Development of Green/Red-Absorbing Chromophores Based on a Coumarin Scaffold That Are Useful as Caging Groups

Gandioso, Albert; Contreras, Sara; Melnyk, Ivanna; Oliva, Javier; Nonell, Santi; Velasco, Dolores; García-Amorós, Jaume; Marchán, Vicente

doi:10.1021/acs.joc.7b00788

Cited by 64 publications

(98 citation statements)

References 54 publications

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“…After reaction with N ‐(tert‐butoxycarbonyl)glycine (Boc‐gly‐OH) and deprotection, this gave the coumarin‐caged glycine 3 (Figures S2 and S3, Supporting Information) . Coumarin 1 was chosen as caging group as it is expected to be photochemically active in the visible region due to the electron‐donating diethylamino group . The kinetics of the elementary photochemical reaction of 3 has been investigated recently by flash‐photolysis but not under steady illumination.…”

Section: Methodsmentioning

confidence: 99%

Coumarin‐Caged Polyphosphazenes with a Visible‐Light Driven On‐Demand Degradation

Iturmendi

Theis

Maderegger

et al. 2018

Macromol. Rapid Commun.

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Polymers that, upon photochemical activation with visible light, undergo rapid degradation to small molecules are described. Through functionalization of a polyphosphazene backbone with pendant coumarin groups sensitive to light, polymers which are stable in the dark could be prepared. Upon irradiation, cleavage of the coumarin moieties exposes carboxylic acid moieties along the polymer backbone. The subsequent macromolecular photoacid is found to catalyze the rapid hydrolytic degradation of the polyphosphazene backbone. Water-soluble and non-water-soluble polymers are reported, which due to their sensitivity toward light in the visible region could be significant as photocleavable materials in biological applications.

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Section: Methodsmentioning

confidence: 99%

Coumarin‐Caged Polyphosphazenes with a Visible‐Light Driven On‐Demand Degradation

Iturmendi

Theis

Maderegger

et al. 2018

Macromol. Rapid Commun.

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“…7bc,15 This modification has been applied in a coumarin-based commercially available dye (AlexaFluor 430) and in the xanthene skeleton for developing deep-red and NIR dyes. 9b, 16 Since we and others have demonstrated the utility of thiocoumarin derivatives to introduce the dicyanomethylene functionality within the coumarin skeleton, 12bcde we first synthesized thiocoumarins 2 13 and 6 by reaction with Lawesson's reagent (LW, Scheme 2). To our delight, condensation with 4pyridylacetonitrile in the presence of a strong base followed by treatment with silver nitrate afforded coumarins 7 and 8 in excellent yields after silica column chromatography (89 % and 84 %, respectively).…”

Section: Design Synthesis and Characterization Of Coupy Scaffoldsmentioning

confidence: 99%

“…13 Although such modifications red-shifted absorption into the green to red region and allowed to obtain new caging groups photoremovable with visible light, the incorporation of several strong EWGs such as nitro was found to have a negative effect on the fluorescence emission of the compounds. 13 Scheme 1. Rational design of the new coumarin-based fluorophores synthesized in this work.…”

Section: Introductionmentioning

confidence: 99%

Redesigning the Coumarin Scaffold into Small Bright Fluorophores with Far-Red to Near-Infrared Emission and Large Stokes Shifts Useful for Cell Imaging

et al. 2018

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Among the palette of previously described fluorescent organic molecules, coumarins are ideal candidates for developing cellular and molecular imaging tools due to their high cell permeability and minimal perturbation of living systems. However, blue-to-cyan fluorescence emission is usually difficult in in vivo applications due to the inherent toxicity and poor tissue penetration of short visible light wavelengths. Here, we introduce a new family of coumarin-based fluorophores, nicknamed COUPY, with promising photophysical properties, including emission in the far-red/near-infrared (NIR) region, large Stokes shifts, high photostability, and excellent brightness. COUPY fluorophores were efficiently synthesized in only three linear synthetic steps from commercially available precursors, with the N-alkylation of a pyridine moiety being the key step at the end of the synthetic route, as it allows for the tuning of the photophysical properties of the resulting dye. Owing to their low molecular weights, COUPY dyes show excellent cell permeability and accumulate selectively in nucleoli and/or mitochondria of HeLa cells, as their far-red/NIR fluorescence emission is easily detected at a concentration as low as 0.5 μM after an incubation of only 20 min. We anticipate that these coumarin scaffolds will open a way to the development of novel coumarin-based far-red to NIR emitting fluorophores with potential applications for organelle imaging and biomolecule labeling.

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“…RuBi does not work for acidic bonds and so many groups have explored different coumarin chromophores as visible-light absorbing photochemical protecting groups. However, even though these chromophores absorb light much more efficiently than RuBi, they seem to have much lower quantum yields, ranging from 0.005 27 – 0.003 28 to as low as 0.0000001 29 . Similar trends are seen when using the BODIPY fluorophore as a photochemical protecting group, with a caged GABA photolysis quantum yield of 0.0003 30 .…”

Section: Resultsmentioning

confidence: 99%

Intracellular Uncaging of cGMP with Blue Light

Agarwal

Zhai

Surmeier

et al. 2017

ACS Chem. Neurosci.

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We have made a new caged cGMP that is photolyzed with blue light. Using our recently developed derivative of 7-diethylaminocourmarin (DEAC) called DEAC450, we synthesized coumarin phosphoester derivatives of cGMP with two negative charges appended to the DEAC450 moiety. DEAC450-cGMP is freely soluble in physiological buffer without the need for any organic co-solvents. With a photolysis quantum yield of 0.18 and an extinction coefficient of 43,000 M−1 cm−1 at 453 nm, DEAC450-cGMP is the most photosensitive caged cGMP made to date. In patch-clamped neurons in acutely isolated brain slices, blue light effectively uncaged cGMP from DEAC450 and facilitated activation of hyperpolarization and cyclic nucleotide gated cation (HCN) channels in cholinergic interneurons. Thus, DEAC450-cGMP has a unique set of optical and chemical properties that make it a useful addition to the optical arsenal available to neurobiologists.

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Development of Green/Red-Absorbing Chromophores Based on a Coumarin Scaffold That Are Useful as Caging Groups

Abstract: TOC ABSTRACT GRAPHIC3

Cited by 64 publications

References 54 publications

Coumarin‐Caged Polyphosphazenes with a Visible‐Light Driven On‐Demand Degradation

Coumarin‐Caged Polyphosphazenes with a Visible‐Light Driven On‐Demand Degradation

Redesigning the Coumarin Scaffold into Small Bright Fluorophores with Far-Red to Near-Infrared Emission and Large Stokes Shifts Useful for Cell Imaging

Intracellular Uncaging of cGMP with Blue Light

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