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.     

Surface modification for nano‐lignocellulose fiber through vapor‐phase‐assisted surface polymerization

This study addresses the inherent issues surrounding surface modification methods of nanofibers and proposes an environmentally friendly and less toxic strategy for the surface modification of hydrophilic nanofiber. From the continuation of our previous work, which discussed the easy production of nanofiber (average size: 127 nm) from oil palm mesocarp fiber (OPMF), in this work, the surface of nanofibers (M‐IL‐OPMF) were modified through vapor‐phase‐assisted surface polymerization (VASP) to improve the affinity of interface between the polymer grafted M‐IL‐OPMF and non‐polar matrix. VASP of ε‐caprolactone was successfully proceeded from the [M‐IL‐OPMF] at 70 °C for 24 h and 72 h, and compositions were estimated to be 35.7% fiber/64.3% polymer and 27.8% fiber/72.2% polymer. To confirm the grafting of PCL, size‐exclusion chromatography (SEC) and Fourier transform infrared (FT‐IR) spectroscopy, thermogravimetry (TG), and dispersibility test in hydrophobic solvent were carried out. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2575–2580     

Development of a solid‐phase microextraction LC–MS/MS method for determination of oxidative stress biomarkers in biofluids

Recently the connection between oxidative stress and various diseases, including cancer and Alzheimer's, attracts notice as a pathway suitable for diagnostic purposes. 8‐Oxo‐deoxyguanosine and 8‐oxo‐deoxyadenosine produced from the interaction of reactive oxygen species with DNA become prominent as biomarkers. Several methods have been developed for their determination in biofluids, including solid‐phase extraction and enzyme‐linked immunosorbent assays. However, still, there is a need for reliable and fast analytical methods. In this context, solid‐phase microextraction offers many advantages such as flexibility in geometry and applicable sample volume, as well as high adaptability to high‐throughput sampling. In this study, a solid‐phase microextraction method was developed for the determination of 8‐oxo‐deoxyguanosine and 8‐oxo‐deoxyadenosine in biofluids. The extractive phase of solid‐phase microextraction consisted of hydrophilic–lipophilic balanced polymeric particles. In order to develop a solid‐phase microextraction method suitable for the determination of the analytes in saliva and urine, several parameters, including desorption solvent, desorption time, sample pH, and ionic strength, were scrutinized. Analytical figures of merit indicated that the developed method provides reasonable interday and intraday precisions (<15% in both biofluids) with acceptable accuracy. The method provides a limit of quantification for both biomarkers at 5.0 and 10.0 ng/mL levels in saliva and urine matrices, respectively.     

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.     

Building an Iron Chromophore Incorporating Prussian Blue Analogue for Photoelectrochemical Water Oxidation

The replacement of traditional ruthenium-based photosensitizers with low-cost and abundant iron analogs is a key step for the advancement of scalable and sustainable dye-sensitized water splitting cells. In this proof-of-concept study, a pyridinium ligand coordinated pentacyanoferrate(II) chromophore is used to construct a cyanide-based CoFe extended bulk framework, in which the iron photosensitizer units are connected to cobalt water oxidation catalytic sites through cyanide linkers. The iron-sensitized photoanode exhibits exceptional stability for at least 5 h at pH 7 and features its photosensitizing ability with an incident photon-to-current conversion capacity up to 500 nm with nanosecond scale excited state lifetime. Ultrafast transient absorption and computational studies reveal that iron and cobalt sites mutually support each other for charge separation via short bridging cyanide groups and for injection to the semiconductor in our proof-of-concept photoelectrochemical device. The reorganization of the excited states due to the mixing of electronic states of metal-based orbitals subsequently tailor the electron transfer cascade during the photoelectrochemical process. This breakthrough in chromophore-catalyst assemblies will spark interest in dye-sensitization with robust bulk systems for photoconversion applications.     

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.     

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.