The thesis is devoted to the development of general methods of preparation of tethered polymer layers with laterally changing properties and investigation of their properties with focus on controlled adsorption and liquid flow. The temperature dependent character of the grafting reaction is used for the design of mono- and bicomponent gradient polymer grafted layers. For this purpose, a special stage providing a lateral temperature gradient is designed. The stage consists of two elements, one heating and one cooling, between which the experimental sample is situated. The versatility of these approaches for both fundamental research and practical applications is demonstrated. In general, the gradient approach is proved to be useful for the combinatorial-like investigations of ultrathin polymer films. The systematic study allowed detailed investigation of the grafting kinetics, the morphologies of the grafted polymer layers, the switching mechanism of the mixed polymer brushes, adsorption of colloid particles. The second approach for the preparation of laterally resolved tethered layers consists of a novel strategy for reversible environment-responsive lithography. This strategy implies local fixation of the morphology of mixed polymer brushes via photocrosslinking by UV irradiation. Irradiated areas lose the ability to switch. Exposure to selective and non-selective solvent allows visualization or erasing of the written information, respectively. It is demonstrated that developed approaches are promising for design of smart sensors, microfluidics devices, combinatorial study of the adsorption (separation and identification) of protein molecules and colloids and for other applications.

The thesis is devoted to the development of general methods of preparation of tethered polymer layers with laterally changing properties and investigation of their properties with focus on controlled adsorption and liquid flow. The temperature dependent character of the grafting reaction is used for the design of mono- and bicomponent gradient polymer grafted layers. For this purpose, a special stage providing a lateral temperature gradient is designed. The stage consists of two elements, one heating and one cooling, between which the experimental sample is situated. The versatility of these approaches for both fundamental research and practical applications is demonstrated. In general, the gradient approach is proved to be useful for the combinatorial-like investigations of ultrathin polymer films. The systematic study allowed detailed investigation of the grafting kinetics, the morphologies of the grafted polymer layers, the switching mechanism of the mixed polymer brushes, adsorption of colloid particles. The second approach for the preparation of laterally resolved tethered layers consists of a novel strategy for reversible environment-responsive lithography. This strategy implies local fixation of the morphology of mixed polymer brushes via photocrosslinking by UV irradiation. Irradiated areas lose the ability to switch. Exposure to selective and non-selective solvent allows visualization or erasing of the written information, respectively. It is demonstrated that developed approaches are promising for design of smart sensors, microfluidics devices, combinatorial study of the adsorption (separation and identification) of protein molecules and colloids and for other applications.

A novel strategy for fabrication of responsive functional polymer films is based on grafting of several different functional polymers onto a solid substrate at high grafting density, resulting in varied types of polymer brushes. Such an arrangement suggests many interesting applications of the multicomponent polymer brushes, regarding their versatile adaptive surfaces, capable for responding to changes of solvent polarity, pH, temperature, electromagnetic field and other stimuli, generally by reversible swelling. Mixed amphiphilic polystyrene-poly(2-vynil pyridine) (PS-P2VP) brushes are an example for responsive class of smart materials, which can switch between hydrophilic and hydrophobic energetic state upon changes in the quality of surrounding media. The switching of wettability was found to operate in a broad range and was selectively controlled in organic solvents and in aqueous solutions. Another example for an adaptive/switching behavior is addressed to a polymer brush with a remarkable response to the pH and the ionic strength variations of the aqueous solutions. Combination of weak polyacrylic acid, PAA, and weak polybase, P2VP, in the anchored layer allowed one with a small shift of the pH, to obtain a significant effect on the surface and the interfacial properties of the material. Both type of polymer brushes were examined as adsorbing materials for nanoparticles and charged synthetic- and bio-macromolecules. Their adaptive properties were successively linked to the results of the adsorption experiments. The simplest case was adsorption of nano-particles, functionalised with strong ionic groups, onto binary, PAA-P2VP, polyelectrolyte brushes. Maintaining a constant charge density of the adsorbing component (strong polyelectrolyte effect), allowed one to cause and manipulate a privileged swelling of one of the weak polyelectrolyte brush layers, without affecting the adsorbate properties, and to regulate the thickness of adsorbed layer only by the pH signal. In the case of adsorption of macromolecules with tuneable electrical charge (polyampholytes and proteins), the system became more complicated, regarding their environmentally responsive properties, similar to that exhibited by the polymer brushes. The driving forces were regulated by the switching performance of the brush, simply by adjusting the pH and/or ionic strength conditions. The adsorbed amount and morphological changes of polyampholyte layers were investigated as function of pH and was performed on mixed amphiphilic and binary polyelectrolyte brushes. A special emphasis was set on the binary brush capability to take the control over the interfacial performance of attaching proteins. It was found, that the sharp environmental response of the adsorbent (the polymer brush) strongly influences the morphology of adsorbed protein layers, their thickness and properties. Changing the polarity of the substrate allowed one to regulate the adsorption processes qualitatively and quantitatively. The significant aggregation of protein molecules on PS-P2VP brush and their disassembly on PAA-P2VP brush at the same solvent conditions, we devote to the hydrophobic-hydrophilic transition, occurred at the surface by replacing PS with PAA. The protein aggregates, monitored on the surface of PS-P2VP, sufficiently decrease their size, when switching the brush energetic state from hydrophobic to hydrophilic by adjusting the pH of the media. This effect was found to be well controlled by the brush switching phenomenon in hydrophilic-hydrophobic direction and vice versa. In conclusion, we showed how the structural reorganization in thin polymer brush layers of different type may dramatically affect their surface properties. The adaptive behavior in response of external stimuli was found to be a basis for highly specific interactions, depending on geometric factors, conformational state and environment.

A novel strategy for fabrication of responsive functional polymer films is based on grafting of several different functional polymers onto a solid substrate at high grafting density, resulting in varied types of polymer brushes. Such an arrangement suggests many interesting applications of the multicomponent polymer brushes, regarding their versatile adaptive surfaces, capable for responding to changes of solvent polarity, pH, temperature, electromagnetic field and other stimuli, generally by reversible swelling. Mixed amphiphilic polystyrene-poly(2-vynil pyridine) (PS-P2VP) brushes are an example for responsive class of smart materials, which can switch between hydrophilic and hydrophobic energetic state upon changes in the quality of surrounding media. The switching of wettability was found to operate in a broad range and was selectively controlled in organic solvents and in aqueous solutions. Another example for an adaptive/switching behavior is addressed to a polymer brush with a remarkable response to the pH and the ionic strength variations of the aqueous solutions. Combination of weak polyacrylic acid, PAA, and weak polybase, P2VP, in the anchored layer allowed one with a small shift of the pH, to obtain a significant effect on the surface and the interfacial properties of the material. Both type of polymer brushes were examined as adsorbing materials for nanoparticles and charged synthetic- and bio-macromolecules. Their adaptive properties were successively linked to the results of the adsorption experiments. The simplest case was adsorption of nano-particles, functionalised with strong ionic groups, onto binary, PAA-P2VP, polyelectrolyte brushes. Maintaining a constant charge density of the adsorbing component (strong polyelectrolyte effect), allowed one to cause and manipulate a privileged swelling of one of the weak polyelectrolyte brush layers, without affecting the adsorbate properties, and to regulate the thickness of adsorbed layer only by the pH signal. In the case of adsorption of macromolecules with tuneable electrical charge (polyampholytes and proteins), the system became more complicated, regarding their environmentally responsive properties, similar to that exhibited by the polymer brushes. The driving forces were regulated by the switching performance of the brush, simply by adjusting the pH and/or ionic strength conditions. The adsorbed amount and morphological changes of polyampholyte layers were investigated as function of pH and was performed on mixed amphiphilic and binary polyelectrolyte brushes. A special emphasis was set on the binary brush capability to take the control over the interfacial performance of attaching proteins. It was found, that the sharp environmental response of the adsorbent (the polymer brush) strongly influences the morphology of adsorbed protein layers, their thickness and properties. Changing the polarity of the substrate allowed one to regulate the adsorption processes qualitatively and quantitatively. The significant aggregation of protein molecules on PS-P2VP brush and their disassembly on PAA-P2VP brush at the same solvent conditions, we devote to the hydrophobic-hydrophilic transition, occurred at the surface by replacing PS with PAA. The protein aggregates, monitored on the surface of PS-P2VP, sufficiently decrease their size, when switching the brush energetic state from hydrophobic to hydrophilic by adjusting the pH of the media. This effect was found to be well controlled by the brush switching phenomenon in hydrophilic-hydrophobic direction and vice versa. In conclusion, we showed how the structural reorganization in thin polymer brush layers of different type may dramatically affect their surface properties. The adaptive behavior in response of external stimuli was found to be a basis for highly specific interactions, depending on geometric factors, conformational state and environment.

The synthesis and polymerization of macromonomers containing a polymerizable styrene head group and a tail of ethylene oxide derivatives of different character were investigated. The synthesis of macromonomers was based on living anionic polymerization of oxiranes. Two monomers were used: 1-ethoxyethyl glycidyl ether (glycidol acetal), which after hydrolysis forms hydrophilic glycidol blocks and glycidyl phenyl ether forming hydrophobic blocks. Polymerizable double bonds were introduced by terminating the living chain with p-(chloromethyl)styrene. However, MALDI-TOF-MS end group analysis showed that all synthesized macromonomers were a mixture of the macromonomer and the non-functionalized oligomer. The degree of functionalization varied from 55 to 75 %. The obtained macromonomers showed amphiphilic properties and formed micelles in water. The determined critical micellization (CMC) concentration for poly(glycidol) macromonomer (DP = 50) was ca. 10 g/L, while the poly(glycidol) block macromonomers with hydrophobic spacer showed CMC on the level 0,7 g/L. The conventional free radical and controlled free radical polymerisation (ATRP) were used for preparation of polymacromonomers with different properties. The radical polymerization of the macromonomers was carried out in water using AVA as initiator and in the mixture of water/benzene (10/1 v/v) using AIBN. Core-shell polymers of different character and molar masses with polydispersity indices from 1,4 -3,0 were obtained. The ATRP carried out in water using PEO macroinitiator led to polymacromonomers with polydispersity indices from 1,1 to 1,3 and desiried molecular weight. In all cases the conversion of macromonomer (able to polymerization) was close to 100%. The polymerization product could easily be separated from the unable to reaction residue.

The synthesis and polymerization of macromonomers containing a polymerizable styrene head group and a tail of ethylene oxide derivatives of different character were investigated. The synthesis of macromonomers was based on living anionic polymerization of oxiranes. Two monomers were used: 1-ethoxyethyl glycidyl ether (glycidol acetal), which after hydrolysis forms hydrophilic glycidol blocks and glycidyl phenyl ether forming hydrophobic blocks. Polymerizable double bonds were introduced by terminating the living chain with p-(chloromethyl)styrene. However, MALDI-TOF-MS end group analysis showed that all synthesized macromonomers were a mixture of the macromonomer and the non-functionalized oligomer. The degree of functionalization varied from 55 to 75 %. The obtained macromonomers showed amphiphilic properties and formed micelles in water. The determined critical micellization (CMC) concentration for poly(glycidol) macromonomer (DP = 50) was ca. 10 g/L, while the poly(glycidol) block macromonomers with hydrophobic spacer showed CMC on the level 0,7 g/L. The conventional free radical and controlled free radical polymerisation (ATRP) were used for preparation of polymacromonomers with different properties. The radical polymerization of the macromonomers was carried out in water using AVA as initiator and in the mixture of water/benzene (10/1 v/v) using AIBN. Core-shell polymers of different character and molar masses with polydispersity indices from 1,4 -3,0 were obtained. The ATRP carried out in water using PEO macroinitiator led to polymacromonomers with polydispersity indices from 1,1 to 1,3 and desiried molecular weight. In all cases the conversion of macromonomer (able to polymerization) was close to 100%. The polymerization product could easily be separated from the unable to reaction residue.