Decorrelating Kinetic and Relaxation Parameters in Exchange Saturation Transfer NMR: A Case Study of N-Terminal Huntingtin Peptides Binding to Unilamellar Lipid Vesicles

The Journal of Physical Chemistry. B
Alberto CecconVitali Tugarinov

Abstract

Dark state exchange saturation transfer (DEST) and lifetime line-broadening (Δ R2, the difference in the measured transverse relaxation rates for the observable species in the presence and absence of exchange with a species characterized by very large intrinsic transverse relaxation rates) have proven to be powerful NMR tools for studying exchange phenomena between a NMR visible species and a high-molecular weight, "dark", NMR invisible state. However, in the exchange regime, where the transverse spin relaxation rates in the bound state ( R2bound) are smaller than the strength of the DEST saturation radio frequency field, typically corresponding to systems below ∼6 MDa, the combination of DEST and Δ R2 data, while sufficient to define the apparent association rate constant, cannot unambiguously determine the population of the bound state pB and R2bound values independently. We show that the latter exchange and relaxation parameters can be decorrelated by the measurement of the maximal value of the contribution of the fast-relaxing magnetization component to the total NMR signal, Cfastmax, an observable that is directly proportional to pB. When integrated into the analysis of DEST/Δ R2 data, Cfastmax provides an indispensable so...Continue Reading

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Citations

Jan 21, 2019·Journal of Biomolecular NMR·Ved Prakash TiwariPramodh Vallurupalli
Dec 14, 2019·Current Opinion in Structural Biology·T Reid Alderson, Lewis E Kay
Apr 28, 2021·Proceedings of the National Academy of Sciences of the United States of America·Xue YangJean Baum
Nov 1, 2019·Israel Journal of Chemistry·Y Randika PereraNicholas C Fitzkee
Jul 3, 2021·International Journal of Molecular Sciences·Arnaud MarquetteBurkhard Bechinger
Sep 3, 2021·The Journal of Physical Chemistry. B·Muhammed Shafeek Oliyantakath HassanVinesh Vijayan

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