Vesicle adsorption and lipid bilayer formation on glass studied by atomic force microscopy

The adsorption of phosphatidylcholine (PC) vesicles (30, 50, and 100 nm nominal diameters) and of dye-labeled PC vesicles (labeled with 6% Texas Red fluorophore (TR) and encapsulated carboxy fluorescein (CF)) to glass surfaces was studied by contact mode atomic force microscopy in aqueous buffer. These studies were performed in part to unravel details of the previously observed isolated rupture of dye-labeled PC vesicles on glass (Johnson, J. M.; Ha, T.; Chu, S.; Boxer, S. G. Biophys. J. 2002, 83, 3371-3379), specifically to differentiate partial rupture, that is, pore formation and leakage of entrapped dye, from full rupture to form bilayer disks. In addition, the adhesion potential of PC vesicles on glass was calculated based upon the adhesion-driven flattening of adsorbed vesicles and a newly developed theoretical model. The vesicles were found to flatten considerably upon adsorption to glass (width-to-height ratio of approximately 5), which leads to an estimate for the adhesion potential and for the critical rupture radius of 1.5 x 10(-4) J/m2 and 250 nm, respectively. Independent of vesicle size and loading with dye molecules, the adsorption of intact vesicles was observed at all concentrations below a threshold concentration, above which the formation of smooth lipid bilayers occurred. In conjunction with previous work (Johnson, J. M.; Ha, T.; Chu, S.; Boxer, S. G. Biophys. J. 2002, 83, 3371-3379), these data show that 6% TR 20 mM CF vesicles adsorb to the surface intact but undergo partial rupture in which they exchange content with the external buffer.     

Effect of the reaction state on the polymerization of p-xylenesulfonium salts

1,4-Phenylenebis(methylene) sulfonium salts were polymerized under different conditions to yield p-xylylene sulfonium salt polyelectrolytes in a broad range of molecular weights. The aqueous reaction mixture formed a reversible gel at initial monomer concentrations higher than 1.0M, but at lower concentrations it remained as an emulsion until reaction completion. The effect of reaction time on intrinsic viscosities and polymer yields for both the emulsion and the gel state is discussed. The higher yields obtained when the reaction was carried out in the presence of a water-immiscible organic solvent were apparently due to the effect of this solvent on increasing the concentration of the reactive intermediate that led to the polyelectrolyte. Both the addition of an organic solvent and the variation of the initial monomer concentrations allowed some control over the molecular weight of the polyelectrolyte formed.     

Fully aromatic thermotropic liquid crystalline polyesters of substituted 4,4′-biphenols. IV. Homopolyesters with terephthalic acid and copolyesters with terephthalic acid and 4-hydroxybenzoic acid

A series of fully aromatic thermotropic polyesters based on mono-, di-, and tetra-substituted biphenols was prepared by the melt polycondensation method and examined for their thermotropic behavior by a variety of experimental techniques. The homopolyesters obtained from substituted biphenols containing either one phenyl or two phenyl groups as substituent(s) and TA formed nematic melts, but the homopolymers of the substituted biphenols containing either four sec-butyl groups or two tert-butyl groups with TA had melting transitions, T_m, above 400°C. Thus, it was not possible to determine whether they formed nematic melts. On copolymerization with 30 mol % HBA most of the resulting copolyesters had much lower T_m values, compared to those of respective homopolyesters, and the copolymers of the biphenol monomer containing the tert-butyl groups formed a nematic melt at an observable temperature. However, the copolymer of the biphenol with sec-butyl groups still had a T_m above 400°C. © 1993 John Wiley & Sons, Inc.     

Exactly alternating silarylene–siloxane polymers. II. The condensation polymerization of arylenedisilanols and bisureidosilanes

A new method for the preparation of exactly alternating silarylene–siloxane polymers by the low temperature step-growth condensation polymerization reaction of arylenedisilanols and bisurei-dosilanes in chlorobenzene was investigated. To obtain high molecular weight products ¹H NMR spectroscopy and gel permeation chromatography were used to monitor the polymerization reaction. By using these procedures 12 different polymers were prepared from 1,4-bis(dimethylhydroxysilyl)-benzene, 4,4′-bis(dimethylhydroxysilyl)phenyl ether, bis(1,1-tetramethylene-3-phenylureido)-dimethylsilane, and bis(1,1-tetramethylene-3-phenylureido)-methylvinylsilane monomers. The polymers were obtained in high yields, purities, and molecular weights.     

Synthesis and electrical conductivity of poly(arylene vinylene). I. Poly(2,5-dimethoxyphenylene vinylene) and poly(2,5-dimethylphenylene vinylene)

The highly conjugated aromatic polymers, poly(2,5-dimethoxyphenylene vinylene) and poly(2,5-dimethylphenylene vinylene), were obtained from their water soluble, sulfonium salt precursor polymers. Films of these polymers were reacted with either AsF₅ or I₂ vapor. Poly(2,5-dimethoxyphenylene vinylene) showed increases in electrical conductivity of up to 14 to 15 orders of magnitude for these two dopants, while an 8 to 9 order of magnitude increase was observed for poly(2,5-dimethylphenylene vinylene) with the same dopants. The synthesis of the precursor polymers, the properties and elimination reactions of films of the precursors, the doping reactions, and the conductivities of the resulting phenylene vinylene films are discussed.     

Thermal and autoxidation reactions of poly-3-methylenecyclobutene and poly-1-methyl-3-methylenecyclobutene

The thermal ring-opening reactions, autoxidation and hydrogenation of polymethy-lenecyclobutene (PMCB) and poly-1-methyl-3-methylenecyclobutene (PMMCB), were investigated. Both polymers were prepared by cationic polymerization and consisted almost entirely of 1,5-repeating units containing cyclobutene rings in the polymer backbone. Both polymers showed well behaved exothermic processes at elevated temperatures which apparently resulted in crosslinking. These processes were investigated by differential scanning calorimetry and interpreted to involve thermal ring-opening reactions. Autoxidation occurred very rapidly in PMCB but much more slowly in PMMCB as predicted by Bolland's rules. Attempts to hydrogenate the cyclobutene rings in both polymers resulted in the occurrence of hydrogenolysis in PMCB and little or no reaction with PMMCB for a Pd-catalyzed reaction and partial hydrogenation of the latter for a diimide reaction.     

Fully aromatic liquid crystalline homopolyesters and copolyesters of 1,1′-binaphthyl-4,4′-diol

A series of fully aromatic, thermotropic polyesters based on 1,1′-binaphthyl-4,4′-diol, BND, was prepared by the melt polycondensation method and characterized for their thermotropic behavior by a variety of experimental techniques. The homopolymer of BND with terephthalic acid formed a nematic melt at 353°C. In contrast, the polyester from BND and 2,6-naphthalenedicarboxylic acid had a melting transition, T_m, above 400°C, so it was not possible with the equipment available to determine whether it formed a nematic melt. All of the copolymers of BND formed nematic melts at much lower T_m values than those of its respective homopolymers, as expected, because of the copolymerization effect of the added monomer. Moreover, all of the copolymers had higher glass transition temperatures, T_g, than those of other liquid crystalline polyesters and higher thermal stabilities. © 1994 John Wiley & Sons, Inc.