Cooperative domains in lipid membranes

Journal of Thermal Analysis and Calorimetry - Phase transitions of multibilayer structures of hydrated L-α-dipalmitoyl- and L-α-dimyristoylphosphatidylcholine (DPPC and DMPC) were studied...     

Modification of properties of ion-exchange membranes. IV. Change of transport properties of cation-exchange membranes by various polyelectrolytes

A change in electrodialytic transport properties of various cation exchange membranes was observed after the membranes had been adsorbed or ion-exchanged with various cationic polyelectrolytes. Transport properties measured in this report were the relative transport number of calcium ion to sodium ion P^Ca_Na, the current efficiency of cations, and the electric resistance of the membrane during the electrodialysis. Weakly basic and strongly basic cationic polyelectrolytes of various molecular weights were used. Though P^Ca_Na of any cation exchange membrane decreased by the adsorption or ion exchange of any cationic polyelectrolyte, the degree of the decrease in P^Ca_Na changed with species and molecular weight of polyelectrolytes and species of cation-exchange membranes. Weakly basic polyelectrolytes and low molecular weight, strongly basic polyelectrolytes were effective in producing a marked decrease in P^Na_Ca of any cation exchange membrane. The effect of strongly basic polyelectrolytes of high molecular weight on P^Ca_Na was weak in most cases. However, if it was possible to make the polyelectrolyte adhere to the surface of the membrane to form a compact coiled structure, any cationic polyelectrolyte was effective in producing a remarkable decrease in P^Ca_Na of any cation-exchange membrane.     

Cytoskeleton mediated effective elastic properties of model red blood cell membranes

The plasma membrane of human red blood cells consists of a lipid bilayer attached to a regular network of underlying cytoskeletal polymers. We model this system at a dynamic coarse-grained level, treating the bilayer as an elastic sheet and the cytoskeletal network as a series of phantom entropic springs. In contrast to prior simulation efforts, we explicitly account for dynamics of the cytoskeletal network, both via motion of the protein anchors that attach the cytoskeleton to the bilayer and through breaking and reconnection of individual cytoskeletal filaments. Simulation results are explained in the context of a simple mean field percolation model and comparison is made to experimental measurements of red blood cell fluctuation amplitudes.     

Reconstituted olfactory receptors in bilayer lipid membranes

Bullfrog olfactory receptors were reconstituted in bilayer lipid membranes (BLMs). Three odorants were presented to the reconstituted system. The three structurally related odorants were diethylsulfide (DES), thiophene (THP) and diethanolsulfide (DOS). The ordorants were presented in pairs. DOS induced a response in the presence of either of the other two odorants. DES and THP did not induce a response in the presence of either of the other two odorants. These observations suggest that there are two substructures, one common to the three odorants and one that is unique to DOS. The results support the notion that olfactory receptors detect certain molecular segments of odorants.     

Modification of transport properties of ion-exchange membranes VIII. Changes in properties of anion exchange membranes on introduction of hydrophobic groups

A copolymer membrane composed of 4-vinylpyridine-styrene-divinylbenezene was reacted with long chain alkyl bromides (octyl bromide, dodecyl bromide, and hexadecyl bromide) in order to introduce hydrophobic groups into the anion exchange membrane by the quaternization reaction. The resulting membranes show a marked increased in fixed ion concentration as a result of lowered water content. Although the electrical resistance of the membranes increased slightly, the apparent diffusion coefficient of hydrochloric acid through the membranes decreased markedly. Complete quaternization of the membranes by methyl iodide after reaction with the long-chain alkyl bromides caused an increase in the water content and in the apparent diffusion coefficient of the acid and a decrease in the current efficiency in electrodialysis of the acid. This is explained by the high water content of the anion exchange membranes quaternized by methyl iodide.     

Translocation of a beta-peptide across cell membranes.

Short cationic peptides derived from DNA-binding proteins, of which HIV Tat is a prototype, can cross the membranes of living cells, and they can bring covalently attached moieties (proteins, drugs) along with them. We show that a beta-amino acid analogue of Tat 47-57 enters HeLa cells with comparable efficiency to Tat 47-57 itself (YGRKKRRQRRR). The beta-peptide is comprised of residues that bear the appropriate side chain at the beta-carbon. Both the alpha- and the beta-peptide were conjugated to fluorescein at the N terminus, and cell penetration was monitored by confocal fluorescence microscopy. Deletion of the three C-terminal arginine residues from the alpha-peptide abolished translocation activity, consistent with prior reports, and deletion of the three C-terminal beta3-homoarginine residues from the beta-peptide had a similarly adverse effect. Thus, alpha- and beta-peptide translocation processes show similar length/charge dependence. The beta-peptide appeared to be largely unfolded in water, which is consistent with the behavior of short Tat-derived alpha-peptides, but in methanol the beta-peptide adopted a helical conformation, in contrast to short Tat-derived alpha-peptides. Our results show that neither altering the oligomeric backbone (amide group spacing) nor increasing the intrinsic propensity to adopt a specific secondary structure affects translocation activity.     

燃料电池用磺化聚酰亚胺质子交换膜材料的制备与性质

以联萘二酐、磺化二胺和含咪唑基团的非磺化二胺单体为原料,制备了一系列高相对分子质量的磺化聚酰亚胺,该类聚合物具有优异的溶解性和良好的成膜性.得到的质子交换膜具有优异的水解稳定性.苯并咪唑碱性基团的存在提高了磺化聚酰亚胺质子交换膜膜的溶胀稳定性和热稳定性、降低了膜的甲醇透过率.质子导电率测试结果表明,IEC值为2.55mequiv·g-1的膜室温条件下的质子导电率为0.121 S·cm-1,高于在相同测试条件下Nafion 117膜的质子导电率(0.09 S·cm-1).     

Modification of properties of ion exchange membranes. VI. Electrodialytic transport properties of cation exchange membranes with a electrodeposition layer of cationic polyelectrolytes

When a cation exchange membrane is immersed in a cationic polyelectrolyte solution to form a thin layer on the membrane surface, the membrane properties are changed: permselectivity between cations with different electric charges (a relative transport number of the calcium ions to sodium ions, P), current efficiency, and electric resistance of the membrane. Here the more compact the cationic polyelectrolyte layer, the more outstanding the change in permselectivity. To make a more compact layer, an electrodeposition method was adopted and a change in the permselectivity of the resultant cation exchange membrane was investigated. By using the electrodeposition method a strongly basic polyelectrolyte with a larger molecular weight effectively changed the permselectivity of the cation exchange membrane: the P value dropped to about 0.3 from about 2.5 of the P of the untreated membrane during electrodialysis of the sodium chloride—calcium chloride system, and an increase in the electric resistance of the membrane (i.e., organic fouling) due to a cationic surface-active agent could be prevented. It is noteworthy that by using the strongly basic polyelectrolyte with a larger molecular weight the electrodeposition method was effective, whereas the immersion method was ineffective. Furthermore, even with the electrodeposition method the cationic polyelectrolyte which had a relatively smaller molecular weight resulted in a more remarkable change in the P value than did that with a larger molecular weight. In the electrodeposition method the amount of polyelectrolyte cohered onto the membrane surface in creased with an increase in the concentration of the polyelectrolyte, and weakly basic polyelectrolyte, and weakly basic polyelectroyte (polyethyleneimine) was also available independent of its molecular weight.     

Nanostructure and properties of sulfonated polyarylenethioethersulfone copolymers as proton exchange fuel cell membranes

A systematic investigation of properties and nanostructure of sulfonated polyarylenethioethersulfone (SPTES) copolymer proton exchange membranes for fuel cell applications has been presented. SPTES copolymers are high temperature resistant (250 °C), and form tough films with excellent proton conductivity up to 170 ± 5 mS/cm (SPTES 70 @ 85 °C, 85%RH). Small angle X‐ray scattering of hydrated SPTES 70 revealed the presence of local water domains (diameter ～5 nm) within the copolymer. The high proton conductivity of the membranes is attributed to the formation of these ionic aggregates containing water molecules, which facilitate proton transfer. AFM studies of SPTES 70 as a function of humidity (25–65%RH) showed an increase in hydrophilic domains with increasing humidity at 22 °C. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2813–2822, 2007     

Wetting properties of model biological membranes

Various aspects of native and model biological membrane wettability are discussed. Among others hydration of mono-, bi-, and multi-layers of lipids as well as wettability of macroscopic surfaces of solid supported lipid films was investigated via apparent contact angle measurements and calculation of the apparent surface free energy of the films. The effects of relative humidity on the layer hydration and contact angle changes are also discussed. Finally, the effect of liposomes and enzymes (due to the hydrolysis reactions) on the hydrophobic/hydrophilic character of the film surfaces is overviewed.     

Viscoelastic properties of hydrogel microcapsule membranes

The viscoelastic properties of poly(L-lysine-alt-terephthalic acid) (PPL) microcapsules were studied as a function of medium pH. An abrupt increase in the apparent relative viscosity of PPL microcapsule suspensions was observed in the pH range between 4.0 and 7.0 due to the increased total particle volume concentration caused by a sudden increase in microcapsule size. Above pH 7.0, the relative viscosity decreased, being indicative of a deformability of the microcapsules. The adiabatic compressibility of PPL microcapsule membranes was the lowest at pH 4.0 and increased remarkably when the pH value departed from 4.0. On the contrary, the membrane density was the highest at pH 4.0 and decreased as medium pH shifted to either side of this value, implying that the microcapsules behave as compact particles at low pH and loose particles at high pH. The amount of hydrated water also showed a similar change when the pH of the medium was altered.     

Effect of cholesterol on the properties of phospholipid membranes. 4. Interatomic voids

The properties of the interatomic voids present in fully hydrated dimyristoylphosphatidylcholine (DMPC)-cholesterol mixed membranes of different compositions are analyzed in detail using a generalized variant of the Voronoi-Delaunay method on the basis of computer simulation results. The systems investigated are chosen from both sides of the DMPC-cholesterol miscibility gap; the pure DMPC bilayer has also been included in the analysis as a reference system. The results obtained show that the empty space is organized in a more compact way, forming larger voids in the presence than in the absence of cholesterol. The voids located in the region of the rigid cholesterol rings become, on average, less spherical, oriented more parallel with the membrane normal axis with increasing cholesterol concentration, whereas an opposite effect of cholesterol is observed in the middle of the membrane among the chain terminal methyl groups. In general, the preferential orientation of the voids is found to strongly correlate with that of the molecules in the hydrocarbon phase of the membranes. The membranes are found to contain rather large voids, the volume of which can be an order of magnitude larger than the largest spherical cavities present in the systems. These voids are elongated or branching channels rather than big empty holes. The voids located among the DMPC and cholesterol molecules are lying preferably parallel with the membrane normal axis. The existence of such empty channels can be of great importance in the cross-membrane permeation of small, uncharged penetrants, in particular, of polar molecules.     

The preparation and cytotoxic properties of211at labelled concanavalin a bound to cell membranes

A method of labelling biologically active proteins with the alpha emmitting halogen²¹¹At is presented. The labelling procedure is discussed with reference to the chemistry of astatine. Proteins which have been labelled retain approximately 50% of their original biological activity. Using cell specific labelled proteins, dose response curves are given indicating that such reagents are extremely cytotoxic, D₃₇ human CML cells=5 atmos²¹¹At/cell. The research potential of²¹¹At labelled biologically active proteins is briefly discussed.     

Transport properties of Nafion membranes modified with tetrapropylammonium ions for direct methanol fuel cell application

This work presents a study of transport properties (proton conductivity, methanol permeability, and water uptake) and acid-base properties of commercial Nafion-112, -115, and -117 membranes modified with tetrapropylammonium (TPA) cations. In the interaction between TPA hydroxide and protons of sulfonate groups in the Nafion matrix, some of the protons are shown to be bound to sulfonate groups and do not participate in transport processes. These findings are confirmed by IR spectroscopy, acid-base titration, and data on proton conductivity of the modified membranes. Proton conductivity of the modified membranes is shown to be effectively described by a percolation model with parameters that agree with published data for commercial Nafion membranes. Based on these results, a model is proposed for the interaction of TPA cations with the sulfonate groups in Nafion membranes. According to this model, TPA cations form hydrophobic clusters in hydrophilic regions of the polymer matrix, thus preventing some of the protonated sulfonate groups from participating in transport processes.     

Cellular uptake and photosensitizing properties of anticancer porphyrins in cell membranes and low and high density lipoproteins

The mechanisms of the phototoxic effect of anticancer porphyrins used in the photodynamic therapy (PDT) of tumours are not yet completely understood. Irradiation of porphyrins gives rise to singlet oxygen which reacts with key residues of proteins, polyunsaturated fatty acids and cholesterol in membranes, leading to inactivation of various enzymes and transporters. Lipoproteins, mainly low density lipoproteins (LDL), are efficient carriers of anticancer porphyrins in blood and can deliver these photosensitizers to tissues through the apolipoprotein (apo) B/E specific LDL receptor pathway. In this review, we discuss some aspects of anticancer porphyrin transport, cellular uptake and photosensitizing properties in cell membranes and lipoproteins.