More specific and oriented interactions, such as hydrogen bonds and shapedependent π–π interactions offer the possibility to control supramolecular
organization in a much more defined way. This is exemplified in Sect. 4. In fact,
the same interactions that dominate the shape of complex macromolecules are also
responsible for the formation of defined aggregates and for the adsorption to
surfaces. They govern self-assembly at the two levels: the internal structure of the
building blocks and the self-assembly of the building blocks. In a simplified
manner, the first role can be viewed as “intramolecular” and the second role as
“intermolecular”. These intra- and intermolecular roles of different interactions are
discussed for all types of macromolecules.
Another type of “interaction” is confinement. We focus on the confinement of
block copolymers and the resulting microphase separation. As one example, the
structure of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) in the
confinement of droplets in miniemulsions is described. To better understand
microphase separation, experimental results are compared to self-consistent field
theory simulations. Then, we consider block copolymers bound to a solid surfaces
and their response to different environmental conditions (Sect. 5). As a third
example of structures and confinement, the incorporation of quantum dots into
the hydrophobic region of polymersomes is demonstrated.
In the last section (Sect. 6) we focus on molecules adsorbed to surfaces. Creating
complex polymer architectures on surfaces is important for applications such as
(bio)sensors and molecular electronics. However, molecular self-assembly usually
relies on weak, reversible interactions leading to inherently fragile structures. To
provide stability as well as enhanced electron transport properties we explore the
possibility of creating covalently linked molecular structures on bulk insulator
surfaces.
In order to better understand the structure and dynamics of polymers, the
formation of complex architectures, and to further improve the function of a
specific material, a whole range of complementary characterization techniques
was required. For example, complex formation of polyelectrolytes has been studied
intensely with light and small angle neutron scattering (SANS). Techniques were
not only applied but also improved and new techniques have been developed. One
example is solid-state NMR. NMR not only yields information on the atomic
structure but also provides dynamic information. Typically, NMR results are
complemented by wide and small angle X-ray scattering (WAXS and SAXS,
respectively) and computer simulations. Another example is high-resolution atomic
force microscopy (AFM). In recent years non-contact AFM has been developed,
which allows imaging of crystalline structures and defects at the atomic level. So
far, however, most studies have been limited to comparatively small organic
molecules deposited under well-controlled ultrahigh vacuum conditions. Therefore,
the technique is constantly being further developed to extend it to “soft” organic
materials and to “real” environments such as in liquids.
Structure Formation of Polymeric Building Blocks: Complex Polymer Architectures
121
organization in a much more defined way. This is exemplified in Sect. 4. In fact,
the same interactions that dominate the shape of complex macromolecules are also
responsible for the formation of defined aggregates and for the adsorption to
surfaces. They govern self-assembly at the two levels: the internal structure of the
building blocks and the self-assembly of the building blocks. In a simplified
manner, the first role can be viewed as “intramolecular” and the second role as
“intermolecular”. These intra- and intermolecular roles of different interactions are
discussed for all types of macromolecules.
Another type of “interaction” is confinement. We focus on the confinement of
block copolymers and the resulting microphase separation. As one example, the
structure of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) in the
confinement of droplets in miniemulsions is described. To better understand
microphase separation, experimental results are compared to self-consistent field
theory simulations. Then, we consider block copolymers bound to a solid surfaces
and their response to different environmental conditions (Sect. 5). As a third
example of structures and confinement, the incorporation of quantum dots into
the hydrophobic region of polymersomes is demonstrated.
In the last section (Sect. 6) we focus on molecules adsorbed to surfaces. Creating
complex polymer architectures on surfaces is important for applications such as
(bio)sensors and molecular electronics. However, molecular self-assembly usually
relies on weak, reversible interactions leading to inherently fragile structures. To
provide stability as well as enhanced electron transport properties we explore the
possibility of creating covalently linked molecular structures on bulk insulator
surfaces.
In order to better understand the structure and dynamics of polymers, the
formation of complex architectures, and to further improve the function of a
specific material, a whole range of complementary characterization techniques
was required. For example, complex formation of polyelectrolytes has been studied
intensely with light and small angle neutron scattering (SANS). Techniques were
not only applied but also improved and new techniques have been developed. One
example is solid-state NMR. NMR not only yields information on the atomic
structure but also provides dynamic information. Typically, NMR results are
complemented by wide and small angle X-ray scattering (WAXS and SAXS,
respectively) and computer simulations. Another example is high-resolution atomic
force microscopy (AFM). In recent years non-contact AFM has been developed,
which allows imaging of crystalline structures and defects at the atomic level. So
far, however, most studies have been limited to comparatively small organic
molecules deposited under well-controlled ultrahigh vacuum conditions. Therefore,
the technique is constantly being further developed to extend it to “soft” organic
materials and to “real” environments such as in liquids.
Structure Formation of Polymeric Building Blocks: Complex Polymer Architectures
121