Spin relaxation measurements of electrostatic bias in intermolecular exploration

Ching Ling Teng, Robert G. Bryant

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

We utilize the paramagnetic contribution to proton spin-lattice relaxation rate constants induced by freely diffusing charged paramagnetic centers to investigate the effect of charge on the intermolecular exploration of a protein by the small molecule. The proton NMR spectrum provided 255 resolved resonances that report how the explorer molecule local concentration varies with position on the surface. The measurements integrate over local dielectric constant variations, and, in principle, provide an experimental characterization of the surface free energy sampling biases introduced by the charge distribution on the protein. The experimental results for ribonuclease A obtained using positive, neutral, and negatively charged small nitroxide radicals are qualitatively similar to those expected from electrostatic calculations. However, while systematic electrostatic trends are apparent, the three different combinations of the data sets do not yield internally consistent values for the electrostatic contribution to the intermolecular free energy. We attribute this failure to the weakness of the electrostatic sampling bias for charged nitroxides in water and local variations in effective translational diffusion constant at the water-protein interface, which enters the nuclear spin relaxation equations for the nitroxide-proton dipolar coupling.

Original languageEnglish (US)
Pages (from-to)199-205
Number of pages7
JournalJournal of Magnetic Resonance
Volume179
Issue number2
DOIs
StatePublished - Apr 1 2006
Externally publishedYes

Fingerprint

Static Electricity
Electrostatics
electrostatics
Protons
Selection Bias
proteins
Free energy
protons
sampling
free energy
Sampling
Pancreatic Ribonuclease
Proteins
Molecules
Spin-lattice relaxation
Water
Charge distribution
spin-lattice relaxation
nuclear spin
charge distribution

Keywords

  • Charge distribution
  • Diffusion
  • Electrostatic
  • Magnetic relaxation
  • Potential

ASJC Scopus subject areas

  • Biophysics
  • Biochemistry
  • Nuclear and High Energy Physics
  • Condensed Matter Physics

Cite this

Spin relaxation measurements of electrostatic bias in intermolecular exploration. / Teng, Ching Ling; Bryant, Robert G.

In: Journal of Magnetic Resonance, Vol. 179, No. 2, 01.04.2006, p. 199-205.

Research output: Contribution to journalArticle

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