Theoretical study on the carbon nanomaterial-supported Pt complex electrocatalysts for efficient and selective chlorine evolution reaction.

Chlorine is an important chemical which has long been produced in chlor-alkali process using dimensionally stable anodes (DSA). However, some serious drawbacks of DSA inspire the development of alternative anodes for chlorine evolution reaction (CER). In this study, we focused on the graphene- and carbon nanotube-supported platinum tetra-phenyl porphyrins as electrocatalysts for CER, which have been theoretically investigated based on density functional theory. Our results reveal that the supported substrates possess potential CER electrocatalytic activity with very low thermodynamic overpotentials (0.012-0.028 V) via Cl* pathway instead of ClO*. The electronic structures analyses showed that electron transfer from the support to the adsorbed chlorine via the Pt center leads to strong Pt-Cl interactions. Furthermore, the supported electrocatalysts exhibited excellent selectivity toward CER because of high overpotentials and reaction barriers of oxygen evolution process. Therefore, our results may pave the way for designing CER electrocatalyst utilizing emerging carbon nanomaterials.

Computational and experimental insight into antituberculosis agent, (E)-benzyl-2-(4-hydroxy-2-methoxybenzylidene) hydrazinecarbodithioate: ADME analysis.

A new Schiff base, (E)-benzyl-2-(4-hydroxy-2-methoxybenzylidene)hydrazinecarbodithioate (compound 1) has been synthesized and experimentally characterized by the IR, UV-Vis, 1H-NMR and mass spectroscopies. The theoretical study of the synthesized compound was evaluated using the density functional theory (DFT) at B3LYP/6-31G+(d,p) basis set. The electronic absorption spectrum of compound 1 was evaluated using time-dependent density functional theory. Besides, in silico studies were done for the prediction of absorption, distribution, metabolism and excretion profiles of compound 1. According to the result, the theoretical data were well fitted with the experimental values. The studied compound has low chemical reactivity and high kinetic stability. In the molecular electrostatic potential map, the negative and positive potential sites were found around electronegative atoms and hydrogen atoms of compound 1, respectively. The 97.75% Lewis and 2.25% non-Lewis structure were present in the studied molecule. The molecular docking results reveal that compound 1 can be used as antituberculosis agent as compare to ethambutol.

Theoretical investigations on the antioxidant potential of a non-phenolic compound thymoquinone: a DFT approach.

Thymoquinone (TQ) is a natural compound present in black cumin which possesses potent antioxidant activity without having any phenolic hydroxyl group which is responsible for antioxidant activity. In the present study, computational calculation based on density functional theory (DFT) was executed to assess systematically the antioxidant behavior of this compound by considering geometrical characteristics, highest occupied molecular orbital - lowest unoccupied molecular orbital (HOMO-LUMO), and molecular electrostatic potential (MEP) surface. Thermochemical parameters correlated to the leading antioxidant mechanisms such as hydrogen atom transfer (HAT), single electron transfer-proton transfer (SETPT), and sequential proton loss electron transfer (SPLET) were studied in gas and water media. In addition, the changes of thermochemical parameters such as free energy change (∆G) and enthalpy change (∆H) were computed for hydrogen abstraction (HA) from TQ to hydroxyl radical in gas and water phases to investigate its free radical scavenging potency. The low and comparable values of bond dissociation enthalpy (BDE), proton dissociation enthalpy (PDE), ionization potential (IP), proton affinity (PA), and electron transfer enthalpy (ETE) revealed the antioxidant activity. The ∆G and ∆H also indicated apposite thermodynamic evidence in favor of antiradical capability of TQ. The attack of the free radical occurred preferentially at 3CH position of the molecule.

Effect of Heating on Compositional Characteristics and Oxidative Stability of Crude and Refined Rice Bran Oil.

The compositional characteristics and oxidative stability of rice bran oil were determined by observing the formation of oxidative products and alteration in chemical composition of oils during microwave or oven heating. The values of oxidative indicators such as free acidity, peroxide, p-anisidine, total oxidation, thiobarbituric acid and color values, increased faster in refined oils compared to crude ones during heating. In gas chromatography analysis, the percentages of total saturated, monounsaturated and polyunsaturated fatty acids in the studied oils such as lab extracted crude rice bran oil, lab extracted and refined rice bran oil, crude rice bran oil from commercial mill and refined rice bran oil from commercial mill were: 23.07 to 23.56, 41.15 to 42.38 and 34.38 to 35.88, respectively. The heating caused the reduction of polyunsaturated fatty acids content with increasing saturated fatty acids content, and these changes were greater in refined rice bran oil indicating extensive lipid oxidation occurred in refined oil. The change in triacylglycerol species content as determined by High-performance liquid chromatography, was lower in crude oil; the higher stability of these species in crude oil could have contribution to reduce oxidation. During thermal treatment, the generation of hydroperoxides, their degradation and formation of secondary oxidative products evaluated by Fourier-transform infrared spectroscopy, were lower in crude oils. However, the rate of formation of oxidative products in lab prepared samples was lower compared to that in the samples collected from commercial mill. Under extreme thermal condition, the order of oxidative stability: lab extracted crude rice bran oil > crude rice bran oil from commercial mill>lab extracted and refined rice bran oil > refined rice bran oil from commercial mill. The present results will be useful to oil seed processing mills in refining of rice bran oil for economic feasibility and better marketability.

Effect of microwave radiation on the antioxidant activity of black cumin seed.

BACKGROUND: Black cumin seed contains considerable amounts of bioactive phenolics that have physiological activity and antioxidant potency, which may be boosted by microwave radiation. The core objective of the study was to evaluate the influence of microwave radiation on the antioxidant activity of cumin seed as a function of pretreatment time and extract concentration. METHODS: In this study, total flavonoid content (TFC) and antioxidant activity of methanol (CME), 70% methanol in water (CMW), ethanol (CEE) and 70% ethanol in water (CEW) extracts of microwaved radiated cumin seed were measured. The antioxidant activity was determined using a Folin-Ciocalteu assay, phosphomolybdenum assay, DPPH radical scavenging activity, H2O2 scavenging activity, hydroxyl radical scavenging activity and reducing power. To predict antioxidant potency, FTIR spectra of extracts were also recorded. RESULTS: Microwave pretreatment significantly reduced the TFC with the pretreatment time. Antioxidant activity increased with increasing pretreatment time and extract concentration in all extracts. Aqueous methanolic extract from radiated seeds appeared to display the highest effectiveness. The results from FT-IR of ex- tracts indicating the existence of multiple functional groups were comparable to those obtained from multiple antioxidative assays. The antioxidant effectiveness of the samples was ranked: CMW > CEW > CME > CEE. CONCLUSIONS: Both treatment duration and extract concentration were found to be critical factors in determin- ing the overall quality of the product. The present study revealed important information for using black cumin seed in developing food products with high antioxidant potency.