Deuteron Quadrupolar Chemical Exchange Saturation Transfer (Q‐CEST) Solid‐State NMR for Static Powder Samples: Approach and Applications to Amyloid‐β Fibrils

Vugmeyster, Liliya; Ostrovsky, Dmitry; Fu, Riqiang

doi:10.1002/cphc.201901053

Title: Deuteron Quadrupolar Chemical Exchange Saturation Transfer (Q‐CEST) Solid‐State NMR for Static Powder Samples: Approach and Applications to Amyloid‐β Fibrils

Journal Article · 08 January 2020 · ChemPhysChem

DOI: https://doi.org/10.1002/cphc.201901053 · OSTI ID:1581839

^[1]; Ostrovsky, Dmitry ^[2]; Fu, Riqiang ^[3]

Department of Chemistry University of Colorado Denver Denver CO 80204 USA
Department of Mathematics University of Colorado Denver Denver CO 80204 USA
National High Field Magnetic Laboratory Tallahassee FL 32310 USA

Abstract We provide an experimental and computational framework for ² H quadrupolar chemical exchange saturation transfer NMR experiments (Q‐CEST) under static solid‐state conditions for the quantification of dynamics on μs‐ms timescales. Simulations using simple 2‐site exchange models provide insights into the relation between spin dynamics and motions. Biological applications focus on two sites of amyloid‐β fibrils in the 3‐fold symmetric polymorph. The first site, the methyl group of A2 of the disordered N‐terminal domain, undergoes diffusive motions and conformational exchange due to transient interactions. Earlier ² H rotating frame relaxation and quadrupolar CPMG measurements are combined with the Q‐CEST approach to characterize the multiple conformational states of the domain. The second site, the methyl group of M35, spans the water‐accessible cavity inside the fibrils’ core and undergoes extensive rotameric exchange. Q‐CEST permits us to refine the rotameric exchange model for this site and allows the more precise determination of populations and rotameric exchange rate constants than line shape analysis.

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Sponsoring Organization:: USDOE

OSTI ID:: 1581839

Journal Information:: ChemPhysChem, Journal Name: ChemPhysChem Journal Issue: 3 Vol. 21; ISSN 1439-4235

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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