Kinetics and electrochemical studies on superoxide

Rate constants for the reaction of superoxide O^- ₂ with various substrates were obtained through stationary electrode polarography theory and technique. In solvent acetonitrile, the substrate and the rate constants of the reaction O^- ₂ + AH^{- k2}Product, are, AH = isopropanol (k₂ < 0.01 M^-1 s^-1); ethanol (k₂ = 1.42 × 10² M^-1 s^-1); methanol (k₂ = 1.1 × 10⁷ M^-1 s^-1), H₂O (k₂ = 1.0 × 10⁵ M^-1 s^-1). In MeCN, O^-2 was found to be rather unreactive towards glucose and acetone but it reacts with fructose and sucrose catalytically. However, in DMF2, O^- ₂reacts with glucose and fructose with k2 order of 105 M-1 s-1. The mechanism of the reaction of O^- ₂ with the substrates (AH) is proposed as O^- ₃ + AH k₂O, AH^k2 _k-1 k [O₂H + AH]^-, _k-2O₂H + A^- with k₁ = 10⁹ M^-1 s^-1 and k^-1 = 10⁸ -10⁹ s^-1. With these values of k_-1 and k₁, k k₂(obs). The reversible E_1/2 for O₂ + e O^- ₂ in various solvents: MeCN, acetone, isopropanol, methanol, H₂O were obtained either directly from the reversible voltammogram or from experimental voltammograms and the rate constants obtained (as above) using stationary electrode polargraphy theory; E_1/2 being -0.82 (MeCN),-0.85 (acetone),-0.72 (isopropanol);-0.66 (MeOH),-0.56 (H2O) vs SCE.     

Redox behavior of juglone in buffered aq.: Ethanol media

The present work reports the redox mechanism of 5-hydroxynaphthalene-1,4-dione (HND), commonly known as juglone, in buffered aqueous media having 50% of ethanol. HND followed different mechanistic routes depending upon the pH of the media and more than one pK_a were evaluated from the changes in the slope of the E_p vs. pH plot. The change of pH from acidic to neutral conditions was found to switch the mechanism from CEC to EE mechanism. Pulse techniques were utilized to determine the number of electrons involved in the oxidation and/or the reduction step and to ensure the nature of the redox process. Based upon the obtained results, an electrode reaction mechanism was proposed. Computational studies of HND supported the experimental results. UV-Visible spectroscopy was also employed for the detailed characterization of the compound in a wide range of pH and for the determination of its pK_a.     

Determination of trace amounts of chromium (VI) by flow injection analysis with chemiluminescence detection

A new sensitive chemiluminescence (CL) method combined with continuous flow injection analysis is described for the determination of Cr(VI). Strong CL signals were generated by Cr(VI)-catalysed oxidation of gallic acid in the presence of potassium permanganate and hydrogen peroxide. Effects of reagent concentrations, temperature, pH, flow rates, mixing coil length and mixing flow sequences on the chemiluminescence intensity were studied. Under the optimised experimental conditions, the relationship between the logarithm of concentration (log?C) of Cr(VI) and the logarithm of intensity (log?I) is linear over the range of 2?×?10^?11 – 5?×?10^?4?mol?L^?1, with the detection limit (3σ) of 4?×?10^?12?mol?L^?1. Relative standard deviation of ten measurements of 1?×?10^?9?mol?L^?1 Cr(VI) is 1.7%. This flow injection analysis (FIA) system proved to be able to analyse up to 40 samples h^?1. Effects of various interferences possibly present in the water samples were investigated. Most cations and anions, as well as organic compounds, did not interfere with the determination of Cr(VI) in water samples. The experimental results obtained for chromium in reference materials were also in good agreement with the certified values.     

Size dependent active effect of CdTe quantum dots on pyrogallol-H2O2 chemiluminescence system for chromium(III) detection

Water-soluble CdTe quantum-dots (QDs) of different sizes and capped with mercaptosuccinic acid were prepared by the microwave irradiation method. The QDs can significantly enhance the chemiluminescence (CL) of the pyrogallol-H₂O₂ system. Those with a diameter of 3.8 nm produce the most intense CL. UV-vis, photoluminescence, and CL spectra were acquired in order to explore the effect. The results showed that the chromium(III) ion in the concentration range from 20 pM to 30 µM enhances CL, and this is exploited for its trace determination.The limit of detection (3σ) is 6 pM, with a relative standard deviation (n?=?11) of 1.7%. A continuous flow injection CL method was developed and applied to the determination of chromium(III) in tap water and lake water samples with satisfactory results.     

Optical and dielectric properties of fluorinated ethylene propylene and tetrafluoroethylene–perfluoro(alkoxy vinyl ether) copolymer films modified by low energy N and C ion beams

Fluorinated ethylene propylene (FEP) and tetrafluoroethylene–perfluoro(alkoxy vinyl ether) (PFA) copolymer films were irradiated in vacuum with 60 keV C⁴⁺ and N⁴⁺ ions to fluences ranging from 1.0×10¹² to 5.0×10¹⁵ cm⁻². Changes in optical and dielectric properties were analyzed by spectroscopic ellipsometry and ultraviolet–visible (UV–vis), Raman and dielectric relaxation spectroscopies. Direct and indirect energy band gap values were determined from the absorption edge in the 200–800 nm region using Tauc's relation. The values of the direct energy gap have been found to be greater than the corresponding values of the indirect energy gap. Significant changes in the index of refraction, and β and γ dielectric relaxations were observed in the case of N⁴⁺ irradiated FEP and PFA samples.     

Grafting of poly(sodium styrenesulfonate) onto gold surface from NaNO<Subscript>3</Subscript> solution

The chemical grafting of thiol terminated poly(sodium styrenesulfonate)(HS-PSSS) chains from sodium nitrate (NaNO_3) salt solution to a gold surface was investigated with a quartz crystal microbalance with dissipation monitoring (QCM-D) in different salt concentrations.It was found that at low salt concentration grafting density of HS-PSSS was low and the grafted chains adopted a mushroom conformation.With the increase of salt concentration polyelectrolyte chains underwent a transition toward coiled stat...     

Thiourea Derivatives,Simple in Structure but Efficient Enzyme Inhibitors and Mercury Sensors

In this study six unsymmetrical thiourea derivatives, 1-isobutyl-3-cyclohexylthiourea (1), 1-tert-butyl-3-cyclohexylthiourea (2), 1-(3-chlorophenyl)-3-cyclohexylthiourea (3), 1-(1,1-dibutyl)-3-phenylthiourea (4), 1-(2-chlorophenyl)-3-phenylthiourea (5) and 1-(4-chlorophenyl)-3-phenylthiourea (6) were obtained in the laboratory under aerobic conditions. Compounds 3 and 4 are crystalline and their structure was determined for their single crystal. Compounds 3 is monoclinic system with space group P2₁/n while compound 4 is trigonal, space group R³:H. Compounds (1–6) were tested for their anti-cholinesterase activity against acetylcholinesterase and butyrylcholinesterase (hereafter abbreviated as, AChE and BChE, respectively). Potentials (all compounds) as sensing probes for determination of deadly toxic metal (mercury) using spectrofluorimetric technique were also investigated. Compound 3 exhibited better enzyme inhibition IC₅₀ values of 50, and 60 µg/mL against AChE and BChE with docking score of −10.01, and −8.04 kJ/mol, respectively. The compound also showed moderate sensitivity during fluorescence studies.     

Phytochemical screening and in-vitro evaluation of pharmacological activities of peels of Musa sapientum and Carica papaya fruit

Aqueous, absolute and 80% ethanolic extract of fruit peels of Musa sapientum and Carica papaya were investigated for their antibacterial activity, measured by disc diffusion method and antioxidant activity, measured by four different methods. Papaya and banana peels were found to contain terpenoids, tannins, alkaloids, saponins steroid, phenols, fixed oils and fats. 80% ethanolic extract of banana peel was found to contain highest total phenolic content (TPC), total flavonoid content (TFC) and antioxidant activity but in papaya peel, highest TPC and reducing activity was shown by water extract while, TFC and radical scavenging activity was given by 80% ethanolic extract. In banana, water extract showed highest antibacterial activity against tested bacteria while in case of papaya, absolute ethanolic extract showed highest antibacterial activity. The present study revealed that peels of banana and papaya fruits are potentially good source of antioxidant and antibacterial agents.     

Extraction procedures in gas chromatographic determination of pesticides

Pesticides are necessary for increasing agricultural productivity; however, their enormous use contaminates air, water and food. Among various organic pesticides, organochlorine pesticides (OCPs) are most persistent; and though their use is banned, they are still used illegally. In contrast to OCPs, organophosphorous pesticides are less persistent and used most extensively, while synthetic pyrethroid pesticides are the least toxic and used as insecticides. Extensive use of these pesticides is vulnerable to the ecosystem. Various extraction methods are used worldwide both by the regulatory bodies and private laboratories for the determination of multi-residue pesticides in leafy vegetables. This mini review presents an update on extraction procedure in gas chromatographic methods of pesticides analysis in various samples with special emphasis on leafy vegetables. We have covered six years of work from 2008–2013, discussing various extraction methods and their applications.     

Numerical Analysis of Unsteady Magneto-Biphase Williamson Fluid Flow with Time Dependent Magnetic Field

Numerical investigation of the dusty Williamson fluid with the dependency of time has been done in current disquisition. The flow of multiphase liquid/particle suspension saturating the medium is caused by stretching of porous surface. The influence of magnetic field and heat generation/absorption is observed. It is assumed that particle has a spherical shape and distributed uniformly in fluid matrix. The unsteady two-dimensional problems are modeled for both fluid and particle phase using conservation of mass, momentum and heat transfer. The finalized model generates the non-dimensioned parameters, namely Weissenberg number, unsteadiness parameter, magnetic parameter,heat generation/absorption parameter, Prandtl number, fluid particle interaction parameter, and mass concentration parameters. The numerical solution is obtained. Locality of skin friction and Nusselt number is deliberately focused to help of tables and graphs. While inferencing the current article it is clearly observed that increment of Williamson parameter, unsteadiness parameter, magnetic parameter, volume fraction parameter, and mass concentration parameter reduces the velocity profile of fluid and solid particles as well. And increment of Prandtl number, unsteadiness parameter,volume fraction parameter, and mass concentration parameter reduces the temperature profile of fluid and solid particles as well.