The α,5‐Dicarboxy‐2‐nitrobenzyl Caging Group, a Tool for Biophysical Applications with Improved Hydrophilicity: Synthesis, Photochemical Properties and Biological Characterization

Abstract

Earlier we reported on the synthesis of α,4-dicarboxy-2-nitrobenyzl caged compounds (Schaper, K. et al. [2002] Eur. J. Org. Chem., 1037-1046). These compounds have the advantage of an increased hydrophilicity compared with the well-established α-carboxy-2-nitrobenzyl caged compounds; however, the release of the active compound becomes slower due to the introduction of the additional carboxy group. Based upon theoretical calculations we predicted that the release would become faster when the additional carboxy group is moved to the 5-position. Here we describe the synthesis and the photochemical and biological characterization of an α,5-dicarboxy-2-nitrobenyzl caged compound. The high hydrophilicity of the new caging group is maintained due to the fact that the additional carboxy moiety is preserved, while the release of the active species from the new derivative is even faster than for the reference, an α-CNB caged compound.

4,5,5-Trimethyl-2,5-dihydrofuran-Based Electron-Withdrawing Groups for NIR-Emitting Push–Pull Dipolar Fluorophores

“…High-resolution mass spectra (HRMS) were recorded at the Centre Commun de Spectrométrie de Masse (UCBL, Villeurbanne, France) or at the Spectropole de St Jérôme (Univ Aix Marseille, France) using a SYNAPT G2 HDMS (Waters) spectrophotometer. Compounds 11 , 12 , 15 , 16 , 17 , 18c and 20c , and TCF were synthesized according to previously reported methods.…”

NMR–spectroscopic investigation of o‐nitrosobenzoic acid

“…It is remarkable that the nitroso side products are always postulated, but very rarely characterized. [19,20] Thus, it is of utmost importance to understand the NMR-spectra of nitrosobenzoic acid 1. This should give the basics for the characterization of other nitroso compounds for a more detailed study of the o-nitrobenzyl photochemistry in general.…”

Mechanism of the Photoinduced Uncaging Reaction of Puromycin Protected by a 6-Nitroveratryloxycarbonyl Group

“…The effect of light on oNB was first mentioned by Ciamician and Silber more than a century ago, and its capability as photoreactive cage has been known since the 1960s. − The photochemical behavior of oNB caging groups has been studied intensively throughout the last years, indicating their high potential and relevance as regulatory tools. , However, these compounds usually absorb in the UV range, which reduces their applicability in living cells. In contrast, substitution with electron-donating groups on the benzene ring induces a bathochromic shift that results in an absorption maximum around 350 nm. , One example of this class of molecules are the DMNB compounds mentioned above, where two methoxy groups are attached on the benzene ring, but 4,5-methylenedioxynitrobenzyl also shows that effect.…”