Photochemical mechanism of DEACM uncaging: a combined time-resolved spectroscopic and computational study

Physical Chemistry Chemical Physics : PCCP
C HamerlaI Burghardt

Abstract

The elementary steps of photocleavage in (coumarin-4-yl)methyl photoremovable protecting groups (PPGs) are elucidated by a combined electronic structure and time-resolved visible pump infrared probe (VIS-pump IR-probe) spectroscopic study. We specifically focus on the [7-(diethylamino)coumarin-4-yl]methyl (DEACM) PPG which has found increasing interest in biological applications over recent years. A series of leaving groups (LGs) are investigated, including azide (DEACM-N3), thiocyanate (DEACM-SCN), carbonate (DEACM-Carb), and a thymine nucleobase (DEACM-T) representing a model system for caged DNA. These systems are found to exhibit vastly different photocleavage time scales, ranging from the subpicosecond scale in the case of DEACM-SCN to ∼35 picoseconds in the case of DEACM-N3 and ∼540 picoseconds in the case of DEACM-Carb. In the case of DEACM-SCN, the appearance of the product is biphasic, with a fast (<ps) and a slower (20 ps) population. Conversely, the free azide and carbonate LGs appear with single exponential kinetics. Consistent with these observations, theoretical analysis based on Time-Dependent Density Functional Theory (TDDFT) studies reveals that the bright S1(π-π*) state features a barrier to dissociation that ...Continue Reading

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Citations

Aug 8, 2021·Chemistry : a European Journal·Volker HermannsAlexander Heckel

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Software Mentioned

DEACM
Carb
TDDFT
LR
PCM
Gaussian16

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