Using the pulsed nature of staircase cyclic voltammetry to determine interfacial electron-transfer rates of adsorbed species

Staircase cyclic voltammetry (SCV) is the digital counterpart of analog cyclic voltammetry (CV). However, when the redox-active species is adsorbed at the electrode surface, the voltammetric peak shapes (width, height, area, and to a lesser extent the reduction potentials) obtained with SCV can be very different from those of CV, even when small potential steps are used. Like analog CV, SCV provides a straightforward method to estimate and subtract the background and charging currents from the desired Faradaic current, while the pulsed nature of SCV provides the time-dependent decay of the Faradaic current, similar to chronoamperometry. Thus, electron-transfer rate constants can be directly measured as a function of applied potential, and no a priori model is required. An SCV equivalent of the square wave "quasi-reversible maximum" of observed peak height versus sampling moment and step size is predicted. The SCV response can only become independent of potential step size and similar to CV at high scan rates (ν > 10 k(0)E(step)), if the current is sampled at half the step interval. The applicability of SCV to studies of redox centers in proteins is illustrated for the two-electron oxidation/reduction of yeast cytochrome c peroxidase, adsorbed at a pyrolytic graphite edge-plane electrode.     

X-ray study of weak interactions in two flavonoids

X-ray diffraction studies were carried out on single crystals of two flavonoids, viz. 5-hydroxy-6,7,4′-trimethoxyflavone, C₁₈H₁₆O₆, (I) and 5-hydroxy-3,7,4′-trimethoxyflavone, C₁₈H₁₆O₆, (II). Crystal structures of both the flavonoids were solved by direct methods and refined by full-matrix least-squares procedures. In both the molecules, the benzopyran moiety is planar. The dihedral angle between the phenyl ring and the benzopyran portion is 5.50(4)° in (I) and 29.11(5)° in (II). In (I), the crystal packing is influenced by O-H…O hydrogen bonds, and weak C-H…O and π…π interactions whereas in (II) the crystal structure is stabilized by the presence of four intermolecular short contacts of the type C-H…O. There is also one C-H…π hydrogen bond with H… centroid distance of <2.7 Å. The molecules are further stabilized by π-π interactions.     

Oxidative fabrication of spherical polycarbazole-based microparticles

A straightforward oxidative liquid phase polymerization (LPP) method has been successfully developed for the fabrication of spherical functional (polyCOOH) polycarbazole-based microparticles from corresponding carbazole-containing monomers. The influence of the chemical structure of starting carbazole monomers on the LPP-based microparticle formation has been deeply examined using scanning electron microscopy (SEM).     

Acetone and ethanol sensing characteristics of magnesium zinc ferrite nano-particulate chemi-resistive sensor

In the present work, acetone and ethanol sensing characteristics of wet chemically prepared magnesium zinc ferrite (MZFO) nano-particles have been investigated. X-ray diffraction and electron microscopy studies are carried out to know the phase formation behaviour and microstructure evolution of the synthesized particles. The gas sensing characteristics (response %, response time, recovery time, etc.) are estimated by varying the operating temperature of the sensor and concentrations of the test vapours. It is observed that the nanocrystalline MZFO-based sensor is more sensitive to acetone than ethanol. In addition, the sensor can detect even 10 ppm of acetone and ethanol vapours. The excellent repeatability of the sensing performances is verified by switching the sensor back and forth between air and test vapours.     

Porous copper template from partially spark plasma-sintered Cu-Zn aggregate via dezincification

Present work deals with the preparation of spark plasma-sintered Cu-Zn aggregate (5, 10 and 20 wt% Zn) with interfacial bonding only starting from elemental powders of Cu and Zn (99.9% purity) and subsequently making of porous template of Cu by dezincification. Sintering is done so as to achieve only interfacial bonding with the aim to maintain maximum potential difference between the Cu and Zn particles during dezincification process in various solutions, viz. 1 N HCl and 3.5 wt% NaCl solutions. X-ray diffraction, optical microscopy and SEM-EDS are carried out to examine microstructural evolution and subsequent changes in hardness with sintering temperatures and different Zn percentages. Dezincification and pore formation are conducted on sintered 0.5 mm thick 12 mm diameter disc samples. The size, distribution and nature of pores in porous templates of Cu are then investigated using optical microscopy and SEM-EDS analysis.     

Segmental interactions,interfacial polarization,and gigantic dielectric permittivity in ethylene vinyl acetate copolymer-carbon nanotube composites

This study reports copolymer composition tailored wrapping of carbon nanotubes, leading to a gigantic dielectric permittivity and peculiar nonlinear rheological response in a nonfluoro copolymer/carbon nanotube (CNT) hybrid system. Specifically, we observed a strong interfacial polarization effect in ethylene vinyl acetate (EVAc) copolymer/CNT nanocomposites, resulting in a dielectric permittivity of approximately 4000 at 10 Hz and 450 (dielectric loss <1) at 1 kHz, with only 1% volume fraction of CNTs and 40% vinyl acetate (VAc) content. No such effect was observed in EVAc with 12% VAc. Extensive amplitude oscillatory rheology studies prompted us to propose a novel hook-wrap-type mechanism, wherein polar interactions act as hooks and nonpolar segments allow wrapping, depending on the optimal interactions between the CNT and copolymer. Raman spectroscopy, small-angle x-ray scattering, and relaxation studies also revealed a significant change in segmental dynamics and mass fractal compactness with a change in the VAc content. This work provides a melt processing-based scalable route to develop polymer dielectrics while advancing the fundamental understanding of polymer-CNT interactions and the underlying mechanisms of dielectric behavior in nanocomposites.     

Optimization of process parameters for improved production of biomass protein from Aspergillus niger using banana peel as a substrate

Food Science and Biotechnology - This study was aimed to optimize the process variables for improved production of biomass protein using Aspergillus niger from banana fruit peel by the use of...     

Structural characterization and mass transfer properties of dense segmented polyurethane membrane: Influence of hard segment and soft segment crystal melting temperature

An attempt has been taken to investigate the microstructure and mass transfer properties of polycaprolactone diol (M_n = 2000 g mol^–1, PCL 2000)‐based dense segmented polyurethane (SPU) membrane as a function of hard segment (HS) content. Structure of SPUs were investigated by Fourier transform infrared analysis, wide angle X‐ray diffraction, differential scanning calorimetry, dynamic mechanical thermal analysis, and scanning electron microscopy (SEM). On the other hand, mass transfer properties were measured by equilibrium sorption, dynamic sorption, and water vapor permeability measurements. From the experimental results, it was observed that with the increasing HS content in SPU the percentage crystallinity decreases, whereas the glassy state storage modulus increases. α transition temperature of polyurethane copolymers also increases with increasing HS content. SEM micrograph shows the dense surface structure of SPU films. Mass transfer rate of dense polyurethane membranes decreases with increasing HS content. In contrast, hydrophilic segment and soft segment crystal melting could enhance the mass transfer properties. POLYM. ENG. SCI., 2008. © 2007 Society of Plastics Engineers