Nickel–Schiff base complex catalyzed C–S cross-coupling of thiols with organic chlorides

We report an efficient, mild and convenient synthetic protocol for the C–S cross-coupling reaction of various aryl, benzyl, allyl chlorides and thiols using 5 mol % Nickel–Schiff base catalyst with NaOH as the base, in DMF at 70 °C. Using this protocol, we have shown that a variety of aryl sulfides can be synthesized in excellent yields from readily available organic chlorides and thiols.     

DNA binding, nuclease activity and cytotoxicity studies of Cu(II) complexes of tridentate ligands

Cu(II) complexes of three tridentate ligands, L(1), L(2) and L(3), [L(1), N-((1H-imidazole-2-yl)methyl)-2-(pyridine-2-yl)ethanamine; L(2), N-((1-methyl-1H-imidazole-2-yl)methyl)-2-(pyridine-2-yl)ethanamine; L(3), 2-(pyridine-2-yl)-N-((pyridine-2-yl)methyl)ethanamine] respectively, were synthesized and characterized. The single crystal X-ray structure of complex 1 reveals the pseudo octahedral coordination geometry around the copper center. Absorption and fluorescence experimental evidence show good DNA binding propensity (in the order of 10(5) M(-1)) of the complexes. Thermal denaturation and circular dichroism (CD) analyses reveal minor structural changes of calf thymus (CT) DNA in presence of complexes and groove and/or surface binding of the complexes to CT-DNA. Kinetic DNA cleavage assay shows pseudo-first-order kinetic reaction between the complex and supercoiled (SC) DNA. In addition, mechanistic SC DNA cleavage results show higher DNA cleavage activity in presence of reducing agent, due to the presence of hydroxyl radicals. In vitro cytotoxicity assay of the complexes demonstrate that the complexes have low toxicity for different cancer cell lines and IC(50) values were between 37 and 156 μM.     

Reinforcement Efficiency of Carbon Nanotubes – Myth and Reality

Different micromechanical models for the prediction of mechanical properties of CNT/polymer composites, taking into consideration filler percolation throughout the matrix, are considered. It is demonstrated that the critical filler volume fraction, where a percolating network of CNTs is forming, marks a “turning point” in the reinforcement efficiency. Expectations for the reinforcing effect of CNTs at concentrations above a percolating threshold with the current technology are in general unrealistic.

     

Spectrophotometric studies of complexation of [60]fullerene with series of aromatic hydrocarbon molecules containing flexible phenyl substituents

The absorption spectra of the electron donor-acceptor complexes of [60]fullerene with five different aromatic hydrocarbon (AH) molecules containing flexible phenyl substituents have been investigated in toluene medium. An absorption band due to charge transfer (CT) transition is observed in each case in the visible region. The experimental CT transition energies are well correlated with the vertical ionization potentials of the AHs studied (through Mulliken's equation) from which we extract degrees of charge transfer, oscillator and transition dipole strengths of the CT complexes. The degrees of CT in the ground state of the complexes have been found to be very low (0.49-0.55%). The formation constants (K) for the complexes of [60]fullerene with the aromatic hydrocarbons have been determined by UV-vis spectroscopy. Both K values and PM3 calculations on [60]fullerene/AH complexes reveal that nature of substitution in the donor moiety as well as steric compatibility with the acceptor molecule govern the process of EDA complex formation.     

Ultrahigh resolution crystal structures of human carbonic anhydrases I and II complexed with "two-prong" inhibitors reveal the molecular basis of high affinity

The atomic-resolution crystal structures of human carbonic anhydrases I and II complexed with "two-prong" inhibitors are reported. Each inhibitor contains a benzenesulfonamide prong and a cupric iminodiacetate (IDA-Cu(2+)) prong separated by linkers of different lengths and compositions. The ionized NH(-) group of each benzenesulfonamide coordinates to the active site Zn(2+) ion; the IDA-Cu(2+) prong of the tightest-binding inhibitor, BR30, binds to H64 of CAII and H200 of CAI. This work provides the first evidence verifying the structural basis of nanomolar affinity measured for two-prong inhibitors targeting the carbonic anhydrases.     

An inventory model for a deteriorating item with displayed stock dependent demand under fuzzy inflation and time discounting over a random planning horizon

An inventory model for a deteriorating item (seasonal product) with linearly displayed stock dependent demand is developed in imprecise environment (involving both fuzzy and random parameters) under inflation and time value of money. It is assumed that time horizon, i.e., period of business is random and follows exponential distribution with a known mean. The resultant effect of inflation and time value of money is assumed as fuzzy in nature. The particular case, when resultant effect of inflation and time value is crisp in nature, is also analyzed. A genetic algorithm (GA) is developed with roulette wheel selection, arithmetic crossover, random mutation. For crisp inflation effect, the total expected profit for the planning horizon is maximized using the above GA to derive optimal inventory decision. On the other hand when inflationary effect is fuzzy then the above expected profit is fuzzy in nature too. Since optimization of fuzzy objective is not well defined, the optimistic/pessimistic return of the expected profit is obtained using possibility/necessity measure of fuzzy event. Fuzzy simulation process is proposed to determine this optimistic/pessimistic return. Finally a fuzzy simulation based GA is developed and is used to maximize the above optimistic/pessimistic return to get optimal decision. The models are illustrated with some numerical examples and some sensitivity analyses have been presented.     

Excitations in doped quantum dot insisted by discontinuous reversals of static electric field: Interplay between pulse and dopant site

We explore the excitation profile of a repulsive impurity doped quantum dot. The quantum dot is subject to a discontinuously reversing static electric field. The dopant impurity potential chosen assumes Gaussian form. The investigation reveals the key role played by the dopant location and the number of pulses offered by the external field to the dot in controlling the excitation rate. Time-dependent Hellman-Feynman theorem has been invoked to understand the extent of energy transfer between field direction and the direction where no field is applied. The combined transition rate from ground to other excited states is also determined to support the findings.