Searching for Improved Photoreleasing Abilities of Organic
Molecules

J 2015

Searching for Improved Photoreleasing Abilities of Organic Molecules

ŠOLOMEK, Tomáš, Hans Jakob WIRZ a Petr KLÁN

Základní údaje

Originální název

Searching for Improved Photoreleasing Abilities of Organic Molecules

Autoři

ŠOLOMEK, Tomáš (703 Slovensko, domácí), Hans Jakob WIRZ (756 Švýcarsko) a Petr KLÁN (203 Česká republika, garant, domácí)

Vydání

Accounts of chemical research, American Chemical Society, 2015, 0001-4842

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10401 Organic chemistry

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

URL

Impakt faktor

Impact factor: 22.003

Kód RIV

RIV/00216224:14310/15:00081563

Organizační jednotka

Přírodovědecká fakulta

DOI

http://dx.doi.org/10.1021/acs.accounts.5b00400

UT WoS

000366871400009

Klíčová slova anglicky

photochemistry; photoremovable protecting groups; DFT calculations

Štítky

AKR, rivok

Změněno: 11. 2. 2016 14:07, prof. RNDr. Petr Klán, Ph.D.

Anotace

V originále

Photoremovable protecting groups (PPGs) are chemical auxiliaries that provide spatial and temporal control over the release of various molecules: bioagents (neurotransmitters and cell-signaling molecules, Ca2+ ions), acids, bases, oxidants, insecticides, pheromones, fragrances, etc. A major challenge for the improvement of PPGs lies in the development of organic chromophores that release the desired bioagents upon continuous irradiation at wavelengths above 650 nm, that is, in the tissue-transparent window. Understanding of the photorelease reaction mechanisms, investigated by laser flash photolysis and rationalized with the aid of quantum chemical calculations, allows for achieving this goal. In particular, simple Hiickel calculations provide useful guidelines for designing new PPGs, because both the lowest excited singlet and triplet states of conjugated systems can be reasonably well described by a single electronic configuration formed by promotion of a single electron from the highest occupied molecular orbital (HOMO) to the lowest unoccupied MO (LUMO) of the ground state configuration. Here we show that Hiickel calculations permit rapid identification of common features in the nodal properties of the frontier orbitals of various chromophores that can be classified into distinct chromophore families. If the electronic excitation involves a substantial electron density transfer to an sp(2) carbon atom at which HOMO and LUMO are nearly disjoint, for example, by virtue of symmetry, favorable photoheterolysis can be expected when the corresponding atom carries a leaving group at the alpha-position. We show examples of photoheterolytic reactions that indicate that the efficiency of photoheterolysis diminishes for chromophores absorbing in the NIR region. We provide a rationale for more efficient photoheterolytic reactions occurring via the triplet state, and we demonstrate the advantages of this mechanistic pathway. Analogies in the structure reactivity relationships of PPGs can therefore lead to new strategies for the development of more efficient NIR-absorbing photoremovable protecting groups.

Návaznosti

GA13-25775S, projekt VaV

Název: Vývoj viditelným světlem aktivovatelných skupin a fluorescenčních značek pro chemii a biologii

Investor: Grantová agentura ČR, Vývoj viditelným světlem aktivovatelných skupin a fluorescenčních značek pro chemii a biologii

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

ŠOLOMEK, Tomáš, Hans Jakob WIRZ a Petr KLÁN. Searching for Improved Photoreleasing Abilities of Organic Molecules. Accounts of chemical research. American Chemical Society, 2015, roč. 48, č. 12, s. 3064-3072. ISSN 0001-4842. Dostupné z: https://dx.doi.org/10.1021/acs.accounts.5b00400.

@article{1335094,
   author = {Šolomek, Tomáš and Wirz, Hans Jakob and Klán, Petr},
   article_number = {12},
   doi = {http://dx.doi.org/10.1021/acs.accounts.5b00400},
   keywords = {photochemistry; photoremovable protecting groups; DFT calculations},
   language = {eng},
   issn = {0001-4842},
   journal = {Accounts of chemical research},
   title = {Searching for Improved Photoreleasing Abilities of Organic Molecules},
   url = {http://pubs.acs.org/doi/10.1021/acs.accounts.5b00400},
   volume = {48},
   year = {2015}
}

TY  - JOUR
ID  - 1335094
AU  - Šolomek, Tomáš - Wirz, Hans Jakob - Klán, Petr
PY  - 2015
TI  - Searching for Improved Photoreleasing Abilities of Organic Molecules
JF  - Accounts of chemical research
VL  - 48
IS  - 12
SP  - 3064-3072
EP  - 3064-3072
PB  - American Chemical Society
SN  - 00014842
KW  - photochemistry
KW  - photoremovable protecting groups
KW  - DFT calculations
UR  - http://pubs.acs.org/doi/10.1021/acs.accounts.5b00400
L2  - http://pubs.acs.org/doi/10.1021/acs.accounts.5b00400
N2  - Photoremovable protecting groups (PPGs) are chemical auxiliaries that provide spatial and temporal control over the release of various molecules: bioagents (neurotransmitters and cell-signaling molecules, Ca2+ ions), acids, bases, oxidants, insecticides, pheromones, fragrances, etc. A major challenge for the improvement of PPGs lies in the development of organic chromophores that release the desired bioagents upon continuous irradiation at wavelengths above 650 nm, that is, in the tissue-transparent window. Understanding of the photorelease reaction mechanisms, investigated by laser flash photolysis and rationalized with the aid of quantum chemical calculations, allows for achieving this goal. In particular, simple Hiickel calculations provide useful guidelines for designing new PPGs, because both the lowest excited singlet and triplet states of conjugated systems can be reasonably well described by a single electronic configuration formed by promotion of a single electron from the highest occupied molecular orbital (HOMO) to the lowest unoccupied MO (LUMO) of the ground state configuration. Here we show that Hiickel calculations permit rapid identification of common features in the nodal properties of the frontier orbitals of various chromophores that can be classified into distinct chromophore families. If the electronic excitation involves a substantial electron density transfer to an sp(2) carbon atom at which HOMO and LUMO are nearly disjoint, for example, by virtue of symmetry, favorable photoheterolysis can be expected when the corresponding atom carries a leaving group at the alpha-position. We show examples of photoheterolytic reactions that indicate that the efficiency of photoheterolysis diminishes for chromophores absorbing in the NIR region. We provide a rationale for more efficient photoheterolytic reactions occurring via the triplet state, and we demonstrate the advantages of this mechanistic pathway. Analogies in the structure reactivity relationships of PPGs can therefore lead to new strategies for the development of more efficient NIR-absorbing photoremovable protecting groups.
ER  -

ŠOLOMEK, Tomáš, Hans Jakob WIRZ a Petr KLÁN. Searching for Improved Photoreleasing Abilities of Organic Molecules. \textit{Accounts of chemical research}. American Chemical Society, 2015, roč.~48, č.~12, s.~3064-3072. ISSN~0001-4842. Dostupné z: https://dx.doi.org/10.1021/acs.accounts.5b00400.

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