Unoriented Membranes Research Articles

Dielectric Properties in Oriented and Unoriented Membranes Based on Poly(Epichlorohydrin-co-Ethylene Oxide) Copolymers: Part III.

The dielectric spectra and conductivity properties of neat poly(epichlorohydrin-co-ethylene oxide)(PECH-co-EO) copolymer and two modified copolymers with a 20% or 40% of dendron 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy] benzoate units were analysed. A process of thermal orientation was applied to the copolymers to fine-tune the molecular motion of the side chains and determine their validity for cation transport materials. The study was conducted using Dielectric Thermal Analysis (DETA). The spectra of the modified unoriented and oriented copolymers consisted of five dielectric relaxations (δ, γ, β, αTg, and αmelting). The analysis of the relaxations processes shows that as the grafting with the dendron units increases, both the lateral and main chains have a greater difficulty moving. The thermal orientation induces in the main chain partial crystallization, including the polyether segments, and modifies the cooperative motion of the main chain associated with the glass transition (αTg). A deep analysis of the electrical loss modulus revealed that the degree of modification only modifies the temperature peak of each relaxation, and this effect is more perceived if the dendron unit content is higher (40%). The thermal orientation process seems equal to the spectra of CP20-O and CP40-O to the point that the degree of modification does not matter. Nevertheless, the fragility index denotes the differences in the molecular motion between both copolymers (40% and 20%) due to the thermal orientation. The study of the electric conductivity showed that the ideal long-range pathways were being altered by neither the thermal orientation process nor the addition of dendrimers. The analysis of the through-plane proton conductivity confirmed that the oriented copolymer with the highest concentration of dendrimers was the best performer and the most suitable copolymer for proton transport materials.

Molecular Mobility in Oriented and Unoriented Membranes Based on Poly[2-(Aziridin-1-yl)ethanol

Unoriented and oriented membranes based on dendronized polymers and copolymers obtained by chemical modification of poly[2-(aziridin-1-yl) ethanol] (PAZE) with the dendron 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy]benzoate were considered. DSC, XRD, CP-MAS NMR and DETA, contribute to characterize the tendency to crystallize, the molecular mobility of the benzyloxy substituent, the dendritic liquid crystalline group and the clearing transition. The orientation of the mesogenic chain somewhat hindered this molecular motion, especially in the full substituted PAZE. The fragility, free volume and thermal expansion coefficients of these membranes near the glass transition are related to the orientation and the addition of the dendritic groups. PAZE-based membranes combine both order and mobility on a supramolecular and macroscopic level, controlled by the dendritic group and the thermal orientation, and open the possibility of preparing membranes with proper channel mobility that promotes selective ionic transport.

Triangle–hinge models for unoriented membranes

Triangle-hinge models [arXiv:1503.08812] are introduced to describe worldvolume dynamics of membranes. The Feynman diagrams consist of triangles glued together along hinges and can be restricted to tetrahedral decompositions in a large N limit. In this paper, after clarifying that all the tetrahedra resulting in the original models are orientable, we define a version of triangle-hinge models that can describe the dynamics of unoriented membranes. By regarding each triangle as representing a propagation of an open membrane of disk topology, we introduce a local worldvolume parity transformation which inverts the orientation of triangle, and define unoriented triangle-hinge models by gauging the transformation. Unlike two-dimensional cases, this local transformation generally relates a manifold to a nonmanifold, but still is a well-defined manipulation among tetrahedral decompositions. We further show that matter fields can be introduced in the same way as in the original oriented models. In particular, the models will describe unoriented membranes in a target spacetime by taking matter fields to be the target space coordinates.

The importance of orientation in proton transport of a polymer film based on an oriented self-organized columnar liquid-crystalline polyether

We prepared membranes based on a liquid-crystalline side-chain polyether obtained by chemical modification of commercial poly(epichlorohydrin) (PECH) with dendrons. This polymer exhibited a columnar structure, which could form an ion channel in the inner part. The columns were successfully oriented by taking advantage of surface interactions between the polymer and hydrophilic substrates, as confirmed by X-ray diffraction analysis (XRD), environmental scanning electron microscopy (ESEM) and optical microscopy between crossed polars (POM). Column orientation was found to be crucial for effective transport: the oriented membranes exhibited proton transport comparable to that of Nafion® N117 and no water uptake. An increase in sodium ion concentration in the feed phase suggested a proton/cation antiport. On the contrary, no proton transport was detected on unoriented membranes based on the same liquid-crystalline side-chain polyether or on unmodified PECH.

Nuclear magnetic resonance evidence for retention of a lamellar membrane phase with curvature in the presence of large quantities of the HIV fusion peptide

The HIV fusion peptide (HFP) is a biologically relevant model system to understand virus/host cell fusion. 2H and 31P NMR spectroscopies were applied to probe the structure and motion of membranes with bound HFP and with a lipid headgroup and cholesterol composition comparable to that of membranes of host cells of HIV. The lamellar phase was retained for a variety of highly fusogenic HFP constructs as well as a non-fusogenic HFP construct and for the influenza virus fusion peptide. The lamellar phase is therefore a reasonable structure for modeling the location of HFP in lipid/cholesterol dispersions. Relative to no HFP, membrane dispersions with HFP had faster 31P transverse relaxation and faster transverse relaxation of acyl chain 2H nuclei closest to the lipid headgroups. Relative to no HFP, mechanically aligned membrane samples with HFP had broader 31P signals with a larger fraction of unoriented membrane. The relaxation and aligned sample data are consistent with bilayer curvature induced by the HFP which may be related to its fusion catalytic function. In some contrast to the subtle effects of HFP on a host-cell-like membrane composition, an isotropic phase was observed in dispersions rich in phosphatidylethanolamine lipids and with bound HFP.

Determining the Orientation of Uniaxially Rotating Membrane Proteins Using Unoriented Samples: A2H,13C, and15N Solid-State NMR Investigation of the Dynamics and Orientation of a Transmembrane Helical Bundle

Membrane protein orientation has traditionally been determined by NMR using mechanically or magnetically aligned samples. Here we show a new NMR approach that abolishes the need for preparing macroscopically aligned membranes. When the protein undergoes fast uniaxial rotation around the bilayer normal, the 0 degrees -frequency of the motionally averaged powder spectrum is identical to the frequency of the aligned protein whose alignment axis is along the magnetic field. Thus, one can use unoriented membranes to determine the orientation of the protein relative to the bilayer normal. We demonstrate this approach on the M2 transmembrane peptide (M2TMP) of influenza A virus, which is known to assemble into a proton-conducting tetrameric helical bundle. The fast uniaxial rotational diffusion of the M2TMP helical bundle around the membrane normal is characterized via 2H quadrupolar couplings, C-H and N-H dipolar couplings, 13C chemical shift anisotropies, and 1H T1rho relaxation times. We then show that 15N chemical shift anisotropy and N-H dipolar coupling measured on these powder samples can be analyzed to yield precise tilt angles and rotation angles of the helices. The data show that the tilt angle of the M2TMP helices depends on the membrane thickness to reduce the hydrophobic mismatch. Moreover, the orientation of a longer M2 peptide containing both the transmembrane domain and cytoplasmic residues is similar to the orientation of the transmembrane domain alone, suggesting that the transmembrane domain regulates the orientation of this protein and that structural information obtained from M2TMP may be extrapolated to the longer peptide. This powder-NMR approach for orientation determination is generally applicable and can be extended to larger membrane proteins.

Magic-angle spinning solid-state NMR of a 144 kDa membrane protein complex: E. coli cytochrome bo3 oxidase

Recent progress in magic-angle spinning (MAS) solid-state NMR (SSNMR) has enabled multidimensional studies of large, macroscopically unoriented membrane proteins with associated lipids, without the requirement of solubility that limits other structural techniques. Here we present initial sample preparation and SSNMR studies of a 144 kDa integral membrane protein, E. coli cytochrome bo(3) oxidase. The optimized protocol for expression and purification yields approximately 5 mg of the enzymatically active, uniformly (13)C,(15)N-enriched membrane protein complex from each liter of growth medium. The preparation retains endogenous lipids and yields spectra of high sensitivity and resolution, consistent with a folded, homogenous protein. Line widths of isolated signals are less than 0.5 ppm, with a large number of individual resonances resolved in the 2D and 3D spectra. The (13)C chemical shifts, assigned by amino acid type, are consistent with the secondary structure previously observed by diffraction methods. Although the structure is predominantly helical, the percentage of non-helical signals varies among residue types; these percentages agree well between the NMR and diffraction data. Samples show minimal evidence of degradation after several weeks of NMR data acquisition. Use of a triple resonance scroll resonator probe further improves sample stability and enables higher power decoupling, higher duty cycles and more advanced 3D experiments to be performed. These initial results in cytochrome bo(3) oxidase demonstrate that multidimensional MAS SSNMR techniques have sufficient sensitivity and resolution to interrogate selected parts of a very large uniformly (13)C,(15)N-labeled membrane protein.

Matrix theory of unoriented membranes and Jordan algebras

We express the equations of motion of unoriented membranes with the help of Jordan algebras.

Phases of supersymmetric gauge theories from M-theory on G2 manifolds

We consider M-theory on compact spaces of G_2 holonomy constructed as orbifolds of the form (CY x S^1)/Z_2 with fixed point set \Sigma on the CY. This describes N=1 SU(2) gauge theories with b_1(\Sigma) chiral multiplets in the adjoint. For b_1=0, it generalizes to compact manifolds the study of the phase transition from the non-Abelian to the confining phase through geometrical S^3 flops. For b_1=1, the non-Abelian and Coulomb phases are realized, where the latter arises by desingularization of the fixed point set, while an S^2 x S^1 flop occurs. In addition, an extremal transition between G_2 spaces can take place at conifold points of the CY moduli space where unoriented membranes wrapped on CP^1 and RP^2 become massless.

Interpretation of ESR and saturation transfer ESR spectra of spin labeled lipids and membranes

This review presents the current status of the spin label technique as applied to model and biological membranes, with emphasis on structural and dynamic parameters that can be deduced from ESR and saturation transfer (ST) ESR spectra. In many cases, a qualitative physical insight is provided in the appearance of ESR and ST-ESR spectra of macroscopical oriented and unoriented membrane systems. A critical discussion is given of the interpretation and analysis of the spectral line shapes.

Location of the carboxyl terminus of bacteriorhodopsin in purple membrane

Purple membrane samples have been prepared by trypsin digestion to have either 10 or 21 residues removed from the carboxyl terminus of the proteins. Electron diffraction of single membranes and x-ray diffraction of unoriented membrane pellets have been carried out on both these specimens and on native purple membranes. the main conclusion from this work is that the carboxyl terminus is almost entirely disordered, being free to take up many positions, and that its removal does not affect the packing in the crystal. The low resolution x-ray diffraction difference map may also suggest the approximate location of the carboxyl terminus.

Circular dichroism of oriented photoreceptor membrane film

The circular dichroism of photoreceptor membrane oriented in multilamellar films has been measured. In the visible region the 500 nm alpha-band increases 4-fold and the 340 nm beta-band is absent compared to unoriented membrane. In the near ultraviolet region, the appearance of a large megative peak at 275 nm, most likely due to tyrosine, is found. These results may be useful for elucidation of the origin of the optical activity in rhodopsin.