Oxo-hydroxy tautomerism and phototautomerism of 2-quinolinone, 1-isoquinolinone, 3-hydroxyisoquinoline, 2-quinoxalinone, and 4-quinazolinone were studied using the matrix-isolation technique. These compounds contain a benzene ring fused with a heterocyclic ring of 2-pyridinone, 2-pyrazinone, or 4-pyrimidinone. It turned out that direct attachment of a benzene ring to a heterocycle leads to a very pronounced increase of the relative stability of oxo tautomers (in comparison with the tautomerism of the parent compounds 2-pyridinone, 2-pyrazinone, and 4-pyrimidinone). The only exception concerns 3-hydroxyisoquinoline, where fusion with a benzene ring enforces rearrangement of the double- and single-bond system in the oxo tautomer. This destabilizes substantially the oxo form with respect to the hydroxy tautomer. The ratios of population of the oxo and hydroxy tautomers observed in Ar matrixes correspond to the tautomeric equilibria of the compounds in the gas phase. These equilibria were well reproduced by theoretical calculations carried out at the QCISD and QCISD(T) levels. The combined experimental and theoretical results reveal links between aromaticity and tautomerism. Moreover, a UV-induced phototautomeric reaction transforming the oxo forms into the hydroxy tautomers was observed for all (except 3-hydroxyisoquinoline) studied compounds. This photoeffect allowed separation of the IR spectra of the tautomers in question.

We present an overview of the wide range of potential applications of optical methods for monitoring traumatic brain injury. The MEDLINE database was electronically searched with the following search terms: “traumatic brain injury,” “head injury,” or “head trauma,” and “optical methods,” “NIRS,” “near-infrared spectroscopy,” “cerebral oxygenation,” or “cerebral oximetry.” Original reports concerning human subjects published from January 1980 to June 2015 in English were analyzed. Fifty-four studies met our inclusion criteria. Optical methods have been tested for detection of intracranial lesions, monitoring brain oxygenation, assessment of brain perfusion, and evaluation of cerebral autoregulation or intracellular metabolic processes in the brain. Some studies have also examined the applicability of optical methods during the recovery phase of traumatic brain injury . The limitations of currently available optical methods and promising directions of future development are described in this review. Considering the outstanding technical challenges, the limited number of patients studied, and the mixed results and opinions gathered from other reviews on this subject, we believe that optical methods must remain primarily research tools for the present. More studies are needed to gain confidence in the use of these techniques for neuromonitoring of traumatic brain injury patients.

We study fluorescence lifetime of indocyanine green (ICG) using femtosecond laser and sensitive detection based on time-correlated single-photon counting. A time-resolved multichannel spectral system is constructed and applied for determination of the fluorescence lifetime of the ICG in different solvents. Emission properties of ICG in water, milk, and 1% intralipid solution are investigated. Fluorescence of the fluorophore of different concentrations (in a range of 1.7-160 μM) dissolved in different solutions is excited by femtosecond pulses generated with the use of Ti:Sa laser tuned within the range of 740-790 nm. It is observed that fluorescence lifetime of ICG in water is 0.166 ± 0.02 ns and does not depend on excitation and emission wavelengths. We also show that for the diffusely scattering solvents (milk and intralipid), the lifetime may depend on the dye concentration (especially for large concentrations of ICG). This effect should be taken into account when analyzing changes in the mean time of arrival of fluorescence photons excited in ICG dissolved in such optically turbid media.