ABSTRACT:
This project aims at the development of environmentally friendly devices, based on biomolecules, for the conversion of light into electrical energy. Biomolecular solar cells offer many advantages, such as perfect control over both the formation of molecular aggregates and the directionality of electron transfer (ET), essential for improving the efficiency of photoconversion. However, the use of biomolecules in this area is hampered by their poor stability outside the natural environment. The biomolecules herein proposed are short biopolymers (peptides) that possess well-defined helical structures, stable even under extreme conditions of temperature or electrochemical stress and able to effectively mediate ET. The characteristics of our "bionic peptides" stem from their components: natural, non-coded and sterically hindered α-amino acids. By exploiting the stability of their 3D structure, the proposed systems will be used as molecular diodes, directing the current from the light-harvesting dye to the electrode efficiently, disfavoring the charge recombination process, thanks to the dipole moment of the peptide helix. We will test a variety of porphyrin probes, porphyrin-carotene dyads, different anchoring surfaces (TiO2, graphene) and also evaluate an innovative self-assembling biomolecular system capable of converting sunlight into energy with very promising efficiencies (Angew.Chem. Int. Ed. 2019, 58, 7308). The research fellow involved in this project will have the opportunity to expand his/her skills in various fields, as he/she will carry out his/her work in all the research groups of the team, synthesizing the biomolecular systems and carrying out the spectroscopic characterization at DiSC; assembling the dye sensitized solar cells (DSSCs) at DII, and testing their efficiency at DEI.

PUBBLICAZIONI:

1. A. Bertran, S. Ciuti, D. Panariti, C.J. Rogers, H. Wang, J. Zhao, C.R. Timmel, M. Gobbo, A. Barbon, M. Di Valentin, A.M. Bowen, I2BODIPY as a new photoswitchable spin label for light-induced pulsed EPR dipolar spectroscopy exploiting magnetophotoselection, Phys. Chem. Chem. Phys. (2024), Accepted
2. A. Bertran, M.D. Zotti, C.R. Timmel, M.D. Valentin, A.M. Bowen, Determining and controlling conformational information from orientationally selective light-induced triplet–triplet electron resonance spectroscopy for a set of bis-porphyrin rulers, Phys. Chem. Chem. Phys. 26 (2024) 2589–2602. https://doi.org/10.1039/D3CP03454B.
3. S. Ciuti, A. Carella, A. Lucotti, M. Tommasini, A. Barbon, M. Di Valentin, Insights into the phototautomerism of free-base 5, 10, 15, 20-tetrakis(4-sulfonatophenyl) porphyrin, Photochemical & Photobiological Sciences 22 (2023) 1825–1838. https://doi.org/10.1007/s43630-023-00413-5.
4. A. Carella, S. Ciuti, H.T.A. Wiedemann, C.W.M. Kay, A. van der Est, D. Carbonera, A. Barbon, P.K. Poddutoori, M. Di Valentin, The electronic structure and dynamics of the excited triplet state of octaethylaluminum(III)-porphyrin investigated with advanced EPR methods, Journal of Magnetic Resonance 353 (2023) 107515. https://doi.org/10.1016/j.jmr.2023.107515.
5. A. Bertran, L. Morbiato, J. Sawyer, C. Dalla Torre, D.J. Heyes, S. Hay, C.R. Timmel, M. Di Valentin, M. De Zotti, A.M. Bowen, Direct Comparison between Förster Resonance Energy Transfer and Light-Induced Triplet–Triplet Electron Resonance Spectroscopy, J. Am. Chem. Soc. 145 (2023) 22859–22865. https://doi.org/10.1021/jacs.3c04685.
6. A. Jozeliu̅naitė, A. Neniškis, A. Bertran, A.M. Bowen, M. Di Valentin, S. Raišys, P. Baronas, K. Kazlauskas, L. Vilčiauskas, E. Orentas, Fullerene Complexation in a Hydrogen-Bonded Porphyrin Receptor via Induced-Fit: Cooperative Action of Tautomerization and C–H···π Interactions, J. Am. Chem. Soc. 145 (2023) 455–464. https://doi.org/10.1021/jacs.2c10668.
7. S. Ciuti, J. Toninato, A. Barbon, N. Zarrabi, P.K. Poddutoori, A. van der Est, M. Di Valentin, Solvent dependent triplet state delocalization in a co-facial porphyrin heterodimer, Physical Chemistry Chemical Physics 24 (2022) 30051–30061. https://doi.org/10.1039/D2CP04291F.
8. A. Bertran, L. Morbiato, S. Aquilia, L. Gabbatore, M. De Zotti, C.R. Timmel, M. Di Valentin, A.M. Bowen, Erythrosin B as a New Photoswitchable Spin Label for Light-Induced Pulsed EPR Dipolar Spectroscopy, Molecules 27 (2022) 7526. https://doi.org/10.3390/MOLECULES27217526/S1.
9. S. Ciuti, A. Agostini, A. Barbon, M. Bortolus, H. Paulsen, M. Di Valentin, D. Carbonera, Magnetophotoselection in the Investigation of Excitonically Coupled Chromophores: The Case of the Water-Soluble Chlorophyll Protein, Molecules 27 (2022) 3654. https://doi.org/10.3390/MOLECULES27123654.
10. J. Niklas, A. Agostini, D. Carbonera, M. Di Valentin, W. Lubitz, Primary donor triplet states of Photosystem I and II studied by Q-band pulse ENDOR spectroscopy, Photosynth Res 152 (2022) 213–234. https://doi.org/10.1007/s11120-022-00905-y.
11. A. Bertran, A. Barbon, A.M. Bowen, M. Di Valentin, Light-induced pulsed dipolar EPR spectroscopy for distance and orientation analysis, Methods in Enzymology 666 (2022) 171–231. https://doi.org/10.1016/BS.MIE.2022.02.012.
12. S. Ciuti, A. Barbon, M. Bortolus, A. Agostini, E. Bergantino, C. Martin, M. Di Valentin, D. Carbonera, Neuroglobin Provides a Convenient Scaffold to Investigate the Triplet-State Properties of Porphyrins by Time-Resolved EPR Spectroscopy and Magnetophotoselection, Applied Magnetic Resonance (2021) 1–12. https://doi.org/10.1007/S00723-021-01421-3

ATTIVITA'