REACTIVE EXTRACTION OF LEVULINIC ACID FROM AQUEOUS SOLUTIONS WITH TRI-n-OCTYLAMINE (TOA) IN 1-OCTANOL: EQUILIBRIA,KINETICS, AND MODEL DEVELOPMENT

Levulinic acid, a carboxylic acid containing a ketone structure, can be used as an acidulant in foods and beverages. Reactive extraction is a promising alternative for the recovery of carboxylic acids from aqueous streams. The design of an amine extraction process requires kinetic data for the acid-amine + solvent system used. In this study, equilibrium and kinetic data on the extraction of levulinic acid from aqueous solutions using tri-n-octylamine (TOA) in 1-octanol have been determined. The mass transfer coefficients of levulinic acid, TOA, and 2:1 levulinic acid-amine complex in 1-octanol were calculated from the acetic acid mass transfer coefficient, which was determined by measuring its fluxes of simple diffusion from kerosene to water. Based on the Hatta number and the criterion given by Doraiswamy and Sharma, the reaction regime has been found to be instantaneous reaction regime occurring at the interface on the organic phase side. An extraction model comprising equilibrium complexation constant w.r.t 2:1 levulinic acid-TOA complex formation, K_E2i (14.794 (m³ kmol^?1)²), and complex mass transfer coefficient, k_B2A (2.193 × 10^?6 m s^?1), has been developed.     

Studies on High Density Polyethylene in the Far-field Region in Ultrasonic Welding of Plastics

Polyethylene (PE) is an extremely versatile plastic and has the largest sales turnover than other plastics. With new uses for PE, researchers continue to find innovative technologies to process and join the material. Ultrasonic welding is one such process that is rapidly emerging as a major joining process for thermoplastics because of its reliability, ease of operation, fastness, and economic feasibility. Amorphous polymers are ideal materials for ultrasonic welding, but semicrystalline polymers are difficult to weld in the far-field region. This paper deals with the far field welding of semicrystalline polymer/high-density polyethylene (HDPE). The temperature distribution has been modeled for varying lengths of the specimen using Ansys to predict the temperature spikes, which can be related to the performance of the joints achieved. Experimental work studied the temperature at the joint interface and the variation in tensile strength for different lengths of the specimen.     

Studies on the Cell Structure and Mechanical Properties of NR/Latex Reclaim/HSR Based Micrqcellular Sheets

In natural rubber/high styrene resin microcellular sheets, part of natural rubber was replaced by latex reclaim prepared from waste latex products. The mechanical properties and cell structure of the products were evaluated. It was found that latex reclaim can replace about 30% of natural rubber without affecting the technical properties of the microcellular sheets.     

Electric and dielectric study of cobalt substituted MgMn nanoferrites synthesized by solution combustion technique

Cobalt substituted Mg–Mn nanoferrites with formulae Mg_0.9Mn_0.1Co_xFe_2?xO₄, x=0.0, 0.1, 0.2 and 0.3, have been synthesized for the first time by the solution combustion technique. The effects of Co²⁺ ions on the dc resistivity, dielectric constant and dielectric loss tangent of Mg–Mn nanoferrites at room temperature are presented in this paper. X-ray diffraction confirmed the formation of a single phase spinel structure. Particle size was found to increase, 20.9–23.9 nm, with increasing Co²⁺ concentration. The dc resistivity was increased by two order of magnitude with substitution of Co²⁺ ions while the dielectric constant was found to be decreasing with the increasing concentration of cobalt ions. The value of dc resistivity obtained for Mg_0.9Mn_0.1Fe₂O₄ nanoferrite in our work is greater than the value obtained for the same composition prepared by the conventional ceramic technique. Further, the dielectric constant and dielectric loss tangent were observed to be decreasing with the increase in frequency.     

Accelerated Hot Corrosion Studies of D-Gun-Sprayed Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>–50% Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Coating on Boiler Steel and Fe-Based Superalloy

In the current investigation, Cr₂O₃–50% Al₂O₃ coating was deposited on ASTM-SA213-T-22 boiler steel and Fe-based superalloy Superfer 800H by D-gun spray process. The high-temperature corrosion performance of the coated as well as bare alloys was evaluated in Na₂SO₄–60%V₂O₅ molten salt, an aggressive environment at 900 °C under cyclic conditions. The kinetics of the corrosion were analyzed by the change in weight measurements which were taken after each cycle (i.e., 1-h heating in a tube furnace followed by 20-min cooling in ambient air) for a total period of 50 cycles. The X-ray diffraction and scanning electron microscopy/energy-dispersive X-ray analysis techniques were used for the analysis of corrosion products. During investigations, it was found that both the selected bare alloys have suffered intensive spallation in the form of removal of their oxide scales, which may be attributed to the formation of non-protective Fe₂O₃-dominated oxide scales, whereas the coated alloys have shown lesser weight gains along with better adhesiveness of the oxide scales with the substrate till the end of the experiment. The oxides of chromium and aluminum were the main phases revealed in the oxide scales of the coated specimens, which are reported to be protective against the hot corrosion.     

Essential Oil of <Emphasis Type="Italic">Artemisia scoparia</Emphasis> Inhibits Plant Growth by Generating Reactive Oxygen Species and Causing Oxidative Damage

We investigated the chemical composition and phytotoxicity of the essential oil extracted from leaves of Artemisia scoparia Waldst. et Kit. (red stem wormwood, Asteraceae). GC/GC-MS analyses revealed 33 chemical constituents representing 99.83% of the oil. The oil, in general, was rich in monoterpenes that constitute 71.6%, with β-myrcene (29.27%) as the major constituent followed by (+)-limonene (13.3%), (Z)-β-ocimene (13.37%), and γ-terpinene (9.51%). The oil and β-myrcene were evaluated in a dose–response bioassay under laboratory conditions for phytotoxicity against three weeds—Avena fatua, Cyperus rotundus, and Phalaris minor. A significant reduction in germination, seedling growth, and dry matter accumulation was observed in the test weeds. At the lowest treatment of 0.07 mg/ml Artemisia oil, germination was reduced by 39%, 19%, and 10.6% in C. rotundus, P. minor, and A. fatua, respectively. However, the inhibitory effect of β-myrcene was less. In general, a dose-dependent effect was observed and the growth declined with increasing concentration. Among the three weeds, the inhibitory effect was greatest on C. rotundus, so it was selected for further studies. We explored the explanation for observed growth inhibition in terms of reactive oxygen species (ROS: lipid peroxidation, membrane integrity, and amounts of conjugated dienes and hydrogen peroxide)-induced oxidative stress. Exposure of C. rotundus to Artemisia oil or β-myrcene enhanced solute leakage, indicating membrane disintegration. There were increased levels of malondialdehyde and hydrogen peroxide, indicating lipid peroxidation and induction of oxidative stress. We conclude that Artemisia oil inhibits plant root growth through generation of ROS-induced oxidative damage.     

Optimization of preparation conditions on the dielectric properties of polyaniline

The dielectric response in the microwave field of polyaniline prepared at different temperatures and using different inorganic and organic dopants was studied. Chemical oxidative polymerization of aniline was done at low temperature (0–5°C), at room temperature, and at high (60°C) temperature using different inorganic dopants like HCl, HNO₃, H₂SO₄, HClO₄, etc. Polyaniline was also prepared with different organic dopants like camphor sulfonic acid, Toluene sulfonic acid, and Naphthalene sulfonic acid. All polymers formed were characterized using IR, TGA, DSC, and SEM, etc. The dielectric responses of all polymers are studied using cavity perturbation technique in the microwave field. The studies indicates that the polyaniline prepared with perchloric acid at room temperature shows higher conductivity and absorption coefficient compared with all other samples. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Relative importance of the lift force on heavy particles due to turbulence driven secondary flows

Saffman lift forces on dense particles due to gradients in both streamwise and cross-stream velocities in a downward, fully developed turbulent square duct flow at Re_τ = 360 are studied using large eddy simulations. Volume fraction of the dispersed phase is low enough (≤ 10^− 5) that the one-way coupling approach is reasonable, i.e., two-way coupling and particle-particle collisions are not considered. Eulerian and Lagrangian approaches are used to treat the continuous and dispersed phases, respectively. Subgrid stresses are modeled with the dynamic subgrid kinetic energy model of Kim and Menon [W.W. Kim and S. Menon. Application of the localized dynamic subgrid-scale model to turbulent wall-bounded flows, AIAA 97-0210, 1997.]. The particle equation of motion includes drag, lift forces due to both the streamwise and cross-stream velocity gradients, gravity, and is integrated using the fourth-order accurate Runge-Kutta scheme. Dependence of particle drag and lift forces on duct cross-sectional location and particle response time is demonstrated using the mean value contours and probability density functions (PDFs) of particle forces. It is shown that the streamwise component of the mean drag force experienced by particles of all response times is a deceleration force, i.e. on average, fluid streamwise velocity lags the particle streamwise velocity. Secondly, the two wall-normal (or lateral) components of the mean drag force are oriented such that the particles experience a net mean force toward the duct corners. PDFs of particle drag force components show that smaller response time particles experience a wider range of drag force about the mean value, as compared to the more inertial particles. Contours of mean wall-normal lift forces due to streamwise velocity gradients show that this force predominantly acts toward the duct walls and that the maximum lift force occurs close to the walls. PDFs of lift force due to streamwise velocity gradients show that the range of fluctuations increases with particle response time, but the dependence on particle response time is weaker compared to drag force. Lift forces due to cross-stream velocity gradients are at least an order of magnitude smaller than lift forces due to streamwise velocity gradients and are found to decrease in their range of fluctuations with particle response time. It is demonstrated that lift forces due to secondary flow velocity gradients are not as important as those due to streamwise velocity gradients in a square duct flow.     

Cover Feature: Superior Proton-Transfer Catalytic Promiscuity of Cytochrome c in Self-Organized Media (7/2021)

Evolutionarily elderly proteins commonly feature greater catalytic promiscuity. Cytochrome c is among the first set of proteins in evolution to have known prospects in electron transport and peroxidative properties. Here, we report that cyt c is also a proficient proton-transfer catalyst and enhances the Kemp elimination (KE; model reaction to show proton transfer catalytic property) by ∼750-fold on self-organized systems like micelles and vesicles. The self-organized systems mimic the mitochondrial environment in vitro for cyt c. Using an array of biophysical and biochemical mutational assays, both acid–base and redox mechanistic pathways have been explored. The histidine moiety close to hemin group (His18) is mainly responsible for proton abstraction to promote the concerted E2 pathway for KE catalysis when cyt c is in its oxidized form; this has also been confirmed by a H18A mutant of cyt c. However, the redox pathway is predominant under reducing conditions in the presence of dithiothreitol over the pH range 6–7.4. Interestingly, we found almost 750-fold enhanced KE catalysis by cyt c compared to aqueous buffer. Overall, in addition to providing mechanistic insights, the data reveal an unprecedented catalytic property of cyt c that could be of high importance in an evolutionary perspective considering its role in delineating the phylogenic tree and also towards generating programmable designer biocatalysts.