Journal ArticleDOI
Photochemical reaction mechanisms of 2-nitrobenzyl compounds: methyl ethers and caged ATP.
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TLDR
The mechanism of methanol photorelease from 2-nitrobenzyl methyl ether and adenosine-5'-triphosphate-[P(3)-(1-(2-nitrophenyl)ethyl)] ester ('caged ATP', 3) was studied and the cyclic intermediates B were identified for the first time as the products formed by the decay of the aci-tautomers A in solution.Abstract:
The mechanism of methanol photorelease from 2-nitrobenzyl methyl ether (1) and 1-(2-nitrophenyl)ethyl methyl ether (2), and of ATP release from adenosine-5‘-triphosphate-[P3-(1-(2-nitrophenyl)ethyl)] ester (‘caged ATP', 3) was studied in various solvents by laser flash photolysis with UV−vis and IR detection In addition to the well-known primary aci-nitro transients (A, λmax ≈ 400 nm), two further intermediates preceding the release of methanol, namely the corresponding 1,3-dihydrobenz[c]isoxazol-1-ol derivatives (B) and 2-nitrosobenzyl hemiacetals (C), were identified The dependencies of the reaction rates of A−C on pH and buffer concentrations in aqueous solution were studied in detail Substantial revision of previously proposed reaction mechanisms for substrate release from 2-nitrobenzyl protecting groups is required: (a) A novel reaction pathway of the aci-tautomers A prevailing in buffered aqueous solutions, eg, phosphate buffer with pH 7, was found (b) The cyclic intermediates B were identifiread more
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Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy
Petr Klán,Tomáš Šolomek,Christian G. Bochet,Aurélien Blanc,Richard S. Givens,Marina Rubina,Vladimir V. Popik,Alexey Kostikov,Jakob Wirz +8 more
TL;DR: The review covers the knowledge on photoremovable protecting groups and includes all relevant chromophores studied in the time period of 2000–2012 and the most relevant earlier works are discussed.
Journal ArticleDOI
Photochemical Reactions as Key Steps in Organic Synthesis
TL;DR: Photochemical Electron-Transfer Reactions with a Catalytic Sensitizer 1068 6.1.1 Photochemical Extrusion of Small Molecules 1067 6.2.2 Photochemical Rearrangings 1061 4.4.3.
Journal ArticleDOI
o-Nitrobenzyl Alcohol Derivatives: Opportunities in Polymer and Materials Science
TL;DR: The use of o-nitrobenzyl group (o-NB) in polymer chemistry has been extensively studied in this article, including the use of O-NB-based cross-linkers for photodegradable hydrogels, o-NB side chain functionalization in (block) copolymers, and oNB functionalization for thin film patterning for self-assembled monolayers.
Journal ArticleDOI
o‐Nitrobenzyl Photolabile Protecting Groups with Red‐Shifted Absorption: Syntheses and Uncaging Cross‐Sections for One‐ and Two‐Photon Excitation
Isabelle Aujard,Chouaha Benbrahim,Marine Gouget,Odile Ruel,Jean-Bernard Baudin,Pierre Neveu,Ludovic Jullien +6 more
TL;DR: The o-nitrobenzyl platform for designing photolabile protecting groups with red-shifted absorption that could be photolyzed upon one- and two-photon excitation is evaluated and the difficulty in enlarging the corresponding action uncaging cross-sections is emphasized in view of the observed trend of their quantum yield of uncaging.
Journal ArticleDOI
Selective in vivo metabolic cell-labeling-mediated cancer targeting
Hua Wang,Ruibo Wang,Kaimin Cai,Hua He,Yang Liu,Jonathan Yen,Zhiyu Wang,Ming Xu,Yiwen Sun,Xin Zhou,Qian Yin,Li Tang,Iwona T. Dobrucki,Lawrence W. Dobrucki,Eric J. Chaney,Stephen A. Boppart,Timothy M. Fan,Stéphane Lezmi,Xuesi Chen,Lichen Yin,Jianjun Cheng +20 more
TL;DR: This work inhibits the cell-labeling activity of tetraacetyl-N-azidoacetylmannosamine (Ac4ManAz) by converting its anomeric acetyl group to a caged ether bond that can be selectively cleaved by cancer-overexpressed enzymes and thus enables the overexpression of azido groups on the surface of cancer cells.
References
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TL;DR: In this article, the unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio using DFT, MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set.
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Molecular excitation energies to high-lying bound states from time-dependent density-functional response theory: Characterization and correction of the time-dependent local density approximation ionization threshold
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Approximate evaluations of the electrostatic free energy and internal energy changes in solution processes
Stanislav Miertus,Jacopo Tomasi +1 more
TL;DR: In this article, a procedure for introducing solvent effects in the molecular hamiltonian of a solute is re-elaborated to get approximate solutions of the corresponding classical electrostatic problem.