Direct observation of ground-state lactam-lactim tautomerization using temperature-jump transient 2D IR spectroscopy

作者：Peng Chunte Sam; Baiz Carlos R; Tokmakoff Andrei^*

来源：Proceedings of the National Academy of Sciences, 2013, 110(23): 9243-9248.

DOI：10.1073/pnas.1303235110

• keto-enol tautomerism
• multidimensional
• time-resolved spectroscopy
• ultrafast

We provide a systematic characterization of the nanosecond ground-state lactam-lactim tautomerization of pyridone derivatives in aqueous solution under ambient conditions using temperature-jump transient 2D IR spectroscopy. Although electronic excited-state tautomerization has been widely studied, experimental work on the ground electronic state, most relevant to chemistry and biology, is lacking. Using 2D IR spectroscopy, lactam and lactim tautomers of 6-chloro-2-pyridone and 2-chloro-4-pyridone are unambiguously identified by their unique cross-peak patterns. Monitoring the correlated exponential relaxation of these signals in response to a laser temperature jump provides a direct measurement of the nanosecond tautomerization kinetics. By studying the temperature, concentration, solvent, and pH dependence, we extract a thermodynamic and kinetic characterization and conclude that the tautomerization proceeds through a two-state concerted mechanism. We find that the intramolecular proton transfer is mediated by bridging water molecules and the reaction barrier is dictated by the release of a proton from pyridone, as would be expected for an efficient Grothuss-type proton transfer mechanism.

• 出版日期2013-6-4