Lanthanide Bioinorganic Chemistry

The backsides of leaves obtained from plants found on the San José State University campus grounds were pressed onto an ammonium mineral salts medium (ATCC medium: 784 AMS) that either lacked (left side) or contained (right side) 20 µM LaCl3. They were then incubated at room temperature for 1 week. In testing some but not all leaves, the addition of La3+ allowed more methanol-using bacteria (pink) to grow. Recent work has suggested that a particular enzyme in these methanol-using bacteria requires lanthanides.1

The recent discovery and crystallization of a rare earth element-dependent methanol dehydrogenase enzyme has inspired our group to investigate the active site, which is composed of a lanthanide cation and a pyrroloquinoline quinone (PQQ) cofactor.2 We have characterized the active site using DFT methods to understand the electronic structure of both the cerium cation and the PQQ cofactor.3 Through the synthesis of PQQ surrogates we have also explored the electronic structure and electrochemical properties of the cofactor.4 We expect that understanding of the unique electronics of the active site will allow us to prepare new lanthanide-based dehydrogenation catalysts.

            

References

  1. Reproduced from: Skovran, E.; Martinez-Gomez, N. C. Science 2015348, 862.
  2. Pol, A.; Barends, T. R. M.; Dietl, A.; Khadem, A. F.; Eygensteyn, J.; Jetten, M. S. M.; Op den Camp, H. J. M. Environ. Microbiol. 2014, 16, 255.
  3. Bogart, J. A.; Lewis, A. J.; Schelter, E. J. Chem-Eur J. 2015, 21, 1743.
  4. Dorfner, W. L.; Carroll, P. J.; Schelter, E. J. Org. Lett. 2015, 17, 1850.