Nature's Polyoxometalate Chemistry: X-ray Structure of the Mo Storage Protein Loaded with Discrete Polynuclear Mo-O Clusters

Kowalewski B, Poppe J, Demmer U, Warkentin E, Dierks T, Ermler U, Schneider K (2012)
Journal of the American Chemical Society 134(23): 9768-9774.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
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Abstract / Bemerkung
Some N-2-fixing bacteria prolong the functionality of nitrogenase in molybdenum starvation by a special Mo storage protein (MoSto) that can store more than 100 Mo atoms. The presented 1.6 angstrom X-ray structure of MoSto from Azotobacter vinelandii reveals various discrete polyoxomolybdate clusters, three covalently and three noncovalently bound Mo-8, three Mo5-7, and one Mo-3 clusters, and several low occupied, so far undefinable clusters, which are embedded in specific pockets inside a locked cage-shaped (alpha beta)(3) protein complex. The structurally identical Mo-8 clusters (three layers of two, four, and two MoOn octahedra) are distinguishable from the [Mo8O26](4-) cluster formed in acidic solutions by two displaced MoOn octahedra implicating three kinetically labile terminal ligands. Stabilization in the covalent Mo-8 cluster is achieved by Mo bonding to His alpha 156-N-epsilon 2 and Glu alpha 129-O-epsilon 1. The absence of covalent protein interactions in the noncovalent Mo-8 cluster is compensated by a more extended hydrogen-bond network involving three pronounced histidines. One displaced MoOn octahedron might serve as nucleation site for an inhomogeneous Mo5-7 cluster largely surrounded by bulk solvent. In the Mo-3 cluster located on the 3-fold axis, the three accurately positioned His140-N-epsilon 2 atoms of the alpha subunits coordinate to the Mo atoms. The formed polyoxomolybdate clusters of MoSto, not detectable in bulk solvent, are the result of an interplay between self- and protein-driven assembly processes that unite inorganic supramolecular and protein chemistry in a host-guest system. Template, nucleation/protection, and catalyst functions of the polypeptide as well as perspectives for designing new clusters are discussed.
Erscheinungsjahr
2012
Zeitschriftentitel
Journal of the American Chemical Society
Band
134
Ausgabe
23
Seite(n)
9768-9774
ISSN
0002-7863
eISSN
1520-5126
Page URI
https://pub.uni-bielefeld.de/record/2517966

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Kowalewski B, Poppe J, Demmer U, et al. Nature's Polyoxometalate Chemistry: X-ray Structure of the Mo Storage Protein Loaded with Discrete Polynuclear Mo-O Clusters. Journal of the American Chemical Society. 2012;134(23):9768-9774.
Kowalewski, B., Poppe, J., Demmer, U., Warkentin, E., Dierks, T., Ermler, U., & Schneider, K. (2012). Nature's Polyoxometalate Chemistry: X-ray Structure of the Mo Storage Protein Loaded with Discrete Polynuclear Mo-O Clusters. Journal of the American Chemical Society, 134(23), 9768-9774. doi:10.1021/ja303084n
Kowalewski, B., Poppe, J., Demmer, U., Warkentin, E., Dierks, T., Ermler, U., and Schneider, K. (2012). Nature's Polyoxometalate Chemistry: X-ray Structure of the Mo Storage Protein Loaded with Discrete Polynuclear Mo-O Clusters. Journal of the American Chemical Society 134, 9768-9774.
Kowalewski, B., et al., 2012. Nature's Polyoxometalate Chemistry: X-ray Structure of the Mo Storage Protein Loaded with Discrete Polynuclear Mo-O Clusters. Journal of the American Chemical Society, 134(23), p 9768-9774.
B. Kowalewski, et al., “Nature's Polyoxometalate Chemistry: X-ray Structure of the Mo Storage Protein Loaded with Discrete Polynuclear Mo-O Clusters”, Journal of the American Chemical Society, vol. 134, 2012, pp. 9768-9774.
Kowalewski, B., Poppe, J., Demmer, U., Warkentin, E., Dierks, T., Ermler, U., Schneider, K.: Nature's Polyoxometalate Chemistry: X-ray Structure of the Mo Storage Protein Loaded with Discrete Polynuclear Mo-O Clusters. Journal of the American Chemical Society. 134, 9768-9774 (2012).
Kowalewski, Björn, Poppe, Juliane, Demmer, Ulrike, Warkentin, Eberhard, Dierks, Thomas, Ermler, Ulrich, and Schneider, Klaus. “Nature's Polyoxometalate Chemistry: X-ray Structure of the Mo Storage Protein Loaded with Discrete Polynuclear Mo-O Clusters”. Journal of the American Chemical Society 134.23 (2012): 9768-9774.

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