Experimental confirmation of transformation pathways between inverse double diamond and gyroid cubic phases

A macroscopically oriented double diamond inverse bicontinuous cubic phase (QIID) of the lipid glycerol monooleate is reversibly converted into a gyroid phase (QIIG). The initial QIID phase is prepared in the form of a film coating the inside of a capillary, deposited under flow, which produces a sample uniaxially oriented with a ⟨110⟩ axis parallel to the symmetry axis of the sample. A transformation is induced by replacing the water within the capillary tube with a solution of poly(ethylene glycol), which draws water out of the QIID sample by osmotic stress. This converts the QIID phase into a QIIG phase with two coexisting orientations, with the ⟨100⟩ and ⟨111⟩ axes parallel to the symmetry axis, as demonstrated by small-angle X-ray scattering. The process can then be reversed, to recover the initial orientation of QIID phase. The epitaxial relation between the two oriented mesophases is consistent with topologypreserving geometric pathways that have previously been hypothesized for the transformation. Furthermore, this has implications for the production of macroscopically oriented QIIG phases, in particular with applications as nanomaterial templates.

Interactions between lipid-free apolipoprotein-AI and a lipopeptide incorporating the RGDS cell adhesion motif

The interaction of a designed bioactive lipopeptide C16-GGGRGDS, comprising a hexadecyl lipid chain attached to a functional heptapeptide, with the lipid-free apoliprotein, Apo-AI, is examined. This apolipoprotein is a major component of high density lipoprotein and it is involved in lipid metabolism and may serve as a biomarker for cardiovascular disease and Alzheimers’ disease. We find via isothermal titration calorimetry that binding between the lipopeptide and Apo-AI occurs up to a saturation condition, just above equimolar for a 10.7 μM concentration of Apo-AI. A similar value is obtained from circular dichroism spectroscopy, which probes the reduction in α-helical secondary structure of Apo-AI upon addition of C16-GGGRGDS. Electron microscopy images show a persistence of fibrillar structures due to self-assembly of C16-GGGRGDS in mixtures with Apo-AI above the saturation binding condition. A small fraction of spheroidal or possibly “nanodisc” structures was observed. Small-angle X-ray scattering (SAXS) data for Apo-AI can be fitted using a published crystal structure of the Apo-AI dimer. The SAXS data for the lipopeptide/ Apo-AI mixtures above the saturation binding conditions can be fitted to the contribution from fibrillar structures coexisting with flat discs corresponding to Apo-AI/lipopeptide aggregates.

Predicting the orientation of lipid cubic phase films

Lipid cubic phase films are of increasingly widespread importance, both in the analysis of the cubic phases themselves by techniques including microscopy and X-ray scattering, and in their applications, especially as electrode coatings for electrochemical sensors and for templates for the electrodeposition of nanostructured metal. In this work we demonstrate that the crystallographic orientation adopted by these films is governed by minimization of interfacial energy. This is shown by the agreement between experimental data obtained using grazing-incidence small-angle X-ray scattering (GI-SAXS), and the predicted lowest energy orientation determined using a theoretical approach we have recently developed. GI-SAXS data show a high degree of orientation for films of both the double diamond phase and the gyroid phase, with the [111] and [110] directions respectively perpendicular to the planar substrate. In each case, this matches the lowest energy facet calculated for that particular phase.

Time-dependent gel to gel transformation of a peptide based supramolecular gelator

A dipeptide with a long fatty acid chain at its N-terminus gives hydrogels in phosphate buffer in the pH range 7.0–8.5. The hydrogel with a gelator concentration of 0.45% (w/v) at pH 7.46 (physiological pH) provides a very good platform to study dynamic changes within a supramolecular framework as it exhibits remarkable change in its appearance with time. Interestingly, the first formed transparent hydrogel gradually transforms into a turbid gel within 2 days. These two forms of the hydrogel have been thoroughly investigated by using small angle X-ray scattering (SAXS), powder X-ray diffraction (PXRD), field emission scanning electron microscopic (FE-SEM) and high-resolution transmission electron microscopic (HR-TEM) imaging, FT-IR and rheometric analyses. The SAXS and low angle PXRD studies substantiate different packing arrangements for the gelator molecules for these two different gel states (the freshly prepared and the aged hydrogel). Moreover, rheological studies of these two gels reveal that the aged gel is stiffer than the freshly prepared gel.

Microphase separation induced in the melt of Pluronic copolymers by blending with a hydrogen bonding urea–urethane end-capped supramolecular polymer

Blending with a hydrogen-bonding supramolecular polymer is shown to be a successful novel strategy to induce microphase-separation in the melt of a Pluronic polyether block copolymer. The supramolecular polymer is a polybutadiene derivative with urea–urethane end caps. Microphase separation is analysed using small-angle X-ray scattering and its influence on the macroscopic rheological properties is analysed. FTIR spectroscopy provides a detailed picture of the inter-molecular interactions between the polymer chains that induces conformational changes leading to microphase separation.

Experimental evidence for proposed transformation pathway from the inverse hexagonal to inverse diamond cubic phase from oriented lipid samples

A macroscopically oriented inverse hexagonal phase (HII) of the lipid phytantriol in water is converted to an oriented inverse double diamond bicontinuous cubic phase (QIID). The initial HII phase is uniaxially oriented about the long axis of a capillary with the cylinders parallel to the capillary axis. The HII phase is converted by cooling to a QII D phase which is also highly oriented, where the cylindrical axis of the former phase has been converted to a ⟨110⟩ axis in the latter, as demonstrated by small-angle X-ray scattering. This epitaxial relationship allows us to discriminate between two competing proposed geometric pathways to convert HII to QIID. Our findings also suggest a new route to highly oriented cubic phase coatings, with applications as nanomaterial templates.

The expected imprint of flux rope geometry on suprathermal electrons in magnetic clouds

Magnetic clouds are a subset of interplanetary coronal mass ejections characterized by a smooth rotation in the magnetic field direction, which is interpreted as a signature of a magnetic flux rope. Suprathermal electron observations indicate that one or both ends of a magnetic cloud typically remain connected to the Sun as it moves out through the heliosphere. With distance from the axis of the flux rope, out toward its edge, the magnetic field winds more tightly about the axis and electrons must traverse longer magnetic field lines to reach the same heliocentric distance. This increased time of flight allows greater pitch-angle scattering to occur, meaning suprathermal electron pitch-angle distributions should be systematically broader at the edges of the flux rope than at the axis. We model this effect with an analytical magnetic flux rope model and a numerical scheme for suprathermal electron pitch-angle scattering and find that the signature of a magnetic flux rope should be observable with the typical pitch-angle resolution of suprathermal electron data provided ACE's SWEPAM instrument. Evidence of this signature in the observations, however, is weak, possibly because reconnection of magnetic fields within the flux rope acts to intermix flux tubes.

Whistler mode wave growth and propagation in the prenoon magnetosphere

Pitch-angle scattering of electrons can limit the stably trapped particle flux in the magnetosphere and precipitate energetic electrons into the ionosphere. Whistler-mode waves generated by a temperature anisotropy can mediate this pitch-angle scattering over a wide range of radial distances and latitudes, but in order to correctly predict the phase-space diffusion, it is important to characterise the whistler-mode wave distributions that result from the instability. We use previously-published observations of number density, pitch-angle anisotropy and phase space density to model the plasma in the quiet pre-noon magnetosphere (defined as periods when AE<100nT). We investigate the global propagation and growth of whistler-mode waves by studying millions of growing ray paths and demonstrate that the wave distribution at any one location is a superposition of many waves at different points along their trajectories and with different histories. We show that for observed electron plasma properties, very few raypaths undergo magnetospheric reflection, most rays grow and decay within 30 degrees of the magnetic equator. The frequency range of the wave distribution at large L can be adequately described by the solutions of the local dispersion relation, but the range of wavenormal angle is different. The wave distribution is asymmetric with respect to the wavenormal angle. The numerical results suggest that it is important to determine the variation of magnetospheric parameters as a function of latitude, as well as local time and L-shell.

Ultralow-frequency modulation of whistler-mode wave growth

Measurements from ground-based magnetometers and riometers at auroral latitudes have demonstrated that energetic (~30-300keV) electron precipitation can be modulated in the presence of magnetic field oscillations at ultra-low frequencies. It has previously been proposed that an ultra-low frequency (ULF) wave would modulate field and plasma properties near the equatorial plane, thus modifying the growth rates of whistler-mode waves. In turn, the resulting whistler-mode waves would mediate the pitch-angle scattering of electrons resulting in ionospheric precipitation. In this paper, we investigate this hypothesis by quantifying the changes to the linear growth rate expected due to a slow change in the local magnetic field strength for parameters typical of the equatorial region around 6.6RE radial distance. To constrain our study, we determine the largest possible ULF wave amplitudes from measurements of the magnetic field at geosynchronous orbit. Using nearly ten years of observations from two satellites, we demonstrate that the variation in magnetic field strength due to oscillations at 2mHz does not exceed ±10% of the background field. Modifications to the plasma density and temperature anisotropy are estimated using idealised models. For low temperature anisotropy, there is little change in the whistler-mode growth rates even for the largest ULF wave amplitude. Only for large temperature anisotropies can whistler-mode growth rates be modulated sufficiently to account for the changes in electron precipitation measured by riometers at auroral latitudes.

Wide-angle X-ray scattering study of structural parameters in non-crystalline polymers

The paper presents an analysis of WAXS (wide-angle X-ray scattering) data which aids an understanding of the structure of non-crystalline polymers. Experimental results are compared with calculations of scattering from possible models. Evidence is presented which supports the view that the chains in molten PE do not lie parallel but have a conformation in accord with the predictions of energy calculations. However, the evidence indicates that in “molten” PTFE the chains lie parallel over distances well in excess of their diameters. WAXS-based proposals are made for the conformations of a-PMMA and a-PS.

Wide-angle X-ray scattering for swollen and glassy poly(2-hydroxyethyl methacrylate)

The wide angle X-ray scattering from glassy poly(2-hydroxyethyl methacrylate) (1) is presented together with that obtained from oriented and swollen samples. The scattering is compared with that previously reported for poly(methyl methacrylate) (PMMA) and the structure discussed in relation to this polymer. The chain conformation is similar to that of PMMA, although some measure of molecular interlocking appears to reduce the main interchain peak while correlated regions of inaccessible free volume between the substantial side groups are held responsible for the main peak at s = 1,25 Å−1.

Application of cylindrical distribution functions to wide-angle X-ray scattering from oriented polymers

A systematic approach is presented for obtaining cylindrical distribution functions (CDF's) of noncrystalline polymers which have been oriented by extension. The scattering patterns and CDF's are also sharpened by the method proposed by Deas and by Ruland. Data from atactic poly(methyl methacrylate) and polystyrene are analysed by these techniques. The methods could also be usefully applied to liquid crystals.

Conformational analysis of oriented non-crystalline polymers using wide angle X-ray scattering

A procedure is presented for obtaining conformational parameters from oriented but non-crystalline polymers. This is achieved by comparison of the experimental wide angle X-ray scattering with that calculated from models but in such a way that foreknowledge of the orientation distribution function is not required. X-ray scattering intensity values for glassy isotactic poly(methylmethacrylate) are analysed by these techniques. The method could be usefully applied to other oriented molecular systems such as liquid crystalline materials.

Small- and waiting-time behaviour of the thin-film-equation

We consider the small-time behavior of interfaces of zero contact angle solutions to the thin-film equation. For a certain class of initial data, through asymptotic analyses, we deduce a wide variety of behavior for the free boundary point. These are supported by extensive numerical simulations. © 2007 Society for Industrial and Applied Mathematics

Water wave scattering by finite arrays of circular structures

The scattering of small amplitude water waves by a finite array of locally axisymmetric structures is considered. Regions of varying quiescent depth are included and their axisymmetric nature, together with a mild-slope approximation, permits an adaptation of well-known interaction theory which ultimately reduces the problem to a simple numerical calculation. Numerical results are given and effects due to regions of varying depth on wave loading and free-surface elevation are presented.