Complete NMR assignments of bioactive rotameric (3 → 8) biflavonoids from the bark of Garcinia hombroniana

The genus Garcinia is reported to possess antimicrobial, anti‐inflammatory, anticancer, hepatoprotective and anti‐HIV activities. Garcinia hombroniana in Malaysia is used to treat itching and as a protective medicine after child birth. This study was aimed to isolate the chemical constituents from the bark of G. hombroniana and explore their possible pharmacological potential. Ethyl acetate extract afforded one new (1) and six (2–7) known 3 → 8 rotameric biflavonoids. Their structures were elucidated by UV, IR and NMR (1D and 2D) spectroscopy together with electron ionization/ESI mass spectrometric techniques and were identified as (2R, 3S) volkensiflavone‐7‐O‐rhamnopyranoside (1), volkensiflavone (2), 4″‐O‐methyl‐volkensiflavone (3), volkensiflavone‐7‐O‐glucopyranoside (4), morelloflavone (5), 3″‐O‐methyl‐morelloflavone (6) and morelloflavone‐7‐O‐glucopyranoside (7). The absolute configuration of compound 1 was assigned by circular dichroism spectroscopy as 2R, 3S. The coexistence of conformers of isolated biflavonoids in solution at 25 °C in different solvents was confirmed by variable temperature NMR studies. At room temperature (25 °C), compounds 1–7 exhibited duplicate NMR signals, while at elevated temperature (90 °C), a single set of signals was obtained. Compound 5 showed significant in vitro antioxidant activities against 1,1‐diphenyl‐2‐picrylhydrazyl and 2,2′‐azino‐bis‐3‐ethyl benzthiazoline‐6‐sulfonic acid radicals. The antibacterial studies showed that compounds 5 and 6 are the most active against Staphylococcus aureus, Bacillus subtilis and Escherichia coli. Compounds 3 and 6 also showed moderate antituberculosis activity against H₃₈Rv. Based on the research findings, G. hombroniana could be concluded as a rich source of flavanone–flavone (3 → 8) biflavonoids that exhibit rotameric behaviour at room temperature and display significant antioxidant and antibacterial activities. Copyright © 2014 John Wiley & Sons, Ltd.     

Kinetic modeling of ZnO-rGO catalyzed degradation of methylene blue

Photodegradation of organic pollutants strongly depends on design of metal oxide semiconductor photocatalysts. Graphene, if composited with ZnO, can effectively enhance its photocatalytic performance for the eradication of pollutants from aqueous medium. Here in, ZnO-rGO is reported as highly active catalyst for degradation of methylene blue. A 200-mg/L solution of methylene blue dye was completely degraded within 1 h in comparison to 74% and 56% degradation over ZnO and rGO, respectively. The commonly used mechanisms of heterogeneous catalytic reactions, the Langmuir-Hinshelwood mechanism, and the Eley-Rideal mechanisms, were used to describe the reaction kinetics. The Langmuir-Hinshelwood mechanism was found as more favorable in this study. Apparent activation energy, E_ap, true activation energy, E_T, entropy, ΔS, and enthalpy, ΔH were calculated as 36.2 kJ/mol, 13.1 kJ/mol, 197.5 J/mol, and 23.1 kJ/mol, respectively.     

SOME HETEROCYCLIC PHOSPHOROCHLORIDATES AND THE FORMATION OF OTHER HETEROCYCLIC ORGANOPHOSPHORUS COMPOUNDS

Abstract

Pyrrolidine, morpholine, and β-hydroxyethylmorpholine have been phosphorylated with phosphorus oxychloride, phenylphosphorodichloridate, p-chlorophenylphosphorodichloridate and thiophosphoryl chloride. The resultant phosphorodichloridates have been condensed with a wied range of nucleophilic reagents, e.g. amines, hydrazines, phenols and isobutanol. Piperazine with phosphorus oxychloride (2 mols) gave the N(1) N(4)-diphosphorotetrachloridate, which was characterized as the tetracyclohexylamidate. β-Hydroxyethylpiperazine was similarly phosphorylated to the N,O-diphosphorotetrachloridate which was characterized as the tetraphenylhydrazidate.

Condensation of pyrrolidine (2 mols) with phosphorus oxychloride (1 mol) afforded N,N′-dipyrrolidinophosphorochloridate which was reacted with phenylhydrazide and sodium azide. The phosphoroazide with triphenylphosphine afforded the corresponding triphenylphosphinimine. N-Phenyl N′-pyrrolidinophosphorochloridate with aqueous pyridine gave the corresponding pyrophosphoramide and the stability of the pyrophosphoramide towards hydrolysis was examined. 1,2-Cyclohexanediol was phosphorylated with phenylphosphorodichloridate and thiophosphorylchloride. Trans-4-t-Butylcyclohexyl N,N′-diphenylhydrazinophosphorothioate by reaction with formaldehyde gave a tetra-azaphosphorine P-sulfide. Trans-4-t-Butylcyclohexyl N-phenyl N′-phenylphosphorodiamidic hydrazide reacted with 1,4-dibromobut-2-ene to give a 1,2-diazahex-4-ene.     

Numerical Investigation of Graphene as a Back Surface Field Layer on the Performance of Cadmium Telluride Solar Cell

This paper numerically explores the possibility of ultrathin layering and high efficiency of graphene as a back surface field (BSF) based on a CdTe solar cell by Personal computer one-dimensional (PC1D) simulation. CdTe solar cells have been characterized and studied by varying the carrier lifetime, doping concentration, thickness, and bandgap of the graphene layer. With simulation results, the highest short-circuit current (I_sc = 2.09 A), power conversion efficiency (η = 15%), and quantum efficiency (QE~85%) were achieved at a carrier lifetime of 1 × 10³ μs and a doping concentration of 1 × 10¹⁷ cm⁻³ of graphene as a BSF layer-based CdTe solar cell. The thickness of the graphene BSF layer (1 μm) was proven the ultrathin, optimal, and obtainable for the fabrication of high-performance CdTe solar cells, confirming the suitability of graphene material as a BSF. This simulation confirmed that a CdTe solar cell with the proposed graphene as the BSF layer might be highly efficient with optimized parameters for fabrication.     

Exogenous Sodium Nitroprusside Mitigates Salt Stress in Lentil (Lens culinaris Medik.) by Affecting the Growth,Yield, and Biochemical Properties

Soil salinity disrupts the physiological and biochemical processes of crop plants and ultimately leads to compromising future food security. Sodium nitroprusside (SNP), a contributor to nitric oxide (NO), holds the potential to alleviate abiotic stress effects and boost tolerance in plants, whereas less information is available on its role in salt-stressed lentils. We examined the effect of exogenously applied SNP on salt-stressed lentil plants by monitoring plant growth and yield-related attributes, biochemistry of enzymes (superoxide dismutase (SOD), catalase (CAT), and peroxidase (POD)) amassing of leaf malondialdehyde (MDA) and hydrogen peroxide (H₂O₂). Salinity stress was induced by NaCl application at concentrations of 50 mM (moderate salinity) and 100 mM (severe salinity), while it was alleviated by SNP application at concentrations of 50 µM and 100 µM. Salinity stress severely inhibited the length of roots and shoots, the relative water content, and the chlorophyll content of the leaves, the number of branches, pods, seeds, seed yield, and biomass per plant. In addition, MDA, H₂O₂ as well as SOD, CAT, and POD activities were increased with increasing salinity levels. Plants supplemented with SNP (100 µM) showed a significant improvement in the growth- and yield-contributing parameters, especially in plants grown under moderate salinity (50 mM NaCl). Essentially, the application of 100 µM SNP remained effective to rescue lentil plants under moderate salinity by regulating plant growth and biochemical pathways. Thus, the exogenous application of SNP could be developed as a useful strategy for improving the performance of lentil plants in salinity-prone environments.     

Rating players in test match cricket

In general, the evaluation of player performance in test cricket is based on measures such as batting and bowling averages. These measures have a number of limitations, among which is that they fail to take into account the context in which runs are made or conceded and wickets are taken or given away. Furthermore, batting and bowling averages do not allow the comparison of performances in these two disciplines; this is because batting and bowling performances are measured using different metrics. With these issues in mind, we develop a new player rating system for test cricket. We use multinomial logistic regression to model match outcome probabilities session by session. We then use these probabilities to measure the overall contribution of players to the match outcome based on their individual batting, bowling and fielding contributions during each session. Our measure of contribution has the potential for rating players over time and for determining the ‘best’ player in a match, a series or a calendar year. We use results from 104 matches (2010–2012) to illustrate the method.     

Effect of spin–orbit coupling on spin transport at graphene/transition metal interface

In spite of large spin coherence length in graphene due to small spin–orbit coupling, the created potential barrier and antiferromagnetic coupling at graphene/transition metal (TM) contacts strongly reduce the spin transport behavior in graphene. Keeping these critical issues in mind in the present work, ferromagnetic (Co, Ni) nanosheets are grown on graphene surface to elucidate the nature of interaction at the graphene/ferromagnetic interface to improve the spin transistor characteristics. Temperature dependent magnetoconductance shows unusual behavior exhibiting giant enhancement in magnetoconductance with increasing temperature. A model based on spin–orbit coupling operated at the graphene/TM interface is proposed to explain this anomalous result. We believe that the device performance can be improved remarkably tuning the spin–orbit coupling at the interface of graphene based spin transistor. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Synthesis and biological evaluation of benzimidazole pendant cyanopyrimidine derivatives as anticancer agents

Thirteen new benzimidazole pendant cyanopyrimidine derivatives were synthesized. The compounds were synthesized through multistep reaction protocol. The structures of synthesized derivatives were studied by EI-MS, ¹H NMR, FT-IR and elemental analysis. All the compounds were studied for their anticancer activity at National Cancer Institute. Except compound 7j , all the compounds unveiled cytotoxicity against cancer cells. The most active compound 7a had shown highest value of growth inhibition of 88.44% and 84.19% against HOP-92 and T-47D cancer cell lines.