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11.07.2022 - 15.07.2022, Celeste Hotel, on UCF main campus, Orlando, Florida
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MUST2022 Conference- succesfully concluded
New scientific highlights- by MUST PIs Chergui and Richardson
FELs of Europe prize for Jeremy Rouxel- “Development or innovative use of advanced instrumentation in the field of FELs”
Ruth Signorell wins Doron prizefor pioneering contributions to the field of fundamental aerosol science
New FAST-Fellow Uwe Thumm at ETH- lectures on Topics in Femto- and Attosecond Science
International Day of Women and Girls in Science- SSPh asked female scientists about their experiences
New scientific highlight- by MUST PIs Milne, Standfuss and Schertler
EU XFEL Young Scientist Award for Camila Bacellar,beamline scientist and group leader of the Alvra endstation at SwissFEL
Prizes for Giulia Mancini and Rebeca Gomez CastilloICO/IUPAP Young Scientist Prize in Optics & Ernst Haber 2021
Nobel Prize in Chemistry awarded to RESOLV Member Benjamin List- for the development of asymmetric organocatalysis
NCCR MUST at Scientifica 2021- Lightning, organic solar cells, and virtual molecules
#NCCRWomen- NCCR MUST celebrates 50 years women’s right to vote in Switzerland
Kick-Off dynaMENT Mentoring for Women in Natural Sciences- with Ursula Keller as plenary speaker

Sequential Proton Coupled Electron Transfer (PCET)

March 23, 2016

Dynamics Observed over 8 Orders of Magnitude in Time

Charge transfer mechanisms lay at the heart of chemistry and biochemistry. Proton coupled electron transfers (PCET) are central in biological processes such as photosynthesis and in the respiratory chain, where they mediate long-range charge transfers. These mechanisms are normally difficult to harness experimentally due to the intrinsic complexity of the associated biological systems. Metal-peptide cations experience both electron and proton transfers upon photoexcitation, proving an amenable model system to study PCET.

The authors report on a time-resolved experiment designed to follow this dual charge transfer kinetics in [HG3W+Ag]+ (H = histidine, G = glycine, W = tryptophan) on time scales ranging from femtoseconds to milliseconds. While electron transfer completes in less than 4 ps, it triggers a proton transfer lasting over hundreds of microseconds.

Molecular dynamics simulations conducted in the group of Markus Meuwly show that the rate of formation of a PT-reactive structure (H-bond between indoleNH on tryptophan and imidazoleN on histidine) strongly depends on the initial peptide structure. In particular, while this rate is in the nanosecond range when starting from an extended conformation, it is considerably longer when starting from compact peptide conformations as in the initial metal complex. In other words, molecular dynamics simulations show that conformational dynamic plays an important role in slowing down this reaction.

The experimental study covers 8 orders of magnitude in time and shows that the 4 ps electron transfer induces a proton transfer hundreds of microseconds later. The combined experimental and computational approach provides a view of PCET as a single phenomenon despite its very wide time-domain span.

Reference: MacAleese, L., S. Hermelin, K. El Hage, P. Chouzenoux, A. Kulesza, R. Antoine, L. Bonacina, M. Meuwly, J.-P. Wolf and P. Dugourd (2016). Sequential Proton Coupled Electron Transfer (PCET): Dynamics Observed over 8 Orders of Magnitude in Time. J. Am. Chem. Soc. (10.1021/jacs.5b12587) MacAleese-2016 (807 KB).
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