Radicals serve as a source of polarization in dynamic nuclear polarization, but may also act as polarization sink, in particular at low field. Additionally, if the couplings between the electron spins and different nuclear reservoirs are stronger than any of the reservoirs' couplings to the lattice, radicals can mediate hetero-nuclear polarization transfer. Here, we report radical-enhanced C relaxation in pyruvic acid doped with trityl. Up to 40 K, we find a linear carbon field dependence between 5 mT and 2 T. We model the dependence quantitatively, and find that the presence of trityl accelerates direct hetero-nuclear polarization transfer at low fields, while at higher fields C relaxation is diffusion limited. Measurements of hetero-nuclear polarization transfer up to 600 mT confirm the predicted radical-mediated proton-carbon mixing.
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Prog Nucl Magn Reson Spectrosc
February 2023
NMR Research Centre and Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560012, India. Electronic address:
The scalar couplings that result in the splitting of the signals in the NMR spectrum arise due to the interaction of the nuclear spins, whereby the spin polarization is transmitted through chemical bonds. The interaction strengths depend inter alia on the number of consecutive chemical bonds intervening between the two interacting spins and on the molecular conformation. The pairwise interaction of many spins in a molecule resulting in a complex spectrum poses a severe challenge to analyse the spectrum and hence the determination of magnitudes and signs of homo- and heteronuclear couplings.
View Article and Find Full Text PDFJ Biomol NMR
April 2023
Department of Biochemistry, Molecular Biology & Biophysics, University of Minnesota, 6-155 Jackson Hall, 312 Church St. SE, Minneapolis, MN, 55455, USA.
The nuclear Overhauser effect (NOE) is one of NMR spectroscopy's most important and versatile parameters. NOE is routinely utilized to determine the structures of medium-to-large size biomolecules and characterize protein-protein, protein-RNA, protein-DNA, and protein-ligand interactions in aqueous solutions. Typical [H,H] NOESY pulse sequences incorporate water suppression schemes to reduce the water signal that dominates H-detected spectra and minimize NOE intensity losses due to unwanted polarization exchange between water and labile protons.
View Article and Find Full Text PDFPhys Chem Chem Phys
November 2022
Institute of Biological Interfaces 4, Karlsruhe Institute of Technology, Eggenstein-Leopoldshafen, 76344, Germany.
Radicals serve as a source of polarization in dynamic nuclear polarization, but may also act as polarization sink, in particular at low field. Additionally, if the couplings between the electron spins and different nuclear reservoirs are stronger than any of the reservoirs' couplings to the lattice, radicals can mediate hetero-nuclear polarization transfer. Here, we report radical-enhanced C relaxation in pyruvic acid doped with trityl.
View Article and Find Full Text PDFSaudi J Biol Sci
January 2021
Chemistry of Natural Compounds Department, Pharmaceutical and Drug Industries Research Division, National Research Center, El-Behoos st., Dokki-Cairo 12622, Egypt.
Antibacterial and cytotoxic activities of , fractions and pure compounds were evaluated. The cytotoxic assays for HCT116, HePG2 and MCF7 showed a significant IC: 54.7 and 76.
View Article and Find Full Text PDFMagn Reson Chem
July 2018
School of Chemistry, University of Southampton, Southampton, UK.
Quantum-rotor-induced polarization is closely related to para-hydrogen-induced polarization. In both cases, the hyperpolarized spin order derives from rotational interaction and the Pauli principle by which the symmetry of the rotational ground state dictates the symmetry of the associated nuclear spin state. In quantum-rotor-induced polarization, there may be several spin states associated with the rotational ground state, and the hyperpolarization is typically generated by hetero-nuclear cross-relaxation.
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