Statistical Physics Approach to Liquid Crystals: Dynamics of Mobile Potts Model Leading to Smectic Phase,Phase Transition by Wang–Landau Method

We study the nature of the smectic–isotropic phase transition using a mobile 6-state Potts model. Each Potts state represents a molecular orientation. We show that with the choice of an appropriate microscopic Hamiltonian describing the interaction between individual molecules modeled by a mobile 6-state Potts spins, we observe the smectic phase dynamically formed when we cool the molecules from the isotropic phase to low temperatures (T). In order to elucidate the order of the transition and the low-T properties, we use the high-performance Wang–Landau flat energy-histogram technique. We show that the smectic phase goes to the liquid (isotropic) phase by melting/evaporating layer by layer starting from the film surface with increasing T. At a higher T, the whole remaining layers become orientationally disordered. The melting of each layer is characterized by a peak of the specific heat. Such a succession of partial transitions cannot be seen by the Metropolis algorithm. The successive layer meltings/evaporations at low T are found to have a first-order character by examining the energy histogram. These results are in agreement with experiments performed on some smectic liquid crystals.     

Determination of Sulfide by Hematoxylin Multiwalled Carbon Nanotubes Modified Carbon Paste Electrode

This study investigates a new approach for the amperometric determination of sulfide using a hematoxylin multiwalled carbon nanotubes modified carbon paste electrode (HM‐MWCNTs/CPE). The experimental results show that HM‐MWCNTs/CPE significantly enhances the electrocatalytic activity towards sulfide oxidation. Cyclic voltammetric studies show that the peak potential of sulfide shifted from +400 mV at unmodified CPE to +175 mV at HM‐MWCNTs/CPE. The currents obtained from amperometric measurements at optimum conditions were linearly correlated with the concentration of sulfide. The calibration curve was obtained for sulfide concentrations in the range of 0.5–150×10^?6 mol L^?1. The detection limit was found to be 0.2×10^?6 mol L^?1 for the amperometric method. The proposed method was successfully applied to a river water sample in Pardubice, Czech Republic.     

On the exactness of a theorem of G.A. Fomin

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Second-generation mimics of ganglioside GM1 oligosaccharide: a three-dimensional view of their interactions with bacterial enterotoxins by NMR and computational methods

As a step to delineate a strategy of ligand design for cholera toxin (CT), NMR studies were performed on several mimics of the GM1 ganglioside oligosaccharide. The conformation of these analogues was investigated first in solution and then upon binding to cholera toxin by transferred nuclear Overhauser effect (TR-NOE) measurements. It was demonstrated that CT selects a conformation similar to the global minima of the free saccharides from the ensemble of presented conformations. No evidence of major conformational distortions was obtained, but one or two of the available conformers of the hydroxyacid side chain appear to be selected in the bound state. The NMR data were interpreted with the aid of computer models, generated and analyzed by using a combination of different approaches (MacroModels' MC/EM and MC/SD, Autodock, and GRID). Analysis of the NMR data supported by computational studies allowed us to interpret the experimental observations and to derive workable models of the ligand:toxin complexes. These models suggest that the higher affinity of the (R)-lactic acid derivative 3 may stem from lipophilic interactions with a hydrophobic area in the toxin binding site located in the vicinity of the sialic acid side chain binding region of the CT:GM1 complex, and formed by the side chain of Ile-58 and Lys-34. Thus, the models obtained have allowed us to make useful design suggestions for the improvement of ligand affinity.     

Flow-through sensor based on derivative synchronous fluorescence spectrometry for the simultaneous determination of pyrene,benzo(e)pyrene and benzo(ghi)perylene in water

A flow-through/first derivative synchronous spectrofluorimetric sensor for the determination of PAH has been described. This sensor has been used for the simultaneous determination of PAH mixtures (pyrene, benzo(e)pyrene and benzo(ghi)perylene). Linear calibration ranges between 10 and 500 ng/ml with acceptable precision (repeatability, expressed as relative standard deviation, smaller than 4.6%, and sampling frequency of 12 h(-1)) have been obtained. The method has been applied to the determination of the target analytes in spiked water samples with excellent results (recoveries between 94 and 108%).     

Carbohydrate-based DNA ligands: sugar-oligoamides as a tool to study carbohydrate-nucleic acid interactions

Sugar-oligoamides have been designed and synthesized as structurally simple carbohydrate-based ligands to study carbohydrate-DNA interactions. The general design of the ligands 1-3 has been done as to favor the bound conformation of Distamycin-type gamma-linked covalent dimers which is a hairpin conformation. Indeed, NMR analysis of the sugar-oligoamides in the free state has indicated the presence of a percentage of a hairpin conformation in aqueous solution. The DNA binding activity of compounds 1-3 was confirmed by calf thymus DNA (ct-DNA) NMR titration. Interestingly, the binding of the different sugar-oligoamides seems to be modulated by the sugar configuration. Semiquantitative structural information about the DNA ligand complexes has been derived from NMR data. A competition experiment with Netropsin suggested that the sugar-oligoamide 3 bind to DNA in the minor groove. The NMR titrations of 1-3 with poly(dA-dT) and poly(dG-dC) suggested preferential binding to the ATAT sequence. TR-NOE NMR experiments for the sugar-oligoamide 3-ct-DNA complex both in D(2)O and H(2)O have confirmed the complex formation and given information on the conformation of the ligand in the bound state. The data confirmed that the sugar-oligoamide ligand is a hairpin in the bound state. Even more relevant to our goal, structural information on the conformation around the N-glycosidic linkage has been accessed. Thus, the sugar asymmetric centers pointing to the NH-amide and N-methyl rims of the molecule have been characterized.