The present paper describes a new enzyme from animal tissues which catalyzes the keto-enol tautomeriaation of the phenylpyruvic acids. Preliminary accounts of this tautomerase have been published (1, 2). The enzyme has not yet proved to be essential in any biological reaction, but a physiological role may be expected since specific tautomers of a-keto acids are substrates or products in some re...

The potential energy profiles for proton-transfer reactions of 2-hydroxypyridine and its complexes with water were determined by MP2, CASSCF and MR-CI calculations with the 6-31G** basis set. The tautomerization reaction between 2-hydroxypyridine (2HP) and 2-pyridone (2PY) does not take place at room temperature because of a barrier of approximately 35 kcal/mol for the ground-state pathway. The...

We report the experimental determination of the intramolecular enol-enol tautomerization rate of an unsymmetric β-diketone, benzoylacetone, with femtosecond transient absorption in the ultraviolet. Initially, there is an equilibrium of two possible enolic structures in solution, which is disturbed upon UV excitation by exciting a disproportionate fraction of one enolic form. Comparison to symme...

palladium (ii) coordination complexes catalyze the reaction of alcohols with ketones to yield ethers. during the catalytic cycle, the alcohol adds selectively to the β-carbon (anti-markovnikov). in this work, mechanism and kinetics for the reaction of methanol with methyl vinyl ketone (mvk), being catalyzed by pd, has been theoretically investigated in detail. using quantum mechanical approach,...

We have investigated deuterium-substitution and solvent effects for the keto-enol tautomerization of acetylacetone (Hacac) confined in 10 – 100 nm scale spaces (called extended-nano spaces) based on NMR spectroscopic results, and elucidated the tautomeric reaction mechanisms in the extended-nano spaces.

Oxybenzone is a common constituent of many commercially available sunscreens providing photoprotection from ultraviolet light incident on the skin. Femtosecond transient electronic and vibrational absorption spectroscopies have been used to investigate the nonradiative relaxation pathways of oxybenzone in cyclohexane and methanol after excitation in the UVA region. The present data suggest that...

The structures and relative stabilities of the complexes formed by uracil and its sulfur derivatives, namely, 2-thio-, 4-thio, and 2,4-dithio-uracil when interacting with Ca(2+) in the gas phase have been analyzed by means of density functional theory (DFT) calculations carried out at the B3LYP/6-311++G(3df,2p)//B3LYP/6-31+G(d,p) level. For uracil and 2,4-dithiouracil, where the two basic sites...

Metal-free organic triplet emitters are an emerging class of semiconducting material. Among them, molecules with tunable emission responsive to environmental stimuli have shown great potential in solid-state lighting, sensors, and anti-counterfeiting systems. Here, a novel excited-state intramolecular proton transfer (ESIPT) system is proposed showing the activation thermally activated delayed ...

Thiotropolone isolated in argon and xenon matrices (as monomers) or a neat solid the crystalline amorphous state) at low temperature was found to exist only thione-enol form. Visible light irradiation (λ ≥ 400 nm) leads → thiol-keto tautomerization under conditions 15 K. The assignment of IR spectra two thiotropolone tautomers (thione-enol thiol-keto) carried out with support B3LYP/6-311+G(2d,p...