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New Photoremovable Protecting Groups for Carboxylic Acids with High Photolytic Efficiencies at Near‐UV Irradiation. Application to the Photocontrolled Release of L ‐Glutamate
Author(s) -
Specht Alexandre,
Thomann JeanSébastien,
Alarcon Karine,
Wittayanan Weerawut,
Ogden David,
Furuta Toshiaki,
Kurakawa Yuji,
Goeldner Maurice
Publication year - 2006
Publication title -
chembiochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.05
H-Index - 126
eISSN - 1439-7633
pISSN - 1439-4227
DOI - 10.1002/cbic.200600111
Subject(s) - chemistry , photodissociation , diastereomer , quantum yield , irradiation , photochemistry , absorbance , glutamate receptor , carboxylic acid , yield (engineering) , medicinal chemistry , stereochemistry , organic chemistry , chromatography , fluorescence , biochemistry , physics , receptor , materials science , quantum mechanics , nuclear physics , metallurgy
We report here the syntheses and the photolytic properties of 3‐(4,5‐dimethoxy‐2‐nitrophenyl)‐2‐butyl (DMNPB) esters as new photoremovable groups for carboxylic acids, and their use for the caging of L ‐glutamate. A high‐yielding synthesis of the DMNPB esters led to a 4:1 threo / erythro diastereomeric mixture, which could be separated by HPLC. While these esters were stable in neutral buffer, photolysis at 364 nm induced a ≥95 % release of the carboxylic acid, with a 0.26 quantum yield for L ‐glutamate formation. L ‐Glutamate release was also possible by two‐photon photolysis with an action cross section of 0.17 GM at 720 nm. Laser photolysis at 350 nm generated a transient species at around 410 nm, attributed to a quinonoid aci‐nitro intermediate that decayed in the submillisecond time range ( t 1/2 =0.53 ms) for the faster γ ‐ L ‐glutamyl threo ‐esters. Given the absorbance of these esters ( λ max =350 nm; ε =4500), the threo DMNPB esters represent new caging groups that can be efficiently photolyzed at near‐UV wavelengths. An efficient and rapid photolytic release of L ‐glutamate has been demonstrated on hippocampal neurons in primary culture.