Jon M. Goetz

Location of Fluorotryptophan Sequestered in an Amphiphilic Nanoparticle by Rotational-Echo Double-Resonance NMR

Rotational-echo double-resonance (REDOR) 13C NMR spectra (with 19F dephasing) have been obtained of 6-fluorotryptophan complexed by a polymeric amphiphilic nanosphere consisting of a polystyrene core covalently attached to a poly(acrylic acid)-polyacrylamide shell. The REDOR spectra show that aromatic carbons from the polystyrene core and oxygenated carbons in the poly(acrylic acid)-polyacrylamide shell are both proximate to the 19F of 6-fluorotryptophan. Molecular modeling restrained by distances inferred from the REDOR spectra suggests that all of the 6-fluorotryptophans are in the shell but within 10 A of the core-shell interface.

Two-dimensional transferred-echo double resonance study of molecular motion in a fluorinated polycarbonate

A two-dimensional version of the transferred-echo double resonance (TEDOR) experiment is introduced to measure strong heteronuclear magnetic dipolar interactions between rare spins. A quantitative description of this 2D-TEDOR experiment is given for an I-S pair of spins undergoing relative motion. 2D-TEDOR calculations are consistent with data for a calibration model: the directly bound 13C-31P pair in [3-13C]glyphosate, HO31(3)P13CH2NHCH2COOH. Analysis shows that the indirect spin-spin interaction and the dipole-dipole interaction have opposite signs in this system. The 2D-TEDOR experiment is then used to measure heteronuclear 13C-19F interactions in a fluorinated polycarbonate in which an aromatic proton is replaced by a fluorine on every fourth ring. Results from the 2D-TEDOR experiment show that the aromatic ring flips that occur in ordinary polycarbonate are blocked for a fluorinated ring.