxidative DNA damage product, 8-hydroxydeoxyguanosine (8-OHdG). The molecularly imprinted polymer film was fabricated by electropolymerization of melamine in the presence of 8-OHdG, on glutaraldehyde/poly 1,5-diaminonaphthalene modified EPPG. The imprinted sensor surface was characterized by using Field Emission Scanning Electron Microscopy, Electron Impedance Spectroscopy, Cyclic Voltammetry, Square Wave Voltammetry and UV-visible spectroscopy. The calibration response was linear over a concentration range of 20×10-9-3×10-6M of 8-OHdG with sensitivity and limit of detection (3σ/b) as 10.59µM/µA and 3×10-9M respectively. The common metabolites in urine, like uric acid, ascorbic acid, xanthine, hypoxanthine do not interfere up to 100-fold concentration. The imprinted sensor is also successfully employed for the determination of 8-OHdG in human urine sample of a renal failure patient.

Determination of 8-Hydroxydeoxyguanosine: A potential biomarker of oxidative stress, using carbon-allotropic nanomaterials modified glassy carbon sensor.

A voltammetric sensor for the determination of 8-Hydroxydeoxyguanosine (8-OHdG); an important, sensitive and integral biomarker of oxidative stress and related pathological conditions like carcinogenesis, renal disorders, mental retardations, diabetes etc. has been fabricated. The synergistic behavior of two allotropic forms of carbon, which are electrochemically reduced graphene oxide (ErGO) and multiwalled carbon nanotubes (MWCNTs), has been exploited for the surface modification. The resulting modified surface has been characterized using Field Emission Scanning Electron Microscopy, X-ray diffraction, Electrochemical Impedance Spectroscopy and voltammetric behavior. The fabricated sensor exhibited excellent electrocatalytic effect towards oxidation of 8-OHdG and also showed substantial increment in sensitivity. The modified sensor showed a sensitivity of 0.1965µA/µM in the linear range of 3-75µM, whereas, a slope of 0.0046µA/µM was obtained for unmodified GCE. A limit of detection as low as 35nM has been obtained using the glassy carbon surface modified sensor. The proposed method was also successfully applied for the quantification of 8-OHdG in the presence of common interfering biomolecules like ascorbic acid, uric acid, xanthine, hypoxanthine etc. and also in human urine samples.

Graphene modified glassy carbon sensor for the determination of aspirin metabolites in human biological samples.

A graphene modified glassy carbon (GR/GCE) sensor has been developed for the determination of aspirin metabolites 2,3- and 2,5-dihydroxybenzoic acids (2,3- and 2,5-DHB). The modified sensor was characterized by Field Emission Scanning Electron Microscopy and Electrochemical Impedance Spectroscopy. The electrochemical behavior of 2,3- and 2,5-DHB was investigated by cyclic and square wave voltammetry. The modified sensor exhibited excellent electrocatalytic activity for the oxidation of 2,3- and 2,5-DHB, leading to a remarkable enhancement in the peak current as compared to the bare sensor. The results were attributed to the enhanced surface area and high conductivity of GR. The anodic peak currents of 2,3- and 2,5-DHB were found to be linear in the concentration range of 1-150 µM and 1-200 µM with the detection limits of 47 nM and 51 nM, respectively. The sensor was capable to determine 2,5-DHB effectively without any interference from the uric acid and other metabolites present in the urine samples. The practical utility of GR/GCE has been successfully demonstrated for the determination of 2,5-DHB in the urine samples of persons undergoing treatment with aspirin.

Gold nanoparticles decorated poly-melamine modified glassy carbon sensor for the voltammetric estimation of domperidone in pharmaceuticals and biological fluids.

The electrochemical response of an unmodified glassy carbon (GCE), poly-melamine/GCE and gold nanoparticle (AuNP)/poly-melamine/GCE is compared in the present protocol for the sensitive and selective determination of domperidone (DOM). The AuNPs were synthesized in the laboratory and characterized using UV-visible spectroscopy and Transmission Electron Microscopy (TEM). Melamine was electropolymerized onto the glassy carbon surface using cyclic voltammetry and was investigated using Field Emission Scanning Electron Microscopy (FE-SEM) and Electrochemical Impedance Spectroscopy (EIS). The AuNP/poly-melamine/GCE exhibited the best electrochemical response among the three electrodes for the electro-oxidation of DOM, that was inferred from the EIS, cyclic and square wave voltammetry. The modified sensor showed a sensitive, stable and linear response in the concentration range of 0.05-100µM with a detection limit of 6nM. The selectivity of the proposed sensor was assessed in the presence of high concentration of major interfering molecules as xanthine, hypoxanthine, and uric acid. The analytical application of the sensor for the quantification of DOM in pharmaceutical formulations and biological fluids as urine and serum was also investigated and the results demonstrated a recovery of >95% with R.S.D of <5%.

A categorical review on electroanalytical determination of non-narcotic over-the-counter abused antitussive drugs.

Dextromethorphan (DXM) and diphenhydramine (DPH) are two commonly used over-the-counter non-narcotic antitussive drugs. Recent reports reveal the widespread abuse of DXM and DPH due to their euphoric and alcohol-like effects. Due to their medicinal importance as well as the apparent increase in their use as abused drugs, it has become critical to determine them in samples of biological, clinical and pharmaceutical interest. The electrochemical techniques for drug analysis have gathered considerable attention due to their pronounced selectivity, sensitivity and simplicity. The given review presents a compilation of published voltammetric and potentiometric methods developed for determination of DXM and DPH. It critically highlights the analytical performances, revealing the recent trends and progress in the specified approach for their analysis. The review forms a basis for further progress in this field and development of improved electrochemical sensors to determine the drug.

Electroanalysis of antitubercular drugs in pharmaceutical dosage forms and biological fluids: a review.

Tuberculosis remains a major global public health problem. Given the need for extensive analysis of antitubercular drugs, the development of sensitive, reliable and facile analytical methods to determine these compounds becomes necessary. Electrochemical techniques have inherent advantages over other well-established analytical methods, this review aiming to provide an updated overview of the latest trends (from 2006 till date) in the voltammetric determination of antitubercular drugs. Furthermore, the advantages and limitations of these methods are critically discussed. The review reveals that in spite of using a variety of chemically modified electrodes to determine antitubercular drugs, there is still a dearth of applicability of the voltammetric methods to quantify these compounds in human body fluids, especially in blood plasma.

A novel nanogold-single wall carbon nanotube modified sensor for the electrochemical determination of 8-hydroxyguanine, a diabetes risk biomarker.

An electrochemical study of the oxidation of 8-hydroxyguanine (8-OH-Gua) at gold nanoparticles attached to single walled carbon nanotube modified edge plane pyrolytic graphite electrode (AuNP-SWCNT/EPPGE) has been carried out to develop a method for the self diagnosis of diabetes. The level of 8-OH-Gua, an important biomarker of oxidative DNA damage, is higher in urine of diabetic patients than control subjects. A detailed comparison has been made between the square wave voltammetric (SWV) response of SWCNT/EPPGE and AuNP-SWCNT/EPPGE towards the oxidation of 8-OH-Gua in respect of several essential analytical parameters viz. sensitivity, detection limit, peak current and peak potential. The AuNP-SWCNT/EPPGE exhibited a well defined anodic peak at potential of ~221 mV for the oxidation of 8-OH-Gua as compared to ~312 mV using SWCNT/EPPGE at pH=7.2. Under optimized conditions linear calibration curve for 8-OH-Gua is obtained over a concentration range of 0.01-10.0 nM in phosphate buffer solution (PBS) of pH=7.2 with detection limit and sensitivity of 5.0 (±0.1) pM and 4.9 (±0.1) µA nM(-1), respectively. The oxidation of 8-OH-Gua occurred in a pH dependent process and the electrode reaction followed adsorption controlled pathway. The electrode exhibited an efficient catalytic response with good reproducibility and stability. The method has been found selective and successfully implemented for the determination of 8-OH-Gua in urine samples of diabetic patients.

Molecularly imprinted sensor based on o-aminophenol for the selective determination of norepinephrine in pharmaceutical and biological samples.

An electrochemical sensor has been developed for the selective determination of norepinephrine (NE) using the molecularly imprinted technique. The imprinted polymer film at the surface of glassy carbon electrode is prepared by the electropolymerization of o-aminophenol in the presence of NE. Imprinted polymer film was characterized by atomic force microscopy (AFM), field emission scanning electron microscopy (FE-SEM), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The imprinted sensor showed a well-defined anodic peak at a potential of ~198 mV in phosphate buffer of pH 7.2 using square wave voltammetry. A linear increase in peak current was found with the increasing concentration of NE in the range from 50×10(-9) to 10×10(-6)mol L(-1)and the limit of detection (3σ/b) was found to be 4.9×10(-10)mol L(-1). The imprinted sensor has been successfully employed to ascertain the content of NE in the commercially available pharmaceutical preparations. The biological applicability of the developed sensor has been delineated by the determination of NE in human plasma and urine samples using the standard addition method. The proposed sensor exhibited high degree of selectivity for NE in comparison to other structurally similar biomolecules present in biological samples, along with long term stability, good reproducibility and excellent capacity of regeneration of molecular recognition sites.

In vitro chloramphenicol detection in a Haemophilus influenza model using an aptamer-polymer based electrochemical biosensor.

A sensitive and selective electrochemical biosensor is developed for the determination of chloramphenicol (CAP) exploring its direct electron transfer processes in in-vitro model and pharmaceutical samples. This biosensor exploits a selective binding of CAP with aptamer, immobilized onto the poly-(4-amino-3-hydroxynapthalene sulfonic acid) (p-AHNSA) modified edge plane pyrolytic graphite. The electrochemical reduction of CAP was observed in a well-defined peak. A quartz crystal microbalance (QCM) study is performed to confirm the interaction between the polymer film and the aptamer. Cyclic voltammetry (CV) and square wave voltammetry (SWV) were used to detect CAP. The in-vitro CAP detection is performed using the bacterial strain of Haemophilus influenza. A significant accumulation of CAP by the drug sensitive H. influenza strain is observed for the first time in this study using a biosensor. Various parameters affecting the CAP detection in standard solution and in in vitro detection are optimized. The detection of CAP is linear in the range of 0.1-2500 nM with the detection limit and sensitivity of 0.02 nM and 0.102 µA/nM, respectively. CAP is also detected in the presence of other common antibiotics and proteins present in the real sample matrix, and negligible interference is observed.

Polymelamine modified edge plane pyrolytic graphite sensor for the electrochemical assay of serotonin.

A sensitive and novel electrochemical method has been developed for the determination of an important neurotransmitter, serotonin, using a polymelamine modified edge plane pyrolytic graphite sensor (EPPGS). Melamine was used for the modification of sensor by electropolymerizing it at the surface of EPPGS in acidic medium to form a layer of conducting polymer. Field emission scanning electron microscopy (FE-SEM) and electrochemical impedance spectroscopy (EIS) were used for the characterization of the surface of polymer modified sensor. The electrochemical measurements were carried out using square wave voltammetry and cyclic voltammetry. The polymelamine modified sensor exhibited excellent electrocatalytic activity towards the electrochemical oxidation of serotonin, exhibiting a larger peak current and shift of peak potential to less positive potentials as compared to the unmodified sensor. The dynamic range for the serotonin determination was found between 1-100 µm and 0.1-100 µm with detection limit of 492 nM and 30 nM for unmodified and polymer modified sensors, respectively. The determination of serotonin in human blood serum and urine has been carried out. The common metabolites such as ascorbic acid, dopamine, xanthine and hypoxanthine do not interfere in the determination up to 10-fold concentration, revealing good selectivity of the proposed sensor.

Carbon nanotube embedded poly 1,5-diaminonapthalene modified pyrolytic graphite sensor for the determination of sulfacetamide in pharmaceutical formulations.

An electrochemically conductive single-walled carbon nanotube (SWCNT) embedded poly 1,5-diaminonapthalene (DAN) modified sensor has been developed for the determination of sulfacetamide (SFA). The surface morphology of the modified sensor has been characterized by FE-SEM, which revealed good dispersion of the carbon nanotube in polymer matrix. SFA was quantified using square wave voltammetry in phosphate buffer of pH 7.2, which acted as supporting electrolyte during analysis. The modified sensor exhibited an effective catalytic response towards the oxidation of SFA with excellent reproducibility and stability. The peak current of SFA was found to be linear in the concentration range of 0.005-1.5 mM and detection limit and sensitivity of 0.11 µM (S/N=3) and 23.977 µA mM(-1), respectively were observed. The analytical utility of method was checked by determining the SFA in various pharmacological dosage forms. The results obtained from the voltammetry were validated by comparing the results with those obtained from HPLC. The proposed method is sensitive, simple, rapid and reliable and is useful for the routine analysis of SFA in pharmaceutical laboratories.

Detection of norfloxacin and monitoring its effect on caffeine catabolism in urine samples.

A multi-walled carbon nano tube (MWCNT) modified pyrolytic graphite (MPG) electrode is prepared and applied to detect norfloxacin (NFX) based on its electrochemical reduction. The experimental parameters affecting the NFX determination were optimized in terms of MWCNT amount, pH, reaction time, and square wave frequency. The dynamic range for the NFX analysis ranged between 1.2 and 1000µM with a detection limit of 40.6±3.3nM. The effect of NFX on the catabolism of caffeine has been studied by determining its concentration in the urine samples after the prolonged administration of NFX using the MPG electrode. The results show that the catabolism of caffeine is inhibited by ~65% after five days of NFX administration, consequently the caffeine concentration in the urine sample is increased, which is reflected in terms of ~2.5 times increase in the peak current of caffeine. The determinations of NFX and caffeine were selective and the method was successfully applied in biological fluids and pharmaceutical tablets for the test compound analysis. In future this method can be useful for the selective determination of NFX and studying its effect on caffeine catabolism.

AuNPs-poly-DAN modified pyrolytic graphite sensor for the determination of Cefpodoxime Proxetil in biological fluids.

A sensitive and selective electrochemical method for Cefpodoxime Proxetil (CP) determination has been developed by incorporating gold nanoparticles (AuNPs) onto the poly-1,5-diaminonapthalene layer (p-DAN) coated pyrolytic graphite. The modified sensor was characterized by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The sensor exhibited an effective catalytic response towards oxidation of CP with excellent reproducibility and stability. The peak current of CP was found to be linear in the range of 0.1-12 µM and detection limit and sensitivity of 39 nM (S/N=3) and 4.621 µA µM(-1), respectively, were observed. The method was successfully applied for the determination of CP in pharmaceutical formulations and human urine samples. The common metabolites present in human urine such as uric acid, ascorbic acid, xanthine and hypoxanthine did not interfere in the determination. A comparison of the results obtained by using developed method with high performance liquid chromatography (HPLC) indicated a good agreement. The method is simple, sensitive, rapid and precise and is useful for the routine determination of CP in pharmaceutical dosages and biological samples.

A review on determination of steroids in biological samples exploiting nanobio-electroanalytical methods.

The applications of nanomaterial modified sensors, molecularly imprinting polymer based, aptamer based, and immunosensors have been described in the determination of steroids using electroanalytical techniques. After a brief description of the steroids and assays in biological fluids, the principles of electrochemical detection with the advantages and the limitations of the various sensors are presented. The nanomaterial modified sensors catalyze the oxidation/reduction of steroids and are suitable for sensing them in environmental samples and biological fluids. The determination of steroids based on their reduction has been found more useful in comparison to oxidation as the common metabolites present in the biological fluids do not undergo reduction in the usual potential window and hence, do not interfere in the determination. The sensors based on immunosensors and aptamers were found more sensitive and selective for steroid determination. Conducting polymer modified bio-sensors and microchip devices are suggested as possible future prospects for the ultra sensitive and simultaneous determination of steroids and their metabolites in various samples.

Investigation on the downregulation of dopamine by acetaminophen administration based on their simultaneous determination in urine.

A highly sensitive and selective method is developed for the simultaneous detection of dopamine (DA) and acetaminophen (AP) by reactive blue-4 (RB4) dye entrapped poly1,5-diaminonaphthalne (polyDAN) composite film layer. The polyDAN-RB4 composite is electrochemically developed at glassy carbon electrode. The polymeric film, characterized by XPS and SEM is able to catalyze the oxidation of DA and AP. Two well-defined oxidation peaks are observed in the differential pulse voltammogram (DPV). The experimental parameters affecting the analytical performance are optimized in terms of RB4 concentration, temperature, and pH. The dynamic range for DA and AP analysis is between 0.1-150 and 0.2-164µM with a detection limit of 0.061±0.002 and 0.083±0.003µM, respectively. The anionic form of the polyDAN-RB4 composite repels common metabolites present in serum and urine, and hence no interference is observed. The effect of AP on the DA concentrations in urine is also studied after the oral administration of a single as well as multiple doses. The DA concentrations have been found to decrease nearly 50±3% after prolonged AP administration.

Ag ion irradiated based sensor for the electrochemical determination of epinephrine and 5-hydroxytryptamine in human biological fluids.

A promising and highly sensitive voltammetric method has been developed for the first time for the determination of epinephrine (EP) and 5-hydroxytryptamine (5-HT) using 120 MeV Ag ion irradiated multi-walled carbon nano tube (MWCNT) based sensor. The MWCNT were irradiated at various fluences of 1e12, 3e12 and 1e13 ions cm(-2) using palletron accelerator. The simultaneous determination of EP and 5-HT has been carried out in phosphate buffer solution of pH 7.20 using square wave voltammetry and cyclic voltammetry. Experimental results suggested that irradiation of MWCNT by Ag ions enhanced the electrocatalytic activity due to increase in effective surface area and insertion of Ag ions, leading to a remarkable enhancement in peak currents and shift of peak potentials to less positive values as compared to the unirradiated MWCNT (pristine). The developed sensor exhibited a linear relationship between peak current and concentration of EP and 5-HT in the range 0.1-105 µM with detection limit (3σ/b) of 2 nM and 0.75 nM, respectively. The practical utility of irradiation based MWCNT sensor has been demonstrated for the determination of EP and 5-HT in human urine and blood samples.

Electrochemical sensor for the sensitive determination of norfloxacin in human urine and pharmaceuticals.

Electrochemical determination of Norfloxacin (NF) has been presented at edge plane (EPPGS) and basal plane pyrolytic graphite sensors (BPPGS) by using square wave voltammetry at physiological pH 7.2. An increased peak current with a shift of peak potential to less positive value was observed at EPPGS as compared to BPPGS. The effect of pH, scan rate and analyte concentration has been examined. The peak current was found to be linear to the concentration of NF in the range 0.5 × 10(-6) to 50.0 × 10(-6)mol L(-1) for EPPGS and the detection limit (3σ/b) was found to be 28.3 × 10(-8)mol L(-1). The method has been successfully used to determine the content of NF in the pharmaceutical preparations. Biological relevance of the developed method has been described by the determination of NF in human urine samples of the patients undergoing treatment with NF. The method is selective and NF can be determined without any interference from common urine metabolites such as uric acid and ascorbic acid.