Photochromic coenzyme Q derivatives: switching redox potentials with light

Simeth, Nadja A.; Kneuttinger, Andrea Christa; Sterner, Reinhard; König, Burkhard

doi:10.1039/c7sc00781g

Cited by 29 publications

(35 citation statements)

References 57 publications

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“…GFP/YFP) such that orthogonal photocontrol is not possible; (3) azobenzenes face restricted substituent scope for cytosolic applications as photopharmaceuticals, since if strong ortho/para-electron-donating groups (OH, NH2 etc) or pushpull substituent configurations are present, this causes µs relaxation rates meaning that the products are not bulk photoisomerisable under biocompatible conditions in aqueous media (especially problematic since these substituents are powerful point interaction groups for establishing ligand-target interactions and specificity). Only recently has the range of photoswitchable scaffolds incorporated into bioactive pharmacophores been expanded to include dithienylethenes 51 and hemithioindigos, 39 and the development of novel scaffolds with promising photoswitchability is recognised as a valuable milestone even before achieving cellular applications. 52 Here we aim to usefully expand the toolbox of photoswitches for chemical biology, by demonstrating that styrylbenzothiazoles (SBTs) -a chemical scaffold with simplicity comparable to that of azobenzenes -can deliver spatiotemporally-precise, photoswitching-based control over critical cell biology processes, but with (1) added biochemical/metabolic robustness important for intracellular targets and in vivo application, (2) full orthogonality to common imaging conditions enabling easy adoptation of the photoswitch in existing biological systems, (3) alternative ranges of isomerisation-tolerant substituents (eg.…”

Section: Discussion and Outlookmentioning

confidence: 99%

Photoswitchable microtubule inhibitors enabling robust, GFP-orthogonal optical control over the tubulin cytoskeleton

Gao

Kraus

Wranik

et al. 2019

Preprint

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Here we present GFP-orthogonal optically controlled reagents for reliable and repetitive in cellulo modulation of microtubule dynamics and its dependent processes. Optically controlled reagents ("photopharmaceuticals") have developed into powerful tools for high-spatiotemporal-precision control of endogenous biology, with numerous applications in neuroscience, embryology, and cytoskeleton research. However, the restricted chemical domain of photopharmaceutical scaffolds has constrained their properties and range of applications. Styrylbenzothiazoles are an as-yet unexplored scaffold for photopharmaceuticals, which we now rationally design to feature potent photocontrol, switching microtubule cytoskeleton function off and on according to illumination conditions. We show more broadly that this scaffold is exceptionally chemically and biochemically robust as well as substituent-tolerant, and offers particular advantages for intracellular biology through a range of desirable photopharmaceutical and drug-like properties not accessible to the current classes of photoswitches. We expect that these reagents will find powerful applications enabling robust, high precision, optically controlled cell biological experimentation in cytoskeleton research and beyond. Introduction:Molecular photoswitches have been used to install optical control over a broad range of phenomena, with applications from material sciences 1,2 through to reversible photocontrol of ligand binding affinities 3 and manipulation of diverse cellular processes in chemical biology 4,5 . For studies of temporally-regulated and spatially anisotropic biological systems, particularly those that simultaneously support several cellular functions, photoswitchable inhibitors conceptually enable a range of powerful studies not accessible with other tool systems. [6][7][8] A prime example of such spatiotemporally regulated, multifunctional systems is the microtubule (MT) cytoskeleton. This complex cellular network plays central roles in nearly all directed mechanical processes, such as intracellular transport and cell motility; its crucial function in cell proliferation has also made it a central anticancer drug target. 9-11 Yet, whereas cytoskeleton research typically aims to study a subset of MT-dependent processes that are spatially and/or temporally localised, nearly all MT inhibitors reported as tool compounds for biological research are drugs that are active wherever they are distributed, including at sites and at times where drug activity is not desired. 12 This restricts the scope of applications and utility of these inhibitors for selective research into the various, highly dynamic, anisotropic processes dependent on MTs. 13 The structure of the colchicine site MT inhibitor combretastatin A-4 (CA4; Fig 1a) 14 has recently inspired photoswitchable solutions to the problem of achieving spatiotemporal control over MT inhibition. CA4 is a stilbene whose Z-isomer (cis) binds tubulin, acts as a low nanomolar cytotoxin in cellulo, and reached Phase III trials as an ...

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Section: Discussion and Outlookmentioning

confidence: 99%

Photoswitchable microtubule inhibitors enabling robust, GFP-orthogonal optical control over the tubulin cytoskeleton

Gao

Kraus

Wranik

et al. 2019

Preprint

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“…Among them, photochromic molecules are particularly attractive for the ability to convert between (at least) two states by noninvasive and rapid optical stimuli with a potential of high spatial and temporal resolution . Additionally, multiple photochromic molecules have been developed, which in addition to light respond to a secondary stimulus, such as the presence of ions, oxidants/reductants, or acids/bases . On the one hand, the second stimulus can gate the photochromism, leading to potential applications for example in logic devices.…”

Section: Figurementioning

confidence: 99%

Proton‐Gated Ring‐Closure of a Negative Photochromic Azulene‐Based Diarylethene

et al. 2020

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Proton-responsive photochromic molecules are attractive for their ability to react on non-invasive rapid optical stimuli and the importance of protonation/deprotonation processes in various fields. Conventionally, their acidic/basic sites are on hetero-atoms, which are orthogonal to the photoactive p-center. Here, we incorporate azulene, an acid-sensitive pure hydrocarbon, into the skeleton of a diarylethene-type photoswitch. The latter exhibits a novel proton-gated negative photochromic ring-closure and its optical response upon protonation in both open and closed forms is much more pronounced than those of diarylethene photoswitches with hetero-atom based acidic/basic moieties. The unique behavior of the new photoswitch can be attributed to direct protonation on its p-system, supported by 1 H NMR and theoretical calculations. Our results demonstrate the great potential of integrating non-alternant hydrocarbons into photochromic systems for the development of multi-responsive molecular switches.

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“…These interesting two‐way gating performances have been applied as photocontrollable adhesives for connecting/disconnecting nanoparticles[33a] and polymers (Figure b,c). [33b] Very recently, König and co‐workers “placed” a quinone on the ethene bridge which was able to mimic the coenzyme Q redox factor . During photoisomerization, the structure of the quinone bridges reversibly changed, altering the redox potential of the diarylethene.…”

Section: Designing New Members For Diarylethene Familymentioning

confidence: 99%

Section: Designing New Members For Diarylethene Familymentioning

confidence: 99%

The Endeavor of Diarylethenes: New Structures, High Performance, and Bright Future

Zhang

Tian

2018

Advanced Optical Materials

206

127

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Photochromism is a term that describes the photoreversible isomerization between two different states or isomers with distinct performances. Among all the photochromic molecule family, diarylethene is considered one of the most popular star molecules on account of its fast photoresponsibility, excellent thermal stability, fatigue resistance, high photoreaction quantum yield, and conversion ratio as well as good performances in both solution and solid phases. In the past decades, the development of diarylethene is witnessed in molecule design, solution applications, surface/interface assembly, bulky crystals and polymers, optic‐electronic devices fabrication, and biotechnology. This review mainly focuses on the latest development of diarylethenes in recent five years and commences with the newly designed molecular structures with functional ethene bridges and aryl moieties. The application of diarylethenes in materials science, soft materials, molecular data processing, and biomaterials, is further discussed in prospect. A brief summary is given in the end of the review together with some perspectives.

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Photochromic coenzyme Q derivatives: switching redox potentials with light

Abstract: A photochromic coenzyme Q derivative could be activated through irradiation with orange light and initiate redox reactions with Hantzsch ester and on isolated mitochondria.

Cited by 29 publications

References 57 publications

Photoswitchable microtubule inhibitors enabling robust, GFP-orthogonal optical control over the tubulin cytoskeleton

Photoswitchable microtubule inhibitors enabling robust, GFP-orthogonal optical control over the tubulin cytoskeleton

Proton‐Gated Ring‐Closure of a Negative Photochromic Azulene‐Based Diarylethene

The Endeavor of Diarylethenes: New Structures, High Performance, and Bright Future

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