Karplus equation

Graph of the Karplus relation J_HH(φ) = 12 cos^{^2}φ - cosφ+2 obtained for ethane derivatives ^[1]

The Karplus equation, named after Martin Karplus, describes the correlation between ³J-coupling constants and dihedral torsion angles in nuclear magnetic resonance spectroscopy:^[2]

J(\phi )=A\cos \,2\phi +B\cos \,\phi +C

where J is the ³J coupling constant, $\phi$ is the dihedral angle, and A, B, and C are empirically derived parameters whose values depend on the atoms and substituents involved.^[3] The relationship may be expressed in a variety of equivalent ways e.g. involving cos 2φ rather than cos² φ —these lead to different numerical values of A, B, and C but do not change the nature of the relationship.

The relationship is used for ³J_H,H coupling constants. The superscript "3" indicates that a ¹H atom is coupled to another ¹H atom three bonds away, via H-C-C-H bonds. (Such H atoms bonded to neighbouring carbon atoms are termed vicinal).^[4] The magnitude of these couplings are generally smallest when the torsion angle is close to 90° and largest at angles of 0 and 180°.

This relationship between local geometry and coupling constant is of great value throughout nuclear magnetic resonance spectroscopy and is particularly valuable for determining backbone torsion angles in protein NMR studies.

References

^ Minch, M. J. (1994). "Orientational Dependence of Vicinal Proton-Proton NMR Coupling Constants: The Karplus Relationship". Concepts in Magnetic Resonance. 6: 41–56. doi:10.1002/cmr.1820060104.
^ Dalton, Louisa (2003-12-22). "Karplus Equation". Chemical & Engineering News. 81 (51): 37. doi:10.1021/cen-v081n036.p037.
^ Karplus, Martin (1959). "Contact Electron-Spin Coupling of Nuclear Magnetic Moments". J. Chem. Phys. 30 (1): 11–15. Bibcode:1959JChPh..30...11K. doi:10.1063/1.1729860.
^ Karplus, Martin (1963). "Vicinal Proton Coupling in Nuclear Magnetic Resonance". J. Am. Chem. Soc. 85 (18): 2870–2871. doi:10.1021/ja00901a059.

External links

[Minch1994-1] Minch, M. J. (1994). "Orientational Dependence of Vicinal Proton-Proton NMR Coupling Constants: The Karplus Relationship". Concepts in Magnetic Resonance. 6: 41–56. doi:10.1002/cmr.1820060104.

[Dalton2003-2] Dalton, Louisa (2003-12-22). "Karplus Equation". Chemical & Engineering News. 81 (51): 37. doi:10.1021/cen-v081n036.p037.

[Karplus1959-3] Karplus, Martin (1959). "Contact Electron-Spin Coupling of Nuclear Magnetic Moments". J. Chem. Phys. 30 (1): 11–15. Bibcode:1959JChPh..30...11K. doi:10.1063/1.1729860.

[Karplus1963-4] Karplus, Martin (1963). "Vicinal Proton Coupling in Nuclear Magnetic Resonance". J. Am. Chem. Soc. 85 (18): 2870–2871. doi:10.1021/ja00901a059.

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