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.     

A review on recent advances in hierarchically porous metal and metal oxide nanostructures as electrode materials for supercapacitors and non-enzymatic glucose sensors

The remarkable significance of electrode materials in industrial processes, energy, sustainability and diabetes monitoring has captivated scientists to develop advance nanomaterials for the benefit of life across the globe. Here in, the recent developments in nanostructured porous metal and metal oxide composite materials for supercapacitor applications and non-enzymatic glucose sensors (NEGS) has been extensively discussed. The essential and active electrode materials from the research and application perspective has been emphasized in detail. We have also evaluated the worthiness, taxonomical classification, efficiency, specific capacitance and sensitivity of these materials for the aforementioned potential applications. Eventually, we concluded the review by providing the aspect ratio, surface morphology, particle size and specific surface area of these materials that plays an indispensable role for their promising potential applications.     

Bucillamine Inhibits UVB-Induced MAPK Activation and Apoptosis in Human HaCaT Keratinocytes and SKH-1 Hairless Mouse Skin

Ultraviolet B (UVB) radiation is known as a culprit in skin carcinogenesis. We have previously reported that bucillamine (N-[2-mercapto-2-methylpropionyl]-L-cysteine), a cysteine derivative with antioxidant and anti-inflammatory capacity, protects against UVB-induced p53 activation and inflammatory responses in mouse skin. Since MAPK signaling pathways regulate p53 expression and activation, here we determined bucillamine effect on UVB-mediated MAPK activation in vitro using human skin keratinocyte cell line HaCaT and in vivo using SKH-1 hairless mouse skin. A single low dose of UVB (30 mJ cm⁻²) resulted in increased JNK/MAPK phosphorylation and caspase-3 cleavage in HaCaT cells. However, JNK activation and casaspe-3 cleavage were inhibited by pretreatment of HaCaT cells with physiological doses of bucillamine (25 and 100 µm ). Consistent with these results, bucillamine pretreatment in mice (20 mg kg⁻¹) inhibited JNK/MAPK and ERK/MAPK activation in skin epidermal cells at 6–12 and 24 h, respectively, after UVB exposure. Moreover, bucillamine attenuated UVB-induced Ki-67-positive cells and cleaved caspase-3-positive cells in mouse skin. These findings demonstrate that bucillamine inhibits UVB-induced MAPK signaling, cell proliferation and apoptosis. Together with our previous report, we provide evidence that bucillamine has a photoprotective effect against UV exposure.     

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.     

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.     

Structural relaxation and aging scaling in the Coulomb and Bose glass models

We employ Monte Carlo simulations to study the relaxation properties of the two-dimensional Coulomb glass in disordered semiconductors and the three-dimensional Bose glass in type-II superconductors in the presence of extended linear defects. We investigate the effects of adding non-zero random on-site energies from different distributions on the properties of the correlation-induced Coulomb gap in the density of states (DOS) and on the non-equilibrium aging kinetics highlighted by the density autocorrelation functions. We also probe the sensitivity of the system’s equilibrium and non-equilibrium relaxation properties to instantaneous changes in the density of charge carriers in the Coulomb glass or flux lines in the Bose glass.     

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.     

Origin of arrhythmias in a heart model

An investigation of the nonlinear dynamics of a heart model is presented. The model compartmentalizes the heart into one part that beats autonomously (the x oscillator), representing the pacemaker or SA node, and a second part that beats only if excited by a signal originating outside itself (the y oscillator), representing typical cardiac tissue. Both oscillators are modeled by piecewise linear differential equations representing relaxation oscillators in which the fast time portion of the cycle is modeled by a jump. The model assumes that the x oscillator drives the y oscillator with coupling constant $\alpha$. As $\alpha$ decreases, the regular behavior of y oscillator deteriorates, and is found to go through a series of bifurcations. The irregular behavior is characterized as involving a large amplitude cycle followed by a number n of small amplitude cycles. We compute critical bifurcation values of the coupling constant, ${\alpha }_n$, using both numerical methods as well as perturbations.