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Depending on the connectivity of solubilizing oligoethylene glycol (OEG) side chains to the π‐cores of amphiphilic naphthalene and perylene bisimide dyes, self‐assembly in water occurs either upon heating or cooling. Herein, we show that this effect originates from differences in the enwrapping capability of the π‐cores by the OEG chains. Rylene bisimides bearing phenyl substituents with three OEG chains attached directly to the hydrophobic π‐cores are strongly sequestered by the OEG chains. These molecules self‐assemble at elevated temperatures in an entropy‐driven process according to temperature‐ and concentration‐dependent UV/Vis spectroscopy and calorimetric dilution studies. In contrast, for rylene bisimides in which phenyl substituents with three OEG chains are attached via a methylene spacer, leading to much weaker sequestration, self‐assembly originates upon cooling in an enthalpy‐driven process. Our explanation for this controversial behavior is that the aggregation in the latter case is dictated by the release of “high energy water” from the hydrophobic π‐surfaces as well as dispersion interactions between the π‐scaffolds which drive the self‐assembly in an enthalpically driven process. In contrast, for the former case we suggest that in addition to the conventional explanation of a dehydration of hydrogen‐bonded water molecules from OEG units it is in particular the increase in conformational entropy of back‐folded OEG side chains upon aggregation that provides the pronounced gain in entropy that drives the aggregation process. Thus, our studies revealed that a subtle change in the attachment of solubilizing substituents can switch the thermodynamic signature for the self‐assembly of amphiphilic dyes in water from enthalpy‐ to entropy‐driven.
In this paper, we bridge the gap between procedural content generation (PCG) and user-generated content (UGC) by proposing and demonstrating an interactive agent-based model of self-assembling ensembles that can be directed though user input. We motivate these efforts by considering the opportunities technology provides to pursue game designs based on according game design frameworks. We present three different use cases of the proposed model that emphasize its potential to (1) self-assemble into predefined 3D graphical assets, (2) define new structures in the context of virtual environments by self-assembling layers on the surfaces of arbitrary 3D objects, and (3) allow novel structures to self-assemble only considering the model’s configuration and no external dependencies. To address the performance restrictions in computer games, we realized the prototypical model implementation by means of an efficient entity component system (ECS). We conclude the paper with an outlook on future steps to further explore novel interactive, dynamic PCG mechanics and to ensure their efficiency.