In Search of the Perfect Photocage: Structure Reactivity Relationships in meso-Methyl BODIPY Photoremovable Protecting Groups

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Publikace nespadá pod Filozofickou fakultu, ale pod Přírodovědeckou fakultu. Oficiální stránka publikace je na webu muni.cz.

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SLANINA Tomáš SHRESTHA Pradeep PALAO UTIEL Eduardo KAND Dnyaneshwar PETERSON Julie A. DUTTON Andrew S. RUBINSTEIN Naama WEINSTAIN Roy WINTER Arthur H. KLÁN Petr

Rok publikování 2017
Druh Článek v odborném periodiku
Časopis / Zdroj Journal of the American Chemical Society
Fakulta / Pracoviště MU

Přírodovědecká fakulta

Citace
Doi http://dx.doi.org/10.1021/jacs.7608532
Klíčová slova P-HYDROXYPHENACYL; VISIBLE-LIGHT; CAGED GABA; REACTION-MECHANISMS; STOKES SHIFT; GREEN LIGHT; DYES; DERIVATIVES; ATP; PHOTOCHEMISTRY
Popis A detailed investigation of the photophysical parameters and photochemical reactivity of meso-methyl BODIPY photoremovable protecting groups was accomplished through systematic variation of the leaving group (LG) and core substituents as well as substitutions at boron. Efficiencies of the LG release were evaluated using both steady-state and transient absorption spectroscopies as well as computational analyses to identify the optimal structural features. We find that the quantum yields for photorelease with this photocage are highly sensitive to substituent effects. In particular, we find that the quantum yields of photorelease are improved with derivatives with higher intersystem crossing quantum yields, which can be promoted by core heavy atoms. Moreover, release quantum yields are dramatically improved by boron alkylation, whereas alkylation in the meso-methyl position has no effect. Better LGs are released considerably more efficiently than poorer LGs. We find that these substituent effects are additive, for example, a 2,6-diiodo-B-dimethyl BODIPY photocage features quantum yields of 28% for the mediocre LG acetate and a 95% quantum yield of release for chloride. The high chemical and quantum yields combined with the outstanding absorption properties of BODIPY dyes lead to photocages with uncaging cross sections over 10 000 M-1 cm(-1), values that surpass cross sections of related photocages absorbing visible light. These new photo cages, which absorb strongly near the second harmonic of an Nd:YAG laser (532 nm), hold promise for manipulating and interrogating biological and material systems with the high spatiotemporal control provided by pulsed laser irradiation, while avoiding the phototoxicity problems encountered with many UV-absorbing photocages. More generally, the insights gained from this structure reactivity relationship may aid in the development of new highly efficient photoreactions.
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