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

J 2017

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

SLANINA, Tomáš, Pradeep SHRESTHA, Eduardo PALAO UTIEL, Dnyaneshwar KAND, Julie A. PETERSON et. al.

Základní údaje

Originální název

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

Autoři

SLANINA, Tomáš (203 Česká republika, domácí), Pradeep SHRESTHA (840 Spojené státy), Eduardo PALAO UTIEL (724 Španělsko, domácí), Dnyaneshwar KAND (376 Izrael), Julie A. PETERSON (840 Spojené státy), Andrew S. DUTTON (840 Spojené státy), Naama RUBINSTEIN (376 Izrael), Roy WEINSTAIN (376 Izrael), Arthur H. WINTER (840 Spojené státy) a Petr KLÁN (203 Česká republika, garant, domácí)

Vydání

Journal of the American Chemical Society, WASHINGTON, American Chemical Society, 2017, 0002-7863

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10400 1.4 Chemical sciences

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Impakt faktor

Impact factor: 14.357

Kód RIV

RIV/00216224:14310/17:00099992

Organizační jednotka

Přírodovědecká fakulta

DOI

http://dx.doi.org/10.1021/jacs.7608532

UT WoS

000414115800052

Klíčová slova anglicky

P-HYDROXYPHENACYL; VISIBLE-LIGHT; CAGED GABA; REACTION-MECHANISMS; STOKES SHIFT; GREEN LIGHT; DYES; DERIVATIVES; ATP; PHOTOCHEMISTRY

Štítky

NZ, rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 5. 4. 2018 13:55, Ing. Nicole Zrilić

Anotace

V originále

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.

Návaznosti

LM2011028, projekt VaV

Název: RECETOX ? Národní infrastruktura pro výzkum toxických látek v prostředí

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, RECETOX Národní infrastruktura pro výzkum toxických látek v prostředí

LO1214, projekt VaV

Název: Centrum pro výzkum toxických látek v prostředí (Akronym: RECETOX)

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, Centrum pro výzkum toxických látek v prostředí

Citovat

SLANINA, Tomáš, Pradeep SHRESTHA, Eduardo PALAO UTIEL, Dnyaneshwar KAND, Julie A. PETERSON, Andrew S. DUTTON, Naama RUBINSTEIN, Roy WEINSTAIN, Arthur H. WINTER a Petr KLÁN. In Search of the Perfect Photocage: Structure Reactivity Relationships in meso-Methyl BODIPY Photoremovable Protecting Groups. Journal of the American Chemical Society. WASHINGTON: American Chemical Society, 2017, roč. 139, č. 42, s. 15168-15175. ISSN 0002-7863. Dostupné z: https://dx.doi.org/10.1021/jacs.7608532.

@article{1407991,
   author = {Slanina, Tomáš and Shrestha, Pradeep and Palao Utiel, Eduardo and Kand, Dnyaneshwar and Peterson, Julie A. and Dutton, Andrew S. and Rubinstein, Naama and Weinstain, Roy and Winter, Arthur H. and Klán, Petr},
   article_location = {WASHINGTON},
   article_number = {42},
   doi = {http://dx.doi.org/10.1021/jacs.7608532},
   keywords = {P-HYDROXYPHENACYL; VISIBLE-LIGHT; CAGED GABA; REACTION-MECHANISMS; STOKES SHIFT; GREEN LIGHT; DYES; DERIVATIVES; ATP; PHOTOCHEMISTRY},
   language = {eng},
   issn = {0002-7863},
   journal = {Journal of the American Chemical Society},
   title = {In Search of the Perfect Photocage: Structure Reactivity Relationships in meso-Methyl BODIPY Photoremovable Protecting Groups},
   volume = {139},
   year = {2017}
}

TY  - JOUR
ID  - 1407991
AU  - Slanina, Tomáš - Shrestha, Pradeep - Palao Utiel, Eduardo - Kand, Dnyaneshwar - Peterson, Julie A. - Dutton, Andrew S. - Rubinstein, Naama - Weinstain, Roy - Winter, Arthur H. - Klán, Petr
PY  - 2017
TI  - In Search of the Perfect Photocage: Structure Reactivity Relationships in meso-Methyl BODIPY Photoremovable Protecting Groups
JF  - Journal of the American Chemical Society
VL  - 139
IS  - 42
SP  - 15168-15175
EP  - 15168-15175
PB  - American Chemical Society
SN  - 00027863
KW  - P-HYDROXYPHENACYL
KW  - VISIBLE-LIGHT
KW  - CAGED GABA
KW  - REACTION-MECHANISMS
KW  - STOKES SHIFT
KW  - GREEN LIGHT
KW  - DYES
KW  - DERIVATIVES
KW  - ATP
KW  - PHOTOCHEMISTRY
N2  - 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.
ER  -

SLANINA, Tomáš, Pradeep SHRESTHA, Eduardo PALAO UTIEL, Dnyaneshwar KAND, Julie A. PETERSON, Andrew S. DUTTON, Naama RUBINSTEIN, Roy WEINSTAIN, Arthur H. WINTER a Petr KLÁN. In Search of the Perfect Photocage: Structure Reactivity Relationships in meso-Methyl BODIPY Photoremovable Protecting Groups. \textit{Journal of the American Chemical Society}. WASHINGTON: American Chemical Society, 2017, roč.~139, č.~42, s.~15168-15175. ISSN~0002-7863. Dostupné z: https://dx.doi.org/10.1021/jacs.7608532.

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