Efficient and accurate determination of 13C T1 and T1ρ relaxation time constants of high-mobility polymers from limited-resolution spectra with optimized pulse sequences and data fitting.

Abstract

The pulse sequences for the measurement of 13C T1 and T1ρ relaxation time constants in soft organic solids were modified to include steady-state nuclear Overhauser enhancement with direct polarization (ssNOE/DP). The increased signal intensities with ssNOE are particularly well-suited for highly mobile and structurally heterogeneous polymers and proteins like elastin. The phase cycling of these experiments was modified to yield datasets that require less time, with more accurate results. The "3D-fitting process" was developed and then optimized for natural-abundance 13C spectra of elastin, with its characteristic and significant overlap. A comparison of 3D-fitting with the similarly purposed SPORT (Geppi and Forte, 1999) illustrates that the former is more robust, with smaller uncertainty values and higher precision.