ArticleProceedings of the National Academy of Sciences of the United States of America2013
Direct observation of ground-state lactam-lactim tautomerization using temperature-jump transient 2D IR spectroscopy.
Article in Proceedings of the National Academy of Sciences of the United States of America, 2013. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 22 papers.
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Who cites it
22 citing papers in PubMed.
- Full Conjugation in a Polymer with Non-conjugated Piperazine-2,5-dione Units via Energy-minimized Lactam-to-Lactim Tautomerization Enables Water-gated Transistor Fluoride Sensors.Angewandte Chemie (International ed. in English) · 2025Article
- Biomolecular infrared spectroscopy: making time for dynamics.Chemical science · 2024Review
- Ru-Controlled Thymine Tautomerization Frozen by a kMolecules (Basel, Switzerland) · 2023Article
- Structural Insights Into Tautomeric Dynamics in Nucleic Acids and in Antiviral Nucleoside Analogs.Frontiers in molecular biosciences · 2021Review
- Temperature-Jump 2D IR Spectroscopy with Intensity-Modulated CW Optical Heating.The journal of physical chemistry. B · 2020Article
- Modeling the vibrational couplings of nucleobases.The Journal of chemical physics · 2020Article
- Coordination to lanthanide ions distorts binding site conformation in calmodulin.Proceedings of the National Academy of Sciences of the United States of America · 2018Article
- Direct observation of single-molecule hydrogen-bond dynamics with single-bond resolution.Nature communications · 2018Article
- Transient two-dimensional vibrational spectroscopy of an operating molecular machine.Nature communications · 2017Article
- Watching Proteins Wiggle: Mapping Structures with Two-Dimensional Infrared Spectroscopy.Chemical reviews · 2017Review
- Nanoplasmonic mid-infrared biosensor forLight, science & applications · 2017Article
- Weakened N3 Hydrogen Bonding by 5-Formylcytosine and 5-Carboxylcytosine Reduces Their Base-Pairing Stability.ACS chemical biology · 2016Article
- Applications of two-dimensional infrared spectroscopy.The Analyst · 2015Review
- A protonation-coupled feedback mechanism controls the signalling process in bathy phytochromes.Nature chemistry · 2015Article
- Kinetics of exchange between zero-, one-, and two-hydrogen-bonded states of methyl and ethyl acetate in methanol.The journal of physical chemistry. B · 2015Article
- Two-dimensional IR spectroscopy of the anti-HIV agent KP1212 reveals protonated and neutral tautomers that influence pH-dependent mutagenicity.Proceedings of the National Academy of Sciences of the United States of America · 2015Article
- Role of tautomerism in RNA biochemistry.RNA (New York, N.Y.) · 2015Review
- Tautomerism provides a molecular explanation for the mutagenic properties of the anti-HIV nucleoside 5-aza-5,6-dihydro-2'-deoxycytidine.Proceedings of the National Academy of Sciences of the United States of America · 2014Article
- Ultrafast 2D IR microscopy.Optics express · 2014Article
- Article
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3 authors.
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Abstract
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.
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