Hybrid Architectures at the Nanoscale: Constructing Materials through Electrostatic Interactions

Nature's intricate biomolecular assemblies inspire crafting nano- and microscale functional materials. Comprising nucleotides, amino acids, and saccharides, these structures orchestrate cellular functions with precision. Replicating this complexity artificially is challenging, but nanoscale techniques, especially nature-mimicking self-assembly, offer atomic-level precision through non-covalent interactions. Electrostatic self-assembly stands out for versatility, enabling diverse functional materials. This reversible process facilitates the exact arrangement of charged components. Moreover, the utilization of biomolecule-based materials as building blocks in nanomaterials presents a promising avenue, leading to the development of highly biocompatible functional systems. This convergence of principles is exemplified in this thesis, which demonstrates how functional and self-assembling biohybrid materials can be constructed precisely by synergistically combining DNA origami and protein cages with molecular glues. Thus, Publication I opens the study by designing hybrid bundles, uniting cationic dyes like zinc phthalocyanine with negatively charged DNA origami. This synergy enhances optical properties and stability, effectively showcasing the potential of electrostatic self-assembly in customizing material traits. Publication II extends the study by introducing Janus-type phthalocyanines with two different DNA origami structures, resulting in optically active biohybrids resistant to aggregation. This underscores the role of ionic strength in self-assembly and disassembly processes, deepening the insights into biohybrid material formation. Publication III delves into crystalline assemblies, harnessing electrostatic self-assembly of pillar[5]arene with apoferritin, unveiling promising prospects for water remediation. This endeavor highlights the versatile capabilities of biomolecular self-assembly in addressing pressing environmental challenges. Publication IV demonstrates the formation of protein-protein co-crystals involving cationic fluorescent protein and negatively charged apoferritin, thereby showcasing robust optical properties with potential applications in biological light-emitting diodes. In summation, the collective body of work presented in this thesis underscores the potential of electrostatic self-assembly in crafting intricate biohybrid materials. These findings provide understanding of electrostatic self-assembly, establishing a path for preparing cutting-edge nanomaterials with applications in nanomedicine, optoelectronics, and water treatment. This research effectively links intricate biomolecular assemblies and synthetic constructs, potentially finding utility in novel solutions across multifarious sectors.