J-coupling

J-coupling (also called indirect dipole dipole coupling) is the coupling between two nuclear spins due to the influence of bonding electrons on the magnetic field running between the two nuclei. J-coupling contains information about dihedral angles which can be estimated using Karplus equation.

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Discovery

In October 1951, EL Hahn and D.E. Maxwell reported a spin echo experiment which indicates the existence of an interaction between two protons in dichloroacetaldehyde. In the echo experiment, two short, intent pulses of radiofrequency are applied to spin ensemble at the nuclear resonance condition and are separated by time interval of τ. The echo appears with a given maximum amplitude at time 2τ. For each setting of τ, the maximum of the echo signal is measured and plotted as a function of τ. If the spin ensemble consists of magnetic moment, a monotonic decay in the echo envelope is obtained. In Hahn-Maxwell experiment, the decay was modulated by two frequencies: one frequency was in correspondence with the difference in chemical shift between two non equivalent spins and a second frequency, J, that was smaller and independent of magnetic field strength. (J/2π = 0.7 cycle per second)

Such interaction came as a great surprise. The direct interaction between two magnetic dipole is dependent on the relative position of two nuclei in such a way that when averaged on all various orientation of the molecule it equals to zero.

In November 1951, NF Ramsey and EM Purcell, proposed a mechanism that explained the observation and gave rise to an interaction of the form I₁.I₂. The mechanism is the magnetic interaction between each nucleus and the electron spin of its own atom together with the exchange coupling of the electron spins with each other.

In 1990s, direct evidence has been found for the presence of J-couplings between magnetically active nuclei on both sides of the hydrogen bond.^[1][2]Initially, it was surprising to observe such couplings across hydrogen bonds since we usually associate J-couplings with the presence of purely covalent bonds. However, it is now well established that the H-bond J-couplings follow the same electron-mediated polarization mechanism as their covalent counterparts.^[3]

J-coupling Hamiltonian

The hamiltonian of a molecular system may be taken as:

H = D₁ +D₂ +D₃.

D₁ = electron orbital-orbital, spin-orbital, spin-spin and electron spin-external field interactions

D₂ = magnetic interactions between nuclear spin and electron spin

D₃ = direct interaction of nuclei with each other

for a singlet molecular state and frequent molecular collisions, D₁ and D₃ are almost zero. The full form of J-coupling interaction between spins I_j and I_k on the same molecule is:

H = 2π I_j. J_jk. I_k

where J_jk is the j-coupling tensor, a 3x3 real matrix. It depends on molecular orientation. In isotropic liquid it reduces to a number, so called scalar coupling. In 1D NMR, scalar coupling leads to oscillations in FID as well as splitting of lines in the spectrum.

Measurement of J-coupling

The Quantitative J correlation developed by Ad Bax et al. in 1994 is commonly the method of choice for accurate measurements of J couplings.^[4][5]

References

Classics:

• E. L. Hahn and D. E. Maxwell (1951). "Chemical Shift and Field Independent Frequency Modulation of the Spin Echo Envelope". Physical Review 84 (6): 1246. doi:10.1103/PhysRev.84.1246.
• N. F. Ramsey and E. M. Purcell (1952). "Interactions between Nuclear Spins in Molecules". Physical Review 85 (1): 143. doi:10.1103/PhysRev.85.143.

Other references:

1. ^ P. Blake, B. Lee, M. Summers, M. Adams, J.-B. Park, Z. Zhou and A. Bax (1992). "Quantitative measurement of small through-hydrogen-bond and ‘through-space’ ¹H-¹¹³Cd and ¹H-¹⁹⁹Hg J couplings in metal-substituted rubredoxin from Pyrococcus furiosus". Journal of Biomolecular NMR 2 (5): 527-533. doi:10.1007/BF02192814.
2. ^ P. R. Blake, J. B. Park, M. W. W. Adams and M. F. Summers (1992). "Novel observation of NH--S(Cys) hydrogen-bond-mediated scalar coupling in cadmium-113 substituted rubredoxin from Pyrococcus furiosus". J. Am. Chem. Soc. 114 (12): 4931-4933. doi:10.1021/ja00038a084.
3. ^ Andrew J. Dingley, Florence Cordier and Stephan Grzesiek (2001). "An introduction to hydrogen bond scalar couplings". Concepts in Magnetic Resonance 13 (2): 103 - 127. doi:10.1002/1099-0534(2001)13:2%3C103::AID-CMR1001%3E3.0.CO;2-M.
4. ^ E. de Alba and N. Tjandra (2006). "Interference between Cross-correlated Relaxation and the Measurement of Scalar and Dipolar Couplings by Quantitative J". Journal of Biomolecular NMR 35 (1): 1-16. doi:10.1007/s10858-006-0028-4.
5. ^ G. W. Vuister and A. Bax (1993). "Quantitative J correlation: a new approach for measuring homonuclear three-bond J(HNHα) coupling constants in ¹⁵N-enriched proteins". J. Am. Chem. Soc. 115 (17): 7772-7777. doi:10.1021/ja00070a024.

See also

• Magnetic dipole-dipole interaction (dipolar coupling)
• Residual dipolar coupling
• Exclusive correlation spectroscopy (ECOSY)