Poly(para toluene sulphonic acid) and gold nanoparticles modified glassy carbon electrode for simultaneous voltammetric sensing of xanthine and hypoxanthine.

A voltammetric sensor has been developed for the individual as well as simultaneous determination of xanthine (XA) and hypoxanthine (HX) based on an electroactive-polymerised layer of para toluene sulphonic acid and gold nanoparticles composite modified glassy carbon electrode ([p(PTSA)]/AuNPs/GCE)]. Under optimized conditions, an enhancement in the oxidation currents with well-separated and well-resolved peak position and a lower shift in the peak potentials were observed. By square wave voltammetry, the simultaneous determinations of XA and HX were achieved in the linear ranges 6.00 × 10-4 M to 3.00 × 10-6 M and 5.00 × 10-4 M to 1.00 × 10-5 M with detection limits of 4.09 × 10-7 M and 4.10 × 10-7 M, respectively. The mechanistic aspects were unveiled from linear sweep voltammetric studies and found that the electrode processes were diffusion-controlled. Finally, the sensor was successfully employed for the simultaneous determination of spiked amount of XA and HX in synthetic urine and serum samples.

Tannic Acid Capped Copper Nanoclusters as a Cost-Effective Fluorescence Probe for Hemoglobin Determination.

For the first time, we report on a copper nanoclusters based fluorescence sensor for hemoglobin (Hgb). The aggregation-induced quenching of tannic acid capped copper nanoclusters' (TACuNCs) fluorescence by a Hgb-H2O2 mixture that mimics the Fenton's reagent is used here for the selective determination of Hgb. It is possible to effectively determine Hgb using this sensitive and cost-effective sensor in the linear range of 5.0 × 10-8 to 4.0 × 10-9 M with a detection limit of 5.6 × 10-10 M. The practical utility of the sensor is evident from the good recovery values obtained from Hgb spiked with artificial blood serum.

Possible Effects of Perchlorate Contamination of Drinking Water on Thyroid Health.

BACKGROUND: Perchlorate is an anion that occurs as a contaminant in groundwater. It originates from the improper disposal of ammonium perchlorate, a component of rocket fuel. The objective of this study was to explore whether the exposure to perchlorate in drinking water had an impact on the thyroid function of the population residing near an ammonium perchlorate plant in Kerala. Methodology. Using an ecological study design, we compared the serum levels of thyroid-stimulating hormone, thyroxine, and thyroid peroxidase antibodies among a representative sample of 289 study subjects from the area surrounding the ammonium perchlorate enrichment plant to 281 study subjects in a control area. RESULTS: The perchlorate concentration in the groundwater varied from 1600 ppb to 57,000 ppb in the 10 samples from the contaminated area and was below 24 ppb in all locations in the control area. No significant differences were found in the mean serum TSH concentration and mean T4 levels between the subjects from the contaminated area and the control area. On regression analysis, perchlorate contamination was not found to be a significant predictor of TSH. CONCLUSION: This study did not find any significant association between perchlorate in drinking water and changes in thyroid hormone levels. Our findings indicate the need for further investigation of this hypothesis using urinary perchlorate as a measure of individual exposure.

Redox-Active Monolayers Self-Assembled on Gold Electrodes-Effect of Their Structures on Electrochemical Parameters and DNA Sensing Ability.

The background: The monolayers self-assembled on the gold electrode incorporated transition metal complexes can act both as receptor ("host" molecules) immobilization sites, as well as transducer for interface recognitions of "guest" molecules present in the aqueous solutions. Their electrochemical parameters influencing the sensing properties strongly depend on the transition metal complex structures. The objectives: The electrochemical characterization of the symmetric terpyridine-M2+-terpyridine and asymmetric dipyrromethene-M2+-terpyridine complexes modified with ssDNA probe covalently attached to the gold electrodes and exploring their ssDNA sensing ability were the main aims of the research presented. The methods: Two transition metal cations have been selected: Cu2+ and Co2+ for creation of redox-active monolayers. The electron transfer coefficients indicating the reversibility and electron transfer rate constant measuring kinetic of redox reactions have been determined for all SAMs studied using: Cyclic Voltammetry, Osteryoung Square-Wave Voltammetry, and Differential Pulse Voltammetry. All redox-active platforms have been applied for immobilization of ssDNA probe. Next, their sensing properties towards complementary DNA target have been explored electrochemically. The results: All SAMs studied were stable displaying quasi-reversible redox activity. The linear relationships between cathodic and anodic current vs. san rate were obtained for both symmetric and asymmetric SAMs incorporating Co2+ and Cu2+, indicating that oxidized and reduced redox sites are adsorbed on the electrode surface. The ssDNA sensing ability were observed in the fM concentration range. The low responses towards non-complementary ssDNA sequences provided evidences for sensors good selectivity. The conclusions: All redox-active SAMs modified with a ssDNA probe were suitable for sensing of ssDNA target, with very good sensitivity in fM range and very good selectivity. The detection limits obtained for SAMs incorporating Cu2+, both symmetric and asymmetric, were better in comparison to SAMs incorporating Co2+. Thus, selection of the right transition metal cation has stronger influence on ssDNA sensing ability, than complex structures.

Biothiols induced colour change of silver nanoparticles: A colorimetric sensing strategy.

A sensor for the detection and determination of bio-thiols (glutathione (GSH) and cysteamine (Cyste)) has been developed by integrating the distinguished distance related optical characteristics of silver nanoparticles with the simplicity of colorimetric technique. In presence of these analytes, shift in surface plasmon resonance (SPR) absorption of silver nanoparticles (AgNPs) with change in its colour was observed. Yellow coloured AgNPs solution becomes colourless in presence of GSH and changes to red in presence of Cyste. FTIR, TEM and DLS studies were used to confirm the mechanism. The difference in absorption of AgNPs in the absence and presence of GSH was found to vary linearly in the range 1.00×10-5M to 5.00×10-7M concentration range with limit of detection at 3.68×10-7M. The method can also be applied to quantify Cyste in the range 1.10×10-6M to 5.00×10-8M with limit of detection at 1.80×10-8M. The utility of the proposed colorimetric assay is validated by determination of GSH and Cyste in artificial blood serum.

Fluorescence Turn off Sensor for Brilliant Blue FCF- an Approach Based on Inner Filter Effect.

A nanosensor with fluorometric readout based on L-cysteine capped cadmium sulphide quantum dots for discriminative detection and determination of Brilliant blue FCF (BB) (in 0.5 M Tris buffer solution of pH 9.5) over other synthetic food colourants is developed. Mechanism of the nanosensor is based on inner filter effect (IFE). The addition of BB into quantum dot solution might induce the quenching of fluorescence. The nanosensor described in this report reveals its simplicity and flexibility due to less laborious and more cost-effective synthesis. The developed fluorescence sensor showed excellent selectivity towards BB, and allows the detection as low as 3.50 × 10-7 M. The developed sensor exhibited a linear concentration range of 4.00 × 10-5 to 4.50 × 10-6 M. More importantly, the proposed sensor exhibit sensitive responses toward BB in food samples such as sports drink and candies, demonstrating its potential in food analysis, which might be significant in food quality control in the future.

Manganese porphyrin sensor for the determination of bromate.

The electro reductive behavior and determination of bromate on [5, 10, 15, 20-tetrakis (4-methoxyphenylporphyrinato] Manganese (III) chloride (TMOPPMn(III)Cl) modified Gold electrode(GE) was investigated by Square wave voltammetry (SWV). Bromate showed an irreversible reduction peak at -164 mV in 0.1 M pH 7 Na2SO4 solution. The cathodic peak of bromate showed a reduction in potential of 88 mV on modifying GE with a porphyrin film. The peak current varied linearly with concentration with a detection limit of 3.56 × 10(-9) M. The influence of pH, scan rate, supporting electrolyte and interferents on the reduction peak current of bromate were studied. The developed sensor was proposed for the determination of bromate in bread samples and compared with the standard method.

"Turn On" Fluorescence Determination of Nitrite Using Green Synthesized Carbon Nanoparticles.

Although several methods have been reported for the determination of nitrite, development of simple, rapid,cost-effective, and sensitive sensors still remains a great challenge.Here, a simple yet very sensitive fluorescent method for the rapid determination of nitrite has been developed. The fluorescent assay is based on the aggregation of PEG6000 coated carbon nanoparticles (PCNs) in the presence of NO2(-) ions resulting in fluorescence enhancement. The assay response was linear in a concentration range of 3.84 × 10(-8) M to 4.97 × 10(-9) M with a detection limit of 2.32 × 10(-9) M. The proposed sensor exhibited good selectivity towards NO2(-) and was successfully applied for the determination of nitrite in milk, borewell water and soil samples.

Study of kinetic parameters and development of a voltammetric sensor for the determination of butylated hydroxyanisole (BHA) in oil samples.

Electrochemical behavior of artificial antioxidant, butylated hydroxyanisole (BHA), was investigated at a glassy carbon electrode modified with poly L- cysteine [poly (L- Cys/GCE)]. BHA exhibits a pair of well - defined redox peak on L- cysteine modified GCE with Epa = 69 mV and Epc = 4 mV. The modified electrode showed good electrocatalytic activity towards the oxidation of BHA under optimal conditions and exhibited a linear response in the range from 1.0 × 10(-5) to 1.0 × 10(-6) M with a correlation coefficient of 0.998. The limit of detection was found to be 4.1 × 10(-7) M. The kinetics parameters of the proposed sensor such as heterogeneous electron transfer rate, k s , and charge transfer coefficient,α, was calculated and found to be 1.20 s(-1) and 0.575 respectively. The average surface concentration of BHA on the surface of poly (L- Cys/GCE) was calculated to be 3.18 × 10(-4) mol cm(-2). The analytical utility of the proposed sensor was evaluated by the successful determination of BHA in coconut oil and sesame oil samples.

Quantum dots (QDs) based fluorescent sensor for the selective determination of nimesulide.

Fluorescent PET (Photoinduced Electron Transfer) has been of particular growth in recent times. A novel PET based fluorescent sensor using unmodified CdSe quantum dots (QDs) has been developed for the trace determination of Nimesulide (NIM). The sensor is based on the selective fluorescence quenching of quantum dots by NIM in presence of other NSAIDs and is found that intensity of quenching is linearly related to NIM concentration in the range 8.2 × 10(-7) - 4.01 × 10(-5) M. The mechanism of interaction is discussed. Finally, the potential application of the proposed method for the trace determination of NIM in pharmaceutical formulation is demonstrated.

Electroanalysis of trimethoprim on metalloporphyrin incorporated glassy carbon electrode.

Trimethoprim (TMP) is a bacteriostatic antibiotic mainly used in the prophylaxis and treatment of urinary tract infections. It belongs to the class of chemotherapeutic agents known as dihydrofolate reductase inhibitors. Its use is associated with idiosyncratic reactions, including liver toxicity and agranulocytosis. In order to determine TMP electrochemically, a metalloporphyrin modified glassy carbon electrode was prepared by coating [5,10,15,20- tetrakis(4-methoxyphenyl) porphyrinato]Mn (III)chloride (TMOPPMn(III)Cl) solution on the surface of the electrode. The electrochemical behaviour of TMP in Phosphate buffer solution (PBS) on TMOPPMn(III)Cl modified glassy carbon electrode (TMOPPMn(III)Cl/GCE) was explored using differential pulse voltammetry (DPV). The voltammograms showed enhanced oxidation response at the TMOPPMn (III)Cl/GCE with respect to the bare GCE for TMP, attributable to the electrocatalytic activity of TMOPPMn(III)Cl. Electrochemical parameters of the oxidation of TMP on the modified electrode were analyzed. The electro-oxidation of TMP was found to be irreversible, pH dependent and adsorption controlled on the modified electrode. It is found that the oxidation peak current is proportional to the concentration of TMP over the range 6 × 10⁻8 - 1 × 10⁻6 M with a very low detection limit of 3 × 10⁻9 M at 2 min open circuit accumulation. The repeatability expressed as relative standard deviation (RSD) for n = 9 was 3.2% and the operational stability was found to be 20 days. Another striking feature is that equimolar concentration of sulfamethoxazole did not interfere in the determination of TMP. Applicability to assay the drug in urine and tablet samples has also been studied.

A PVC plasticized sensor for Ni(II) ion based on a simple ethylenediamine derivative.

A new PVC membrane ion selective electrode which is highly selective towards Ni(II) ions was constructed using a Schiff base containing a binaphthyl moiety as the ionophore. The sensor exhibited a good Nernstian response for nickel ions over the concentration range 1.0x10(-1)-5.0x10(-6) M with a lower limit of detection of 1.3x10(-6) M. It has a fast response time and can be used for a period of 4 months with a good reproducibility. The sensor is suitable for use in aqueous solutions in a wide pH range of 3.6-7.4 and works satisfactorily in the presence of 25% (v/v) methanol or ethanol. The sensor shows high selectivity to nickel ions over a wide variety of cations. It has been successfully used as an indicator electrode in the potentiometric titration of nickel ions against EDTA and also for the direct determination of nickel content in real samples: effluent samples, chocolates and hydrogenated oils.