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.     

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.     

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.     

Isolation and Identification of Bioactive Compounds from Bidens spp. Using HPLC-DAD and GC-MS Analysis and Their Biological Activity as Anticancer Molecules

The genus Bidens a member of family Compositae, is widely documented as an ethno-medicinally important genus of plants. In the present study, anticancer potential of three ethno-medicinally important species i.e., B. bipinnata, B. biternata and B. pilosa were tested. For in-vitro evaluation, an MTT (Thiazolyl blue tetrazolium bromide) assay was performed against cervical cancer cells (HeLa), hepatocellular carcinoma (HepG), and adenocarcinoma human alveolar basal epithelial cells (A549). For in vivo evaluation, Artemia salina, Danio rerio, and Caenorhabditis elegans were used. Among all the tested extracts, the ethanol extract of B. biternata appeared to have highest anticancer activity, and the compounds responsible for this activity were identified to be Tris (2,4-di-tert-butylphenyl), 4-hydroxy-2,4′-dimethoxychalcone, and 2,4-di-tert-butylphenol. This is the first report of the isolation of Tris (2,4-di-tert-butylphenyl) phosphate from the genus Bidens and the first report of 4-hydroxy-2,4′-dimethoxychalcone and 2,4-di-tert-butylphenol from B. biternata. Among the isolated compounds, 4-hydroxy-2,4′-dimethoxychalcone showed the highest anticancer activity with an LD50 value of 236.7 µg/mL. Therefore, this compound carries promising potential for being established as a pharmaceutical for chemoprevention and chemotherapy.     

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.     

Quantum dots assisted laser desorption/ionization mass spectrometric detection of carbohydrates: qualitative and quantitative analysis

A quantum dots (QDs) assisted laser desorption/ionization mass spectrometric (QDA‐LDI‐MS) strategy was proposed for qualitative and quantitative analysis of a series of carbohydrates. The adsorption of carbohydrates on the modified surface of different QDs as the matrices depended mainly on the formation of hydrogen bonding, which led to higher MS intensity than those with conventional organic matrix. The effects of QDs concentration and sample preparation method were explored for improving the selective ionization process and the detection sensitivity. The proposed approach offered a new dimension to the application of QDs as matrices for MALDI‐MS research of carbohydrates. It could be used for quantitative measurement of glucose concentration in human serum with good performance. The QDs served as a matrix showed the advantages of low background, higher sensitivity, convenient sample preparation and excellent stability under vacuum. The QDs assisted LDI‐MS approach has promising application to the analysis of carbohydrates in complex biological samples. Copyright © 2016 John Wiley & Sons, Ltd.     

Micellar parameters of diblock copolymers and their interactions with ionic surfactants

The interactions of non-ionic amphiphilic diblock copolymer poly（oxyethylene/oxybutylene）(E₃₉B₁₈) with anionic surfactant sodium dodecyl sulphate（SDS） and cationic surfactant hexadecyltrimethylammonium bromide（CTAB） were studied by using various techniques such as surface tension,conductivity,steady-state fluorescence and dynamic light scattering.Surface tension measurements were used to determine the critical micelle concentration（CMC） and thereby the free energy of micellization(△G_mic),free energy of adsorption(△G_ads),surface excess concentration（Γ） and minimum area per molecule（A）.Conductivity measurements were used to determine the critical micelle concentration（CMC）,critical aggregation concentration（CAC）,polymer saturation point（PSP）,degree of ionization（α） and counter ion binding（β）. Dynamic light scattering experiments were performed to check the changes in physiochemical properties of the block copolymer micelles taken place due to the interactions of diblock copolymers with ionic surfactants.The ratio of the first and third vibronic peaks（I₁/I₃） indicated the polarity of the pyrene micro environment and was used for the detection of micelle as well as polymer-surfactant interactions.Aggregation number（N）,number of binding sites（n） and free energy of binding （△G_b） for pure surfactants as well as for polymer-surfactant mixed micellar systems were determined by the fluorescence quenching method.     

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.     

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...     

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.