Dual-light control of nanomachines that integrate motor and modulator subunits

Foy, Justin T.; Li, Quan; Goujon, Antoine; Colard-Itté, Jean-Rémy; Fuks, Gad; Moulin, Émilie; Schiffmann, Olivier; Dattler, Damien; Funeriu, Daniel P.; Giuseppone, Nicolas

doi:10.1038/nnano.2017.28

Cited by 229 publications

(189 citation statements)

References 34 publications

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“…Light is another trigger of choice offering the advantage of precise photopatterning and allows to alter hydrogels' mechanical properties either permanently by implementing photocleavable groups or reversibly using photochromic molecules, such as spiropyrans or azobenzenes . Following the latter strategy, noncovalent physical gels typically lead to materials with light‐induced sol–gel transitions, whereas covalent chemical gels can exhibit more finely tuneable phenomena such as photoinduced motion, or softening/hardening. Photoswitchable hydrogels exhibiting modulation of their mechanical properties have been described; however, their activation requires UV light, which displays several drawbacks related to its damaging character for the materials and its surrounding, as well as its limited light penetration …”

Section: Introductionmentioning

confidence: 99%

Reversible Modulation of Elasticity in Fluoroazobenzene‐Containing Hydrogels Using Green and Blue Light

Zhao

Bonasera

Nöchel

et al. 2017

Macromol. Rapid Commun.

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Gels are especially sensitive to their environment and can be designed to readily respond to variations in, typically, pH or temperature. [5] Light is another trigger of choice offering the advantage of precise photopatterning [4] and allows to alter hydrogels' mechanical properties either permanently by implementing photo cleavable groups [6] or reversibly using photochromic molecules, such as spiro pyrans [7,8] or azobenzenes. [9] Following the latter strategy, noncovalent physical gels typically lead to materials with light induced sol-gel transitions, [10][11][12][13] whereas covalent chemical gels can exhibit more finely tuneable phenomena such as pho toinduced motion, [14][15][16][17][18] or softening/ hardening. Photoswitchable hydrogels exhibiting modulation of their mechanical properties have been described; [16,19] how ever, their activation requires UV light, which displays several drawbacks related to its damaging character for the materials and its surrounding, as well as its limited light penetration. [20] Here, we present a polyethylene glycol (PEG) hydrogel incorporating ortho fluoroazobenzenes [21] as cross linkers (see F4-azo-PEG; Figure 1) and exhibiting reversible photomodula tion of elasticity using blue and green light. Ortho fluoroazoben zenes (abbreviated to F azos in the following) were selected as photochromic moieties due to their full addressability with visible light and very high thermal stabilities of the thermo dynamically less stable Z isomers. F azos were functionalized in para positions with amide linkers, since such electron with drawing groups maximize the separation of E and Z isomers' n→π* bands in the visible region [22] (see Figure 2a) and hence promote higher photoisomerization yields using blue (Z→E) or green (E→Z) light. Results and DiscussionF4-azo-PEG gel samples were prepared via strain promoted click cycloaddition between a tetra armed PEG macromon omer (M n = 10 kg mol −1 ) terminated with azide groups (tetra-N3-PEG) and the F azo derivative functionalized with aza dibenzocyclooctynes [23,24] (F4-azo-bis-DBCO). This reac tion typically exhibits fast kinetics at room temperature and does not necessitate the presence of a Cu catalyst, which might be beneficial for the formation of the gel, since once the gelation starts, diffusion of the reactants is reduced. The two starting materials were dissolved in stoichiometric amount in Synthetic Macromolecular Machines Hydrogels are soft materials that have found multiple applications in biomedicine and represent a good platform for the introduction of molecular switches and synthetic machines into macromolecular networks. Tuning their mechanical properties reversibly with light is appealing for a variety of advanced applications and has been demonstrated in the past; however, their activation typically requires the use of UV light, which displays several drawbacks related to its damaging character and limited penetration in tissues and materials. This study circumvents this limitation by introducing all-visible ortho-fluor...

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Section: Introductionmentioning

confidence: 99%

Reversible Modulation of Elasticity in Fluoroazobenzene‐Containing Hydrogels Using Green and Blue Light

Zhao

Bonasera

Nöchel

et al. 2017

Macromol. Rapid Commun.

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“…They can be regarded as miniaturized power engines of molecular machines [1] and intriguing applications have already been shown in recent years. [4] Currently,there are anumber of motor designs available,w hich use different molecular setups, [5] mechanisms of motion, [5b-f,6] and energy inputs to drive the directional motion. [4] Currently,there are anumber of motor designs available,w hich use different molecular setups, [5] mechanisms of motion, [5b-f,6] and energy inputs to drive the directional motion.…”

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confidence: 99%

Direct Observation of Hemithioindigo‐Motor Unidirectionality

et al. 2017

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Hemithioindigo molecular motors undergo very fast unidirectional rotation upon irradiation with visible light, which has prevented a complete analysis of their working mechanism. In this work, we have considerably slowed down their motion by using a new synthesis for sterically hindered motor derivatives. This method allowed the first observation of all four intermediate states populated during rotation. The exact order in which each isomeric state is formed under irradiation conditions was elucidated using low temperature H NMR spectroscopy in conjunction with other analytical methods. At the same time, complete unidirectionality could also be directly shown. Access to slowly rotating hemithioindigo motors opens up a plethora of new applications for visible-light-induced unidirectional motions, especially in areas such as catalysis, smart materials, and supramolecular chemistry.

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“…Thed evelopment of new reaction methodologies and advanced (macro)molecular architectures and topologies will further fuel the design of polymer networks with fascinating behaviors [275][276][277][278] and improved mechanical properties.I n addition, practical, scalable synthetic strategies are necessary to meet the existential need for sustainable polymer networks, [279,280] next-generation energy storage/harvesting materials,separations membranes,and catalysts.Finally,new tools for the generation of polymer network databases amenable to advanced computational screening and machine learning are highly sought after. [281] Thus,t here is no doubt that this field will continue to witness exciting progress for the foreseeable future.…”

Section: Discussionmentioning

confidence: 99%

Polymer Networks: From Plastics and Gels to Porous Frameworks

2020

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Polymer networks, which are materials composed of many smaller components—referred to as “junctions” and “strands”—connected together via covalent or non‐covalent/supramolecular interactions, are arguably the most versatile, widely studied, broadly used, and important materials known. From the first commercial polymers through the plastics revolution of the 20th century to today, there are almost no aspects of modern life that are not impacted by polymer networks. Nevertheless, there are still many challenges that must be addressed to enable a complete understanding of these materials and facilitate their development for emerging applications ranging from sustainability and energy harvesting/storage to tissue engineering and additive manufacturing. Here, we provide a unifying overview of the fundamentals of polymer network synthesis, structure, and properties, tying together recent trends in the field that are not always associated with classical polymer networks, such as the advent of crystalline “framework” materials. We also highlight recent advances in using molecular design and control of topology to showcase how a deep understanding of structure–property relationships can lead to advanced networks with exceptional properties.

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Dual-light control of nanomachines that integrate motor and modulator subunits

Cited by 229 publications

References 34 publications

Reversible Modulation of Elasticity in Fluoroazobenzene‐Containing Hydrogels Using Green and Blue Light

Reversible Modulation of Elasticity in Fluoroazobenzene‐Containing Hydrogels Using Green and Blue Light

Direct Observation of Hemithioindigo‐Motor Unidirectionality

Polymer Networks: From Plastics and Gels to Porous Frameworks

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