Understanding the acceleration in the ring-opening of lactones delivered by microwave heating

This paper reports the first detailed study focussed upon identifying the influence that microwave heating (MWH) has upon the mechanic steps involved in the tin catalysed ring-opening of lactones such as ?-caprolactone (CL). Direct comparison of conventional (CH) and microwave (MWH) heated kinetic studies showed that a key factor in the reduction of the polymerisation cycle time with MWH was the elimination of the induction period associated with in situ catalyst manufacture and initiation. NMR studies demonstrated that the most significant mechanistic change contributing to the observed induction time reduction/elimination was faster initiation (i.e., reaction of the initiatior/catalyst complex with the first monomer unit). Consequently, analysis of the dielectric properties of the reaction components predicted that this MWH induced change was related to the selective volumetric heating of both the catalyst and the monomer. Furthermore, this indication of the greater significance of the initiation step in defining the length of the induction period suggests that this is the rate determining step of the process, whether conducted by CH or MWH. Increasing the catalyst concentration was demonstrated to produce significant reductions in reaction heat-up time and to induce a significant (up to 30 °C) overshoot in reaction mixture bulk temperature in with MWH only. Thus supporting the conclusion that selective heating of the organometallic species in the system contributes directly to differences in the reaction conditions and which need to be taken into account when drawing comparisons with CH systems. Consequently, both effects were concluded to be thermally generated from selective volumetric heating.     

Asymmetric aldol reactions catalyzed by the promiscuous aldo–ketoreductase enzyme

The promiscuous aldo–ketoreductase (AKR) enzyme is used as a sustainable biocatalyst for the first time to catalyze asymmetric aldol reactions in aqueous medium. The reactions between aromatic aldehydes and cyclic/acyclic ketones give the corresponding products in moderate yields and enantioselectivities in the presence of water. The influence of solvents, the mole ratio of substrates, and enzyme concentration are investigated. The mechanism of the AKR1A1-catalyzed aldol reaction is also discussed.     

Effect of Experimental Variables on the Combustion Characteristics of Water-in-Diesel Emulsion Fuels

Water-in-diesel (W/D) emulsion fuels were prepared through an ultrasonic processor by using high energy emulsification method. Accordingly, the physical and chemical properties were analyzed. A decrease in viscosity was found in the emulsion fuel in contrast to the neat diesel which signifies the enhanced fluidity of the fuel. The emulsion fuel was then used to carry combustion tests in an internal combustion engine. A decrease in exhaust temperature was observed when a high surfactant to water ratio was used, which lead to minimal heat loss. As water is emulsified with diesel, effectiveness of combustion is improved rather than neat diesel fuel. It was also explored that the addition of water-in-diesel is influential in terms of reduction in exhaust gas emission such as carbon dioxide, carbon monoxide, ammonia from the internal combustion engine. Therefore, this type of emulsion fuel would be a useful contribution in the fuel economy, but also in making it environmentally friendly since diesel fuel is now considered one of the leading fuels causing ecological contamination.     

In vitro dielectrophoresis of HEK cell migration for stimulating chronic wound epithelialization

This article describes a dielectrophoresis (DEP)-based simulation and experimental study of human epidermal keratinocyte (HEK) cells for wounded skin cell migration toward rapid epithelialization. MyDEP is a standalone software designed specifically to study dielectric particles and cell response to an alternating current (AC) electric field. This method demonstrated that negative dielectrophoresis (N_DEP) occurs in HEK cells at a wide frequency range in highly conductive medium. The finite element method was used to characterize particle trajectory based on DEP and drag force. The performance of the system was assessed using HEK cells in a highly conductive EpiLife suspending medium. The DEP experiment was performed by applying sinusoidal wave AC potential at the peak-to-peak voltage of 10 V in a tapered aluminum microelectrode array from 100 kHz to 1 MHz. We experimentally observed the occurrence of NDEP, which attracted HEK cells toward the local electric field minima in the region of interest. The DIPP-MotionV software was used to track cell migration in the prerecorded video via an automatic marker and estimate the average speed and acceleration of the cells. The results showed that HEK cell migration was accomplished approximately at 6.43 μm/s at 100 kHz with 10 V, and F_DEP caused the cells to migrate and align at the target position, which resulted in faster wound closures because of the application of an electric field frequency to HEK cells in random locations.     

Identification of phytobioconstituents present in Simmondsia chinensis L. seeds extract by GC-MS analysis

Simmondsia chinensis L. commonly called as Jojoba and belongs to family Simmondsiaceae. It has shown positive pharmacological activities of these compounds which include antidiabetic, antirheumatic, anthelminthic, antipsoriatic, antioxidant, antiepileptic, antigonorrheal, analgesic, anti-inflammatory, and pesticidal activity of jojoba. The multifaceted action of numerous bioactives existing in the seed extract with therapeutic activity have attracted great research interest by pharmaceutical industries. n-hexane extract of Simmondsia chinensis L. (SC) Seeds was analysed by gas chromatography-mass spectroscopy for identification and characterization of phytobioconstituents and its therapeutic claim by traditional system. The major compounds discovered in SC seeds extract are cis-9-octadecen-1-ol (24.85%), 9-octadecen-1-ol, (Z)- (18.24%), Stigmast-5-en-3-ol (14.10%), Ergost-5-en-3-ol, (3-β)-ol (5.26%), (Z)-14-tricosenyl formate (5.24%), Thiositosteroldisulfide (3.64%), Silane, Dimethyl (dimethylpentyloxysilyloxy) tetradecyloxy- (3.41%), Ergost-5-ene, 3-methoxy-, (3β,24R)- (2.55%), Ergosta-5,22-dien-3-ol (2.22%), 1,19-eicosadiene (2.17%), Pentacosane (2.02%), Stigmasta-5,22-dien-3-ol (1.64%), 1,19-eicosadiene (1.57%), 9-octadecen-1-ol, (Z)- (1.46%), 9,19-cyclo-9β-lanostan-3β-ol, 24-methylene- (1.14%), (9Z)-9-octadecenyl palmitate (1.50%), Hexadecanoic acid, 9-octadecenyl ester, (Z) (1.37%), 9Z)-9-octadecenyl (9Z)-9-hexadecenoate (1.01%). The hexane extract of Simmondsia chinensis seeds comprises various polar and nonpolar phytobioconstituents. These compounds were established qualitatively via GC-MS evaluation. GC-MS reports will be promising in pharmaceutical sector in identification of variety of Phytobioconstituents in distinct plant extracts, polyherbal extract and the standardization of particular plant materials.     

Adsorption of cationic methylene blue dye using microwave-assisted activated carbon derived from acacia wood: Optimization and batch studies

This study assesses the performance of optimized acacia wood-based activated carbon (AWAC) as an adsorbent for methylene blue (MB) dye removal in aqueous solution. AWAC was prepared via a physicochemical activation process that consists of potassium hydroxide (KOH) treatment, followed by carbon dioxide (CO₂) gasification under microwave heating. By using response surface methodology (RSM), the optimum preparation conditions of radiation power, radiation time, and KOH-impregnation ratio (IR) were determined to be 360 W, 4.50 min, and 0.90 g/g respectively, which resulted in 81.20 mg/g of MB dye removal and 27.96% of AWAC’s yield. Radiation power and IR had a major effect on MB dye removal while radiation power and radiation time caused the greatest impact on AWAC’s yield. BET surface area, mesopore surface area, and pore volume of optimized AWAC were found to be 1045.56 m²/g, 689.77 m²/g, and 0.54 cm³/g, respectively. Adsorption of MB onto AWAC followed Langmuir and pseudo-second order for isotherm and kinetic studies respectively, with a Langmuir monolayer adsorption capacity of 338.29 mg/g. Mechanism studies revealed that the adsorption process was controlled by film diffusion mechanism and indicated to be thermodynamically exothermic in nature.     

Biomedical Applications of Scutellaria edelbergii Rech. f.: In Vitro and In Vivo Approach

In the current study, in vitro antimicrobial and antioxidant activities and in vivo anti-inflammatory and analgesic activities of Scutellaria edelbergii Rech. f. (crude extract and subfractions, i.e., n-hexane, ethyl acetate (EtOAc), chloroform, n-butanol (n-BuOH) and aqueous) were explored. Initially, extraction and fractionation of the selected medicinal plant were carried out, followed by phytochemical qualitative tests, which were mostly positive for all the extracts. EtOAc fraction possessed a significant amount of phenolic (79.2 ± 0.30 mg GAE/g) and flavonoid (84.0 ± 0.39 mg QE/g) content. The EtOAc fraction of S. edelbergii exhibited appreciable antibacterial activity against Gram-negative (Escherichia coli and Klebsiella pneumoniae) strains and significant zones of inhibition were observed against Gram-positive bacterial strains (Bacillus subtilis and Staphylococcus aureus). However, it was found inactive against Candida Albicans and Fusarium oxysporum fungal strains. The chloroform fraction was the most effective with an IC₅₀ value of 172 and 74 µg/mL against DPPH (1,1-Diphenyl-2-picryl-hydrazyl) and ABTS assays, in comparison with standard ascorbic acid 59 and 63 µg/mL, respectively. Moreover, the EtOAc fraction displayed significant in vivo anti-inflammatory activity (54%) using carrageenan-induced assay and significant (55%) in vivo analgesic activity using acetic acid-induced writing assay. In addition, nine known compounds, ursolic acid (UA), ovaul (OV), oleanolic acid (OA), β-sitosterol (BS), micromeric acid (MA), taraxasterol acetate (TA), 5,3′,4′-trihydroxy-7-methoxy flavone (FL-1), 5,7,4′-trihydroxy-6,3′-dimiethoxyflavone (FL-2) and 7-methoxy catechin (FL-3), were isolated from methanolic extract of S. edelbergii. These constituents have never been obtained from this source. The structures of all the isolated constituents were elucidated by spectroscopic means. In conclusion, the EtOAc fraction and all other fractions of S. edelbergii, in general, displayed a significant role as antibacterial, free radical scavenger, anti-inflammatory and analgesic agents which may be due to the presence of these constituents and other flavonoids.     

Indium-doped ZnOas efficient photosensitive material for sunlight driven hydrogen generation and DSSC applications: integrated experimental and computational approach

Electricity generation using simple and cheap dye-sensitized solar cells and photocatalytic water splitting to produce future fuel, hydrogen, directly under natural sunlight fascinated the researchers worldwide. Herein, synthesis of indium-doped wurtzite ZnO nanostructures with varying molar percentage of indium from 0.25 to 3.0% with concomitant characterization indicating wurtzite structure is reported. The shift of (002) reflection plane to higher 2θ degree with increase in indium-doping thus is a clear evidence of doping of indium in zinc oxide nanoparticles. Surface morphological as well as microstructural studies of In@ZnO exhibited generation of ZnO nanoparticles and nanoplates of diameter 10–30 nm. The structures have been correlated well using computational density functional (DFT) studies. Diffuse reflectance spectroscopy depicted the extended absorbance of these materials in the visible region. Hence, the photocatalytic activity towards hydrogen generation from water under natural sunlight as well as efficient DSSC fabrication of these newly synthesized materials has been demonstrated. In-doped ZnO exhibited enhanced photocatalytic activity towards hydrogen evolution (2465 μmol/h/g) via water splitting under natural sunlight. DSSC fabricated using 2% In-doped ZnO exhibited an efficiency of 3.46% which is higher than other reported In-doped ZnO based DSSCs.

     

Kinetic Behavior of Quaternary Ammonium Hydroxides in Mixed Methane and Carbon Dioxide Hydrates

This study evaluates the kinetic hydrate inhibition (KHI) performance of four quaternary ammonium hydroxides (QAH) on mixed CH₄ + CO₂ hydrate systems. The studied QAHs are; tetraethylammonium hydroxide (TEAOH), tetrabutylammonium hydroxide (TBAOH), tetramethylammonium hydroxide (TMAOH), and tetrapropylammonium hydroxide (TPrAOH). The test was performed in a high-pressure hydrate reactor at temperatures of 274.0 K and 277.0 K, and a concentration of 1 wt.% using the isochoric cooling method. The kinetics results suggest that all the QAHs potentially delayed mixed CH₄ + CO₂ hydrates formation due to their steric hindrance abilities. The presence of QAHs reduced hydrate formation risk than the conventional hydrate inhibitor, PVP, at higher subcooling conditions. The findings indicate that increasing QAHs alkyl chain lengths increase their kinetic hydrate inhibition efficacies due to better surface adsorption abilities. QAHs with longer chain lengths have lesser amounts of solute particles to prevent hydrate formation. The outcomes of this study contribute significantly to current efforts to control gas hydrate formation in offshore petroleum pipelines.     

Heterocyclic Substitutions Greatly Improve Affinity and Stability of Folic Acid towards FRα. an In Silico Insight

Folate receptor alpha (FRα) is known as a biological marker for many cancers due to its overexpression in cancerous epithelial tissue. The folic acid (FA) binding affinity to the FRα active site provides a basis for designing more specific targets for FRα. Heterocyclic rings have been shown to interact with many receptors and are important to the metabolism and biological processes within the body. Nineteen FA analogs with substitution with various heterocyclic rings were designed to have higher affinity toward FRα. Molecular docking was used to study the binding affinity of designed analogs compared to FA, methotrexate (MTX), and pemetrexed (PTX). Out of 19 FA analogs, analogs with a tetrazole ring (FOL03) and benzothiophene ring (FOL08) showed the most negative binding energy and were able to interact with ASP81 and SER174 through hydrogen bonds and hydrophobic interactions with amino acids of the active site. Hence, 100 ns molecular dynamics (MD) simulations were carried out for FOL03, FOL08 compared to FA, MTX, and PTX. The root mean square deviation (RMSD) and root mean square fluctuation (RMSF) of FOL03 and FOL08 showed an apparent convergence similar to that of FA, and both of them entered the binding pocket (active site) from the pteridine part, while the glutamic part was stuck at the FRα pocket entrance during the MD simulations. Molecular mechanics Poisson-Boltzmann surface accessible (MM-PBSA) and H-bond analysis revealed that FOL03 and FOL08 created more negative free binding and electrostatic energy compared to FA and PTX, and both formed stronger H-bond interactions with ASP81 than FA with excellent H-bond profiles that led them to become bound tightly in the pocket. In addition, pocket volume calculations showed that the volumes of active site for FOL03 and FOL08 inside the FRα pocket were smaller than the FA–FRα system, indicating strong interactions between the protein active site residues with these new FA analogs compared to FA during the MD simulations.