The equilibrium and kinetics of intermolecular hydrogen bonding in nitroarene anion radical–alcohol system: 1,3‐dinitro‐benzene anion radical – R–OH (R═CH3–, C2H5–, (CH3)2 CH–)

To explore the possibility of hydrogen bonding of a stable anion radical with DNA – component sugar, hormones, steroid, and so on (through hydroxyl group), as a first step, the possibility of hydrogen bonding of 1,3‐dinitrobenzene anion radical (1,3‐DNB^??) with aliphatic alcohols was studied. It was found that 1,3‐DNB^?? anion radical undergoes hydrogen bonding with alcohols: methanol, ethanol, and 2‐proponal. The hydrogen‐bonding equilibrium constant K_eq and the (hydrogen‐bonding) rate constants k₂ were evaluated through the use of linear scan and cyclic voltammetry theory and techniques. The K_eq was found to be in the range of 1.4–6.0 m ^?1, whereas the rate constants k₂ were found to be in the range of 1.5–3.6 m ^?1 s^?1, depending upon the hydrogen‐bonding agent and the equation used for the calculation of the rate constants. The hydrogen‐bonding number n was found to be around 0.5 or 1.0. The implication of this study in, for example, the replication of DNA, the prevention of the formation of super oxide, and so on is discussed. Copyright © 2012 John Wiley & Sons, Ltd.     

A Review on Mechanistic Insight of Plant Derived Anticancer Bioactive Phytocompounds and Their Structure Activity Relationship

Cancer is a disorder that rigorously affects the human population worldwide. There is a steady demand for new remedies to both treat and prevent this life-threatening sickness due to toxicities, drug resistance and therapeutic failures in current conventional therapies. Researchers around the world are drawing their attention towards compounds of natural origin. For decades, human beings have been using the flora of the world as a source of cancer chemotherapeutic agents. Currently, clinically approved anticancer compounds are vincristine, vinblastine, taxanes, and podophyllotoxin, all of which come from natural sources. With the triumph of these compounds that have been developed into staple drug products for most cancer therapies, new technologies are now appearing to search for novel biomolecules with anticancer activities. Ellipticine, camptothecin, combretastatin, curcumin, homoharringtonine and others are plant derived bioactive phytocompounds with potential anticancer properties. Researchers have improved the field further through the use of advanced analytical chemistry and computational tools of analysis. The investigation of new strategies for administration such as nanotechnology may enable the development of the phytocompounds as drug products. These technologies have enhanced the anticancer potential of plant-derived drugs with the aim of site-directed drug delivery, enhanced bioavailability, and reduced toxicity. This review discusses mechanistic insights into anticancer compounds of natural origins and their structural activity relationships that make them targets for anticancer treatments.     

Synthesis of chalcone precursor via Cu(I) catalyzed 1,3-dipolar reaction of functionalized acetylene and pyrazole embedded dipole

A new class of functionalized pyrazole bearing 1,2,3-triazole has been synthesized via Cu(I) mediated 1,3-dipolar cycloaddition of pyrazole bearing azide with various aromatic/heteroaromatic bearing terminal dipolarophile (acetylene). Structures of the newly synthesized compounds were explicated by analytical and spectral analysis. All the newly synthesized compounds were evaluated for their in-vitro antibacterial and antioxidant activity. Among the synthesized compound, triazole bearing 2,5-thiazolidinone 5b (20 ± 0.70) and triazole bearing thiocarboamide 5e (19 ± 0.70) showed good antibacterial activity against Escherichia coli and Pseudomonas aeruginosa, respectively. The newly synthesized compounds further tested for their ability to bleach DPPH radical using DPPH scavenging assay. Among the synthesized compounds 1,2,3-triazole bearing 2,5-thiazolidinone 5b (58.81%) exhibited good DPPH scavenging activity compared to the rest of the compounds. From the X-ray and Hirshfield analysis, it was observed that compound 3 , crystallizes in a triclinic crystal system with a P-1 space group. The major intercontacts present in these molecules are H…H (39.7%), C…H (23.9%), N…H (20.3%).     

Influence of Salinity Stress on Color Parameters,Leaf Pigmentation,Polyphenol and Flavonoid Contents,and Antioxidant Activity of Amaranthus lividus Leafy Vegetables

This is the first attempt to evaluate the impact of four salinity levels on the color parameters, pigments, polyphenols, flavonoids, and antioxidant capacities of four promising A. lividus genotypes. The color parameters, such as the yellowness/blueness (b*) and the chroma (C*); the antioxidant components, such as the polyphenols and flavonoids; and the antioxidant capacities of the leaves were remarkably increased by 39, 1, 5, 10 and 43%, respectively, at 50 mM of NaCl, and by 55, 5, 60, 34, 58 and 82%, respectively, at 100 mM NaCl concentrations. The green tower and SA6 genotypes were identified as tolerant varieties. The total phenolic content (TPC) and the total flavonoid content (TFC) played vital roles in scavenging reactive oxygen species (ROS), and they would be beneficial for the human diet and would serve as good antioxidants for the prevention of aging, and they are also essential to human health. A correlation study revealed the strong antioxidant capacities of the pigments and antioxidant components that were studied. It was revealed that A. lividus could tolerate a certain level of salinity stress without compromising the antioxidant quality of the final product. Taken together, our results suggest that A. lividus could be a promising alternative crop for farmers, especially in saline-prone areas in the tropical and subtropical regions.     

Slow Relaxation of Magnetization in an Isostructural Series of Zinc–Lanthanide Complexes: An Integrated EPR and AC Susceptibility Study

We report the synthesis, structure, and spectroscopic and dynamic magnetic properties of a series of heterodinuclear complexes, [ZnLn(LH₄)₂](NO₃)₃ ? 6 H₂O (Ln=Nd, Tb, Dy, Ho, Er, and Yb), with the singly deprotonated form of a new compartmentalized Schiff‐base ligand, LH₅. The Ln^III ions in these systems show a distorted square‐antiprism geometry with an LnO₈ coordination sphere. EPR spectroscopy and DC magnetic studies have shown that the anisotropic nature of the complexes is far more complicated than predicted on the basis of a simple electrostatic model. Among the investigated systems, only the Dy^III derivative showed single‐ion magnet behavior, in zero and an applied magnetic field, both in pure polycrystalline samples and in a series of polycrystalline samples with different degrees of dilution at the single‐crystal level in the isostructural Y^III derivative. The rich dynamics observed as functions of frequency, field, and temperature reveals that multiple relaxation mechanisms are at play, resulting in a barrier of 189 cm^?1, which is among the highest reported for a dinuclear Zn–Dy system. Analysis of the dynamic behavior as a function of dilution degree further evidenced the persistence of non‐negligible intermolecular interactions, even at the lowest concentration of 1 %.     

Theoretical and experimental studies on solubility and reactivity behavior of lysergol,elymoclavine, and dihydrolysergol

Lysergol, elymoclavine (Δ^9,10 and Δ^8,9 regioisomers), and dihydrolysergol are important members of ergolines. The present work reports their comparative study in gas and solvent phase (water) that has been performed both experimentally and theoretically. Theortical calculations have been carried within the density functional theory formalism to analyze the structural and electronic properties of these molecules with B3LYP hybrid exchange–correlational fuctional in conjunction with 6‐311++G (d,p) basis set. Hessian calculations are performed at B3LYP/6‐31G (d,p) level of theory in gas phase as well as other solvent phases. Solvent phase calculations are performed using Onsager reaction field model as implemented in Gaussian 03. A good agreement has been found between experimental and theoretical infrared and nuclear magnetic resonance (NMR) spectra. The calculated NMR data has been analyzed statistically. Stability of these regioisomers has been analyzed in terms of the energy gap between highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO–LUMO gap). Calculations for lysergol and elymoclavine in water as solvent were carried to examine the effect of solvent on the HOMO–LUMO levels and energy of these molecules. © 2012 Wiley Periodicals, Inc.     

Definitions of the degree of polarization of a light beam

A necessary and sufficient condition is derived for certain ad hoc expressions that are frequently used in the literature to represent correctly the degree of polarization of a light beam.