(Coumarin‐4‐yl)methyl Esters as Highly Efficient, Ultrafast Phototriggers for Protons and Their Application to Acidifying Membrane Surfaces

Kinetics of fluorescence changes on top of three different lipid bilayers due to lateral proton migration. The observation area was located at a distance of 70 μm from the area of proton release. Because all FPE molecules are surrounded by DPhPC or DPhPE molecules, they are anticipated to accept protons, which are released from these molecules. GMO does not possess ionizable moieties so that in case of two-dimensional diffusion, proton release from one FPE molecule seems to be required before the next FPE molecule may pick up the proton. Despite the huge differences in proton release rates from the different lipids, τ max for all three lipid bilayers was similar. That is, lateral proton diffusivity is independent of the choice of the lipid. The buffer contained 0.1 mM Capso (pH 9.0) and 100 mM NaCl. The F1 Wv/+ mice were then backcrossed to A/J mice for 10 generations, creating A/J N10 Wv/+ mice. These were then crossed to B6 Wv/+ mice to create F1 wildtype and F1 Wv/Wv mice for study. A/J mice had an increased airway resistance compared to B6 mice, and F1 mice had a naïve AHR phenotype equivalent to their parental A/J strain. F1 Wv/Wv mice displayed an airway resistance similar to normoresponsive B6 mice. Values represent mean ± SE, n = at least 10 in each group.

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“…In addition, we found that D B on PC membranes is orders of magnitude larger (10)(11)(12) than suggested by the "jump" model (Eq. 1).…”

mentioning

confidence: 54%

Protons migrate along interfacial water without significant contributions from jumps between ionizable groups on the membrane surface

Springer

Hagen²,

Cherepanov³

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

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102

140

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“…Thus, the release of phosphoric acid, methanesulfonic acid, or sulfuric acid derivatives from their coumarin-caged precursors 151 has been employed as a proton trigger in studies of proton-dependent cellular signal transduction (Scheme 57). 307 The release occurred within 2 ns, giving a significant drop in the pH of up to three units. It was also noted that hydrophobic phosphate derivatives penetrate cell membranes whereas charged sulfate was membrane-impermeant.…”

Section: Coumarin-4-ylmethyl Groupsmentioning

confidence: 99%

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

et al. 2012

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“…Based on the same principles, derivatives of anthraquinone (aqmoc) [43], pyrene [44], coumarin [45][46][47][48][49][50][51][52][53], and phenanthrene have each been used in certain instances (Scheme 13.12) [54]. …”

Section: Benzyl Alcohol Derivativesmentioning

confidence: 99%

“…An extra bonus here is the three-dimensional spatial control (standard photolysis allows control within a plane, whereas the focusing point addresses the third, orthogonal dimension). Chromophores with a large two-photon absorption (2PA) cross-section are still rare, although a few have been described during the past decade (Scheme 13.33) [49,52,[124][125][126][127][128][129][130][131][132]. As noted in the above sections, PPGs constitute a quite large family of protecting groups, and are definitely not limited to the standard ortho-nitrobenzylic derivatives.…”

Section: Two-photons Absorptionmentioning

confidence: 99%

Photolabile Protecting Groups in Organic Synthesis

Bochet

Blanc

2009

Handbook of Synthetic Photochemistry

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Protecting groups are crucial tools in organic synthesis, and their involvement increases with the length of a synthetic route. However, as their number increases within the same molecule, the problem of their individual and selective removal becomes a critical issue. This is well known as the orthogonality problem. Two groups are called orthogonal if they can be removed selectively under specific reaction conditions without mutual interference, and in any given sequence [1]. Unfortunately, the dimensions in the space of orthogonal groups are limited. Such dimensions are traditionally acidic, basic, nucleophilic, reductive, and oxidative conditions. A few more exotic specific conditions exist (and are highly desirable), and photolability is clearly one of these. It is attractive because no other reagent than light is required, thus limiting the chances of interference. Of course, the intrinsic photoreactivity of the remaining functional groups of the molecule is a liability, and many of the chapters in this Handbook have covered this topic. Thus, in order to have only reactivity at the desired sitethat is, removal of the protecting groupit is necessary to have a high absorbance of that group and a high quantum yield for its cleavage, to ensure that only short irradiation times are required.As the field of photolabile protecting groups (PPGs) has been reviewed on several occasions [2][3][4][5][6][7][8], the aim of this chapter is not to update the existing catalogues of groups. Indeed, when photolability has been selected as a candidate to solve a problem, the plethora of groupssometimes with contradictory behaviors and reaction conditionsmight deter even the most daring synthetic chemist. In an attempt to better guide the experimentalist, the decision was taken to divide the groups into major families based on a specific reaction, and then to list the variations on the groups, detailing their effects on reactivity. The application of photolabile protecting groups to the chemical functions is reported in Appendix 13.6, followed by a list of typical conditions and yields for protection and deprotection procedures.Handbook of Synthetic Photochemistry. Edited

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(Coumarin‐4‐yl)methyl Esters as Highly Efficient, Ultrafast Phototriggers for Protons and Their Application to Acidifying Membrane Surfaces

Cited by 87 publications

References 26 publications

Protons migrate along interfacial water without significant contributions from jumps between ionizable groups on the membrane surface

Protons migrate along interfacial water without significant contributions from jumps between ionizable groups on the membrane surface

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

Photolabile Protecting Groups in Organic Synthesis

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