Photopharmacology: Beyond Proof of Principle

Velema, Willem A.; Szymański, Wiktor; Feringa, Bernard

doi:10.1021/ja413063e

Cited by 973 publications

(1,056 citation statements)

References 116 publications

(257 reference statements)

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“…[7][8][9][10][11][12] Applications differ markedly in the environment the photoswitch is exposed to,b ei td ifferent solvents, [13,14] matrices or surfaces,a nd understanding how ag iven photoswitch behaves in various environments is crucial for its success in any applications. Donor-acceptor Stenhouse adducts (DASAs,F igure 1a) were introduced in 2014 [17,18] and feature important advantages as compared to traditional photoswitches,i ncluding visible light responsiveness [11,19,20] and negative photochromism.…”

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Solvent Effects on the Actinic Step of Donor–Acceptor Stenhouse Adduct Photoswitching

et al. 2018

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Donor–acceptor Stenhouse adducts (DASAs) are negative photochromes that switch with visible light and are highly promising for applications ranging from smart materials to biological systems. However, the strong solvent dependence of the photoswitching kinetics limits their application. The nature of the photoswitching mechanism in different solvents is key for addressing the solvatochromism of DASAs, but as yet has remained elusive. Here, we employ spectroscopic analyses and TD‐DFT calculations to reveal changing solvatochromic shifts and energies of the species involved in DASA photoswitching. Time‐resolved visible pump‐probe spectroscopy suggests that the primary photochemical step remains the same, irrespective of the polarity and protic nature of the solvent. Disentangling the different factors determining the solvent‐dependence of DASA photoswitching, presented here, is crucial for the rational development of applications in a wide range of different media.

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Solvent Effects on the Actinic Step of Donor–Acceptor Stenhouse Adduct Photoswitching

et al. 2018

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“…[1,2] Azobenzenes are among the most studied photoswitchable compounds,s ince they are easily synthesized and highly stable. [3,4] Their high extinction coefficients and isomerization quantum yields enable repeated photoswitching with low-intensity light.…”

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Photoisomerization of Arylazopyrazole Photoswitches: Stereospecific Excited‐State Relaxation

Wang

Cui

et al. 2016

Angew Chem Int Ed

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Electronic structure calculations and nonadiabatic dynamics simulations (more than 2000 trajectories) are used to explore the Z-E photoisomerization mechanism and excitedstate decayd ynamics of two arylazopyrazole photoswitches. Tw oc hiral S 1 /S 0 conical intersections with associated enantiomeric S 1 relaxation paths that are barrierless and efficient (timescale of ca. 50 fs) were found. Forthe parent arylazopyrazole( Z8) both paths contribute evenly to the S 1 excited-state decay, whereas for the dimethyl derivative (Z11) each of the two chiral cis minima decays almost exclusively through one specific enantiomeric S 1 relaxation path. To our knowledge,the Z11 arylazopyrazole is thus the first example for nearly stereospecific unidirectional excited-state relaxation.Photoswitchable compounds have many potential applications ranging from photopharmacology through optochemical genetics to data storage. [1,2] Azobenzenes are among the most studied photoswitchable compounds,s ince they are easily synthesized and highly stable. [3,4] Their high extinction coefficients and isomerization quantum yields enable repeated photoswitching with low-intensity light. Photoinduced isomerization leads to ar emarkable change of the shape and length of these azobenzenes,w hich has been exploited, for example,intuning the folding and unfolding of peptides and proteins. [5][6][7][8] Many azobenzenes have been explored experimentally and computationally in the past decade, [9][10][11][12][13][14][15][16][17][18][19][20][21][22] but there remain af ew drawbacks that limit their broad application. These include incomplete photoswitching because of overlapping absorbance of the two isomers and fast thermal rearrangement of the cis isomer (Z)b ack to the trans isomer (E). To improve overall performance,many groups have explored the properties of azobenzene variants by altering the substituents on the aromatic rings,f or example,i nb ridged and orthohydroxy azobenzenes. [23][24][25][26][27][28][29][30] Recently,n ovel classes of azoheterocycle photoswitches were reported, [31][32][33][34][35][36] especially arylazopyrazoles,w hich provide quantitative photoswitching and high thermal stability (ca. 1000 days). [35,36] Thea bsorption band maxima of the Eand Z-isomers of arylazopyrazoles are found to be well separated, which enables quantitative two-way photoswitching.[35] Furthermore,t he substitution on the heterocyclic ring offers photophysical and photochemical properties that cannot be accessed with azobenzenes.H owever,t he photoinduced isomerization mechanism and the dynamical behavior of these arylazopyrazoles are still unexplored at the atomistic level. Obvious questions that remain are: 1) Whether azobenzenes and arylazopyrazoles share similar photophysical and photochemical mechanisms and 2) whether they show analogous dynamical behavior (lifetimes,c onical intersections,p ath selectivities). Ad etailed mechanistic understanding will be helpful to further improve their performance through rational design. Motivated by ...

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“…6 Furthermore, the spatiotemporal control of chemical reactions could contribute to evolutions of various fields such as material sciences 34 and drug discovery. 35 Although the prospective utility of the spatiotemporal control of chemical reactions with the stimuli-responsive catalysts is enormous, most of the demonstrated spatiotemporal controls of chemical reactions are simple and are not distinguished from the practical point of view at the present stage. The field of stimuli-responsive dynamic cooperative catalysts is still immature.…”

Section: Resultsmentioning

confidence: 99%

Stimuli-responsive Cooperative Catalysts Based on Dynamic Conformational Changes toward Spatiotemporal Control of Chemical Reactions

Imahori

Kurihara

2014

Chemistry Letters

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Photopharmacology: Beyond Proof of Principle

Cited by 973 publications

References 116 publications

Solvent Effects on the Actinic Step of Donor–Acceptor Stenhouse Adduct Photoswitching

Solvent Effects on the Actinic Step of Donor–Acceptor Stenhouse Adduct Photoswitching

Photoisomerization of Arylazopyrazole Photoswitches: Stereospecific Excited‐State Relaxation

Stimuli-responsive Cooperative Catalysts Based on Dynamic Conformational Changes toward Spatiotemporal Control of Chemical Reactions

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