A highly oriented cubic phase formed by lipids under shear

We demonstrate the formation of a macroscopically oriented inverse bicontinuous cubic (QII) lipid phase from a sponge (L3) phase by controlled hydration during shear flow. The L3 phase was the monoolein/ butanediol/water system; the addition of water reduces the butanediol concentration, inducing the formation of a diamond (QIID) cubic phase, which is oriented by the shear flow. The phenomenon was reproduced in both capillary and Couette geometries, indicating that this represents a robust general route for the production of highly aligned bulkQII samples, with applications in nanomaterial templating and protein research

Assessing final-year practical work through group projects

The final year project is a valuable research experience for undergraduates and can be one of the most rewarding aspects of their degree course. With increasing student numbers it is becoming more difficult to supervise students effectively, as truly independent enquiry-based working requires significant supervision, time and resource. To address this, the Department of Chemistry at the University of Reading has recently explored the use of group projects for final year practical work. Students work in teams of 3 to 5 and are presented with a research problem to investigate. These are genuine problems where the answer is unknown and the work open-ended. The students must work together to investigate the problem, dividing the work and sharing results in a manner that more closely resembles project working outside of academia. The students’ output is assessed through a variety of means including a group presentation and report. The projects were successful, with all students completing the work to a satisfactory level and developing strong team-working skills. This paper will outline some of the issues faced in the first year of delivery, and the steps taken to alleviate them

Kinetics and mechanism of the interconversion of inverse bicontinuous cubic mesophases

This paper describes time-resolved x-ray diffraction data monitoring the transformation of one inverse bicontinuous cubic mesophase into another, in a hydrated lipid system. The first section of the paper describes a mechanism for the transformation that conserves the topology of the bilayer, based on the work of Charvolin and Sadoc, Fogden and Hyde, and Benedicto and O'Brien in this area. We show a pictorial representation of this mechanism, in terms of both the water channels and the lipid bilayer. The second section describes the experimental results obtained. The system under investigation was 2:1 lauric acid: dilauroylphosphatidylcholine at a hydration of 50% water by weight. A pressure-jump was used to induce a phase transition from the gyroid (Q(II)(G)) to the diamond (Q(II)(D)) bicontinuous cubic mesophase, which was monitored by time-resolved x-ray diffraction. The lattice parameter of both mesophases was found to decrease slightly throughout the transformation, but at the stage where the Q(II)(D) phase first appeared, the ratio of lattice parameters of the two phases was found to be approximately constant for all pressure-jump experiments. The value is consistent with a topology-preserving mechanism. However, the polydomain nature of our sample prevents us from confirming that the specific pathway is that described in the first section of the paper. Our data also reveal signals from two different intermediate structures, one of which we have identified as the inverse hexagonal (H-II) mesophase. We suggest that it plays a role in the transfer of water during the transformation. The rate of the phase transition was found to increase with both temperature and pressure-jump amplitude, and its time scale varied from the order of seconds to minutes, depending on the conditions employed

Determination of orientations of aromatic groups in self-assembled peptide fibrils by polarised Raman spectroscopy

In this paper we describe a novel combination of Raman spectroscopy, isotope editing and X-ray scattering as a powerful approach to give detailed structural information on aromatic side chains in peptide fibrils. The orientation of the tyrosine residues in fibrils of the peptide YTIAALLSPYS with respect to the fibril axis has been determined from a combination of polarised Raman spectroscopy and X-ray diffraction measurements. The Raman intensity of selected tyrosine bands collected at different polarisation geometries is related to the values and orientation of the Raman tensor for those specific vibrations. Using published Raman tensor values we solved the relevant expressions for both of the two tyrosine residues present in this peptide. Ring deuteration in one of the two tyrosine side chains allowed for the calculation to be performed individually for both, by virtue of the isotopic shift that eliminates band overlapping. Sample disorder was taken into account by obtaining the distribution of orientations of the samples from X-ray diffraction experiments. The results provide previously unavailable details about the molecular conformation of this peptide, and demonstrate the value of this approach for the study of amyloid fibrils

Ultrathin uniform platinum nanowires via a facile route using an inverse hexagonal surfactant phase template

We present an attractive method for the fabrication of long, straight, highly crystalline, ultrathin platinum nanowires. The fabrication is simply achieved using an inverse hexagonal (HII) lyotropic liquid crystal phase of the commercial surfactant phytantriol as a template. A platinum precursor dissolved within the cylindrical aqueous channels of the liquid crystal phase is chemically reduced by galvanic displacement using stainless steel. We demonstrate the production of nanowires using the HII phase in the phytantriol/water system which we obtain either by heating to 55 °C or at room temperature by the addition of a hydrophobic liquid, 9-cis-tricosene, to relieve packing frustration. The two sets of conditions produced high aspect nanowires with diameters of 2.5 and 1.7 nm, respectively, at least hundreds of nanometers in length, matching the size of the aqueous channels in which they grow. This versatile approach can be extended to produce highly uniform nanowires from a range of metals

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

Control of Pore and Wire Dimensions in Mesoporous Metal Nanowire Networks through Curvature Modulation in Lipid Templates:Implications for Use as Electrodes

This paper presents the production of mesoporous metals with periodic 3D nanostructures, showing control over the lattice parameter and therefore pore and wire dimensions. The materials have "single diamond"(Fd3m) symmetry and are produced by deposition within a "cubic phase"template of the lipid phytantriol, in a process previously published. The current work shows a mechanism for tuning the nanoscale dimensions of the metal by the addition of a cosurfactant that progressively reduces the lipid bilayer curvature in the template. This swells its lattice parameter and therefore that of the deposited metal. Mesoporous platinum samples were characterized using X-ray scattering, electron microscopy, and electrochemical analysis. The structures exhibit unit cell sizes ranging from 13 to 20 nm, with wire thicknesses from 3.0 to 5.3 nm and estimated pore dimensions from 6.2 to 8.8 nm. The size control in these materials provides a mechanism for control of electrochemical behavior in electrocatalysis and sensors. Furthermore, the use of the templates in other metal and semiconductor materials suggests that size control offers possibilities for metamaterials with designed optoelectronic properties. </p

Local orientational disorder in peptide fibrils probed by a combination of residue-specific 13C-18O labelling, polarised infrared spectroscopy and molecular combing

A novel combination of site-specific isotope labelling, polarised infrared spectroscopy and molecular combing reveal local orientational ordering in the fibril-forming peptide YTIAALLSPYSGGRADS. Use of 13C-18O labelled alanine residues demonstrates that the Nterminal end of the peptide is incorporated into the cross-beta structure, while the C-terminal end shows orientational disorde

Modification of β-Sheet Forming Peptide Hydrophobic Face: Effect on Self-Assembly and Gelation

β-Sheet forming peptides have attracted significant interest for the design of hydrogels for biomedical applications. One of the main challenges is the control and understanding of the correlations between peptide molecular structure, the morphology, and topology of the fiber and network formed as well as the macroscopic properties of the hydrogel obtained. In this work, we have investigated the effect that functionalizing these peptides through their hydrophobic face has on their self-assembly and gelation. Our results show that the modification of the hydrophobic face results in a partial loss of the extended β-sheet conformation of the peptide and a significant change in fiber morphology from straight to kinked. As a consequence, the ability of these fibers to associate along their length and form large bundles is reduced. These structural changes (fiber structure and network topology) significantly affect the mechanical properties of the hydrogels (shear modulus and elasticity)