Surface characterization and manipulation of polyampholytic hydrogel coatings

Abstract: This thesis is dedicated to building up fundamental knowledge about polyampholytic hydrogels, which are developed in our group for anti-fouling purposes. Charge-balanced polymers, where positive and negative charges balance each other, have emerged as interesting candidates for many applications in materials science. We have prepared charge-balanced materials by forming thickness gradients of oppositely charged polyelectrolytes, and use these as model systems for a systematic investigation of the materials and their responses to environmental changes. These hydrogel gradients were sequentially grafted from substrates via surface-initiated photografting and photopolymerization (SIPGP) of cationic and anionic polyelectrolytes. At some thickness ratios, these form a charge-balanced system where the net surface charge is zero, and with certain similarity to zwitterionic systems. The surface charge of the hydrogels is the principal parameter regulating non-specific protein adsorption, and among other things, we demonstrate that the position of the fouling-resistant charge-neutral region can be manipulated upon pH changes. The chemical compositions of the hydrogel gradients were characterized by microscopic infrared spectroscopy. Optical analysis by spectroscopic ellipsometry and imaging surface plasmon resonance were used to monitor the swelling of the hydrogel films, and protein adsorption onto these in real-time. Surface forces, i.e. the interactions with the hydrogels from an intermolecular perspective, which are related mainly to electrostatic and steric forces, were probed by direct force measurement using atomic force microscopy. Force curves were used to determine the surface charge distribution over the hydrogels, and to indicate the correlation between surface charge and protein adsorption. In the later work, hydrogel gradients were patterned as arrayed spots. Their thicknesses and surface roughness provide further information about the polymer structure and provides a basis for relating ellipsometric swelling profiles to thicknesses as obtained by atomic force microscopy. Finally, it is demonstrated how charged hydrogel films can be used as spacers to tune the optimum distance between silver nanoparticles and fluorophores for metal-enhanced fluorescence (MEF). The aim of this work is to understand polyampholytic hydrogels from various perspectives: surface charges and their distribution, the polymer structure, and surface interactions. The knowledge and experience obtained contribute to the general understanding of zwitterionic materials, and to the development of anti-fouling coatings, optical sensing platforms and other applications of charge-balanced hydrogels.