Characterization of supported membranes on topographically patterned polymeric elastomers and their applications to microcontact printing

This article describes the fluorescence microscopy and imaging ellipsometry-based characterization of supported phospholipid bilayer formation on elastomeric substrates and its application in microcontact printing of spatially patterned phospholipid bilayers. Elastomeric stamps, displaying a uniformly spaced array of square wells (20, 50, and 100 mum linear dimensions), are prepared using poly(dimethyl)siloxane from photolithographically derived silicon masters. Exposing elastomeric stamps, following UV/ozone-induced oxidation, to a solution of small unilamellar phospholipid vesicles results in the formation of a 2D contiguous, fluid phospholipid bilayers. The bilayer covers both the elevated and depressed regions of the stamp and exhibits a lateral connectivity allowing molecular transport across the topographic boundaries. Applications of these bilayer-coated elastomeric stamps in microcontact printing of lipid bilayers reveal a fluid-tearing process wherein the bilayer in contact regions selectively transfers with 75-90% efficiency, leaving behind unperturbed patches in the depressed regions of the stamp. Next, using cholera-toxin binding fluid POPC bilayers that have been asymmetrically doped with ganglioside Gm1 ligand in the outer leaflets, we examine whether the microcontact transfer of bilayers results in the inversion of the lipid leaflets. Our results suggest a complex transfer process involving at least partial bilayer reorganization and molecular re-equilibration during (or upon) substrate transfer. Taken together, the study sheds light on the structuring of lipid inks on PDMS elastomers and provides clues regarding the mechanism of bilayer transfer. It further highlights some important differences in stamping fluid bilayers from the more routine applications of stamping in the creation of patterned self-assembled monolayers.     

Physical properties of elastomers for design and development

The measurement of physical properties underlies the design of products, the development of rubber compounds and polyurethane formulations, and much of quality assurance. However, the properties considered for these purposes have changed little in over half a century. With the development of new design methods and increasing demands on industry in terms of specifications and quality, many of the current test methods and resulting properties have little direct relevance. It is part of the British Rubber Manufacturers Association (BRMA) strategy on Research and Development to encourage work in this field and this communication outlines some of the reasons for change.     

The pressure dependence of the dielectric constant and density of acetonitrile at three temperatures

The static dielectric constant of liquid acetonitrile is reported at 10, 25, and 40°C and at pressures up to 3 kbar. Densities of pure acetonitrile were measured where needed in order to analyze the dielectric measurements using the Kirkwood-Fröhlich equation. The Kirkwood correlation factorg _K was found to be less than unity with a positive temperature but negative pressure coefficient, suggesting an increasing anticorrelation of dipoles with decreased temperature and increased pressure. Theg _K factors are analyzed by a dipole pair-bonding model as outlined by Dannhauser and Flueckinger in which the lowg _K values are attributed to the presence of dimers consisting of completely anticorrelated dipoles. The implication of this model on other measurements, especially MNR relaxation studies, is examined.     

Comparative analysis of the membrane-active properties of gossypol derivatives and their polymeric complexes

It has beeen shown that water-soluble complexes of gossypol derivatives obtained by their immobilization on polyvinylpyrrolidone posses a lower membrane activity than the initial substances. The degree of interaction of the substances under investigation with biomembranes has been determined from the change in the intensity of the flourescence of I-anilinonaphthalene-8-sulfonic acid (ANS).Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 375–381, May–June, 1995. Original article submitted October 14, 1994.     

Comparison between properties of polyether polytriazole elastomers and polyether polyurethane elastomers

In order to explore the application of click chemistry in the field of elastomer materials, the comparison between the properties of polyurethane and polytriazole elastomers has been carried out. Propargyl‐terminated ethylene oxide‐tetrahydrofuran copolymer (PTPET) has been prepared from the ethylene oxide‐tetrahydrofuran copolymer (PET) by end modification. Using polyisocyanate N100 and polyazide compounds as cross‐linkers, PET polyurethane and PTPET polytriazole elastomers have been prepared through urethane and copper‐catalyzed azide‐alkyne huisgen [3 + 2] dipolar cycloaddition reactions, respectively. Mechanical properties indicate that, to be different from those of polyurethane elastomers, the modulus E and stress σ_b of polytriazole elastomers increase at first, and then decrease with the increase in R. At around the stoichiometric ratio, the modulus E and stress σ_b reach a maximum, and the strain ε_b reaches a minimum. Swelling tests demonstrate that the M_c of polytriazole elastomers has a minimum value at the stoichiometric ratio. The dynamic mechanical analysis indicates that both polyurethane and polytriazole elastomers have the same glass transition temperature of ?64°C, although polytriazole elastomers exhibit lower dissipation factor tan δ. Thermal analysis shows that polytriazole elastomers have better thermal stability than polyurethane elastomers. Copyright © 2014 John Wiley & Sons, Ltd.     

Investigation of physico-chemical properties and structural parameters of diene-vinyl aromatic thermoplastic elastomers as a polymeric base of adhesive compositions

Adhesion and mechanical properties of vinyl aromatic thermoplastic elastomers on the Russian market were studied. Significant differences between the materials were shown that are due to differences in the chemical natures and structural parameters of block copolymers.     

Thermoplastic elastomers by hydrogen bonding 4. Influence of hydrogen bonding on the temperature dependence of the viscoelastic properties

The temperature dependence of the viscoelastic properties of thermoreversible polybutadiene networks based on hydrogen bond linkages is analyzed from the logarithmic shift factors loga _T . For binary hydrogen bond complexes thermorheologically simple behavior is observed. The temperature dependence of loga _T is described by the Williams-Landel-Ferry (WLF) equation. The thermoreversible linkages cause an increase in the apparent activation enthalpy of flow which is related to the number of complexing sites in the polymer. Thermorheologically complex behavior is observed in a system with more complex association.     

Adsorption properties of tea polyphenols onto three polymeric adsorbents with amide group

Macroporous crosslinked poly(N-methyl-N-p-vinylbenzylacetamide) (PMVBA), poly(N-methyl-N-p-vinylbenzylurea) (PMVBU), and poly(N-methylacrylamide) (PMA) were prepared and their adsorption behaviors for tea polyphenols (TP) were investigated in aqueous solution. The results indicated that their adsorption capacities for TP followed an order as: PMVBU>PMVBA>PMA. The adsorption isotherms were fitted to Freundlich isotherm and adsorption enthalpies were calculated. It was found that Freundlich isotherm was suitable to characterize the adsorption process and their adsorption enthalpies for TP gave the same order as: PMVBU>PMVBA>PMA. Surface energy heterogeneity was analyzed by Do's model and the surface of PMVBU was shown to be the most homogeneous. Analysis of adsorption mechanism suggested that multiple hydrogen bonding, hydrophobic interaction, and pi-pi stacking were responsible for the adsorption of TP onto the adsorbents.     

Synthesis of thermoplastic elastomers based on PET glycolysates: Study of their dielectric properties

Thermoplastic elastomers based on PET glycolysates were synthesized in the molten state according to a multistep process. Their chemical structures were studied (¹H NMR, triple detection, steric exclusion chromatography) as well as their thermal properties (ATG, DSC) and their morphology (AFM). Influence of hard segments composition on the different properties was investigated with the same ratio soft/hard segment. DSC study showed that these compounds had thermal properties similar to those of conventional thermoplastic elastomers (low T_g and high T_m). The association of PET with PBT segments seemed to harm the hard segments crystallization. SEC analyses showed that the compounds obtained had low molecular weights. Two factors seemed to explain the difference in properties between the compounds with and without glycolysate: a lower molecular weight of the TPE containing glycolysate, and a lower organization for materials containing both PET and PBT segments in respect to copolymer without glycolysate and containing solely PBT segments.Dielectric measurements showed properties close to those usually encountered for insulators used in electrical engineering. Glycolysate-free materials exhibited the best properties (high resistivity, low loss factor, slight variation of permittivity) and the materials exhibited interesting insulating properties (breakdown voltage up than 35 kV/mm_RMS, resistivity around 10⁹ Ωm). An improvement of the synthesis methodology with the use of catalyst might result in a significant enhancement of the dielectric properties, already promising for this type of materials.     

Application of the DSC analysis of thermoplastic polyurethane elastomers to a comparative study of their technological properties

The fusion and crystallization enthalpies, dynamic viscosity of melts and tensile properties of a series of commercially available thermoplastic polyurethane elastomers (TPU) were estimated. The DSC analysis has been proved as useful to prediction of the processability and tensile properties of TPU's with a similiar hard segment content.

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Zusammenfassung Schmelz- und Erstarrungsenthalpie, die dynamische Viskosität der Schmelze und Zugdehnungseigenschaften bei einer Reihe von im Handel erhältlichen thermoplastischen Polyurethanelastomere (TPU) wurden ermittelt. DSC-Anaiyse erwies sich als ein geeignetes Mittel zur Vorhersage der Verarbeitungsfähigkeit und der Zugdehnungseigenschaften von TPU mit ähnlichem Hartsegmentanteil.

     

Synthesis and properties of cholesteric liquid crystalline elastomers

The synthesis of new side-chain cholesteric liquid crystalline elastomers, containing the flexible non-mesogenic crosslinking agent M-1 and the cholesteric monomer M-2, is described by a one-step hydrosilication reaction. The chemical structures of the monomers and network polymers obtained were confirmed by FT-IR spectroscopy. Their mesogenic properties and phase behavior were investigated by differential scanning calorimetry, polarizing optical microscopy, and x-ray diffraction measurements. The influence of the crosslinking units on the phase behavior is discussed. The network polymers showed elasticity, reversible phase transitions, and cholesteric Grandjean texture. The experimental results demonstrated that the glass transition temperatures and isotropization temperatures of network elastomers decreased as the concentration of crosslinking units was increased, but the cholesteric phase was not disturbed.     

Ultimate tensile properties of elastomers. VII. Effect of crosslink density on time–temperature dependence

Data on tensile strength and elongation at break for a series of Viton A-HV vulcanizates are discussed. The data were obtained at various extension rates at temperatures from ?5 to 230°C (25 ? T — T_g ? 260°C) on seven vulcanizates having crosslink densities v_e (estimated from C₁ in the Mooney-Rivlin equation) from 0.46 × 10^?5 to 24.4 × 10^?5 mole/cm³. At an extension rate of 1 min^?1, an increase in v_e affects the tensile strength σ_b (based on the undeformed cross-sectional area) and the true tensile strength σ_bσ_b (based on the cross-sectional area of a deformed specimen) as follows: σ_b is essentially constant at a low temperature; it passes through a decided maximum at intermediate temperatures; and it increases to a plateau at elevated temperatures. In contrast, λ_bσ_b decreases markedly at all temperatures, an exception being the most lightly crosslinked vulcanizate(s). Application of time—temperature superposition to the ultimate-property data gave log a_T; its temperature dependence is that typical of nonpolar rubbery polymers. Data on the vulcanizates were compared in corresponding temperature states by plotting log 273σ_b/T, log 273λ_bσ_b/T, and (λ_b — 1)/(λ_b — 1)_max against logt_b/(t_b)_max, where t_b is the temperature-reduced time to break and (t_b)_max is the value at which the ultimate extension ratio λ_b attains its maximum, (λ_b)_max. Except for the most lightly crosslink vulcanizate, the comparison shows that 273λ_bσ_b/T and (λ_b — 1)/(λ_b — 1)_max are substantially independent of (or only weakly dependent on) crosslink density, that 273λ_b/T increases with v_e, and that 273λ_b/T ∝? v_e^0.6 and λ_b ∝? v_e^?0.4 at a large value of t_b/(t_b)_max.     

Synthesis and properties of room-temperature self-healing polyurethane elastomers

Two kinds of polyurethane elastomers were synthesized. One containing acylhydrazone bonds was named TPIA. The other containing both acylhydrazone and disulfide bonds was named TPID. Self-repairable ability and reprocessability of these two elastomers were studied. The results show that: The polyurethane elastomer TPIA can automatically repair damage to it under acidic conditions. After self-healing for 24 h, the strength and the elongation value at break recovered to 32% and 55% of the originality, respectively. The polyurethane elastomer TPID can automatically repair damage to it under visible light at room temperature. After 24 h of self-healing time, 75% of the original strength and 100% of the original elongation values at break were obtained. These two polyurethane elastomers can be reprocessed in their cured state by just applying temperature and pressure.     

Pervaporation selectivity as a function of pressure and sorption properties of a polymeric film membrane

Results obtained in an experimental study of the pervaporation of binary solutions with a cellulose hydrate (cellophane) nonporous film membrane are discussed. A primary attention is given to the sorption and the effect of the residual pressure of the permeate on the separation characteristics.     

Melting points and other properties of ionic liquids,with emphasis on the pressure dependence

The focus of this letter is on melting points (T _m) of ‘green’ ionic liquids, which have values of T _m around room temperature. To aid in their chemical interpretation, we place some emphasis on T _m as a function of pressure p, in cases where such experimental information is available. Finally, some comments are made on the effects of pressure via isothermal compressibility κ _T and the velocity v _s of sound. Some measurements of κ _T and v _s as a function of p are invoked.     

Optimum folding pathways of proteins: their determination and properties

We develop a dynamic optimization technique for determining optimum folding pathways of proteins starting from different initial configurations. A coarse-grained Go model is used. Forces acting on each bead are (i) the friction force, (ii) forces from bond length constraints, (iii) excluded volume constraints, and (iv) attractive forces between residue pairs that are in contact in the native state. An objective function is defined as the total attractive energy between nonbonded residues, which are neighbors in the native state. The objective function is minimized over all feasible paths, satisfying bond length and excluded volume constraints. The optimization problem is nonconvex and contains a large number of constraints. An augmented Lagrangian method with a penalty barrier function was used to solve the problem. The method is applied to a 36-residue protein, chicken villin headpiece. Sequences of events during folding of the protein are determined for various pathways and analyzed. The relative time scales are compared and scaled according to experimentally measured events. Formation times of the helices, turn, and the loop agree with experimental data. We obtain the overall folding time of the protein in the range of 600 ns-1.2 micros that is smaller than the experimental result of 4-5 micros, showing that the optimal folding times that we obtain may be possible lower bounds. Time dependent variables during folding and energies associated with short- and long-range interactions between secondary structures are analyzed in modal space using Karhunen-Loeve expansion.     

New polymeric chemical sensors for determination of lead ions

New polymeric electrochemical sensors for determining the content of lead were suggested. As the active substance of the polymeric membranes of the sensors was used N,N′-tetrabutyldipicolinamide, the compound exhibiting a high extractive capacity for heavy metal ions. The selectivity of the sensors with respect to lead ions in the presence of copper, cadmium, and zinc in a considerable excess was studied.     

Stereoselective synthesis and determination of the cytotoxic properties of spicigerolide and three of its stereoisomers

Stereoselective syntheses of the naturally occurring, cytotoxic lactone spicigerolide and three nonnatural stereoisomers thereof are described. The commercially available sugar l-rhamnose was in all cases the chiral starting material. Key steps in each of these syntheses were asymmetric Brown allylations and ring-closing metatheses. The cytotoxic activities of the four lactones against a range of tumoral lines were then determined.