Light waveguiding in bioinspired peptide nanostructures.

Basic optical properties of bioinspired peptide nanostructures are deeply modified by thermally mediated refolding of peptide secondary structure from α-helical to ß-sheet. This conformational transition is followed by the appearance in the ß-sheet structures of a wideband optical absorption and fluorescence in the visible region. We demonstrate that a new biophotonic effect of optical waveguiding recently observed in peptide/protein nanoensembles is a structure-sensitive bimodal phenomenon. In the primary α-helical structure input, light propagates via optical transmission window demonstrating conventional passive waveguiding, based on classical optics. In the ß-sheet structure, fluorescent (active) light waveguiding is revealed. The latter can be attributed to completely different physical mechanism of exciton-polariton propagation, characterized by high effective refractive index, and can be observed in nanoscale fibers below diffraction limit. It has been shown that peptide material requirements for passive and active waveguiding are dissimilar. Original biocompatibility and biodegradability indicate high potential future applications of these bioinspired waveguiding materials in precise photobiomedicine towards advanced highly selective bioimaging, photon diagnostics, and optogenetics.

Proton-Transfer-Induced Fluorescence in Self-Assembled Short Peptides.

We employ molecular dynamics (MD) and time-dependent density functional theory (TDDFT) to explore the fluorescence of hydrogen-bonded dimer and trimer structures of cyclic FF (Phe-Phe) molecules. We show that in some of these configurations a photon can induce either an intra-molecular proton transfer, or an inter-molecular proton transfer that can occur in the excited S1 and S2 states. This proton transfer, taking place within the hydrogen bond, leads to a significant red-shift that can explain the experimentally observed visible fluorescence in biological and bioinspired peptide nanostructures with a ß-sheet biomolecular arrangement. Finally, we also show that such proton transfer is highly sensitive to the geometrical bonding of the dimers and trimers and that it occurs only in specific configurations allowed by the formation of hydrogen bonds.

Peptide Nanophotonics: From Optical Waveguiding to Precise Medicine and Multifunctional Biochips.

Optical waveguiding phenomena found in bioinspired chemically synthesized peptide nanostructures are a new paradigm which can revolutionize emerging fields of precise medicine and health monitoring. A unique combination of their intrinsic biocompatibility with remarkable multifunctional optical properties and developed nanotechnology of large peptide wafers makes them highly promising for new biomedical light therapy tools and implantable optical biochips. This Review highlights a new field of peptide nanophotonics. It covers peptide nanotechnology and the fabrication process of peptide integrated optical circuits, basic studies of linear and nonlinear optical phenomena in biological and bioinspired nanostructures, and their passive and active optical waveguiding. It is shown that the optical properties of this generation of bio-optical materials are governed by fundamental biological processes. Refolding the peptide secondary structure is followed by wideband optical absorption and visible tunable fluorescence. In peptide optical waveguides, such a bio-optical effect leads to switching from passive waveguiding mode in native α-helical phase to an active one in the ß-sheet phase. The found active waveguiding effect in ß-sheet fiber structures below optical diffraction limit opens an avenue for the future development of new bionanophotonics in ultrathin peptide/protein fibrillar structures toward advanced biomedical nanotechnology.

Peptide Integrated Optics.

Bio-nanophotonics is a wide field in which advanced optical materials, biomedicine, fundamental optics, and nanotechnology are combined and result in the development of biomedical optical chips. Silk fibers or synthetic bioabsorbable polymers are the main light-guiding components. In this work, an advanced concept of integrated bio-optics is proposed, which is based on bioinspired peptide optical materials exhibiting wide optical transparency, nonlinear and electrooptical properties, and effective passive and active waveguiding. Developed new technology combining bottom-up controlled deposition of peptide planar wafers of a large area and top-down focus ion beam lithography provides direct fabrication of peptide optical integrated circuits. Finding a deep modification of peptide optical properties by reconformation of biological secondary structure from native phase to ß-sheet architecture is followed by the appearance of visible fluorescence and unexpected transition from a native passive optical waveguiding to an active one. Original biocompatibility, switchable regimes of waveguiding, and multifunctional nonlinear optical properties make these new peptide planar optical materials attractive for application in emerging technology of lab-on-biochips, combining biomedical photonic and electronic circuits toward medical diagnosis, light-activated therapy, and health monitoring.