Nuclear Overhauser effect

The Nuclear Overhauser Effect (NOE) is the transfer of nuclear spin polarization from one nuclear spin population to another via cross-relaxation. It is a common phenomenon observed by nuclear magnetic resonance (NMR) spectroscopy. The theoretical basis for the NOE was described and experimentally verified by Anderson and Freeman in 1962.[1] The NOE is an extension of the seminal work of American physicist Albert Overhauser who in 1953 proposed that nuclear spin polarization could be enhanced by the microwave irradiation of the conduction electrons in certain metals.[2] The general Overhauser effect was first demonstrated experimentally by T. R. Carver and C. P. Slichter, also in 1953.[3] Another early explication and experimental observation of the NOE was by Kaiser in 1963 [4] in an NMR experiment where the spin polarization was transferred from one population of nuclear spins to another, rather than from electrons spins to nuclear spins. However, the theoretical basis and the applicable Solomon equations[5] had already been published by Ionel Solomon in 1955[6].

Subsequent to its discovery, the NOE was shown to be highly useful in NMR spectroscopy for characterizing and refining organic chemical structures.[7] In this application, the NOE differs from the application of spin-spin coupling in that the NOE occurs through space, not through chemical bonds. Thus, atoms that are in close proximity to each other can give a NOE, whereas spin coupling is observed only when the atoms are connected by 2-3 chemical bonds. The inter-atomic distances derived from the observed NOE can often help to confirm a precise molecular conformation, i.e. the three-dimensional structure of a molecule. In 2002, Kurt Wüthrich was awarded the Nobel Prize in Chemistry for demonstrating that the NOE could be exploited using two-dimensional NMR spectroscopy to determine the three-dimensional structures of biological macromolecules in solution (see: "The Nobel Prize in Chemistry 2002". http://nobelprize.org/nobel_prizes/chemistry/laureates/2002/. Retrieved 201103324.  ).

Some examples of two-dimensional NMR experimental techniques exploiting the NOE include:

References

  1. ^ Anderson, W. A.; Freeman, R. (1962). "Influence of a Second Radiofrequency Field on High-Resolution Nuclear Magnetic Resonance Spectra". The Journal of Chemical Physics 37 (1): 411–5. Bibcode 1962JChPh..37...85A. doi:10.1063/1.1732980. http://link.aip.org/link/?JCPSA6/37/85/1. 
  2. ^ Overhauser, Albert W. (1953). "Polarization of Nuclei in Metals". Physical Review 92 (2): 411–5. Bibcode 1953PhRv...92..411O. doi:10.1103/PhysRev.92.411. http://link.aps.org/doi/10.1103/PhysRev.92.411. Retrieved 2009-01-20. 
  3. ^ Carver, T. R.; Slichter, C. P. (1953). "Polarization of Nuclear Spins in Metals". Physical Review 92 (1): 212–213. Bibcode 1953PhRv...92..212C. doi:10.1103/PhysRev.92.212.2. http://link.aps.org/doi/10.1103/PhysRev.92.212.2. 
  4. ^ Kaiser, R. (1962). "Use of the Nuclear Overhauser Effect in the Analysis of High‐Resolution Nuclear Magnetic Resonance Spectra". The Journal of Chemical Physics 39 (1): 2435. Bibcode 1962JChPh..37...85A. doi:10.1063/1.1734045. http://link.aip.org/link/?JCPSA6/37/85/1. 
  5. ^ http://chem.iitm.ac.in/professordetails/chandrakumar/msc_lectures/MSc_Lecture_Notes/The_Solomon_equations.pdf The Solomon Equations and NOE
  6. ^ I. Solomon. Relaxation Processes in a System of Two Spins. Phys. Rev. 99, 559 (1955)
  7. ^ Anet, F. A. L.; Bourn, A. J. R (1965). "Nuclear Magnetic Resonance Spectral Assignments from Nuclear Overhauser Effects". Journal of the American Chemical Society 87 (22): 5250–5251. doi:10.1021/ja00950a048. http://pubs.acs.org/doi/abs/10.1021/ja00950a048.