Novel glycoconjugates of diospyrin, a quinonoid plant product: synthesis and evaluation of cytotoxicity against human malignant melanoma (A375) and laryngeal carcinoma (Hep2)

Glycoside derivatives of diospyrin (1) were synthesized for the first time, and the cytotoxicity of the novel compounds vis-à-vis their precursors were evaluated against two human cancer cell lines, viz. malignant melanoma (A375) and laryngeal carcinoma (Hep2). The IC(50) values were in the low micromolar range for all the compounds tested, and A375 cells showed comparatively greater sensitivity than Hep2. Most of the compounds exhibited enhanced activity as compared to the plant-derived quinonoid precursor of the series (1), while the aminophenyl mannosyl (6) was found to be the most effective derivative. In A375 cells, 6 (IC(50) = 0.02 microM) showed the maximum increase in cytotoxicity (approximately 35-fold) over that of 1 (IC(50) = 0.82 microM). Again, when the glycosides were evaluated at a given concentration (0.1 microM) for their relative capacity to generate ROS from A375 cells, the compound 6 could produce the highest amount of ROS. Incidentally, this derivative also showed a comparatively lower toxicity (IC(50) approximately 41 microM) when tested against normal human peripheral blood mononuclear cells, indicating a fair prospect of its development as a novel chemotherapeutic agent for the treatment of malignant melanoma.     

Characterization of InGaGdN layers prepared by molecular beam epitaxy

Gd‐doped InGaN layers were prepared by plasma‐assisted molecular‐beam epitaxy in search of new functional diluted magnetic semiconductors for their potential use in spintronics. The local structure around the Gd atoms was examined by the Gd L_III‐edge of X‐ray absorption fine structure. It was found that the majority of Gd atoms substitutionally occupied the cation sites in the InGaGdN layers. Clear hysteresis and saturation magnetization were observed from the magnetization versus field curves examined by means of a superconducting quantum interference device magnetometer at low and room temperatures. In addition, the incorporation of extra shallow donors by co‐doping InGaN with both Gd and Si showed higher magnetization than the undoped InGaGdN. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Extremal behavior of a coupled continuous time random walk

Coupled continuous time random walks (CTRWs) model normal and anomalous diffusion of random walkers by taking the sum of random jump lengths dependent on the random waiting times immediately preceding each jump. They are used to simulate diffusion-like processes in econophysics such as stock market fluctuations, where jumps represent financial market microstructure like log returns. In this and many other applications, the magnitude of the largest observations (e.g. a stock market crash) is of considerable importance in quantifying risk. We use a stochastic process called a coupled continuous time random maxima (CTRM) to determine the density governing the maximum jump length of a particle undergoing a CTRW. CTRM are similar to continuous time random walks but track maxima instead of sums. The many ways in which observations can depend on waiting times can produce an equally large number of CTRM governing density shapes. We compare densities governing coupled CTRM with their uncoupled counterparts for three simple observation/wait dependence structures.     

Single-Component Molecular Conductor [Cu(dmdt)(2)] with Three-Dimensionally Arranged Magnetic Moments Exhibiting a Coupled Electric and Magnetic Transition

Crystals of the single-component molecular conductor [Cu(dmdt)(2)] (dmdt = dimethyltetrathiafulvalenedithiolate) were prepared as a molecular system, with three-dimensionally arranged magnetic moments embedded in "sea" of π conduction electrons. [Cu(dmdt)(2)] had fairly large room-temperature conductivity (110 S?cm(-1)) and exhibited weakly metallic behavior near room temperature. Below 265 K, the resistivity (R) increased very slowly with decreasing temperature and then increased rapidly, indicating a transition from a highly conducting state to an insulating state near 95 K. The magnetic susceptibility showed Curie-Weiss behavior at 100-300 K (C = 0.375 emu/mol, Θ = 180 K). The Curie constant and the high-temperature resistivity behavior indicate that conduction electrons and three-dimensionally arranged magnetic moments coexist in the crystal. The ESR intensity increased down to about 95 K. The ESR signal was broadened and decreased abruptly near 95 K, suggesting that electric and antiferromagnetic transitions occurred simultaneously near 95 K. The crystal structure was determined down to 13 K. To examine the stability of the twisted conformation of Cu complex with dithiolate ligands, the dihedral angle dependence of the conformational energy of an isolated M(L)(2)(n-) molecule was calculated, which revealed the dihedral angle dependence on the ligand (L) and the oxidation state of the molecule (n). High-pressure four-probe resistivity measurements were performed at 3.3-9.3 GPa using a diamond anvil cell. The small resistivity increase observed at 3.3 GPa below 60 K suggested that the insulating transition observed at ambient pressure near 95 K was essentially suppressed at 3.3 GPa. The intermolecular magnetic interactions were examined on the basis of simple mean field theory of antiferromagnetic transition and the calculated intermolecular overlap integrals of the singly occupied molecular orbital (SOMO) of Cu(dmdt)(2).     

Fractional Dispersion,Lévy Motion,and the MADE Tracer Tests

The macrodispersion experiments (MADE) at the Columbus Air Force Base in Mississippi were conducted in a highly heterogeneous aquifer that violates the basic assumptions of local second-order theories. A governing equation that describes particles that undergo Lévy motion, rather than Brownian motion, readily describes the highly skewed and heavy-tailed plume development at the MADE site. The new governing equation is based on a fractional, rather than integer, order of differentiation. This order (), based on MADE plume measurements, is approximately 1.1. The hydraulic conductivity (K) increments also follow a power law of order =1.1. We conjecture that the heavy-tailed K distribution gives rise to a heavy-tailed velocity field that directly implies the fractional-order governing equation derived herein. Simple arguments lead to accurate estimates of the velocity and dispersion constants based only on the aquifer hydraulic properties. This supports the idea that the correct governing equation can be accurately determined before, or after, a contamination event. While the traditional ADE fails to model a conservative tracer in the MADE aquifer, the fractional equation predicts tritium concentration profiles with remarkable accuracy over all spatial and temporal scales.     

DYE LASER INTRACAVITY ABSORPTION AS AN OPTICAL PROBE IN CONDENSED PHASE AND BIOLOGICAL SYSTEMS

Abstract— A sensitive optical method to monitor local environmental changes in biological systems is described. It utilizes the high optical amplification typical to any dye laser cavity by installing the investigated system inside the laser resonator. Very small changes in the optical density of a probe dye can be detected and related to the dye's state of aggregation or in another demonstration to its adsorption on differently charged micelles and liposomes. When further developed, this technique can prove to be a very sensitive method to measure membrane potentials, changes in molecular environment and molecular dynamics. The pulsed laser used is advantageous to a continuous source used in fluorescence and absorption methods reducing photodynamic damage.     

Multiple scale perturbation for second-order non-linear differential equations

Asymptotic solutions of a class of second-order non-linear differential equations with variable coefficients are studied. For large values of the parameter, the differential equations are of the singular-perturbation type and approximations are constructed by the generalized method of multiple scales.     

Direct observation of odd-even effect for chiral alkyl alcohols in solution using vibrational circular dichroism spectroscopy

The odd-even effect of chiral alkyl alcohols, (S)-CH(3)CHOHC(n)()H(2)(n)()(+1) (n = 2-8), in solution state has been observed spectroscopically for the first time. The vibrational circular dichroism (VCD) bands at 1148 cm(-)(1) exhibit a clear odd-even effect. The observed VCD bands of (R)-(-)-2-hexanol correspond well to those predicted (population weighted). Density functional theory calculations indicate that the most prevalent conformations in solution are the all-trans forms. The odd-even effect of the VCD bands is ascribed to the alternating terminal methyl motions in the alkyl chains relative to fixed motions near the chiral center in the trans conformations. The conformational sensitivity of VCD for the chiral alcohols in the solution state may be useful for the design of liquid crystals and ligands in the future.