Liquid crystal phase formation by biopolymers

This review discusses liquid crystal phase formation by biopolymers in solution. Lyotropic mesophases have been observed for several classes of biopolymer including DNA, peptides, polymer/peptide conjugates, glycopolymers and proteoglycans. Nematic or chiral nematic (cholesteric) phases are the most commonly observed mesophases, in which the rod-like fibrils have only orientational order. Hexagonal columnar phases are observed for several systems (DNA, PBLG, polymer/peptide hybrids) at higher concentration. Lamellar (smectic) phases are reported less often, although there are examples such as the layer arrangement of amylopectin side chains in starch. Possible explanations for the observed structures are discussed. The biological role of liquid crystal phases for several of these systems is outlined. Commonly, they may serve as a template to align fibrils for defined structural roles when the biopolymer is extruded and dried, for instance in the production of silk by spiders or silkworms, or of chitin in arthropod shells. In other cases, liquid crystal phase formation may occur in vivo simply as a consequence of high concentration, for instance the high packing density of DNA within cell nuclei.

Dynamics of shear-induced orientation transitions in block copolymers

This review discusses liquid crystal phase formation by biopolymers in solution. Lyotropic mesophases have been observed for several classes of biopolymer including DNA, peptides, polymer/peptide conjugates, glycopolymers and proteoglycans. Nematic or chiral nematic (cholesteric) phases are the most commonly observed mesophases, in which the rod-like fibrils have only orientational order. Hexagonal columnar phases are observed for several systems (DNA, PBLG, polymer/peptide hybrids) at higher concentration. Lamellar (smectic) phases are reported less often, although there are examples such as the layer arrangement of amylopectin side chains in starch. Possible explanations for the observed structures are discussed. The biological role of liquid crystal phases for several of these systems is outlined. Commonly, they may serve as a template to align fibrils for defined structural roles when the biopolymer is extruded and dried, for instance in the production of silk by spiders or silkworms, or of chitin in arthropod shells. In other cases, liquid crystal phase formation may occur in vivo simply as a consequence of high concentration, for instance the high packing density of DNA within cell nuclei.

Self-assembly of an amyloid peptide fragment–PEG conjugate: lyotropic phase formation and influence of PEG crystallization

The self-assembly of PEGylated peptides containing a modified sequence from the amyloid beta peptide, YYKLVFF, has been studied in aqueous solution. Two PEG molar masses, PEG1k and PEG3k, were used in the conjugates. It is shown that both YYKLVFF–PEG hybrids form fibrils comprising a peptide core and a PEG corona. The fibrils are much longer for YYKLVFF–PEG1k, pointing to an influence of PEG chain length. The beta-sheet secondary structure of the peptide is retained in the conjugate. Lyotropic liquid crystal phases, specifically nematic and hexagonal columnar phases, are formed at sufficiently high concentration. Flow alignment of these mesophases was investigated by small-angle neutron scattering with in situ steady shearing in a Couette cell. On drying, PEG crystallization occurs leading to characteristic peaks in the X-ray diffraction pattern, and to lamellar structures imaged by atomic force microscopy. The X-ray diffraction pattern retains features of the cross-beta pattern from the beta-sheet structure, showing that this is not disrupted by PEG crystallization.

Self-assembly of PEGylated peptide conjugates containing a modified amyloid β-peptide fragment

The self-assembly of PEGylated peptides containing a modified sequence from the amyloid beta peptide, FEK LVFF, has been studied in aqueous solution. PEG molar masses PEG1k, PEG2k, and PEG10k were used in the conjugates. It is shown that the three FFK LVFF-PEG hybrids form fibrils comprising a FFKLVFF core and a PEG corona. The beta-sheet secondary structure of the peptide is retained in the FFK LVFF fibril core. At sufficiently high concentrations, FEK LVFF-PEG1k and FEK LVFF-PEG2k form a nema tic phase, while PEG10k-FEK LVFF exhibits a hexagonal columnar phase. Simultaneous small angle neutron scattering/shear flow experiments were performed to study the shear flow alignment of the nematic and hexagonal liquid crystal phases. On drying, PEG crystallization occurs without disruption of the FFK LVFF beta-sheet structure leading to characteristic peaks in the X-ray diffraction pattern and FTIR spectra. The stability of beta-sheet structures was also studied in blends of FFKLVFF-PEG conjugates with poly(acrylic acid) (PAA). While PEG crystallization is only observed up to 25% PAA content in the blends, the FFK LVFF beta-sheet structure is retained up to 75% PAA.

Preparation of films of a highly aligned lipid cubic phase

We demonstrate a method by which we can produce an oriented film of an inverse bicontinuous cubic phase (QII D) formed by the lipid monoolein (MO). By starting with the lipid as a disordered precursor (the L3 phase) in the presence of butanediol, we can obtain a film of the QII D phase showing a high degree of in-plane orientation by controlled dilution of the sample under shear within a linear flow cell. We demonstrate that the direction of orientation of the film is different from that found in the oriented bulk material that we have reported previously; therefore, we can now reproducibly form QII D samples oriented with either the [110] or the [100] axis aligned in the flow direction depending on the method of preparation. The deposition of MO as a film, via a moving fluid− air interface that leaves a coating of MO in the L3 phase on the capillary wall, leads to a sample in the [110] orientation. This contrasts with the bulk material that we have previously demonstrated to be oriented in the [100] direction, arising from flow producing an oriented bulk slug of material within the capillary tube. The bulk sample contains significant amounts of residual butanediol, which can be estimated from the lattice parameter of the QII D phase obtained. The sample orientation and lattice parameters are determined from synchrotron small-angle X-ray scattering patterns and confirmed by simulations. This has potential applications in the production of template materials and the growth of protein crystals for crystallography as well as deepening our understanding of the mechanisms underlying the behavior of lyotropic liquid-crystal phases.

Small-angle x-ray scattering study of flow alignment of a thermotropic liquid crystal in the nematic and smectic phases

WThe capillary flow alignment of the thermotropic liquid crystal 4-n-octyl-4′-cyanobiphenyl in the nematic and smectic phases is investigated using time-resolved synchrotron small-angle x-ray scattering. Samples were cooled from the isotropic phase to erase prior orientation. Upon cooling through the nematic phase under Poiseuille flow in a circular capillary, a transition from the alignment of mesogens along the flow direction to the alignment of layers along the flow direction (mesogens perpendicular to flow) appears to occur continuously at the cooling rate applied. The transition is centered on a temperature at which the Leslie viscosity coefficient α3 changes sign. The configuration with layers aligned along the flow direction is also observed in the smectic phase. The transition in the nematic phase on cooling has previously been ascribed to an aligning-nonaligning or tumbling transition. At high flow rates there is evidence for tumbling around an average alignment of layers along the flow direction. At lower flow rates this orientation is more clearly defined. The layer alignment is ascribed to surface-induced ordering propagating into the bulk of the capillary, an observation supported by the parallel alignment of layers observed for a static sample at low temperatures in the nematic phase.

Morphology of polymer networks formed in the chiral and non chiral phases of an anti-ferroelectric liquid crystal

We introduced photo-polymer networks into the various liquid crystalline phases of the antiferroelectric liquid crystal AS612 and studied the effects of these networks by measuring the temperature dependence of the Bragg wavelengths selectively reflected. After polymerization, the decrease in Bragg wavelengths with respect to the original values is consistent with a shorter helical pitch due to polymer network shrinkage. Also, by removing the liquid crystalline material, we are able to image the residual polymer network using scanning electron microscopy and polarized light microscopy. The polymer strands are a few microns thick and the networks show both chiral and non-chiral features.

A SAXS study of flow alignment of thermotropic liquid crystal mixtures

We report on the capillary flow behaviour of thermotropic liquid crystal mixtures containing 4-n-octyl-4'-cyanobiphenyl (8CB) and 4-n-pentyl-4'-cyanobiphenyl (5CB). The liquid crystal mixtures are studied in the Nematic (N) and Smectic (SA) phases at room temperature. Polarised optical microscopy (POM), rheology and simultaneous X-ray diffraction (XRD)/capillary flow experiments are performed to characterise the system. Polarised optical microscopy reveals a dramatic change in optical texture when the 5CB content is increased from 20 to 30% in the mixtures. X-ray diffraction results show that the system goes through a SA-N phase transition, such that the mixtures are smectic for 10-20% 5CB and nematic for 30-90% 5CB. Smectic mixtures flow with the layers aligned along the flow direction (mesogens perpendicular to flow) while nematic mixtures flow with the mesogens aligned in the flow direction. Simultaneous XRD/shear flow experiments show that the SA-N transition is independent of the flow rate in the range 1-6 ml min-1. The correlation length of the liquid crystal order decreases with increasing 5CB content. Rheology is used to prove that the correlation length behaviour is related to a reduction in the viscosity of the mixture.

Synthesis and crystal structure of a 3-D zinc phosphate, [C5N2H14][Zn-2(PO3(OH))(3)], containing (4.8) net sheets

A new 3-D zinc phosphate, [C5N2H14][Zn-2(PO3(OH))(3)], has been synthesised under solvothermal conditions in the presence of 1-methylpiperazine. The structure, determined by single-crystal X-ray diffraction at 293 K (RMM = 520.9, orthorhombic, space group P2(1)2(1)2(1); a = 10.0517(2) &ANGS;, b = 10.4293(2) &ANGS; and c = 14.9050(5) &ANGS;; V = 1562.52 &ANGS;(3); Z = 4; R(F) = 2.60%, wR(F) = 2.93%), consists of vertex linked ZnO4 and PO3(OH) tetrahedra assembled into (4.8) net sheets which in turn are linked through further PO3(OH) units to generate a 3-D framework. 1-Methylpiperazinium cations reside within the 3-D channel system, held in place by a strong network of hydrogen bonds. The (4.8) net sheets occur in a number of zeolite structures e.g. ABW and GIS and related zinc phosphate phases. © 2004 Academie des sciences. Published by Elsevier SAS. All rights reserved.

Pressure-jump X-ray studies of liquid crystal transitions in lipids

In this paper, we give an overview of our studies by static and time-resolved X-ray diffraction of inverse cubic phases and phase transitions in lipids. In 1, we briefly discuss the lyotropic phase behaviour of lipids, focusing attention on non-lamellar structures, and their geometric/topological relationship to fusion processes in lipid membranes. Possible pathways for transitions between different cubic phases are also outlined. In 2, we discuss the effects of hydrostatic pressure on lipid membranes and lipid phase transitions, and describe how the parameters required to predict the pressure dependence of lipid phase transition temperatures can be conveniently measured. We review some earlier results of inverse bicontinuous cubic phases from our laboratory, showing effects such as pressure-induced formation and swelling. In 3, we describe the technique of pressure-jump synchrotron X-ray diffraction. We present results that have been obtained from the lipid system 1:2 dilauroylphosphatidylcholine/lauric acid for cubic-inverse hexagonal, cubic-cubic and lamellar-cubic transitions. The rate of transition was found to increase with the amplitude of the pressure-jump and with increasing temperature. Evidence for intermediate structures occurring transiently during the transitions was also obtained. In 4, we describe an IDL-based 'AXCESS' software package being developed in our laboratory to permit batch processing and analysis of the large X-ray datasets produced by pressure-jump synchrotron experiments. In 5, we present some recent results on the fluid lamellar-Pn3m cubic phase transition of the single-chain lipid 1-monoelaidin, which we have studied both by pressure-jump and temperature-jump X-ray diffraction. Finally, in 6, we give a few indicators of future directions of this research. We anticipate that the most useful technical advance will be the development of pressure-jump apparatus on the microsecond time-scale, which will involve the use of a stack of piezoelectric pressure actuators. The pressure-jump technique is not restricted to lipid phase transitions, but can be used to study a wide range of soft matter transitions, ranging from protein unfolding and DNA unwinding and transitions, to phase transitions in thermotropic liquid crystals, surfactants and block copolymers.

Solid phases of cyclopentane: combined experimental and simulation study

The phase diagram of cyclopentane has been studied by powder neutron diffraction, providing diffraction patterns for phases I, II, and III, over a range of temperatures and pressures. The putative phase IV was not observed. The structure of the ordered phase III has been solved by single-crystal diffraction. Computational modeling reveals that there are many equienergetic ordered structures for cyclopentane within a small energy range. Molecular dynamics simulations reproduce the structures and diffraction patterns for phases I and III and also show an intermediate disordered phase, which is used to interpret phase II.

Formation of crystalline macrocyclic phases during electrophilic precipitation-polycondensation syntheses of poly(arylene ether ketone)s

Elongated crystalline particles formed as by-products during poly(arylene ether ketone) synthesis by electrophilic precipitation-polycondensation of 4,4'-diphenoxybenzophenone with terephthaloyl chloride or isophthaloyl chloride, thought previously to be polymer-whiskers, have now been identified as macrocyclic phases. Single crystal X-ray analysis of the needle-like particles formed in the reaction with terephthaloyl chloride, using the microdiffraction technique with synchrotron radiation, revealed that they consist of a macrocylic compound containing ten phenylene units, i.e. the [2 + 2] cyclic dimer. An analogous structure has also been demonstrated for the corresponding macrocycle derived from the reaction of 4,4-diphenoxybenzophenone with isophthaloyl chloride. Chloroform extraction of the products of the two polycondensations dissolved the macrocyclic material (but not the linear polymer), and analysis of the extracts by MALDI-TOF mass spectrometry demonstrated the presence in both cases of homologous families of macrocyclic products. Higher yields of macrocycles were obtained under pseudo-high dilution conditions, enabling the [2 + 2] cyclodimers from reactions of 4,4'-diphenoxybenzophenone with both terephthaloyl and isophthaloyl chloride to be isolated as pure compounds and fully characterised. (C) 2003 Published by Elsevier Ltd.

Synthesis and crystal structure of a 3-D zinc phosphate, [C5N2H14][Zn2(PO3(OH))3], containing (4.8) net sheets

A new 3-D zinc phosphate, [C5N2H14][Zn-2(PO3(OH))(3)], has been synthesised under solvothermal conditions in the presence of 1-methylpiperazine. The structure, determined by single-crystal X-ray diffraction at 293 K (RMM = 520.9, orthorhombic, space group P2(1)2(1)2(1); a = 10.0517(2) &ANGS;, b = 10.4293(2) &ANGS; and c = 14.9050(5) &ANGS;; V = 1562.52 &ANGS;(3); Z = 4; R(F) = 2.60%, wR(F) = 2.93%), consists of vertex linked ZnO4 and PO3(OH) tetrahedra assembled into (4.8) net sheets which in turn are linked through further PO3(OH) units to generate a 3-D framework. 1-Methylpiperazinium cations reside within the 3-D channel system, held in place by a strong network of hydrogen bonds. The (4.8) net sheets occur in a number of zeolite structures e.g. ABW and GIS and related zinc phosphate phases. © 2004 Academie des sciences. Published by Elsevier SAS. All rights reserved.

Memory effects in liquid crystal elastomers

Free-standing monodomain liquid crystal elastomer samples are shown to have a complete memory of the orientational configuration at the time of cross-linking. This memory is demonstrated through samples in which the parent polymer system is first aligned in a magnetic field prior to cross-linking. These films show reversible nematic-isotropic phase transitions and x-ray scattering patterns characteristic of nematic phases. The liquid crystal elastomer films exhibit a remarkable memory effect, in that the sample may be held at temperatures well above the nematic-isotropic transition for extended periods ( > 2 weeks), but on cooling into the liquid crystal phase region, both the original director alignment and the degree of preferred orientation are recovered. It is demonstrated that these novel memory effects are equilibrium in nature. The origins of this phenomena in terms of coupling between the mesogenic side-chains and the polymer network are discussed.

Crystal design approaches for the synthesis of paracetamol co-crystals

Crystal engineering principles were used to design three new co-crystals of paracetamol. A variety of potential cocrystal formers were initially identified from a search of the Cambridge Structural Database for molecules with complementary hydrogen-bond forming functionalities. Subsequent screening by powder X-ray diffraction of the products of the reaction of this library of molecules with paracetamol led to the discovery of new binary crystalline phases of paracetamol with trans-1,4- diaminocyclohexane (1); trans-1,4-di(4-pyridyl)ethylene (2); and 1,2-bis(4-pyridyl)ethane (3). The co-crystals were characterized by IR spectroscopy, differential scanning calorimetry, and 1H NMR spectroscopy. Single crystal X-ray structure analysis reveals that in all three co-crystals the co-crystal formers (CCF) are hydrogen bonded to the paracetamol molecules through O−H···N interactions. In co-crystals (1) and (2) the CCFs are interleaved between the chains of paracetamol molecules, while in co-crystal (3) there is an additional N−H···N hydrogen bond between the two components. A hierarchy of hydrogen bond formation is observed in which the best donor in the system, the phenolic O−H group of paracetamol, is preferentially hydrogen bonded to the best acceptor, the basic nitrogen atom of the co-crystal former. The geometric aspects of the hydrogen bonds in co-crystals 1−3 are discussed in terms of their electrostatic and charge-transfer components.