Orthogonal hexatic smectic phase-rare or common?

The hexatic smectic B (Hex B) phase is commonly encountered among hydrogen-bonded liquid crystal materials. Among enaminoketone and Schiff's base compounds, twenty homologous series (c. 10² compounds) exhibiting orthogonal mono-or bi-layer hexatic phases were identified by combined microscopy and DSC. Phase transitions from crystal B (CrB) of S_f to Hex B as well as from Hex B to S_f, S_a or S_c phases were observed within the range 50 to 190°C. Temperature ranges of the Hex B phase detectable by DSC varied from 0.2 to 20°C. Within two groups of three-ring enaminoketones, the formation of the Hex B phase was found to be controlled by both inductive and mesomeric components of the Hammett constants of the terminal substituents of the molecules.     

Modification and optimization of the united-residue (UNRES) potential energy function for canonical simulations. I. Temperature dependence of the effective energy function and tests of the optimization method with single training proteins

We report the modification and parametrization of the united-residue (UNRES) force field for energy-based protein structure prediction and protein folding simulations. We tested the approach on three training proteins separately: 1E0L (beta), 1GAB (alpha), and 1E0G (alpha + beta). Heretofore, the UNRES force field had been designed and parametrized to locate native-like structures of proteins as global minima of their effective potential energy surfaces, which largely neglected the conformational entropy because decoys composed of only lowest-energy conformations were used to optimize the force field. Recently, we developed a mesoscopic dynamics procedure for UNRES and applied it with success to simulate protein folding pathways. However, the force field turned out to be largely biased toward -helical structures in canonical simulations because the conformational entropy had been neglected in the parametrization. We applied the hierarchical optimization method, developed in our earlier work, to optimize the force field; in this method, the conformational space of a training protein is divided into levels, each corresponding to a certain degree of native-likeness. The levels are ordered according to increasing native-likeness; level 0 corresponds to structures with no native-like elements, and the highest level corresponds to the fully native-like structures. The aim of optimization is to achieve the order of the free energies of levels, decreasing as their native-likeness increases. The procedure is iterative, and decoys of the training protein(s) generated with the energy function parameters of the preceding iteration are used to optimize the force field in a current iteration. We applied the multiplexing replica-exchange molecular dynamics (MREMD) method, recently implemented in UNRES, to generate decoys; with this modification, conformational entropy is taken into account. Moreover, we optimized the free-energy gaps between levels at temperatures corresponding to a predominance of folded or unfolded structures, as well as to structures at the putative folding-transition temperature, changing the sign of the gaps at the transition temperature. This enabled us to obtain force fields characterized by a single peak in the heat capacity at the transition temperature. Furthermore, we introduced temperature dependence to the UNRES force field; this is consistent with the fact that it is a free-energy and not a potential energy function. beta     

X-ray and high resolution selenium-77 solid state NMR spectroscopy as complementary probes to structural studies of organophosphorus diselenides

high resolution solid state NMR spectroscopy was employed to study structural properties of bis(diisopropoxyphosphorothioyl) diselenide 1 and bis(dineopentoxyphosphorothioyl) diselenide 2. The principal elements T_ii of effective dipolar/chemical shift tensor were calculated from spinning sideband intensities employing the WIN-MAS program. The values of anisotropy and asymmetry parameters reflect the distortion of the selenium environment. It was found that the T₃₃ component mostly contributes to changes in the isotropic chemical shifts. CP/MAS experiments were used to decide the assignment of space group by counting the number of crystallographically unique selenium centers in the unit cell. Crystals of diselenide 1 are triclinic, space group P with a=8.485(3) Å, b=8.508(1) Å, c=8.511(2) Å, =98.835(15)°, β=111.653(24)°, γ=93.524(21)°, V=559.5(3) ų, D_c=1.544(2) g/cm³ and Z=1. Refinement using 2222 reflections for 157 variables gives R=0.037. Crystals of diselenide 2 are triclinic, space group P1 with a=9.1418(8) Å, b=9.1465(8) Å, c=9.9200(9) Å, =74.751(8)°, β=74.629(7)°, γ=82.216(7)°, V=769.7(1) ų, D_c=1.365(2) g/cm³ and Z=1. Refinement using 3316 reflections for 297 variables gives R=0.0272.     

Dielectric Studies of the Ordering Due to an External DC Electric Field in Nematic 4,4′-di-n-hexyloxyazoxybenzene

Studies of dielectric permittivity changes under the action of a DC electric field on nematic 4,4′-di-n-hexyloxyazoxybenzene (DHAB) have been performed. Observations of time dependent processes occurring during the application of a voltage were made for samples of 0.5–2 mm thickness as a function of the applied voltage. The dielectric permittivity changes which are related to changes in the ordering of the samples were interpreted in dielectric as well as in electrohydrodynamic terms. Three voltage regions were distinguished which are characterised by ordering due to dielectric orientation, hydrodynamic laminar flow and turbulent flow.     

Enaminoketones as new hydrogen bonded liquid crystals

The relation between molecular structure of enaminoketone derivatives and their mesomorphic properties is discussed. It has been observed that the electron accepting terminal groups (F,Cl,Br,CN) promote formation of orthogonal phases while strongly electron donating groups (OC_nH_2n+1) favour tilted phases. Among the synthesised compounds, materials useful for structural studies of two dimensional (2D) melting in orthogonal, as well as the tilted systems, were found. It has been determined that the heat effects in the melting process from crystalline smectic into liquid-like smectic, through the hexatic state, are correlated to the density changes.