Intramolecular Sensitization of Photocleavage of the Photolabile 2‐(2‐Nitrophenyl)propoxycarbonyl (NPPOC) Protecting Group: Photoproducts and Photokinetics of the Release of Nucleosides

Wöll, Dominik; Smirnova, Julia; Galetskaya, Marina; Prykota, Tamara; Bühler, Jochen; Stengele, Klaus-Peter; Pfleiderer, Wolfgang; Steiner, Ulrich

doi:10.1002/chem.200800613

Cited by 42 publications

(30 citation statements)

References 33 publications

(35 reference statements)

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“…The chromatogram from photolysis of 2 (Figure 2C) showed two major photoproducts that had similar relative retention times when compared with the starting materials to those reported in other systems by Steiner and co-workers. The UV-visible absorption spectra are also analogous to those reported by Steiner and co-workers in their uncaging studies [39, 42] . LC-MS analysis of the reaction confirmed these structural assignments (Supplemental Figure 2).…”

Section: Resultssupporting

confidence: 80%

“…Photolysis of 2 is more complex than 1 , as would be expected from the careful studies of similar systems published by Steiner, Pfleiderer and co-workers [39–42] . HPLC analysis of the photolysis of 2 revealed that it decreased with a similar rate to MNI-Glu.…”

Section: Resultsmentioning

confidence: 89%

“…Photolysis of 2 is more complex than that of 1,a sw ould be expectedf rom the careful studies of similar systems published by Steiner,P fleiderer,a nd co-workers. [39][40][41][42] HPLC analysis of the photolysis of 2 revealed that it decreased with as imilar rate to MNI-Glu. The chromatogram from photolysis of 2 ( Figure 1C,D) showedt wo major photoproducts with relative (to the starting materials) retention times similar to those reported for other systemsb yS teiner and co-workers.T he UV-visible absorption spectra are also analogoust ot hose reported by Steiner and co-workersi nt heir uncagings tudies.…”

Section: Photochemical Propertiesmentioning

confidence: 99%

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Development of Anionically Decorated Caged Neurotransmitters: In Vitro Comparison of 7‐Nitroindolinyl‐ and 2‐(p‐Phenyl‐o‐nitrophenyl)propyl‐Based Photochemical Probes

et al. 2016

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Neurotransmitter uncaging, especially that of glutamate, has been used to study synaptic function for over 30 years. One limitation of caged glutamate probes is the blockade of GABA-A receptor function. This problem comes to the fore when the probes are applied at the high concentrations required for effective 2-photon photolysis. To mitigate such problems one could improve the photochemical properties of caging chromophores and/or remove receptor blockade. We show that addition of a dicarboxylate unit to the widely used MNI-Glu reduced the off-target effects by about 50-70%. When the same strategy was applied to an electron rich 2-(p-phenyl-onitrophenyl)-propyl (PNPP) cage, the pharmacological improvements were not as significant as for MNI. Finally, we used very extensive biological testing of the PNPP-caged Glu (more than 250 uncaging currents at single dendritic spines) to show that nitro-biphenyl caging chromophores have a 2-photon uncaging efficacy similar to that of MNI-Glu.Photochemically protected neurotransmitters offer physiologists a powerful means of controlling important aspects of chemical and electrical signaling in cells from the central nervous system [1][2][3] . Such optical probes, called caged compounds, initially used the orthonitrobenzyl [4] and ortho-nitroveratryl [5] chromophores developed, respectively, by Baltrop and Patchornik. Whilst such chromophores have proved the most widely used of all photochemical protecting groups in both chemistry and biology [6][7][8] , benzyl ester derivatives of biomolecules such as Glu and GABA have some predictable (e.g. hydrolysis at physiological pH), and some unpredictable weaknesses (e.g. GABA-A antagonism) in the context of synaptic physiology [3] .Several studies have sought to address these issues. For example, in 1999 Corrie and coworkers showed that a 7-nitroindolinyl-caged Glu [9] is very stable at physiological pH (i.e. 7.4). Subsequently several studies published by the Corrie/Ogden and Ellis-Davies/Kasai

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Section: Resultssupporting

confidence: 80%

Section: Resultsmentioning

confidence: 89%

Section: Photochemical Propertiesmentioning

confidence: 99%

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Development of Anionically Decorated Caged Neurotransmitters: In Vitro Comparison of 7‐Nitroindolinyl‐ and 2‐(p‐Phenyl‐o‐nitrophenyl)propyl‐Based Photochemical Probes

et al. 2016

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“…234 Steiner and co-workers have also designed and studied covalently linked 9 H -thioxanthen-9-one (the sensitizer) and 2-(2-nitrophenyl)propoxycarbonyl chromophores. 166,233,240b,240g Scheme 111 shows an example of such a compound ( 243 ), in which the sensitizer is attached to the chromophore via a saturated four-bond aliphatic tether. After the sensitizer is excited and the intersystem crosses to the triplet state, the energy is transferred through space to the 2-(2-nitrophenyl)propyl group, which liberates thymidine.…”

Section: Sensitized Releasementioning

confidence: 99%

Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy

et al. 2012

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“…[20] For the most part, however, these derivatives and sensitizers have not proven to be robust replacements for NPPOC in the synthesis of complex microarrays of long oligomers.…”

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confidence: 99%

Next‐Generation o‐Nitrobenzyl Photolabile Groups for Light‐Directed Chemistry and Microarray Synthesis

et al. 2015

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Light as an external trigger is a valuable and easily controllable tool for directing chemical reactions with high spatial and temporal accuracy. Two o-nitrobenzyl derivatives, benzoyl- and thiophenyl-NPPOC, undergo photo-deprotection with significantly improved efficiency over that of the commonly used NPPOC group. The two- and twelvefold increase in photo-deprotection efficiency was proven using photolithograph synthesis of microarrays.

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Intramolecular Sensitization of Photocleavage of the Photolabile 2‐(2‐Nitrophenyl)propoxycarbonyl (NPPOC) Protecting Group: Photoproducts and Photokinetics of the Release of Nucleosides

Abstract: „Meine größte Leistung ist noch nicht publiziert …︁ hoffe ich! Meine größte Motivation ist die Neugier …︁“ Dies und mehr von und über Manuel Alcarazo finden Sie auf Seite 6490.

Cited by 42 publications

References 33 publications

Development of Anionically Decorated Caged Neurotransmitters: In Vitro Comparison of 7‐Nitroindolinyl‐ and 2‐(p‐Phenyl‐o‐nitrophenyl)propyl‐Based Photochemical Probes

Development of Anionically Decorated Caged Neurotransmitters: In Vitro Comparison of 7‐Nitroindolinyl‐ and 2‐(p‐Phenyl‐o‐nitrophenyl)propyl‐Based Photochemical Probes

Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy

Next‐Generation o‐Nitrobenzyl Photolabile Groups for Light‐Directed Chemistry and Microarray Synthesis

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