Exploring the chemistry of ferrocene bioconjugates.

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This NSERC discovery grant proposal focuses on ferrocene-peptide conjugates, their properties in solution and on surfaces, including their electrochemical and materials properties. In particular, we are exploiting the ability of ferrocene peptides to associate to form gel materials based on a nanofibrillar architecture. Such gel materials incorporate large amounts of solvents in their matrix. In this research program, we are exploring factors leading to aggregation and gel formation, among them is the influence of peptide chirality and self-sorting behavior of ferrocene peptide conjugates. ***Our short-term objectives are to expand our discovery-based research of stimuli-responsive and self-sorting Fc-peptide gels to include both organo- and hydrogels and study the effects of chirality on gelation. This has potential implications with regards to our understanding of chemical evolution leading to early life, and may provide insight into why life (in most cases) prefers homochiral peptide systems, and how simple peptide systems organize into more complex structures. Furthermore, we will explore Fc-peptides for film formation on gold substrates and to study their electrochemical properties in an attempt to obtain quantitative information about electron transfer in peptides. The idea is to relate this information based on peptide models back to electron transfer in biological systems. And lastly, we will study the interaction of Fc-peptides with metal ions, specifically for the design of active sites of metalloproteins in solution and on surfaces and will attempt to create a working model for iron-sulfur proteins, including a peptide model for the Rieske protein. ***With a team of students and postdoctoral trainees, this research program will allow us to explore interactions and functions of biomolecules at the molecular level and thus aid in guiding the design of structurally well-defined molecules with known assembly and materials properties. As part of this research program, we will train graduate and undergraduate students in synthetic peptide chemistry, the characterization of materials and provide expert training in electrochemical methods, which will enable our team to contribute significantly to the scholarly activity of the University of Toronto.**