Temporal switching of an amphiphilic self-assembly by a chemical fuel-driven conformational response

Jalani, Krishnendu; Dhiman, Shikha; Jain, Ankit; George, Subi J.

doi:10.1039/c7sc01730h

Cited by 79 publications

(62 citation statements)

References 66 publications

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“…Thordarson and Besenius independently utilized redox activity of sulfide and thioether functional groups, respectively to obtain transient self‐assembly. Our group has shown a transient conformational switching in amphiphilic self‐assembly of a charge‐transfer foldamer by coupling the reducing agent to enzymatic oxidation by glucose oxidase. These reports display the importance of redox chemistry to create transient self‐assembly.…”

Section: Methodsmentioning

confidence: 99%

Redox‐Mediated Transient Reconfiguration of a Supramolecular Assembly

2019

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Dissipative systems, that constantly consume energy for sustenance, are ubiquitous and essential to life. In synthetic systems, the phenomenon promises emergent properties and different structure from the ones existing at thermodynamic equilibrium. It can create reconfigurable and temporally programmable life-like smart materials. In this study, we attempt to create reconfigurable, temporally programmable self-assembly using the redox chemistry of a core-substituted naphthalene diimide derivative. As a result, transient reconfiguration of supramolecular assembly from vesicle to sheet along with transient fluorescence switching with fuel-dependent lifetime is attained. We believe that such a design strategy can advance the synthesis of active, adaptive and autonomous materials.Self-(re)organization, i. e. spatiotemporal ordering is a common phenomenon observed in nature. [1] Cytoskeletal elements, organelles and cells undergo reorganization into different sizes, shapes and composition during the phases of cell division and this reconfiguration facilitates the various functional processes. [2] Nature accomplishes this spatiotemporal control by dissipative self-assembly. [3] In recent years, the adaptation of this in synthetic systems by utilizing chemical fuels, [4] light, [5] enzyme, [6] redox [7] etc. have resulted in unprecedented temporally programmed structures and transient properties such as gelation [8] and ink [5a,9] and functions such as ion-transport, [10] catalysis [11] and photonics. [12] Until now, dissipative self-assembly with assembled transient states has been reported. [13] The current challenge is to move a step further to create self-(re) organization or reconfiguration of self-assembly with temporal regulation. This can result in emergent properties distinguishable from the materials obtained at equilibrium.Amongst various synthetic designs for transient materials, redox-fueled approach stands out due to its applicability in a plethora of chromophoric, charge-transfer and disulfide based molecular systems. Hermans and co-workers applied redox chemistry to attain oscillations in the self-assembly of perylene bisimide chromophores. [14] Thordarson [7b] and Besenius [7c] independently utilized redox activity of sulfide and thioether functional groups, respectively to obtain transient self-assembly. Our group has shown a transient conformational switching [7a] in amphiphilic self-assembly of a charge-transfer foldamer by coupling the reducing agent to enzymatic oxidation by glucose oxidase. These reports display the importance of redox chemistry to create transient self-assembly. In this report, we extend this redox strategy to go from naive transient selfassembly to transient reconfiguration of supramolecular nanostructures.In this study, we address one of the challenges to visualize/ probe the temporal changes during the transient cycle. Coresubstituted naphthalene diimide [15] (cNDIs) are the class of chromophores with distinct absorption and emission features, sensitive to the molecul...

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Section: Methodsmentioning

confidence: 99%

Redox‐Mediated Transient Reconfiguration of a Supramolecular Assembly

2019

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“…[22] This first experimental value of charge carrier mobility in the semiconducting regime complements the previous outstanding conductivity values obtained for TAAin adoped metallic state. [23] In addition, we have shown that the mechanism involved can be used to gain control over the precise placement and orientation of supramolecular polymers in between electrodes,w ith ap recision that cannot yet be achieved by other techniques,u pt ot he bridging of two electrodes of less than 5 mmi nd iameter and over 50 mmi n length by as ingle nanowire.S uch precise control in every aspect of supramolecular polymerization, including localization and orientation at nano-and micrometer scales,is, for the moment, quite unique in the literature.O ther potential implementations resulting from these experiments include for instance:1)spatial control over self-assembly processes in various optoelectronic devices requiring efficient charge transport and ranging from sensors to solar cells, [24,25] 2) use of waste-free electrochemistry tools to control (living) supramolecular polymerization or to create out-of-equilibrium redox environments for self-organized systems, [26] and 3) design of 3D electrical wiring in organogels. To this end, we have used TAAs,b ut one can imagine extending the concept to other molecules with redox functionalities and capable of forming supramolecular polymers or self-assemblies.…”

Section: Angewandte Chemiementioning

confidence: 96%

Supramolecular Electropolymerization

et al. 2018

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Gaining control over supramolecular polymerization mechanisms is of high fundamental interest to understand self-assembly and self-organization processes at the nanoscale.Itisalso expected to significantly impact the design and improve the efficiency of advanced materials and devices. Up to now, supramolecular polymerization has been shown to take place from unimers in solution, mainly by variations of temperature or of concentration. Reported here is that supramolecular nucleation-growth of triarylamine monomers can be triggered by electrochemistry in various solvents.T he involved mechanism offers new opportunities to precisely address in space and time the nucleation of supramolecular polymers at an electrode.T oi llustrate the potential of this methodology,s upramolecular nanowires are grown an oriented over several tens of micrometers between different types of commercially available electrodes submitted to asingle DC electric field, reaching ap recision unprecedented in the literature.

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“…It represents a new tool of fundamental and practical interest for supramolecular chemistry in general. To this end, we have used TAAs, but one can imagine extending the concept to other molecules with redox functionalities and capable of forming supramolecular polymers or self‐assemblies . In addition, we have shown that the mechanism involved can be used to gain control over the precise placement and orientation of supramolecular polymers in between electrodes, with a precision that cannot yet be achieved by other techniques, up to the bridging of two electrodes of less than 5 μm in diameter and over 50 μm in length by a single nanowire.…”

Section: Figurementioning

confidence: 99%

Supramolecular Electropolymerization

et al. 2018

View full text Add to dashboard Cite

Gaining control over supramolecular polymerization mechanisms is of high fundamental interest to understand self‐assembly and self‐organization processes at the nanoscale. It is also expected to significantly impact the design and improve the efficiency of advanced materials and devices. Up to now, supramolecular polymerization has been shown to take place from unimers in solution, mainly by variations of temperature or of concentration. Reported here is that supramolecular nucleation‐growth of triarylamine monomers can be triggered by electrochemistry in various solvents. The involved mechanism offers new opportunities to precisely address in space and time the nucleation of supramolecular polymers at an electrode. To illustrate the potential of this methodology, supramolecular nanowires are grown an oriented over several tens of micrometers between different types of commercially available electrodes submitted to a single DC electric field, reaching a precision unprecedented in the literature.

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Temporal switching of an amphiphilic self-assembly by a chemical fuel-driven conformational response

Abstract: A unique redox active amphiphilic foldamer that undergoes transient conformation changes that amplify into observable morphology changes in its self-assembly.

Cited by 79 publications

References 66 publications

Redox‐Mediated Transient Reconfiguration of a Supramolecular Assembly

Redox‐Mediated Transient Reconfiguration of a Supramolecular Assembly

Supramolecular Electropolymerization

Supramolecular Electropolymerization

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