Time Resolved Infrared Spectroscopy: Kinetic Studies of Weakly Binding Ligands in an Iron–Iron Hydrogenase Model Compound

2012 ◽  
Vol 51 (13) ◽  
pp. 7362-7369 ◽  
Author(s):  
Sohail Muhammad ◽  
Salvador Moncho ◽  
Edward N. Brothers ◽  
Marcetta Y. Darensbourg ◽  
Donald J. Darensbourg ◽  
...  
2016 ◽  
Vol 2 (1) ◽  
pp. e1501014 ◽  
Author(s):  
René Becker ◽  
Saeed Amirjalayer ◽  
Ping Li ◽  
Sander Woutersen ◽  
Joost N. H. Reek

The transition from a fossil-based economy to a hydrogen-based economy requires cheap and abundant, yet stable and efficient, hydrogen production catalysts. Nature shows the potential of iron-based catalysts such as the iron-iron hydrogenase (H2ase) enzyme, which catalyzes hydrogen evolution at rates similar to platinum with low overpotential. However, existing synthetic H2ase mimics generally suffer from low efficiency and oxygen sensitivity and generally operate in organic solvents. We report on a synthetic H2ase mimic that contains a redox-active phosphole ligand as an electron reservoir, a feature that is also crucial for the working of the natural enzyme. Using a combination of (spectro)electrochemistry and time-resolved infrared spectroscopy, we elucidate the unique redox behavior of the catalyst. We find that the electron reservoir actively partakes in the reduction of protons and that its electron-rich redox states are stabilized through ligand protonation. In dilute sulfuric acid, the catalyst has a turnover frequency of 7.0 × 104s−1at an overpotential of 0.66 V. This catalyst is tolerant to the presence of oxygen, thereby paving the way for a new generation of synthetic H2ase mimics that combine the benefits of the enzyme with synthetic versatility and improved stability.


2020 ◽  
Vol 22 (45) ◽  
pp. 26459-26467
Author(s):  
Jessica L. Klocke ◽  
Tilman Kottke

Flavin photoreduction in H2O is elucidated by developing a quantum cascade laser setup for time-resolved infrared spectroscopy on irreversible reactions.


2019 ◽  
Vol 33 (1) ◽  
pp. 1029-1033 ◽  
Author(s):  
Daniel Hallinan ◽  
Maria Grazia De Angelis ◽  
Marco Giacinti Baschetti ◽  
Giulio Sarti ◽  
Yossef A. Elabd

2021 ◽  
Vol 120 (3) ◽  
pp. 8a-9a
Author(s):  
Brennan Ashwood ◽  
Paul J. Sanstead ◽  
Qing Dai ◽  
Chuan He ◽  
Andrei Tokmakoff

1999 ◽  
Vol 274 (9) ◽  
pp. 5508-5513 ◽  
Author(s):  
Frithjof von Germar ◽  
Asier Galán ◽  
Oscar Llorca ◽  
Jose L. Carrascosa ◽  
Jose M. Valpuesta ◽  
...  

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