NMR Studies of Hydrogen Bond Structure and Dynamics: from Crystals, Liquids, Mesoporous Media to Enzymes

Hans H. Limbach 

Free University Berlin (FUB), Takustr. 3, Berlin 14195, Germany

Abstract
http://userpage.chemie.fu-berlin.de/~limbach

Recent applications of low-temperature liquid and solid state NMR spectroscopy in the study of H-transfer and H-bonding are described. "H-transfer NMR" focuses on the kinetics of H and D transfers in weak hydrogen bonds [1], "H-bond NMR" on strong hydrogen bonds [2]. Using low-temperature NMR methods acid-base interactions in polar solvents can be studied. Dipolar solid state NMR of selected systems provides a link between crystallography and the world of NMR parameters. Applications to mesoporous silica host-guest systems [3], transition metal complexes and nanoparticles [4, 5], poly-L-lysine, as well as enzyme models and enzymes are presented.

I thank for their contribution to this work: G. Buntkowsky, Jena, G. S. Denisov, N. S. Golubev, St. Petersburg, I. Shenderovich, P. Tolstoy, Berlin, B. Chaudret, Toulouse, J. Elguero, R. Claramunt, Madrid, D. Silverman, Gainesville, M. Toney, Davis.

[1] H. H. Limbach, in Enz. of NMR: Suppl. Vol. 9, Wiley 2002, pp. 520. Dynamics of H-Transfer in Liquids and Solids.

[2] H. H. Limbach, G. S. Denisov, N. S. Golubev, in Isotope Effects In Chemistry and Biology, A. Kohen, H. H. Limbach, Eds.; 2005; Chapter 7, pp 193. H-Bond Isotope Effects Studied by NMR.

[3] I. G. Shenderovich, G. Buntkowsky, H. H. Limbach et al., J. Phys. Chem. B. 2003, 107, 11924: Pyridine-15N - a Mobile NMR Sensor for Surface Acidity and Surface Defects of Mesoporous Silica.

[4] J. Matthes, G. Buntkowsky, B. Chaudret, H. H. Limbach et al., J. Am. Chem. Soc. 2004, 126, 8366: Bridging the Gap between Hom. and Het. Catalysis: o/p-H2 Conversion, H-Isotope Scrambling and Hydrogenation of Olefins.

[5] T. Pery, K. Pelzer, G. Buntkowsky, K. Philippot, H. H. Limbach, B. Chaudret., Chem. Phys. Chem. 2005, 6, 605: Direct NMR Evidence for the Presence of Mobile Surface Hydrides on Ru-Nanoparticles.

 

Presentation: invited lecture at 18th Conference on Physical Organic Chemistry, Plenary session, by Hans H. Limbach
See On-line Journal of 18th Conference on Physical Organic Chemistry

Submitted: 2006-04-25 19:05
Revised:   2009-06-07 00:44