Functional coatings with colorimetric properties: the influence of electrostatic interaction and hydrogen bonding on the assembly of gold nanoparticles in polymer brushes

The modification of surfaces with thin films is widely used to tailor physical and chemical properties of surfaces. This approach can provide "smart" surfaces with desired tunable properties. Polymer brushes represent a class of thin films, where the polymer chains are chemically end-grafted to the substrate. The chain functionality can be tailored by chemical composition, which allows the brushes to respond to external stimuli. In addition, polymer brushes may sterically stabilize colloids. Thus, polymer brushes are suitable candidates as a matrix for the incorporation of inorganic nanoparticles, like gold nanoparticles (AuNPs). AuNPs induce optical properties due to their surface plasmon resonance (SPR), which results in smart nanocomposite materials with tunable optical properties for the application as colorimetric sensors. The ability to control the particle amount and distribution within a brush matrix has a strong impact on fabrication of colorimetric sensors with optical properties on demand. In order to achieve brush/AuNP composites with desired properties, the thesis focuses on the impact of electrostatic interaction and hydrogen bonding on the formation of brush/AuNP composite materials. Here, pH-sensitive AuNPs are embedded into strong cationic and non-ionic polymer brushes. The electrostatic interactions and hydrogen bondings are tuned by changing the surface charge of the AuNPs through variations of pH value, while the charges of the brushes are not affected. The first part of the present thesis presents the assembly of pH-sensitive AuNPs into cationic polyelectrolyte brushes. In particular, the synergistic use of different characterization techniques clarify directly and indirectly effects of the electrostatic interaction on the structure, morphology and sensitivity of cationic brush/AuNP composites. The second part discusses the influence of using a non-ionic polymer brush on the assembly of pH-sensitive AuNPs. It is shown, that the nature of polymer brush has a crucial impact on the stabilization of incorporated AuNPs. This work demonstrates a novel approach to incorporate negatively charged AuNPs into non-ionic polymer brushes by using an electric field. Finally, the quality of brush/AuNP composites was experimental evaluated in terms of the long-term stability for the future prospect as colorimetric sensors. The thesis presents a fundamental understanding of smart coatings, where the particle-particle interaction as well as particle-brush interaction can be simply controlled by variation in pH value and governs their structure and responsive behavior

Gold nanoparticle distribution in polyelectrolyte brushes loaded at different pH conditions

Composites made of polymer brushes with inclusions of gold nanoparticles (AuNPs) combine the responsive nature of polymer brushes with the optical properties of the AuNPs, which offers the possibility to be used as colorimetric sensors. To this end, it is crucial to know how AuNPs are distributed inside the brush. Here, this distribution was elucidated by neutron reflectometry with contrast variation and a self-consistent reflectivity analysis based on the analytical parameterization of the volume fraction profiles of all chemical components. In contrast to former studies, this analysis allows the determination of the spatial distribution of components separately from each other: polyelectrolyte, AuNP, and water. Cationic poly-[2-(Methacryloyloxy) ethyl] trimethylammonium chloride (PMETAC) brushes were loaded with 5 nm AuNPs, which were coated with a pH-sensitive capping. The pH was varied during the incubation of the brush in the AuNP suspension. At a lower pH, AuNPs form aggregates in suspension and are attached to the brush periphery. They adsorb into the brush but do not fully penetrate it due to their bulkiness. At a higher pH, AuNP suspensions are electrostatically stabilized and the AuNPs penetrate the brush entirely. However, the AuNP distribution over the brush is not homogeneous but decreases gradually toward the substrate. Penetration of the AuNPs leads to a more extended conformation of the brush. According to the results of the detailed analysis of all components, an increase in water content could be excluded as a reason for brush swelling but replacement of water by the AuNP was observed

Functional coatings with colorimetric properties: the influence of electrostatic interaction and hydrogen bonding on the assembly of gold nanoparticles in polymer brushes

The modification of surfaces with thin films is widely used to tailor physical and chemical properties of surfaces. This approach can provide "smart" surfaces with desired tunable properties. Polymer brushes represent a class of thin films, where the polymer chains are chemically end-grafted to the substrate. The chain functionality can be tailored by chemical composition, which allows the brushes to respond to external stimuli. In addition, polymer brushes may sterically stabilize colloids. Thus, polymer brushes are suitable candidates as a matrix for the incorporation of inorganic nanoparticles, like gold nanoparticles (AuNPs). AuNPs induce optical properties due to their surface plasmon resonance (SPR), which results in smart nanocomposite materials with tunable optical properties for the application as colorimetric sensors. The ability to control the particle amount and distribution within a brush matrix has a strong impact on fabrication of colorimetric sensors with optical properties on demand. In order to achieve brush/AuNP composites with desired properties, the thesis focuses on the impact of electrostatic interaction and hydrogen bonding on the formation of brush/AuNP composite materials. Here, pH-sensitive AuNPs are embedded into strong cationic and non-ionic polymer brushes. The electrostatic interactions and hydrogen bondings are tuned by changing the surface charge of the AuNPs through variations of pH value, while the charges of the brushes are not affected. The first part of the present thesis presents the assembly of pH-sensitive AuNPs into cationic polyelectrolyte brushes. In particular, the synergistic use of different characterization techniques clarify directly and indirectly effects of the electrostatic interaction on the structure, morphology and sensitivity of cationic brush/AuNP composites. The second part discusses the influence of using a non-ionic polymer brush on the assembly of pH-sensitive AuNPs. It is shown, that the nature of polymer brush has a crucial impact on the stabilization of incorporated AuNPs. This work demonstrates a novel approach to incorporate negatively charged AuNPs into non-ionic polymer brushes by using an electric field. Finally, the quality of brush/AuNP composites was experimental evaluated in terms of the long-term stability for the future prospect as colorimetric sensors. The thesis presents a fundamental understanding of smart coatings, where the particle-particle interaction as well as particle-brush interaction can be simply controlled by variation in pH value and governs their structure and responsive behavior

Dielectric function of a polymer brush functionalized with gold nanoparticles determined from spectroscopic ellipsometry

Spectroscopic ellipsometry is a powerful technique for measuring the thickness and dielectric function of thin films deposited upon optically reflective surfaces. The dielectric function determines the material optoelectronic properties, however its ellipsometric measurement is challenging in cases when the film thickness and its exact structure in terms of phases and their optical properties, are unknown. The present paper discusses several models of film dielectric function, which may be considered for fitting the ellipsometric spectra of a poly(N-ispropylacrylamide) brush grown at silicon surface and functionalized with gold nanoparticles

Gold nanoparticle distribution in polyelectrolyte brushes loaded at different pH conditions

Composites made of polymer brushes with inclusions of gold nanoparticles AuNPs combine the responsive nature of polymer brushes with the optical properties of the AuNPs, which offers the possibility to be used as colorimetric sensors. To this end, it is crucial to know how AuNPs are distributed inside the brush. Here, this distribution was elucidated by neutron reflectometry with contrast variation and a self consistent reflectivity analysis based on the analytical parameterization of the volume fraction profiles of all chemical components. In contrast to former studies, this analysis allows the determination of the spatial distribution of components separately from each other polyelectrolyte, AuNP, and water. Cationic poly [2 Methacryloyloxy ethyl] trimethylammonium chloride PMETAC brushes were loaded with 5 nm AuNPs, which were coated with a pH sensitive capping. The pH was varied during the incubation of the brush in the AuNP suspension. At a lower pH, AuNPs form aggregates in suspension and are attached to the brush periphery. They adsorb into the brush but do not fully penetrate it due to their bulkiness. At a higher pH, AuNP suspensions are electrostatically stabilized and the AuNPs penetrate the brush entirely. However, the AuNP distribution over the brush is not homogeneous but decreases gradually toward the substrate. Penetration of the AuNPs leads to a more extended conformation of the brush. According to the results of the detailed analysis of all components, an increase in water content could be excluded as a reason for brush swelling but replacement of water by the AuNP was observe

Symmetric Cladding Thin Film Waveguides: From Lossy Media to Disordered Nanostructures

Intrinsic absorption in a waveguiding material is often considered an undesirable effect that severely limits wave propagation. However, with appropriate design of the cladding, waveguides can be made from highly absorbing materials, to the degree that stronger absorption actually increases the propagation length. Here, we discuss the permittivity landscape showing accessible optical properties of lossy materials together with their fitness for symmetric cladding thin film waveguides. The concept of Zenneck wave-like propagation in absorbing materials is extended to thin films of disordered nanocomposites. In an experimental demonstration, we show that despite intrinsic absorption and disorder, a metal–polymer composite itself can support long-range propagation of light. We have used a nanoparticle filled poly­(N-isopropylacrylamide) (PNIPAM) polymer brush that can serve as a functionalized surface. The material supports bounded optical modes with superior propagation length, exceeding its bulk absorption length by far. Waveguiding on lossy nanocomposite surfaces may bring new optical devices that combine the versatility of metal-based nanostructures with the well-defined propagation of thin film waveguides

A grazing incidence neutron spin echo study of near surface dynamics in p(MEO2MA-co-OEGMA) copolymer brushes

Surface-attached architectures of p(MEO2MA-co-OEGMA) copolymers are thermoresponsive PEG analogues with potential applications in biotechnology and medicine. In this respect, structure and dynamics of polymer brushes made of these copolymers are of great interest. In this work, the near surface dynamics of a p(MEO2MA-co-OEGMA) brush with a height of 250 nm was investigated with neutron spin echo spectroscopy under grazing incidence (GINSES) conditions. The brush dynamics was studied at two penetration depths of the neutrons. An influence of the distance from the confining surface on the collective diffusion was found. For the first time, the experiment demonstrates the feasibility of studying thermal fluctuations of macromolecules at a single planar liquid/solid interface by neutron spin echo spectroscopy under grazing incidence

A grazing incidence neutron spin echo study of near surface dynamics in p(MEO2MA-co-OEGMA) copolymer brushes

Surface-attached architectures of p(MEO2MA-co-OEGMA) copolymers are thermoresponsive PEG analogues with potential applications in biotechnology and medicine. In this respect, structure and dynamics of polymer brushes made of these copolymers are of great interest. In this work, the near surface dynamics of a p(MEO2MA-co-OEGMA) brush with a height of 250 nm was investigated with neutron spin echo spectroscopy under grazing incidence (GINSES) conditions. The brush dynamics was studied at two penetration depths of the neutrons. An influence of the distance from the confining surface on the collective diffusion was found. For the first time, the experiment demonstrates the feasibility of studying thermal fluctuations of macromolecules at a single planar liquid/solid interface by neutron spin echo spectroscopy under grazing incidence