Mechanism for the formation of bubble domains

Abstract

The mechanism for the formation and stabilization of acoustic bubble domains is investigated experimentally within the framework of the Akahane and Tako model which is based on the assumption of the formation of a system of defects in the layer of a cholestric liquid crystal, these defects pin the bubble domains. The theory takes no account of the interaction between bubble domains, this being valid in the case of a low density of domain packing. The correlation between the experimental results and theory is quite satisfactory, especially in the region of d/P ₀ < 1.5 where the bubble domain packing density is very low (where d is the thickness of the cholestric layer and P ₀ is the pitch of the helix).     

Structures of Cyanobactin Maturation Enzymes Define a Family of Transamidating Proteases

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Highlights? Boundaries for cyanobactin maturation protease domains determined ? Structures of protease domains for cyanobactin maturation enzymes determined ? Additional structural motif in PatG assists in cyclizing transamidation ? Rational mutagenesis of active site leads to altered catalytic profiles for PatG     

Optical and electrooptical properties of homeoplanar layers of cholesteric liquid crystals

Abstract

A wedge shaped layer of a cholesteric liquid crystal, with the director surface orientations first planar and the other homeotropic, shows two distinctive textures depending on the relation between the local thickness, d, and the equilibrium pitch, P ₀. If d/P ₀ < 1, the texture does not show any domains; the director distribution is reminiscent of a corkscrew. If d/P ₀ > 1, there are linear periodic domains. The domain direction rotates as the thickness of the layer increases. The voltage dependence of light transmission of the homeoplanar cholesteric layer placed between crossed polarizers is less pronounced and more linear than the corresponding dependence for the twisted nematic effect.     

Preparation of copper sulphide clusters in organic-inorganic composites of Langmuir-Blodgett films of amphiphilic Schiff bases

Copper sulphide clusters were prepared in Langmuir-Blodgett films of copper complexes of amphiphilic Schiff bases-3,4-dimethoxy-N-benzylidene hexadeylamine (I) and 3,4-dimethoxy-N-benzylidene-4’-(hexadecylamino) benzylamine (II) The clusters obtained were analysed using UV-Vis spectroscopy and optical microscopy. Brewster angle microscopic studies on monolayers ofI andII at air/water interface showed formation of needle-like domains which seem to cluster faster inI than inII. Atomic force microscopy (AFM) studies also showed fairly uniform sized clusters inII whereas in the case ofI they seem to show varying sizes. From the results it is concluded that π-elongation in the polar head groups leads to controlled cluster sizes in compoundII as compared to those in compoundI.     

Synthesis and mesomorphic properties of 7-alkoxybezopyrano[2,3-c]pyrazol-3-one

A new series of fused polyheterocyclic aromatic compounds, 7-alkoxybezopyrano[2,3-c]pyrazol-3-one (C- n BPP), were synthesised and characterised by infrared, ¹H-nuclear magnetic resonance (NMR), ¹³C-NMR and two-dimensional ¹H-¹³C cosy spectra. Their phase transition behaviour was investigated by differential scanning calorimetry and polarising optical microscopy. All of these compounds showed enantiotropic mesophases with temperature domains of 12–60°C and 22–69°C on heating and cooling processes for a carbon number of the alkoxy chain from 2 to 10. The effect of the length of the alkoxy chain on the mesomorphic properties was discussed. Comparison of C- n BPP and several kinds of coumarin derivatives indicated that the intermolecular hydrogen bonding acted as the driving force of the mesophase formation.     

On the stability of Langmuir films of pyramidic mesogens

Abstract

Pyramidic mesogens forming thermotropic liquid crystal bulk phases were spread in an air-water interface. Pressure surface measurements and polarizing microscopy on the Langmuir films were used to characterize the various states of these pyramidic-like molecules. For two compounds bearing short lateral aliphatic chains, the surface pressure isotherms exhibit a large plateau region corresponding to a metastable monolayer in which the molecules may adopt an ‘edge-on’ arrangement. The coexistence of multilayered, anisotropic, slowly growing domains with the monolayer in the plateau region has been observed at long time scale. The film area relaxation kinetics at constant surface pressure show the existence of two nucleation mechanisms for the formation of these domains.     

The bacitracin biosynthesis operon of Bacillus licheniformis ATCC 10716: molecular characterization of three multi-modular peptide synthetases

Background: The branched cyclic dodecylpeptide antibiotic bacitracin, produced by special strains of Bacillus, is synthesized nonribosomally by a large multienzyme complex composed of the three bacitracin synthetases BA1, BA2 and BA3. These enzymes activate and incorporate the constituent amino acids of bacitracin by a thiotemplate mechanism in a pathway driven by a protein template. The biochemical features of these enzymes have been studied intensively but little is known about the molecular organization of their genes.Results: The entire bacitracin synthetase operon containing the genes bacA-bacC was cloned and sequenced, identifying a modular structure typical of peptide synthetases. The bacA gene product (BA1, 598 kDa) contains five modules, with an internal epimerization domain attached to the fourth; bacB encodes BA2 (297 kDa), and has two modules and a carboxy-terminal epimerization domain; bacC encodes BA3, five modules (723 kDa) with additional internal epimerization domains attached to the second and fourth. A carboxy-terminal putative thioesterase domain was also detected in BA3. A putative cyclization domain was found in BA1 that may be involved in thiazoline ring formation. The adenylation/thioester-binding domains of the first two BA1 modules were overproduced and the detected amino-acid specificity coincides with the first two amino acids in bacitracin. Disruption of chromosomal bacB resulted in a bacitracin-deficient mutant.Conclusions: The genes encoding the bacitracin synthetases BA1, BA2 and BA3 are organized in an operon, the structure of which reflects the modular architecture expected of peptide synthetases. In addition, a putative thiazoline ring formation domain was identified in the BA1 gene.     

The NTB phase in an achiral asymmetrical bent-core liquid crystal terminated with symmetric alkyl chains

ABSTRACT

The characteristics of the twist-bend nematic (N_TB) phase of an achiral asymmetrical rigid bent-core liquid crystal (LC), the ends of which are terminated by symmetric alkyl chains, are reported. The nematic–nematic phase transition and its properties are studied by differential scanning calorimetry (DSC), polarising microscopy and the electro-optic techniques. Large domains of opposite handedness are observed in the absence of the external field in the N_TB phase. Another set of periodic striped pattern consisting of domains with sharp boundaries is formed when a high-frequency electric field with a magnitude above its threshold is applied across a planarly aligned cell. The neighbouring domains are of opposite chirality. The temperature dependence of the heliconical angle θ₀ is determined from the birefringence measurements using Haller’s extrapolation technique. This material shows lower values of the heliconical angle (~9.3° at a temperature of 155°C within the N_TB phase) when compared with the previously reported dimer-based twist-bend nematic LCs (31°±3°).     

Incorporation of lipid domains in Cerasome, a morphologically-stable organic-inorganic vesicular nanohybrid

To extend the concept of the Cerasome, an organic-inorganic vesicular nanohybrid, this paper investigates the preparation and characterization of a “mixed” Cerasome. The system consists of a Cerasome-forming lipid 1, a cationic synthetic lipid 2, and a zwitterionic phospholipid 3. Lipid mixtures of 1 and 2 or 1 and 3 were used to prepare the mixed Cerasomes. Their lipid distributions were examined using differential scanning calorimetry (DSC), which showed that 1 and 2 (or 1 and 3) were phase-separated in the mixed Cerasomes. These results seem to be mainly attributable to the polymerizable nature of 1. Results of scanning electron microscopy (SEM) and energy-dispersive X-ray analysis (EDX) showed that 1 and 3 were both incorporated into a single Cerasome, not macroscopically separated to form separate vesicles from each lipid component. Mixed Cerasomes of 1 and 2 showed high morphological stability against a membrane-solubilizing surfactant, incorporating up to 70% of 2. On the other hand, the mixed Cerasomes from 1 and 3 were less stable than the mixed Cerasomes from 1 and 2. This relative instability might be attributable to differences between the mixed Cerasomes from 1 and 2 and 1 and 3 in terms of their vesicular sizes, lipid domain sizes, and their relative effectiveness for siloxane network formation. These results strongly support the formation of mixed Cerasomes that have lipid domains in-plane. Systems described in this study are useful to prepare variously mixed Cerasomes that have different surface functionalities and in-plane lipid distribution, but which have high morphological stability.     

Synthesis and mesomorphic properties of 2-(4′-alkoxybiphenyl-4-yl)-1H-benzimidazole derivatives

Three series of 2-(4′-alkoxybiphenyl-4-yl)-1H-benzimidazole derivatives (nM-x), which possessed 5-nitrobenzimidazole (nM-N series), benzimidazole (nM-H series) or 5-methylbenzimidazole (nM-M series) units at the end of the molecule, were synthesised and characterised by infrared, ¹H- and ¹³C-nuclear magnetic resonance spectra, electrospray ionisation-mass spectrometry and elemental analysis. Their phase transition behaviour was investigated by differential scanning calorimetry, polarising optical microscopy and X-ray diffraction. All the compounds exhibited enantiotropic smectic mesophases with wide temperature domains for a carbon number in the alkoxy chain from 6 to 16, where the mesophase ranges were 14–91°C and 17–99°C during heating and cooling processes for the nM-N compounds, 7–25°C and 8–49°C for the nM-H compounds and 48–81°C and 52–85°C for the nM-M compounds, respectively. The effect of the length of alkoxy chain on mesomorphic properties was discussed. The nM-N and nM-M exhibited a much wider mesophase range whether during heating or cooling process than the corresponding nM-H series, especially for the longer terminal chain (n > 8), which indicated that the substituent in the benzimidazole moiety was helpful in increasing the mesophase stability.     

New insights into the transitional behaviour of methyl-6-O-(n-dodecanoyl)-α-D-glucopyranoside using variable temperature FTIR spectroscopy and X-ray diffraction

The liquid crystalline behaviour of methyl-6-O-(n-dodecanoyl)-α-D-glucopyranoside, 1, has been characterised using X-ray diffraction and variable temperature Fourier transform infrared (FTIR spectroscopy). 1 exhibits a monotropic interdigitated smectic A phase consisting of bilayers in which the alkyl chains are overlapped. The crystal–isotropic transition is accompanied by a pronounced decrease in the strength of the hydrogen bonding network involving the sugar groups resulting in a marked change in the environment of the alkyl chains. The isotropic phase consists of disordered smectic-like domains stabilised via hydrogen bonding between the sugar groups. At the transition to the smectic A phase, a subtle change in hydrogen bonding is observed which is manifested by a change in the temperature dependence of the OH stretching peak position in the FTIR spectrum. On crystallisation, the strong hydrogen bonding network is re-established accompanied by a change in the conformational distribution of the alkyl chains. A model is proposed in which a combination of hydrogen bonding (enthalpic effects) and conformational arrangements (entropic effects) promotes initially the formation of smectic-like domains in the isotropic phase and subsequently stabilises the smectic A phase by inhibiting the microphase separation leading to the crystal phase.     

A new type of electrohydrodynamic instability in nematic liquid crystals with positive dielectric anisotropy

Abstract

A new type of electrohydrodynamic instability originally reported in nematic liquid crystal mixtures with positive dielectric anisotropy and as moderately thick samples is further studied. The ability of homogeneously aligned nematics with positive dielectric anisotropy, in the presence of a magnetic field, to exhibit Williams domains as a threshold effect is numerically investigated. The variation of the threshold voltage for domain formation and dielectric alignment with dielectric anisotropy is calculated theoretically and compared with the experimental results as moderately thick and thin samples.     

Cellulases and their interaction with cellulose

Most effective cellulolytic enzymes are made of at least two constitutive domains, a catalytic domain and a non-catalytic cellulose-binding domain linked by a flexible peptide. There are several families of catalytic domains and of cellulose-binding domains resulting in a large number of their possible combinations. Removal of the cellulose-binding domain drastically reduces the binding capacity of cellulases to insoluble cellulose while the catalytic efficiency on soluble substrates is usually maintained. Isolated cellulose-binding domains bear most of the binding properties of cellulases (quasi-irreversibility and dispersive effect) but do not hydrolyse cellulose. The multiple types of synergy that cellulases display when acting in combination on cellulose appear to result from their different activities and selectivity, from the substrate microheterogeneity, and sometimes from both.To the memory of Prof. Elwyn T. Reese.     

Synthesis and mesomorphic behaviour of comb-like polymers based on lipopeptides with two hydrophobic chains

Abstract

Polymerizable lipopeptides with two hydrophobic chains were synthesized and transformed into comb-like polymers by radical polymerization. The structure of dry polymerizable lipopeptides and comb-like polymers and of their aqueous solutions was determined by X-ray diffraction. Comb-like polymers exhibit both thermotropic and lyotropic properties. Three types of mesomorphic structure were resolved: smectic B, smectic A and cylindrical hexagonal. The domains of stability of the mesophases and the values of their structural parameters were established.     

Single-component,low molecular weight organic supergelators based on chiral barbiturate scaffolds

ABSTRACT

We report here the first chiral barbiturate to act as a single-component LMOG capable of gelating a variety of chlorinated and aromatic solvents. Solution-based DOSY NMR experiments, solid-state VP-SEM, and X-ray crystallography techniques were used to characterize chloroform-based gels at a variety of size domains. This scaffold provides a simple system to study the dynamics of gelation and self-assembly.     

Novel Orientation Techniques for the Preparation of High-Performance Materials from Semiflexible Polymers

Abstract

A technique is described for postponing the formation of anisotropic domains in semiflexible polymers so as to better orient them along a common direction. A theory has been developed to provide a foundation for this approach and guidance on carrying it out experimentally, and is described in outline form. The primary advantage of this processing route is the improved mechanical properties accompanying the increased orientation. This is illustrated by increases in moduli and ultimate properties of films of some cellulosics, polyisocyanates, and the protein collagen in the form of gelatin.     

Engineering the Substrate Specificity of the DhbE Adenylation Domain by Yeast Cell Surface Display

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Highlights? Yeast surface display to engineer substrate recognition of adenylation (A) domains ? Synthesis of bisubstrate inhibitors for yeast selection of A domain library ? Identifying DhbE mutants specific for 3-hydroxybenzoic acid and 2-aminobenzoic acid ? Key residues in A domain for substrate recognition and transfer     

Some Peculiarities of the Radical Polymerization of Methyl Methacrylate in the Presence of Low Molecular Weight Liquid Crystals

Abstract

Radical polymerization of methyl methacrylate (MMA) in the presence of propylbenzene, benzonitrile, their equimolar mixture, and a mixture of nematic liquid crystals (LC) was studied. Chain transfer reaction and unexpected dependence of the initial polymerization rate on LC concentration were revealed by means of UV spectrophotometry, viscometry, and dilatometry. The chain transfer reaction which occurred at the boundary of LC domains in the polymer matrix caused binding of some of the LC molecules to the macromolecules of PMMA. An increase in the initial rate of polymerization and a decrease of polydispersity were explained with formation of the LC phase because growth of the macroradicals continued not only in the homogeneous polymer phase but simultaneously also at the interfacial boundary between the polymer matrix and the LC phase. It is assumed that the LC molecules anchored to the PMMA matrix can affect the mobility of free LC molecules in the LC domains when an external electric field is applied to LC/polymer composite films.     

Effects of macromolecular topology on the encapsulation and release of phenolphthalein from hyperbranced glycerol modified β-cyclodextrin

Abstract

In the study, CD-g-HPGs with various arm length and arm number were synthesized and characterized by ¹H NMR, 13C NMR and Gel Permeation Chromatographic (GPC). Phenolphthalein (PP), as a small hydrophobic guest was readily encapsulated in the cavity of β-CDs or the hydrophobic aggregation domains stacked by cavities of β-CDs. CD-g-HPGs bearing longer arm length and denser arm number exhibited an increased loading capacity and exerted a profound influence on the release behavior, that is, longer arm accelerated the release, while a higher density of arm number slowed down the release owing to the synergy effect of aggregation and host-guest interaction between β-CD and PP. Via adjusting the host-guest interaction, CD-g-HPGs provided a potential to design efficient carriers or reasonable assemble systems.