Spatially Selective and Density-Controlled Activation of Interfacial Mechanophores

Sulkanen, Audrey; Sung, Jaeuk; Robb, Maxwell J.; Moore, Jeffrey S.; Sottos, Nancy R.; Liu, Gang-yu

doi:10.1021/jacs.8b10257

Cited by 57 publications

(74 citation statements)

References 59 publications

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“…Incorporating a mechanophore into a crosslinking unit is a viable strategy for the preparation of polymeric materials that are mechanically responsive. As reported previously, anthracene–maleimide cycloadducts (Anth–Mal) can serve as mechanophores 34–36,43. In these examples, attachment of polymer chains to the nitrogen of the maleimide and the 9-position of the anthracene led to cycloreversion of the adduct under mechanical stress.…”

Section: Resultsmentioning

confidence: 71%

Anthracene-based mechanophores for compression-activated fluorescence in polymeric networks

et al. 2019

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Section: Resultsmentioning

confidence: 71%

Anthracene-based mechanophores for compression-activated fluorescence in polymeric networks

et al. 2019

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“…4 In the meantime, many color-changing mechanophores and corresponding motifs which change their photoluminescence properties have been investigated. [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] While the latter require auxiliary means for detection, a change of the emission color and/or intensity can often be detected more easily than an absorption color change. 22 Most of the fluorescent mechanophores reported so far, emit in the blue and green wavelength region.…”

Section: ■ Introductionmentioning

confidence: 99%

“…22 Most of the fluorescent mechanophores reported so far, emit in the blue and green wavelength region. For instance, nonemissive anthracene-maleimide Diels-Alder adducts exhibit blue emission after activation [5][6][7][8] and a bathochromic shift of the emission band can be achieved by extension of π-conjugation of the anthracene moiety. 9 1,2-Dioxetane, which is a chemiluminescent mechanophore, exhibits blue emission upon activation.…”

Section: ■ Introductionmentioning

confidence: 99%

Mechanoresponsive Behavior of a Polymer-Embedded Red-Light Emitting Rotaxane Mechanophore

Muramatsu

Sagara

Traeger

et al. 2019

ACS Appl. Mater. Interfaces

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A red-light-emitting photoluminescent supramolecular mechanophore based on an interlocked molecular motif is presented. The rotaxane-based mechanophore contains a cyclic compound featuring a π-extended 4,4-difluoro-4bora-3a,4a-diaza-s-indacene (BODIPY) dye as a red emitter that was threaded onto a dumbbell-shaped molecule containing an electron-poor 1,4,5,8-naphthalenetetracarboxylic diimide quencher at its center. Through two aliphatic hydroxyl groups attached to the dumbbell and the cycle, the mechanophore was covalently embedded into the backbone of a thermoplastic polyurethane elastomer. The mechanophore is only weakly photoluminescent in solution, indicating that the BODIPY's emission is efficiently quenched. Solution-cast films of the rotaxane-containing polymer, by contrast, show an appreciable photoluminescence, which suggests that during film formation some of the emitting cycles are trapped in positions away from the quencher. Interestingly, the emission intensity could be significantly reduced by swelling the films with an organic solvent and the emission increased again upon drying, suggesting that such solvent plasticization causes a reversible rearrangement. In both, dry and solvent-swollen films, uniaxial deformation caused a significant, reversible increase of the emission intensity, on account of mechanically induced shuttling of the emitters away from and back to the quenchers. It is shown that the properties of the polymer can be tuned by the solvent, and that such plasticizing extends the small palette of approaches that allow modification of the activation stress of a given materials system.

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“…Very recently, Liu and co‐workers presented a simple yet powerful way to activate mechanochromic maleimide–anthracene (MA) moeties. [ 50 ] Here, instead of SMFS, the authors opted to use a nanolithography approach, where the AFM probe was used as a stylus ( Figure a). Spatially selected areas of the sample were activated by exerting contact with the AFM probe at very high loads (>350 nN).…”

Section: Challenges and Perspectivesmentioning

confidence: 99%

Triggering Forces at the Nanoscale: Technologies for Single‐Chain Mechanical Activation and Manipulation

Martínez-Tong

Pomposo

Verde‐Sesto

2020

Macromol. Rapid Commun.

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Over the past decades, polymer mechanochemistry has focused on the development and application of advanced force application methods to better understand the mechanochemical response of mechanophores. In this regard, techniques such as ultrasonication and single‐molecule force spectroscopy (SMFS) are used to activate and detect up to thousands of chemical events within a polymer single chain, allowing the researchers to probe the mechanochemical reactivity of these stress‐responsive motifs. Here, the most recent contributions of the single‐molecule force spectroscopy technique to this field are presented, putting emphasis on the fundamental parameters of the technique for triggering specific force responses and on the description of force–extension curves measured for single‐ and multi‐mechanophore polymers. Moreover, new contributions of microscopy‐based techniques in the field of polymer mechanochemistry, as well as the potential application of single‐chain nanoparticles as mechanoresponsive materials, are highlighted.

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Spatially Selective and Density-Controlled Activation of Interfacial Mechanophores

Abstract: These authors contributed equally to this work.

Cited by 57 publications

References 59 publications

Anthracene-based mechanophores for compression-activated fluorescence in polymeric networks

Anthracene-based mechanophores for compression-activated fluorescence in polymeric networks

Mechanoresponsive Behavior of a Polymer-Embedded Red-Light Emitting Rotaxane Mechanophore

Triggering Forces at the Nanoscale: Technologies for Single‐Chain Mechanical Activation and Manipulation

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