1H NMR
spectra at 500 MHz were recorded in D2O at 25 °C using
a Varian Unity Inova 500 spectrometer that was shimmed to give a line
width of ≤0.7 Hz for each peak of the doublet due to the C-1
proton of GAP hydrate, or ≤0.5 Hz for the most downfield peak
of the double triplet due to the C-1 proton of [1-13C]GA
hydrate. Spectra (16–64 transients) were obtained using a sweep
width of 6000 Hz, a pulse angle of 90°, an acquisition time of
6 s, and a relaxation delay of 60 s (4T1) for experiments on the TIM-catalyzed isomerization of GAP in D2O or 120 s (>8T1) for experiments
on the TIM-catalyzed reactions of [1-13C]GA in D2O.33 (link),50 (link) Baselines were subjected to a first-order
drift correction before determination of peak areas. Chemical shifts
are reported relative to HOD at 4.67 ppm.
spectra at 500 MHz were recorded in D2O at 25 °C using
a Varian Unity Inova 500 spectrometer that was shimmed to give a line
width of ≤0.7 Hz for each peak of the doublet due to the C-1
proton of GAP hydrate, or ≤0.5 Hz for the most downfield peak
of the double triplet due to the C-1 proton of [1-13C]GA
hydrate. Spectra (16–64 transients) were obtained using a sweep
width of 6000 Hz, a pulse angle of 90°, an acquisition time of
6 s, and a relaxation delay of 60 s (4T1) for experiments on the TIM-catalyzed isomerization of GAP in D2O or 120 s (>8T1) for experiments
on the TIM-catalyzed reactions of [1-13C]GA in D2O.33 (link),50 (link) Baselines were subjected to a first-order
drift correction before determination of peak areas. Chemical shifts
are reported relative to HOD at 4.67 ppm.
