TY - JOUR

T1 - Surprising absence of strong homonuclear coupling at low magnetic field explored by two-field nuclear magnetic resonance spectroscopy

AU - Zhukov, Ivan V.

AU - Kiryutin, Alexey S.

AU - Wang, Ziqing

AU - Zachrdla, Milan

AU - Yurkovskaya, Alexandra V.

AU - Ivanov, Konstantin L.

AU - Ferrage, Fabien

N1 - Funding Information: Financial support. This work has been supported by the Russian Foundation for Basic Research (RFBR; grant nos. 19-29-10028 and 19-33-90251). Ivan V. Zhukov acknowledges support from the French embassy in the Russian Federation in the framework of the Ostrogradsky Fellowship (grant no. 933824A). Publisher Copyright: © Author(s) 2020

PY - 2020

Y1 - 2020

N2 - Strong coupling of nuclear spins, which is achieved when their scalar coupling 2πJ is greater than or comparable to the difference 1ω in their Larmor precession frequencies in an external magnetic field, gives rise to efficient coherent longitudinal polarization transfer. The strong coupling regime can be achieved when the external magnetic field is sufficiently low, as 1ω is reduced proportional to the field strength. In the present work, however, we demonstrate that in heteronuclear spin systems these simple arguments may not hold, since heteronuclear spin-spin interactions alter the 1ω value. The experimental method that we use is two-field nuclear magnetic resonance (NMR), exploiting sample shuttling between the high field, at which NMR spectra are acquired, and the low field, where strong couplings are expected and at which NMR pulses can be applied to affect the spin dynamics. By using this technique, we generate zero-quantum spin coherences by means of a nonadiabatic passage through a level anticrossing and study their evolution at the low field. Such zero-quantum coherences mediate the polarization transfer under strong coupling conditions. Experiments performed with a 13C-labeled amino acid clearly show that the coherent polarization transfer at the low field is pronounced in the 13C spin subsystem under proton decoupling. However, in the absence of proton decoupling, polarization transfer by coherent processes is dramatically reduced, demonstrating that heteronuclear spin-spin interactions suppress the strong coupling regime, even when the external field is low. A theoretical model is presented, which can model the reported experimental results.

AB - Strong coupling of nuclear spins, which is achieved when their scalar coupling 2πJ is greater than or comparable to the difference 1ω in their Larmor precession frequencies in an external magnetic field, gives rise to efficient coherent longitudinal polarization transfer. The strong coupling regime can be achieved when the external magnetic field is sufficiently low, as 1ω is reduced proportional to the field strength. In the present work, however, we demonstrate that in heteronuclear spin systems these simple arguments may not hold, since heteronuclear spin-spin interactions alter the 1ω value. The experimental method that we use is two-field nuclear magnetic resonance (NMR), exploiting sample shuttling between the high field, at which NMR spectra are acquired, and the low field, where strong couplings are expected and at which NMR pulses can be applied to affect the spin dynamics. By using this technique, we generate zero-quantum spin coherences by means of a nonadiabatic passage through a level anticrossing and study their evolution at the low field. Such zero-quantum coherences mediate the polarization transfer under strong coupling conditions. Experiments performed with a 13C-labeled amino acid clearly show that the coherent polarization transfer at the low field is pronounced in the 13C spin subsystem under proton decoupling. However, in the absence of proton decoupling, polarization transfer by coherent processes is dramatically reduced, demonstrating that heteronuclear spin-spin interactions suppress the strong coupling regime, even when the external field is low. A theoretical model is presented, which can model the reported experimental results.

UR - http://www.scopus.com/inward/record.url?scp=85130981770&partnerID=8YFLogxK

U2 - 10.5194/mr-1-237-2020

DO - 10.5194/mr-1-237-2020

M3 - Article

AN - SCOPUS:85130981770

VL - 1

SP - 237

EP - 246

JO - Magnetic Resonance

JF - Magnetic Resonance

SN - 2699-0016

IS - 2

ER -