Spontaneous induction of the uniform lying helix alignment in bimesogenic liquid crystals for the flexoelectro-optic effect

Using in-plane electric fields, the electrical induction of the uniform lying helix (ULH) alignment in chiral nematic liquid crystals is reported. This process permits spontaneous induction of the ULH alignment to give an in-plane optic axis, without the need for complex processing. Flexoelectro-optic switching is subsequently obtained by holding the in-plane electrodes at a common voltage and addressing via a third, plane-parallel electrode on a second, or upper, substrate to give a field across the device in the viewing direction. For this device, in optimized bimesogenic materials, we demonstrate full intensity modulation and sub-millisecond response times at typical device temperatures. © 2012 American Institute of Physics.

Local Frustration Determines Molecular and Macroscopic Helix Structures

The effect of displaying cytochromes from an amyloid fibre is modelled as perturbation of -strands in a bilayer of helical -sheets, thereby explaining the spiral morphology of decorated amyloid and the dynamic response of morphology to cytochrome conformation. The morphology of the modelled fibre, which consists of minimal energy assemblies of rigid building blocks containing two anisotropic interacting units, depends primarily on the rigid constraints between units rather than the soft interactions between them. The framework is a discrete version of the bilayered frustration principle that drives morphology in Bauhinia seedpods. We show that self-assembly of frustrated long range structures can occur if the building blocks themselves are internally frustrated, e.g. amyloid morphology is governed by the conformation of the misfolded protein nucleating the fibre. Our model supports the idea that any peptide sequence can form amyloid if bilayers can form first, albeit stabilised by additional material such as chaperones or cytochromes. Analysis of experimentally derived amyloid structures supports our conclusions and suggests a range of frustration effects, which natural amyloid fibres may exploit. From this viewpoint, amyloid appears as a molecular example of a more general universal bilayered frustration principle, which may have profound implications for materials design using fibrous systems. Our model provides quantitative guidance for such applications. The relevance to longer length scales was proved by designing the morphology of a series of macroscopic magnetic stacks. Finally, this work leads to the idea of mixing controlled morphologically defined species to generate higher-order assembly and complex functional behaviour. The systematic kinking of decorated fibres and the nested frustration of the Bauhinia seed pod are two outstanding examples.

Numerical simulation of coil-helix transition processes of gelatin

Gelatin is widely used in food, pharmaceutical, and photographic industries due to the coil-helix transition, whereas the structural inhomogeneity considerably affects its essential properties closely connecting with the industrial applications. The spatially structural inhomogeneity of the gelatin caused by the uneven and unstable temperature field is analyzed by the finite element method during the cooling-induced coil-helix transition process. The helix conversion and the crosslinking density as functions of time and spatial grid are calculated by the incremental method. A length distribution density function is introduced to describe the continuous length distributions of two kinds of triple helices.

Evaluation of Effects of Bivalent Cations on the Formation of Purine-rich Triple-Helix DNA by ESI-FT-MS

The GGA triplet repeats are widely dispersed throughout eukaryotic genomes. (GGA)n or (GGT)n oligonucleotides can interact with double-stranded DNA containing (GGA:CCT)n to form triple-stranded DNA. The effects of 8 divalent metal ions (3 alkaline-earth metals and 5 transition metals) on formation of these purine-rich triple-helix DNA were investigated by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-MS). In the absence of metal ions, no triplex but single-strand, duplex, and purine homodimer ions were observed in mass spectra. The triple-helix DNA complexes were observed only in the presence of certain divalent ions. The effects of different divalent cations on the formation of purine-rich triplexes were compared. Transition-metal ions, especially Co2+ and Ni2+, significantly boost the formation of triple-helix DNA, whereas alkaline-earth metal ions have no positive effects on triplex formation. In addition, Ba2+ is notably beneficial to the formation of homodimer instead of triplex.

Helix-sense-selective polymerization of N,N-diphenyl (meth)acrylamide by anionic catalysts

In this paper, the helix-sense-selective polymerization of N,N-diphenyl acrylamide (DPAA) and N,N-diplienyl methacrylamide(DPMAA) were studied with living helix prepolymer as anionic initiator, and the chiral optical properties of the obtained polymers were investigated too. It was shown that optically active polymers of DPAA and DPMAA could be obtained under the experimental condition, and exhibited the same screw sense as that of the prepolymer.

Electric field-induced conformational transition of bovine serum albumin from alpha-helix to beta-sheet

The irreversible conformational transition of bovine serum albumin (BSA) from alpha-helix to beta-sheet, induced by electric field near the electrode surface, was monitored by circular dichroism (CD) with a long optical path thin layer cell (LOPTLC).

HELIX-INDUCED ASYMMETRIC POLYMERIZATION

Asymmetric polymerization could be induced by an already formed optically active living prepolymer with one-handed screw sense helix conformation. The usually formed anionic active centre on the prepolymer could be changed to cationic, radical and even of Ziegler-Natta type. These living prepolymers with various kinds of active centre were all effective to induce a consequent asymmetric polymerization of a monomer which may be other than that in the prepolymer, to afford an optically active helical chain with the same screw sense as that of the prepolymer. Eight monomers have been used in the work. Optical rotation, circular dichroism and gelpermeation chromatography have been taken to prove the helix-induced asymmetric polymerization.

STUDY ON OPTICAL-ROTATORY OF HELIX POLYMER POLY(TRIPHENYLMETHYL METHACRYLATE)

The optical rotatory of helix polymer poly(triphenylmethyl methacrylate) (PTrMA) has been studied. The specific rotation of PTrMA is related with the length of helical chain linearly, while P(n)BAR<6 and P(n)BAR greater-than-or-equal-to 15. When P(n)BAR greater-than-or-equal-to 15, [alpha]D/20 = 1.6 P(n)BAR + 290-degrees. The contribution of each repeating unit to [alpha]D/20 is 1.6-degrees. In the 300-600 nm region, the ORD of PTrMA obeys both the Drude equation and Moffitt equation. The relationship between the [alpha]D of PTrMA and the solvent, concentration and temperature has also been investigated.

Control of the orientational order and nonlinear optical response of the "push-pull" chromophore RuPZn via specific incorporation into densely packed monolayer ensembles of an amphiphilic four-helix bundle peptide: characterization of the peptide-chromophore complexes.

"Push-pull" chromophores based on extended pi-electron systems have been designed to exhibit exceptionally large molecular hyperpolarizabilities. We have engineered an amphiphilic four-helix bundle peptide to vectorially incorporate such hyperpolarizable chromophores having a metalloporphyrin moiety, with high specificity into the interior core of the bundle. The amphiphilic exterior of the bundle facilitates the formation of densely packed monolayer ensembles of the vectorially oriented peptide-chromophore complexes at the liquid-gas interface. Chemical specificity designed into the ends of the bundle facilitates the subsequent covalent attachment of these monolayer ensembles onto the surface of an inorganic substrate. In this article, we describe the structural characterization of these monolayer ensembles at each stage of their fabrication for one such peptide-chromophore complex designated as AP0-RuPZn. In the accompanying article, we describe the characterization of their macroscopic nonlinear optical properties.