o-Nitrobenzyl photolabile protecting groups with red-shifted absorption:: Syntheses and uncaging cross-sections for one- and two-photon excitation

被引:254
作者
Aujard, Isabelle
Benbrahim, Chouaha
Gouget, Marine
Ruel, Odile
Baudin, Jean-Bernard
Neveu, Pierre
Jullien, Ludovic
机构
[1] Ecole Normale Super, Dept Chim, CNRS, UMR 8640, F-75231 Paris 05, France
[2] Ecole Normale Super, Dept Phys, CNRS, UMR 8550, F-75231 Paris, France
关键词
acidity; basicity; cage compounds; donor-acceptor systems; fluorescence correlation spectroscopy;
D O I
10.1002/chem.200501393
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We evaluated the o-nitrobenzyl platform for designing photolabile protecting groups with red-shifted absorption that could be photolyzed upon one- and two-photon excitation. Several synthetic pathways to build different conjugated o-nitrobenzyl backbones, as well as to vary the benzylic position, are reported. Relative to the reference 4,5-dimethoxy-2-nitrobenzyl group, several o-nitrobenzyl derivatives exhibit a large and red-shifted one-photon absorption within the near-UV range. Uncaging after one-photon excitation was studied by measuring UV-visible absorption and steady-state fluorescence emission on model caged ethers and esters. In the whole series investigated, the caged substrates were released cleanly upon photolysis. Quantum yields of uncaging after one-photon absorption lie within the 0.1-1 % range. We observed that these drop as the maximum wavelength absorption of the o-nitrobenzyl protecting group is increased. A new method based on fluorescence correlation spectroscopy (FCS) after two-photon excitation was used to measure the action uncaging cross section for two-photon excitation. The series of o-nitrobenzyl caged fluorescent coumarins investigated exhibit values within the 0.1-0.01 Goeppert-Mayer (GM) range. Such results are in line with the low quantum yields of uncaging associated with cross-sections of 1-50 GM for two-photon absorption. Although the cross-sections for one- and two-photon absorption of o-nitrobenzyl photolabile protecting groups can be readily improved, we emphasize the difficulty in enlarging the corresponding action uncaging cross-sections in view of the observed trend of their quantum yield of uncaging.
引用
收藏
页码:6865 / 6879
页数:15
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