Molecular photoswitches in aqueous environments

Volarić, Jana; Szymański, Wiktor; Simeth, Nadja A.; Feringa, Ben L.

doi:10.1039/d0cs00547a

Cited by 195 publications

(280 citation statements)

References 814 publications

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“…Azobenzene derivatives are the most studied class of molecular switches [12–24] . Large change in molecular geometry and polarity in these materials has been exploited in the development of diverse functional materials and systems [25–30] .…”

Section: Different Classes Of Visible Light‐driven Molecular Switches...mentioning

confidence: 99%

“…Azobenzene derivatives are the most studied class of molecular switches. [12][13][14][15][16][17][18][19][20][21][22][23][24] Large change in molecular geometry and polarity in these materials has been exploited in the development of diverse functional materials and systems. [25][26][27][28][29][30] Out of the two characteristic absorption bands of azobenzene derivatives, the π-π* transition usually lies in the UV region whereas the n-π* transition falls in the visible region.…”

Section: Azobenzene Derivativesmentioning

confidence: 99%

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Visible Light‐Driven Molecular Switches and Motors: Recent Developments and Applications

Wang

Bisoyi

Zhang

et al. 2022

Chemistry A European J

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Inspired by human vision, a diverse range of light‐driven molecular switches and motors have been developed for fundamental understanding and application in material science and biology. Recently, the design and synthesis of visible light‐driven molecular switches and motors have been actively pursued. This emerging trend is partly motivated to avoid the harmful effects of ultraviolet light, which was necessary to drive the classical molecular switches and motors at least in one direction, impeding their employment in biomedical and photopharmacology applications. Moreover, visible light‐driven molecular switches and motors are demonstrated to enable benign optical materials for advanced photonic devices. Therefore, during the past several years, visible light‐driven molecular switches based on azobenzene derivatives, diarylethenes, 1,2‐dicyanodithienylethenes, hemithioindigo derivatives, iminothioindoxyls, donor‐acceptor Stenhouse adducts, and overcrowded alkene based molecular motors have been judiciously designed, synthesized, and used in the development of functional materials and systems for a wide range of applications. In this Review, we present the recent developments toward the design of visible light‐driven molecular switches and motors, with their applications in the fabrication of functional materials and systems in material science, bioscience, pharmacology, etc. The visible light‐driven molecular switches and motors realized so far undoubtedly widen the scope of these interesting compounds for technological and biological applications. We hope this Review article could provide additional impetus and inspire further research interests for future exploration of visible light‐driven advanced materials, systems, and devices.

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Section: Different Classes Of Visible Light‐driven Molecular Switches...mentioning

confidence: 99%

Section: Azobenzene Derivativesmentioning

confidence: 99%

Visible Light‐Driven Molecular Switches and Motors: Recent Developments and Applications

Wang

Bisoyi

Zhang

et al. 2022

Chemistry A European J

View full text Add to dashboard Cite

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“…3,[8][9][10][11] The mechanism of solute-solute interactions in these assemblies is well-established, 1,2,4 whereas the solute-solvent interplay attracted the interest of supramolecular chemists more recently. [12][13][14] Water is a unique medium for self-assembly in Nature, and many exquisite assemblies, [15][16][17][18][19][20][21][22][23][24] low-molecular-weight gels, [25][26][27][28][29] and supramolecular polymers [30][31][32][33][34][35][36] have been developed in aqueous media focusing on various applications, such as biomolecular materials 37,38 and soft actuators. [39][40][41] However, detailed insight into supramolecular polymerization in water is far from being as well understood as it is in organic solvents.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insight into Supramolecular Polymerization in Water Tunable by Molecular Geometry

Crespi

Pfeifer

et al. 2022

CCS Chem

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Supramolecular self-assembly in water is attracting major attention due to the potential of hydrogels and aqueous polymers based on non-covalent bonding for biomedical applications. Although supramolecular polymerization in organic solvents is well established, the key design features, the assembly mechanisms in water and achieving control over the aggregate structures remain challenging. Here, we present the assembly and disassembly of geometrical isomers of a stiff-stilbene bis-urea amphiphile (SA) in pure water. A remarkable feature of this system is that the (E)-isomer forms supramolecular polymers in both pure water and organic solvents. Taking advantage of this unique property, the hydrophobic effect could be studied by comparing the supramolecular assembly in both systems. The assembly process in water follows an enthalpy-driven nucleation-elongation (cooperative) supramolecular polymerization mechanism with a standard Gibbs free energy (ΔG° = -53 kJ mol −1 ), double the value compared to the one found in toluene. This distinctive feature is attributed to the hydrophobic effect in water. Furthermore, we discovered an isomer-dependent assembly process, which can be

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“…This indirect physicochemical refinement highlights a crucial issue of the azo-extension strategy, that is, how to achieve switching in aqueous environment facing the substantial increase in lipophilicity and molecular weight that naturally stems from the attachment of an azobenzene to an existing drug. 62 In response to such a tendency, we have shown that structure-based optimization can help photopharmacology to obtain more elegant molecular designs. Nevertheless, the above-mentioned improvements came at the expense of the inhibitory potencies of our compounds, with the best derivative (compound 15 ) being 1 order of magnitude less potent than the previously reported TMP conjugates ( Table S3 ).…”

Section: Discussionmentioning

confidence: 99%

Hypothesis-Driven, Structure-Based Design in Photopharmacology: The Case of eDHFR Inhibitors

et al. 2022

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Photopharmacology uses light to regulate the biological activity of drugs. This precise control is obtained through the incorporation of molecular photoswitches into bioactive molecules. A major challenge for photopharmacology is the rational design of photoswitchable drugs that show light-induced activation. Computer-aided drug design is an attractive approach toward more effective, targeted design. Herein, we critically evaluated different structure-based approaches for photopharmacology with Escherichia coli dihydrofolate reductase (eDHFR) as a case study. Through the iterative examination of our hypotheses, we progressively tuned the design of azobenzene-based, photoswitchable eDHFR inhibitors in five design–make–switch–test–analyze cycles. Targeting a hydrophobic subpocket of the enzyme and a specific salt bridge only with the thermally metastable cis -isomer emerged as the most promising design strategy. We identified three inhibitors that could be activated upon irradiation and reached potencies in the low-nanomolar range. Above all, this systematic study provided valuable insights for future endeavors toward rational photopharmacology.

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Molecular photoswitches in aqueous environments

Abstract: Molecular photoswitches are inherently lipophilic and do not spontaneously dissolve in water. We describe the effect of water on the photochemical properties and strategies to solubilize organic photoswitches and apply them in aqueous media.

Cited by 195 publications

References 814 publications

Visible Light‐Driven Molecular Switches and Motors: Recent Developments and Applications

Visible Light‐Driven Molecular Switches and Motors: Recent Developments and Applications

Mechanistic Insight into Supramolecular Polymerization in Water Tunable by Molecular Geometry

Hypothesis-Driven, Structure-Based Design in Photopharmacology: The Case of eDHFR Inhibitors

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