Property-selected Asymmetric Azobenzenes for Photoswitchable Ligands

Kuellmer, Florian; Gregor, Lucas; Arndt, Hans‐Dieter

doi:10.26434/chemrxiv-2022-fd950

Cited by 4 publications

(4 citation statements)

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“…A subsequent ring closing metathesis, followed by deprotection, furnished a primary amine, which underwent amide coupling with a variety of azobenzene carboxylic acids. 27 This gave a library of depsipeptides, exemplified by compounds 5-14, which feature a benzomorpholine moiety with different Nsubstituents. Derivatives with an extended linker, such as 15, were explored as well (Fig 2D, Table S6).…”

Section: Design Synthesis and Preliminary Evaluationmentioning

confidence: 99%

Next Generation Opto‐Jasplakinolides Enable Local Remodeling of Actin Networks**

et al. 2022

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The natural product jasplakinolide is a widely used tool compound to stabilize F-actin and influence actin dynamics. We have previously introduced photoswitchable jasplakinolides (optojasps) that are activated with violet light and deactivated with blue light. Based on insights from cryo-electron microscopy and structure-activity relationship (SAR) studies, we now developed a new generation of functionally superior optojasps that are better suited for biological investigations. These compounds are procured through chemical total synthesis and feature rationally designed red-shifted azobenzene photoswitches. Our new optojasps can be activated with longer wavelengths in the visible range (e.g. 440-477 nm) and rapidly return to their inactive state through thermal relaxation. This has enabled the reversible control of F-actin dynamics, as shown through live-cell imaging and cell migration, as well as cell proliferation assays. Brief subcellular activation with blue-green light resulted in highly localized F-actin clusters that gradually dissolved in the dark. Our light-responsive tools can be useful in diverse fields to study actin dynamics with outstanding spatiotemporal precision..

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Section: Design Synthesis and Preliminary Evaluationmentioning

confidence: 99%

Next Generation Opto‐Jasplakinolides Enable Local Remodeling of Actin Networks**

et al. 2022

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“…A subsequent ring closing metathesis, followed by deprotection, furnished a primary amine, which underwent amide coupling with a variety of azobenzene carboxylic acids. 27 This gave a library of depsipeptides, exemplified by compounds 5-14 , which feature a benzomorpholine moiety with different N -substituents. Derivatives with an extended linker, such as 15 , were explored as well (Fig 2D, Table S6 ).…”

Section: Introductionmentioning

confidence: 99%

Next Generation Opto-Jasplakinolides Enable Local Remodeling of Actin Networks

Küllmer

Vepřek

Borowiak

et al. 2022

Preprint

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The natural product jasplakinolide is a widely used tool compound to stabilize F-actin and influence actin dynamics. We have previously introduced photoswitchable jasplakinolides (optojasps) that are activated with violet light and deactivated with blue light. Based on insights from cryo-electron microscopy and structure-activity relationship (SAR) studies, we now developed a new generation of functionally superior optojasps that are better suited for biological investigations. These compounds are procured through chemical total synthesis and feature rationally designed red-shifted azobenzene photoswitches. Our new optojasps can be activated with longer wavelengths in the visible range (e.g. 440-477 nm) and rapidly return to their inactive state through thermal relaxation. This has enabled the reversible control of F-actin dynamics, as shown through live-cell imaging and cell migration, as well as cell proliferation assays. Brief sub-cellular activation with blue-green light resulted in highly localized F-actin clusters that gradually dissolved in the dark. Our light-responsive tools can be useful in diverse fields to study actin dynamics with outstanding spatiotemporal precision.

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“…Several azobenzene substitution patterns have been developed to tune the isomers’ spectra and thus the photoresponsiveness and completion of photoisomerizations . Tetra- ortho- substitutions particularly improve photoswitch performance, without necessarily compromising their function (since most azobenzene photopharmaceuticals are “azo-extension” or “azo-linker” designs, where only the 4,4′ positions determine bioactivity). − Hecht’s tetra- ortho- fluoro pattern gives excellent E → Z isomerization at 500 nm and Z → E isomerization at 400 nm .…”

Section: Introductionmentioning

confidence: 99%

Exhaustive Catalytic ortho-Alkoxylation of Azobenzenes: Flexible Access to Functionally Diverse Yellow-Light-Responsive Photoswitches

Müller-Deku

Thorn‐Seshold

2022

J. Org. Chem.

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We develop the first method for catalytic, exhaustive ortho-alkoxylation of azobenzene photoswitches. Alkoxylation is known to improve the photoswitch properties that control azobenzenes’ success in chemical biology or materials sciences, e.g., better completeness of both E → Z and Z → E photoisomerizations and >100 nm red shift of photoresponse. Our method enables straightforward late-stage diversification of photoswitches with interesting functional handles. We showcase four applications: using it to rationally tune lipophilicity, prepare isotopic tracers for metabolism studies, install full water solubility without ionic charges, and efficiently access previously difficult mixed-substituent photoswitches. We also identified a previously unexplored mixed-substituent tetra-ortho family, difluoro-dialkoxy-azobenzenes, whose photoresponse can outperform previous ‘gold standard’ tetrafluoro-, dichloro-difluoro-, and tetrachloro-azobenzenes in significant ways. We thus expect that both the scaffolds we showcase and the method we develop will impact broadly on photochemistry and photopharmacology.

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Property-selected Asymmetric Azobenzenes for Photoswitchable Ligands

Cited by 4 publications

References 0 publications

Next Generation Opto‐Jasplakinolides Enable Local Remodeling of Actin Networks**

Next Generation Opto‐Jasplakinolides Enable Local Remodeling of Actin Networks**

Next Generation Opto-Jasplakinolides Enable Local Remodeling of Actin Networks

Exhaustive Catalytic ortho-Alkoxylation of Azobenzenes: Flexible Access to Functionally Diverse Yellow-Light-Responsive Photoswitches

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