In Search of the Perfect Photocage: Structure Reactivity Relationships in meso-Methyl BODIPY Photoremovable Protecting Groups
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14310%2F17%3A00099992" target="_blank" >RIV/00216224:14310/17:00099992 - isvavai.cz</a>
Result on the web
<a href="http://dx.doi.org/10.1021/jacs.7608532" target="_blank" >http://dx.doi.org/10.1021/jacs.7608532</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/jacs.7608532" target="_blank" >10.1021/jacs.7608532</a>
Alternative languages
Result language
angličtina
Original language name
In Search of the Perfect Photocage: Structure Reactivity Relationships in meso-Methyl BODIPY Photoremovable Protecting Groups
Original language description
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.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10400 - Chemical sciences
Result continuities
Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>S - Specificky vyzkum na vysokych skolach<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2017
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of the American Chemical Society
ISSN
0002-7863
e-ISSN
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Volume of the periodical
139
Issue of the periodical within the volume
42
Country of publishing house
US - UNITED STATES
Number of pages
8
Pages from-to
15168-15175
UT code for WoS article
000414115800052
EID of the result in the Scopus database
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