Molecular Damage Detection in an Elastomer Nanocomposite with a Coumarin Dimer Mechanophore.
01 Jan 2021-Macromolecular Rapid Communications (John Wiley & Sons, Ltd)-Vol. 42, Iss: 1, pp 2000359
TL;DR: It is shown that the strain-induced scission of the coumarin dimer within the matrix of a particle-reinforced polybutadiene-based co-polymer can be detected and quantified by fluorescence spectroscopy, when cylinders of the nanocomposite are subjected to unconstrained uniaxial stress.
Abstract: Molecular force probes that generate optical responses to critical levels of mechanical stress (mechanochromophores) are increasingly attractive tools for identifying molecular sites that are most prone to failure. Here, a coumarin dimer mechanophore whose mechanical strength is comparable to that of the sulfur-sulfur bonds found in vulcanized rubbers is reported. It is further shown that the strain-induced scission of the coumarin dimer within the matrix of a particle-reinforced polybutadiene-based co-polymer can be detected and quantified by fluorescence spectroscopy, when cylinders of the nanocomposite are subjected to unconstrained uniaxial stress. The extent of the scission suggests that the coumarin dimers are molecular "weak links" within the matrix, and, by analogy, sulfur bridges are likely to be the same in vulcanized rubbers. The mechanophore is embedded in polymer main chains, grafting agent, and cross-linker positions in a polymer composite in order to generate experimental data to understand how macroscopic mechanical stress is transferred at the molecular scale especially in highly entangled cross-linked polymer nanocomposite. Finally, the extent of activation is enhanced by approximately an order of magnitude by changing the regiochemistry and stereochemistry of the coumarin dimer and embedding the mechanophore at the heterointerface of the particle-reinforced elastomer.
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TL;DR: In this paper, a review of a large variety of mechanophores reported in literature is presented, and a critical evaluation of the molecular and macroscopic factors that determine their activation is provided.
Abstract: Mechanochemistry provides a unique approach to investigate macroscopic deformation, failure and healing of polymer materials The development of mechanophores – molecular units that respond to mechanical force – has been instrumental in the success of this endeavor This review aims to provide a critical evaluation of the large variety of mechanophores reported in literature, and to assess the molecular and macroscopic factors that determine their activation Applications in materials science are highlighted, and challenges in polymer mechanochemistry are discussed
150 citations
TL;DR: The CoGEF method is validated as a powerful tool for predicting mechanochemical reactivity, enabling its widespread adoption to support the developing field of polymer mechanochemistry, and a contemporary catalog of over 100 mechanophores developed to date is provided.
Abstract: The development of force-responsive molecules called mechanophores is a central component of the field of polymer mechanochemistry. Mechanophores enable the design and fabrication of polymers for a variety of applications ranging from sensing to molecular release and self-healing materials. Nevertheless, an insufficient understanding of structure-activity relationships limits experimental development, and thus computation is necessary to guide the structural design of mechanophores. The constrained geometries simulate external force (CoGEF) method is a highly accessible and straightforward computational technique that simulates the effect of mechanical force on a molecule and enables the prediction of mechanochemical reactivity. Here, we use the CoGEF method to systematically evaluate every covalent mechanophore reported to date and compare the predicted mechanochemical reactivity to experimental results. Molecules that are mechanochemically inactive are also studied as negative controls. In general, mechanochemical reactions predicted with the CoGEF method at the common B3LYP/6-31G* level of density functional theory are in excellent agreement with reactivity determined experimentally. Moreover, bond rupture forces obtained from CoGEF calculations are compared to experimentally measured forces and demonstrated to be reliable indicators of mechanochemical activity. This investigation validates the CoGEF method as a powerful tool for predicting mechanochemical reactivity, enabling its widespread adoption to support the developing field of polymer mechanochemistry. Secondarily, this study provides a contemporary catalog of over 100 mechanophores developed to date.
79 citations
TL;DR: An in vitro demonstration of an FR-generating mechanophore embedded in biocompatible hydrogels for noninvasive cancer therapy, controlled by high-intensity focused ultrasound (HIFU), that converted to reactive oxygen species (ROS) to effectively kill tumor cells.
Abstract: Significance Biomedical application of mechanophores is the next frontier in polymer mechanochemistry. We report the concept, mechanochemical dynamic therapy (MDT), that utilizes remote, ultrasound-triggered mechanophore activation to enable anticancer activities. We selected an azo-based mechanophore to generate reactive free radicals (FRs) under the control of high-intensity focused ultrasound (HIFU), which subsequently produced ROS. We investigated two sets of in vitro mouse cancer models: 1) melanoma (B16F10) and 2) breast cancer (E0771). Inhibition of growth and decreases in viabilities of both B16F10 and E0771 were observed in correlation to the release of ROS by mechanophore activation. By circumventing the known issues in photodynamic therapy and sonodynamic therapy, we anticipate MDT to be a powerful anticancer tool complementary to other existing cancer treatments. Mechanophores are molecular motifs that respond to mechanical perturbance with targeted chemical reactions toward desirable changes in material properties. A large variety of mechanophores have been investigated, with applications focusing on functional materials, such as strain/stress sensors, nanolithography, and self-healing polymers, among others. The responses of engineered mechanophores, such as light emittance, change in fluorescence, and generation of free radicals (FRs), have potential for bioimaging and therapy. However, the biomedical applications of mechanophores are not well explored. Herein, we report an in vitro demonstration of an FR-generating mechanophore embedded in biocompatible hydrogels for noninvasive cancer therapy. Controlled by high-intensity focused ultrasound (HIFU), a clinically proven therapeutic technique, mechanophores were activated with spatiotemporal precision to generate FRs that converted to reactive oxygen species (ROS) to effectively kill tumor cells. The mechanophore hydrogels exhibited no cytotoxicity under physiological conditions. Upon activation with HIFU sonication, the therapeutic efficacies in killing in vitro murine melanoma and breast cancer tumor cells were comparable with lethal doses of H2O2. This process demonstrated the potential for mechanophore-integrated HIFU combination as a noninvasive cancer treatment platform, named “mechanochemical dynamic therapy” (MDT). MDT has two distinct advantages over other noninvasive cancer treatments, such as photodynamic therapy (PDT) and sonodynamic therapy (SDT). 1) MDT is ultrasound based, with larger penetration depth than PDT. 2) MDT does not rely on sonosensitizers or the acoustic cavitation effect, both of which are necessary for SDT. Taking advantage of the strengths of mechanophores and HIFU, MDT can provide noninvasive treatments for diverse cancer types.
17 citations
TL;DR: In this article, the creation of polymeric materials that self-strengthen in response to a mechanical force is an important objective in the field of polymer chemistry, and the mechanochemical strengthening of these materials is discussed.
Abstract: The creation of polymeric materials that self-strengthen in response to a mechanical force is an important objective in the field of polymer chemistry. Here, the mechanochemical strengthening of cr...
15 citations
TL;DR: The results suggest that nonequilibrium, inhomogeneous local tension distributions in the elastomers lead to greater stress in individual strands than at the same strains under equilibrium loading, but that within the regions of force concentration, mechanochromic onset is determined primarily by a limiting local strain threshold.
Abstract: The molecular processes that accompany dynamic mechanical response to large deformations at high strain rate (≈1000 s-1 or higher) underlie the early stages of damage in materials, but understanding of material response in this regime is typically limited to macroscopic constitutive equations. Here, spiropyran mechanophores are embedded in very short, stress-bearing strands in silicone elastomers, and their mechanochromic response to uniaxial compression is explored in a Split Hopkinson Pressure (or Kolsky) Bar. At strain rates of 1000 s-1 , the onset of mechanochromism occurs at lower strains, but higher stresses, than in the same materials under quasi-static loading. Similar to quasi-static loading, however, a negligible effect of mechanophore structure on the critical strain for colorimetric onset is observed. The results suggest that nonequilibrium, inhomogeneous local tension distributions in the elastomers lead to greater stress in individual strands than at the same strains under equilibrium loading, but that within the regions of force concentration, mechanochromic onset is determined primarily by a limiting local strain threshold.
13 citations
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TL;DR: In this article, the effects of particle size, particle/matrix interface adhesion and particle loading on the stiffness, strength and toughness of such particulate polymer composites are reviewed.
Abstract: There have been a number of review papers on layered silicate and carbon nanotube reinforced polymer nanocomposites, in which the fillers have high aspect ratios. Particulate–polymer nanocomposites containing fillers with small aspect ratios are also an important class of polymer composites. However, they have been apparently overlooked. Thus, in this paper, detailed discussions on the effects of particle size, particle/matrix interface adhesion and particle loading on the stiffness, strength and toughness of such particulate–polymer composites are reviewed. To develop high performance particulate composites, it is necessary to have some basic understanding of the stiffening, strengthening and toughening mechanisms of these composites. A critical evaluation of published experimental results in comparison with theoretical models is given.
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TL;DR: A four-part comprehensive review of technological advancements in the processing, manufacture, sterilization, and crosslinking of UHMWPE for total joint replacements and the development and properties of crosslinked UH MWPE, a promising alternate biomaterial for total Joint replacements are reviewed.
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TL;DR: In this paper, a self-healing fiber-reinforced structural polymer matrix composite material is demonstrated, where a microencapsulated healing agent and a solid chemical catalyst are dispersed within the polymer matrix phase.
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751 citations
408 citations
TL;DR: Embedding mechanophores into an elastomeric poly(dimethylsiloxane) (PDMS) network allows for covalent bond activation under macroscopically reversible deformations, and it is shown that bond activation can be repeated over multiple cycles of tensile elongation with full shape recovery.
Abstract: Covalent mechanochemistry within bulk polymers typically occurs with irreversible deformation of the parent material. Here we show that embedding mechanophores into an elastomeric poly(dimethylsiloxane) (PDMS) network allows for covalent bond activation under macroscopically reversible deformations. Using the colorimetric mechanophore spiropyran, we show that bond activation can be repeated over multiple cycles of tensile elongation with full shape recovery. Further, localized compression can be used to pattern strain-induced chemistry. The platform enables the reversibility of a secondary strain-induced color change to be characterized. We also observe mechanical acceleration of a flex-activated retro-Diels–Alder reaction, allowing a chemical signal to be released in response to a fully reversible deformation.
287 citations