Polyelectrolyte multilayers: An odyssey through interdisciplinary science

This dissertation provides an overview of a self assembled multilayer technique based on the alternating deposition of oppositely charged polyelectrolytes onto charged solid supports. The basic principles and methodologies governing this technique are laid down, and new strategies are built upon the latter, in an effort to develop innovative technologies that would be beneficial for making new products or improving the quality of existing ones.;Fundamental studies to characterize the water content, efficiency of ion-pairing, differential strength of electrostatic interactions, topology, and viscoelastic properties of polyelectrolyte multilayers, PEMUs, are illustrated and conducted. In addition, polyelectrolyte multilayers that are stimulus responsive, or support active and controlled bio-motor protein interactions are described.;Attenuated total reflectance Fourier transform infrared, (ATR), spectroscopy was used to compare the extent of swelling and doping within PAH/PSS and PDADMA/PSS polyelectrolyte multilayers. Unlike PDADMA/PSS, whose water content depended on the solution ionic strength, PAH/PSS was resistant to swelling by salt. It was stable up to 4.0 M sodium chloride, with 6 water molecules per ion-pair. Using the infrared active perchlorate sodium salt, the amount of residual persistent extrinsic sites in both PDADMA/PSS and PAH/PSS was determined to be 3% and 6%, respectively. The free energy of association between the polymer segments, in the presence of sodium perchlorate, was in the order of 4.5 kJ mol-1 and -9.5 kJ mol-1 for PDADMA/PSS and PAH/PSS correspondingly. Thus, indicating the relatively strong electrostatic association between the polymer segments in a PAH/PSS relative to PDADMA/PSS multilayer. Adjusting the pH of the solution in contact with the PAH/PSS multilayer to 11.5 resulted in a first order discontinuous dissociation of the Pol+Pol- bonds.;Techniques used to study the mechanical properties of single muscle fiber were adapted to characterize the topology, viscoelastic behavior, complex modulus and loss factor of PDADMA/PSS multilayers, over a range of frequencies and strain amplitudes. Tensile mode (transient uniaxial stretching) of a PEMU microcoupon using a capacitative-type force transducer located on a modified stage of inverted microscope revealed evidence on the viscous-like behavior of polymer chains within PEMU. Dependence of viscosity was primarily on the ionic strength of the bathing solution, with appreciable stress relaxation occurring at high salt concentrations. Dynamic mechanical analysis was then used to determine the damping properties of PEMU where the length was oscillated sinusoidally, and the resulting force, amplitude and phase shift were observed. Compared to other commercially available polymer damping materials such as acrylic and rubber adhesives, PEMU demonstrated up to 250% enhancement in damping properties over the frequency range of 0.3-10 Hz. This was obtained while the multilayer dry thickness was 3000% less then that of the conventional adhesives.;The synthesis of charged copolymers of poly(N-isopropylacrylamide), (PNIPAM), and their use in constructing thermally responsive PEMU were demonstrated. The temperature dependent water content of the thin film, studied in situ using ATR-FTIR spectroscopy, revealed microscopic and macroscopic transitions at 33 and 45°C, respectively. About 7 water molecules per NIPAM repeat unit were found to be reversibly lost from, or recovered by, the film upon cycling over a temperature range of 10 to 55°C. Assuming that each ion-pair represents a crosslink, swelling theory was used to translate these results into polymer-solvent interaction parameters and enthalpies of mixing for the various polymer components. In addition, the flux of a charged probe molecule, potassium ferricyanide, through the NIPAM-rich multilayer was assessed with rotating disk electrode voltammetry. Thermally reversible modulation of ion transport was demonstrated.;Positive polyelectrolytes were investigated as new surface coatings for promoting in vitro actomyosin motility. Two surface arrangements were studied: a monolayer of the polyelectrolyte PAH, and multilayers consisting of 11-41 layers of alternating polypositive PAH/polynegative PSS electrolytes. For in vitro motility assays, rabbit skeletal muscle heavy meromyosin (HMM) was applied to the PAH surface of both polyelectrolyte mono and multilayers. Myosin driven motion of actin filaments labeled with rhodamine-phalloidin was recorded at 30°C using epifluorescence microscopy. Actin filaments were found to have a mean speed of 2.9±0.08 μm sec-1 on the multilayer surface compared to 2.5±0.06 μm sec-1 on the monolayer surface. Average filament's length and speed increased respectively when nonionic surfactant was added to HMM and ionic strength of the motility buffer increased. Micro-contact printing with a water-insoluble charged block copolymer on PAH produced patterned surfaces that restricted filament motion to PAH tracks.