Dalton Transactions Blog

The ability of hydrogenase enzymes to reversibly catalyse the reduction of protons to form molecular hydrogen (H₂) has attracted a great deal of research interest. Synthetic mimics of the hydrogenase active site could potentially replace expensive platinum catalysts in hydrogen fuel cells. Currently these mimics are significantly less efficient than the natural enzyme and they are oxygen sensitive. It is thought that by creating a stable peptide based enviroment around the mimic, the stability and efficiency could be improved.

Encapsulating a hydrogenase mimic into a hydrogel causes a restriction in isomerisation after photolysis

Researchers from the Hunt and Ulijn groups at the University of Strathclyde and  the Pickett group from the University of East Anglia have successfully encapsulated a [FeFe]-hydrogenase active site mimic into a dipeptide based hydrogelator. Their research has shown that there is a stark difference in the behaviour of the active site mimic in the gel phase compared to the solution phase. Experiments show that the mimic is significantly more stable in the gel phase and is less senstive to water and UV light which could potentially help to improve catalytic activity.

To find out more, read the full Daltons Transactions article…

David Emslie and colleagues from McMaster University describe the synthesis of a new rigid NSN-donor ligand as well as the preparation of uranium(IV) and uranium(III) complexes using this ligand and a previously prepared NON-donor ligand. A combination of cyclic voltammetry, DFT calculations and Atoms In Molecules calculations were used to compare U–SAR₂ and U–OAr₂ bonding and the results indicated increased covalency in U-SAR₂ bonds that is probably due to the short U-S distances and tight C-S-U angles in the complexes.  This work will aid the advancement of approaches for lanthanide/actinide separation in nuclear fuel reprocessing as well as analytical actinide detection.

Rigid NON- and NSN-ligand complexes of tetravalent and trivalent uranium.

Download the full paper below which is being published as part of an upcoming Dalton Transactions special issue, New Talent: the Americas…

Rigid NON- and NSN-ligand complexes of tetravalent and trivalent uranium: comparison of U–OAr₂ and U–SAr₂ bonding
Balamurugan Vidjayacoumar,  Sougandi Ilango,  Matthew J. Ray,  Terry Chu,  Kristopher B. Kolpin,  Nicholas R. Andreychuk,  Carlos A. Cruz,  David J. H. Emslie,  Hilary A. Jenkins and James F. Britten
Dalton Trans., 2012
DOI: 10.1039/C2DT30247K

You may also find this 2010 Dalton Transactions themed issue on New horizons in organo-f-block chemistry interesting.

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