Letters to Nature

Nature 433, 610-613 (10 February 2005) | doi:10.1038/nature03298; Received 14 October 2004; Accepted 14 December 2004

Synthesis of the H-cluster framework of iron-only hydrogenase

Cédric Tard1, Xiaoming Liu1, Saad K. Ibrahim1, Maurizio Bruschi3, Luca De Gioia3, Siân C. Davies1, Xin Yang4, Lai-Sheng Wang4, Gary Sawers2 & Christopher J. Pickett1

  1. Department of Biological Chemistry,
  2. Department of Molecular Microbiology, John Innes Centre, Norwich NR4 7UH, UK
  3. Department of Biotechnology and Biosciences, University of Milano-Bicocca, Piazza della Scienza 2, 20126-Milan, Italy
  4. Department of Physics, Washington State University, 2710 University Drive, Richland, and WR Wiley Environmental Science Laboratory and Chemical Sciences Division, Pacific Northwest National Laboratory, PO Box 999, MS K8-88, Richland, Washington 99352, USA

Correspondence to: Christopher J. Pickett1 Correspondence and requests for materials should be addressed to C.J.P. (Email: chris.pickett@bbsrc.ac.uk).
Crystal structure data for B have been deposited at the Cambridge Crystallographic Data Centre, and allocated the deposition number CCDC 256735.

The metal-sulphur active sites of hydrogenases catalyse hydrogen evolution or uptake at rapid rates. Understanding the structure and function of these active sites—through mechanistic studies of hydrogenases1, 2, 3, 4, synthetic assemblies5, 6, 7, 8, 9, 10, 11, 12 and in silico models13, 14, 15—will help guide the design of new materials for hydrogen production or uptake16. Here we report the assembly of the iron-sulphur framework of the active site of iron-only hydrogenase (the H-cluster), and show that it functions as an electrocatalyst for proton reduction. Through linking of a di-iron subsite to a {4Fe4S} cluster, we achieve the first synthesis of a metallosulphur cluster core involved in small-molecule catalysis. In addition to advancing our understanding of the natural biological system, the availability of an active, free-standing analogue of the H-cluster may enable us to develop useful electrocatalytic materials for application in, for example, reversible hydrogen fuel cells. (Platinum is currently the preferred electrocatalyst for such applications, but is expensive, limited in availability and, in the long term, unsustainable17.)


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