Prof. Daniel T. Gryko from the Institute of Organic Chemistry of the Polish Academy of Sciences (ICHO PAN) in Warsaw, winner of many Foundation for Polish Science (FNP) programs, discovered how long-range electron transfer can occur, along with his collaborators from the Institute – Prof. Agnieszka Szumna (winner of FNP POMOST), Dr. Olga Staszewska-Krajewska, and Dr. Hanna Jędrzejewska – and colleagues from California: Prof. Harry B. Gray from the California Institute of Technology and Prof. Valentine Vullev from the University of California, Riverside. The first author of the paper is Rafał Orłowski from ICHO PAN. The discovery was published in the prestigious journal “Proceedings of the National Academy of Sciences of the USA” (PNAS).
Long-range electron transfer pervades biology, chemistry, and engineering as it is critical for life-sustaining processes, chemical transformations, energy conversion, along with electronic and photonic technologies. Elucidating what governs the rate of electron transfer is not only of great importance for understanding energy flow in biology but can also help in the design and construction of electronic devices.
Prof. Gryko and colleagues discovered ultrafast electron transfer (ET) from donor to acceptor, connected by a system of 20 covalent bonds. Although such large distances between chromophores prevent ET, the scientists observed picosecond ET processes with quantum yields whose kinetics are not greatly affected by reducing the number of amino acids in the linker. A combination of NMR, circular dichroism, and quantum mechanical calculations reveals that intramolecular hydrogen bonds bring the donor (corrole) and acceptor (perylenediimide) closer together in a “scorpion-shaped” molecular architecture, thereby enabling electron transfer. This revolutionary result demonstrates that short peptides – containing just four amino acid moieties – provide a hydrogen bonding network that can mediate electron transfer with extremely high efficiency. This work not only changes the perspective on the design of molecules in which electron transfer occurs but also suggests structural motifs that mediate ET in proteins.
Prof. Gryko is the director of the ICHO PAN. His main scientific interests include the chemistry of porphyrins, especially corroles, which are organic dyes with numerous applications. He received the FNP MASTER professorial grant in 2013. Moreover, he twice won a grant in the FNP TEAM program. In 2017, he was awarded the FNP Prize, which is considered the most important Polish scientific award.
Prof. Agnieszka Szumna from the ICHO PAN is the recipient of many prestigious scientific grants. In 2012, she won the FNP POMOST program (return grants module) implemented by the FNP from the funds of the Operational Program Innovative Economy, under which the FNP awarded grants for conducting research to scientists who raise small children. Thanks to the funding, Prof. Szumna implemented a project entitled “Novel chiral nanospaces for molecular confinement” and established her own research group at the ICHO PAN.
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