Azobenzene photoswitches for biomolecules

Beharry, Andrew A.; Woolley, G. Andrew

doi:10.1039/c1cs15023e

Cited by 1,632 publications

(1,467 citation statements)

References 186 publications

(307 reference statements)

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“…Although these ideas remain to be experimentally validated, identifying general strategies for designing 2P azobenzenes would accelerate the development of new PTLs for optical manipulation of neurophysiology. These measurements may also possibly find wider impact in industrial and research applications where azobenzenes are used as molecular photoswitches, such as optical storage (58) and optomechanical manipulation of biomolecules (59).…”

Section: Discussionmentioning

confidence: 99%

Two-photon brightness of azobenzene photoswitches designed for glutamate receptor optogenetics

Carroll

Berlin

Levitz

et al. 2015

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

100

116

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Mammalian neurotransmitter-gated receptors can be conjugated to photoswitchable tethered ligands (PTLs) to enable photoactivation, or photoantagonism, while preserving normal function at neuronal synapses. "MAG" PTLs for ionotropic and metabotropic glutamate receptors (GluRs) are based on an azobenzene photoswitch that is optimally switched into the liganding state by blue or near-UV light, wavelengths that penetrate poorly into the brain. To facilitate deep-tissue photoactivation with near-infrared light, we measured the efficacy of two-photon (2P) excitation for two MAG molecules using nonlinear spectroscopy. Based on quantitative characterization, we find a recently designed second generation PTL, , to have a favorable 2P absorbance peak at 850 nm, enabling efficient 2P activation of the GluK2 kainate receptor, LiGluR. We also achieve 2P photoactivation of a metabotropic receptor, LimGluR3, with a new mGluR-specific PTL, D-MAG0 460 . 2P photoswitching is efficiently achieved using digital holography to shape illumination over single somata of cultured neurons. Simultaneous Ca 2+ -imaging reports on 2P photoswitching in multiple cells with high temporal resolution. The combination of electrophysiology or Ca 2+ imaging with 2P activation by optical wavefront shaping should make second generation PTL-controlled receptors suitable for studies of intact neural circuits.optogenetics | pharmacology | multiphoton | photoswitch | azobenzene M odern neurobiology relies heavily on optical microscopy to observe, and, increasingly, to manipulate (1, 2), biological processes in live tissue. Among these methods, 2-photon-excited fluorescence microscopy (2PM) with near-infrared (NIR) light has emerged as an important technique for extending optical microscopy to highly scattering tissue (3, 4). Remarkably, barely 25 years after the first 2P-excited fluorescence image was published (5), 2PM is now performed in awake, behaving animals (4, 6-8). Naturally, optical manipulations in the brain can benefit from the many advantages of 2PM (9). In particular, the inherent spatial confinement of 2P absorption is critical for optical manipulation of individual cells (10) in the intact mammalian brain, where it is difficult to control the spatial extent of gene expression or confine soluble reagents. However, 2P-excited optogenetics is not yet as widespread in adoption as 2PM, being widely perceived to require sophisticated optical techniques (11-13) or reagent concentrations that compromise pharmacological specificity (2, 14).The rapid time to adoption of 2PM owes at least some credit to the availability of spectroscopic data on the 2P-excited efficacy, or brightness, of synthetic and genetically encoded fluorophores (15-17). Brightness, defined for fluorophores as the product of absorption cross-section and fluorescence quantum yield, gives the experimenter an objective metric to assess fluorescent reporters and identify appropriate optical parameters, such as the optimal excitation wavelength and range of light intensities (18). By ...

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Section: Discussionmentioning

confidence: 99%

Two-photon brightness of azobenzene photoswitches designed for glutamate receptor optogenetics

Carroll

Berlin

Levitz

et al. 2015

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

100

116

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“…Structural information about the preferred configuration and conformation can be essential to understand different binding properties of the isomers of photo switchable molecules, for example, in biochemical applications 19. Furthermore, the time‐dependent conversion of different isomers can be tracked online by NMR and/or UV/Vis spectroscopy to show the active species present during a reaction.…”

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confidence: 99%

Combined In Situ Illumination‐NMR‐UV/Vis Spectroscopy: A New Mechanistic Tool in Photochemistry

2018

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Synthetic applications in photochemistry are booming. Despite great progress in the development of new reactions, mechanistic investigations are still challenging. Therefore, we present a fully automated in situ combination of NMR spectroscopy, UV/Vis spectroscopy, and illumination to allow simultaneous and time‐resolved detection of paramagnetic and diamagnetic species. This optical fiber‐based setup enables the first acquisition of combined UV/Vis and NMR spectra in photocatalysis, as demonstrated on a conPET process. Furthermore, the broad applicability of combined UVNMR spectroscopy for light‐induced processes is demonstrated on a structural and quantitative analysis of a photoswitch, including rate modulation and stabilization of transient species by temperature variation. Owing to the flexibility regarding the NMR hardware, temperature, and light sources, we expect wide‐ranging applications of this setup in various research fields.

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“…In general, the mechanism of photochromic systems usually relies on either: 1) cis-trans isomerization of C=C or N=N π-bonds [17,18], or 2) the making and breaking of chemical bonds [19]. While the simplicity of the former does lend itself to certain applications [20], we will focus on the latter due to its relevance in the photochemical formation of azaboratabisnorcaradienes (hereafter referred to as "dark isomers", see ppyBMes 2 -DI in Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

Isomerization and rearrangement of boriranes: from chemical rarities to functional materials

Mellerup

Wang

2018

Sci. China Mater.

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Stimuli responsive materials have recently been the subject of tremendous research efforts owing to their numerous potential applications. Although there currently exist many different types of "smart" materials, those based on photoresponsive transformations are especially attractive. In this review, we focus on a relatively new class of photochromic molecules based on the photochemistry of chelate organoborates, which form intensely colored, base-stabilized boriranes. Recent efforts to exploit the reactivity of these systems are summarized, and future prospects in materials science discussed.

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Azobenzene photoswitches for biomolecules

Cited by 1,632 publications

References 186 publications

Two-photon brightness of azobenzene photoswitches designed for glutamate receptor optogenetics

Two-photon brightness of azobenzene photoswitches designed for glutamate receptor optogenetics

Combined In Situ Illumination‐NMR‐UV/Vis Spectroscopy: A New Mechanistic Tool in Photochemistry

Isomerization and rearrangement of boriranes: from chemical rarities to functional materials

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