Yinjun
Chen
a,
Gaëlle
Mellot
b,
Diederik
van Luijk
a,
Costantino
Creton
*b and
Rint P.
Sijbesma
*a
aDepartment of Chemical Engineering & Chemistry and Institute for Complex Molecular Systems, Eindhoven University of Technology, 5600 MB Eindhoven, The Netherlands. E-mail: r.p.sijbesma@tue.nl
bLaboratoire Sciences et Ingénierie de la Matière Molle, ESPCI Paris, PSL University, Sorbonne Université, CNRS, F-75005 Paris, France. E-mail: Costantino.Creton@espci.psl.eu
First published on 5th February 2021
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.
Specifically within polymer materials, the use of mechanochemistry has evolved rapidly as a multi-purpose tool for characterization across length scales, and for creating materials with a novel response to force.15,16 The need to investigate the complex relationship between the molecular structure of a polymer and its mechanical properties as a material has stimulated the development of mechanophores:17 molecular units that can quantify and locate force on the molecular scale, making them unique tools for understanding and predicting macroscopic behavior.18–20 Meanwhile, smart materials can use mechanochemical reactions as triggers to change their own structure (force-responsive materials) or to produce a chemical function useful for catalysis, drug delivery, or soft robotics.21–23 Besides the use that mechanochemistry can have in functional polymer materials, polymers themselves are an excellent environment for studying mechanochemical reactions.24 Strong and flexible linear chains are commonly used to transfer force to a mechanophore, and do so both efficiently and controllably. Thus, the use of polymers as a matrix for mechanochemistry helps to advance the physical chemistry behind this useful group of reactions.
As the toolbox of mechanochemistry is expected to be opened more frequently by researchers in other disciplines, accessibility to all polymer scientists is critical for its successful application. Despite a wealth of application-oriented reviews,25–30 the selection of the correct tool is often challenging, indicating a need for guidelines to choose a suitable force-responsive group and a suitable method to incorporate the mechanophore inside a material to implement its function. This review aims to provide a ‘field guide’ for the implementation of mechanochemistry in synthetic polymers by summarizing the molecules, materials, and methods that have been investigated and applied. It is limited to the use of molecular mechanoresponsive units in polymer materials. Mechanical characterization of biomolecules, inorganic materials, and responsive materials based on microphase separation have been reviewed elsewhere.
Section 2 of this review provides an overview of mechanophores, categorizing them by output and clarifying their activation parameters. In Section 3, the synthesis and activation of mechanophores in polymer materials is discussed, starting with the different ways mechanophores can be implemented in a material, and continuing with their activation in different materials. In Section 4, applications of mechanochemistry in polymers are summarized, paying special attention to the polymer architectures and mechanophores used for each application. Together, these three sections should serve to simplify the daunting task of choosing the right mechanophore implemented in the right manner in the right material, as well as provide a comprehensive overview of the available tools for those looking to expand the available set of mechanophores. The final section concludes the review by summarizing remaining challenges and future applications.
For any application, a suitable mechanophore must meet several criteria. For each type of response, desired parameters should be identified; such as the excitation and emission wavelength of a mechanofluorescent response. A key parameter for any mechanophore is the threshold force at which it is activated. The threshold force is defined here as the offset force at which a mechanical response is observed in a single mechanophore molecule. Experimentally, this can be measured using a Single-Molecule Force Spectroscopy (SMFS) experiment in which a mechanophore is subjected to a tensile test using an AFM probe or with an optical tweezer setup. With both methods, the mechanophore must be covalently attached to two different surfaces which are then pulled apart until a mechanochemical event occurs at a given force. This way of measuring typically requires extensive synthesis to allow robust (notably, force-insensitive) surface functionalization as well as specialized and labor-intensive measurement procedures. For mechanophores of which the threshold force has not been experimentally characterized, computationally-determined force thresholds are provided instead. Most often, threshold forces have been calculated using the Constrained Geometry simulating External Force (CoGEF) method.31 In a CoGEF calculation, the mechanophore is first modelled in its unstrained state, typically using Density Functional Theory (DFT) methods. Then, two anchoring points on opposite sides of the mechanophore are selected and the distance between these points is increased in small steps, selecting for each step the geometry that minimizes the energy. The force profile is extracted from the distance increment and the computed minimal energy, and the activation force is taken as the maximum computed force before a mechanochemical event is found in the simulations. This simulation models events that occur during an SMFS measurement32,33 and generally agrees very well with experimental SMFS data across a wide range of mechanophores. Other types of force-dependent calculations – while generally less accessible – do provide additional insight into details of the potential energy surface and the transition state.15,34
For the purpose of this review, we use a hybrid classification of mechanophores based on whether activation results in a physical spectral response (mechanochromic, mechanofluorescent, mechanoluminescent) or elicits chemical reactivity (mechanocatalytic, mechanoradical, or release and rearrangement). These different classes of mechanophores are discussed with specific emphasis on a comparison of their force sensitivity. The force of activation for a large set of mechanophores has recently been evaluated with COGEF calculations.33
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Fig. 1 (a) Activation of spiropyran by mechanical force or UV light; the reverse reaction is accelerated by visible light. (b) Three of spiropyran derivatives and their single-molecular force spectrum.41 (c) Single-molecular force spectrum of two spiropyran derivatives with varying attachment points.36 (d) Color change of spiropyran in a multiple-network elastomer during uniaxial extension.42 (e) Activation of spirothiopyran by mechanical force or UV light and the reverse reaction by visible light. (f) Activation of spirothiopyran in the backbone of a polyester by sonication in solution.43 (b) is reprinted with permission from ref. 41, Copyright 2018 American Chemical Society. (c) is reprinted with permission from ref. 36, Copyright 2015 American Chemical Society. (d) is reprinted with permission from ref. 42, (published under a Creative Commons license, CC BY-NC), Copyright 2020 AAAS. (f) is reprinted with permission from ref. 43, Copyright 2016 Wiley-VCH. |
The first use of spiropyran as a mechanochromic mechanophore was reported by Moore's group in 2009.35 Colorless spiropyran was incorporated in the centre of a poly(methyl acrylate) (PMA) polymer backbone. Under uniaxial extension, spiropyran units were converted into highly colored merocyanine, resulting in a color change of the PMA material from yellow to purple. After failure, material turned red. While spiropyrans are generally colorless or yellow, the color of merocyanines in a polymer is influenced by the chemical environment,37 and can be blue, purple and red depending on the polarity of the polymer and its water content.42 Moreover, merocyanine containing polymers often show different colors in loading and unloading due to isomerization around the bonds connecting the cyclic subunits (Fig. 1d).44 The striking optical response of spiropyran containing polymers is very easily observed by eye; and as a consequence, this mechanophore has been incorporated in a variety of polymer materials. These studies will be discussed in detail in Sections 3 and 4.
Various pyran analogs such as spirothiopyran (STP),43 naphthopyran (NP),45 and bis-naphthopyran (BNP),46 have been designed with the aim of tuning reactivity, color and critical activation force. Spirothiopyran is a versatile mechanophore, as it features both mechanochromism and force-activated addition reactions of the sulfur atom (Fig. 1e). Ring opening of the thiopyran ring of STP via a 6π electrocyclic ring-opening reaction to thiomerocyanine (TMC) is accompanied by a color change from yellow to green. The nucleophilic thiolate formed after activation is a reactive partner in the thiol–ene click addition reaction with CC double bonds. Weng's group reported the first example of STP-containing mechanochromic polymer materials, where STP was embedded into the backbones of a polyester and a polyurethane. A yellow solution of the polyester turned green after sonication as shown in Fig. 1f, indicating the formation of the thiomerocyanine form of the dye. In the presence of N-ethyl maleimide, the green color quickly disappeared due to reaction with the thiomerocyanine. When 1,6-bismaleimidohexane crosslinker was present, sonication of a thiospiropyran-containing polymer led to crosslinking of the linear polymers into insoluble networks.43 Calculations with CoGEF33 show that the threshold force to activate STP is 2.0 nN – distinctly lower than for SP mechanophores, which have a calculated Fmax of 2.6 nN.33,47
Naphthopyran (NP) is also mechanochromic, with a color change from colorless to yellow when the ring opens (Fig. 2a). The calculated threshold force to activate NP (Fmax = 3.7–4.4 nN, CoGEF) is higher than for SP. The threshold force depends on the attachment points as well as on the nature of the substituents. Fig. 2b shows three types of attachment of polymer chains; only NP5 was activated in tensile tests when covalently crosslinked into PDMS, while NP8 and NP9 were inactive (Fig. 2c).48 Varying the substituents at positions 1 and 3 (Fig. 2a and e) not only gave different colors of the activated merocyanine form, but the critical forces of activation were also different. For instance, in compound 3 the critical force was 4.1–4.4 nN to give a yellow merocyanine; while it was 3.7–3.9 nN for compound 4a–c, with a color change to purple. Each of the six NP's in PDMS studied by Robb et al. gave different mechanochromic behavior. All polymers showed color change; but differences in color intensity due to different concentrations of merocyanine illustrate the variation in threshold forces among these mechanophores (Fig. 2e).49 The compounds also show differences in fading time in the relaxed state because the merocyanines have different stabilities.
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Fig. 2 (a) Activation of naphthopyran (NP) by force and UV light; the reverse reaction is accelerated by heat or visible light. (b) Naphthopyran derivatives with varying polymer attachment points. (c) Images of polymer materials in (b) showed different mechanochromic responsiveness before and after elongation and UV irradiation.48 (d) Naphthopyran mechanophore with pyrrrolidine substituent (e) naphtopyran derivatives and their color changes in naphtopyran-containing PDMS after extension or UV irradiation.49 (b) is adapted with permission from ref. 48, Copyright 2016 American Chemical Society. (c) is adapted with permission from ref. 48, Copyright 2016 American Chemical Society. (e) is adapted with permission from ref. 49, Published by The Royal Society of Chemistry (https://creativecommons.org/licenses/by/3.0/). |
Bisnaphthopyran (BNP) combines two pyran rings and is unique among SP derivatives because it isomerizes via two 6π electrocyclic ring-opening reactions. The two pyran rings can be activated consecutively by UV light, while mechanical force directly activates both pyran rings in a single step, as has been demonstrated by Robb et al. in ultrasonication experiments.46 When one of the pyran rings is activated by UV light, the second ring can be activated by mechanical force as shown in Fig. 3. Each of the states of BNP exhibits a different color. State 1 – with one opened pyran ring – is yellow, while open–open state 2 is purple. In CoGEF simulations, the threshold force to open the first ring is 4.1 nN, while opening the second ring requires a force of at least 4.6 nN.33 This difference is not enough to selectively create a high amount of state 1 in the ultrasonication experiments. In the mechanostationary state, it was assumed that most, if not all, of the open–closed form was the product of electrocyclic ring closure of the open–open state.46
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Fig. 4 (a) Activation of rhodamine and the reverse reaction by stimulation with force and heat or UV, respectively. (b) Rhodamine was embedded into polyurethane film. The film was drawn and showed a color change that fades upon heating.50 (c) Rhodamine integrated into the filler network of a multiple-network elastomer changes color in extension; different fluorescent colors are observed in loading and unloading.52 (d) Bleaching of color in activated elastomer by UV light.52 (e) Three-arm rhodamine modified with double bonds. (b) is reprinted with permission from ref. 50, Copyright 2015 Wiley-VCH. (c) is reprinted with permission from ref. 52, Copyright 2017 American Chemical Society. (d) is adapted with permission from ref. 52, Copyright 2017 American Chemical Society. |
To effectively activate spirorhodamine, the mechanical force transmitted along the polymer chain should induce the scission of the C–N bond in the spirolactam. Activation is influenced by the position of the attachment points and by the electronic properties of the substituents on spirorhodamine. For example, a spirorhodamine-diol was attached to polyurethane at positions 1 and 3 in Fig. 4a.52 The resulting polymer materials show reversible mechanochromism with fluorescent emission in compression (between colorless and reddish). However, when the attachment points were changed from 1+3 to 2+3, mechanical force was not transferred across the C–N bond in spirolacatam, and the spirorhodamine was not activated by force. Furthermore, spirorhodamines with varying substituents on the xanthene part of the molecule show different photochromic responses. Rhodamine with two amino groups52 shows a strong absorption in the blue-green range of the visible spectrum, and UV light induces the transformation of the open form to the spiro form – in contrast to the spirorhodamine with a single amino group on the chromophore (Fig. 4d).50 Trifunctional spirorhodamine (Fig. 4e) was incorporated into the filler network of poly(ethyl acrylate) multiple-network elastomers. The elastomers display a UV-sensitivity that is opposite to that of the polyurethane labelled by spirorhodamine-diols. Furthermore, the elastomers have a red-shifted fluorescence, and the fluorescent color changes from red to yellow when unloading. Interestingly, the fluorescent color can be tailored by incorporating pyrene in the polymer material.53 Upon stretching, the combination of green fluorescence from the pyrene excimer, blue fluorescence from monomeric pyrene and red fluorescence from mechanochemically-activated rhodamine gives rise to white emission.
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Fig. 5 Structure of various fluorescent mechanophores that are activated by force and display covalent bond scission. (a) Anthracene dimer; (b) Anthracene–maleimide adduct; (c) π-Extended anthracene–maleimide adduct; (d) Furan–maleimide adduct;65,66 (e) Coumarin dimer; (f) Dithiomaleimide; (g) Methanone-tethered cinnamate dimer. (h) 2-(2′-Hydroxyphenyl)benzoxazole. |
Other categories of covalent fluorescent mechanophores reported by pioneers include the coumarin dimer (compound 16),67,68 dithiomaleimide moiety (compound 17),69 methanone-tethered cinnamate dimer (compound 18),70 and 2-(2′-hydroxyphenyl)benzoxazole (compound 19).71 Like anthracene adducts, these mechanophores lead to scission of the polymer chain, concomitant with fluorescence. Coumarin dimers have been investigated by Craig et al., who integrated coumarin dimers in the middle of poly(methyl acrylate) chains and characterized the relationship between the activation efficiency of mechanophore and molecular weight of the polymer.67 Dithiomaleimide 17 is notable for being fluorescent before cleavage, thereby being the only example of a mechanophore that loses fluorescence after mechanical activation.69 CoGEF calculations provided a force threshold of 4.3 nN and a cleavage mechanism that started with homogeneous bond scission of the C–S bond,33 although the final reaction products (structure) are not validated in experiment after activation. With the exception of anthracene adducts, many of these fluorescent mechanophores have not yet been taken full advantage of in mechanochemistry for damage research in polymer materials.
Taking this advantage to an extreme, a conjugated polymer of a fluorescent donor doped with an acceptor was shown to be highly sensitive to chain extension.54 Poly(dioctylfluorene-alt-benzothiaziazole) (F8BT) was copolymerized with a small amount of dithienyl benzothiadiazole (DTBT). Förster resonant energy transfer (FRET) between the excited donor and initially ground-state acceptor occurs in all cases; but the extent of transfer depends on the distance between donor and acceptor, which in turn is influenced by stretching the polymer materials. A threshold force of approximately 300 fN was determined experimentally – roughly four orders of magnitude lower than a typical covalent mechanofluorophore. No bonds are broken upon activation, as not a chemical bond but the conformational entropy of the coiled polymer chain is destabilized by the applied force.
Moving towards slightly higher interaction energies, we find supramolecular complexes held together by electrostatic interaction,73 π–π stacking,72 or hydrophobic interactions.74 This category of mechanophores includes dyes of conjugated oligo(p-phenylenevinylene) derivatives (OPV) aggregated by π–π stacking interactions (Fig. 6). The aggregated excimers dissociated in response to tensile deformation and resulted in a luminescent color change from either yellow to green, or from green to blue, depending on the OPV derivatives that were used. Recently, another supramolecular mechanophore was accessed by incorporating a fluorophore–quencher pair into a mechanically interlocked rotaxane (Fig. 7a). Sagara's and Weder's groups74–76 embedded the rotaxane mechanophore into polyurethane elastomers and the elastomers displayed rapid and reversible fluorescence switching upon extension as shown in Fig. 7b. The fluorescent response correlated with the macroscopic deformation and the optical properties could be tailored by varying the chromophores in rotaxane.
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Fig. 6 Conjugated oligo(p-phenylenevinylene) derivatives display different fluorescent colors in aggregated or dissociated states. (a) Two conjugated oligo(p-phenylenevinylene) derivatives. (b) The two dyes in (a) were physically blended into polymer matrix and the materials revealed fluorescent color change in extension.72 (b) is reprinted with permission from ref. 72, Copyright 2020 Springer Nature. |
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Fig. 7 Supramolecular mechanophores prepared by locking fluorophore and quencher in a rotaxane. (a) Three rotaxane mechanophores with different fluorophores. (b) Fluorescent responses of the three rotaxane mechanophores in tensile tests.75 (a) and (b) are adapted with permission from ref. 75, Copyright 2019 American Chemical Society. |
Mechanically active charge-transfer complexes have also been introduced in polymer materials without the stabilization of rotaxane formation. A fluorescent pyrene group was connected to two naphthalene diimide (NDI) groups using a short covalent linker and incorporated in the backbone of a polycaprolactone chain.77 Pyrene forms a charge-transfer complex with the neighboring NDI, locally folding the chain and quenching the fluorescence of pyrene. When the polycaprolactone films were stretched, the interaction between pyrene and NDI was broken and a fluorescent response was observed. Sufficiently soft materials allowed enough mobility for the pyrene and NDI to recombine, quenching the fluorescence and displaying reversible behavior. In amorphous polycaprolactone however, an increasing response was observed even after stretching, presumably due to strain-induced ordering and crystallization of the polymer matrix. A different fluorescent mechanophore based on π–π interactions of a pyrene derivative is the sulfonated derivative (hydroxyethyl)pyrene trisulfonate (HEPTS).78 HEPTS forms aggregates in apolar solvents and in polyurethane materials, thereby shifting to a yellow-emitting fluorescence from the blue emission of non-aggregated HEPTS. Stretching materials made from HEPTS-telechelic polyurethane chains mixed in a non-functionalized material showed a shift in the emission spectrum due to dissociation of the aggregates.
A fluorescent mechanophore stabilized by electrostatic interactions was reported by Jen et al.73 This thermodynamically unstable mechanophore is formed by a Michael addition reaction and is electrostatically-stabilized by a protonated amine (Fig. 8). Mechanical force initiated the reversible elimination, leading to the release of a conjugated dye. When the mechanophores were covalently crosslinked in an epoxy network, a color change was observed at a low onset of deformation of 0.14 accompanied with a fluorescent color change.
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Fig. 8 Breaking an electrostatic interaction by force resulted in a molecular rearrangement. This rearrangement leads to the release of 3-cyano-4,5,5-trimethyl-5H-furan-2-ylidene malononitrile dye; and materials showed a color change, including fluorescent color switching with varying degrees of compressive strain.73 Adapted with permission from ref. 73, Copyright 2016 Wiley-VCH. |
Mechanophores that display photoluminescence due to reduced molecular mobility are a recent addition to the mechanochemical toolbox. Films made from hyperbranched poly(amido amine)s were reported to displayed an increased fluorescent intensity at near-zero strain (Fig. 9).79 These materials contain tertiary amines in close proximity to amide groups. The fluorescent properties of these materials, classified as unconventional macromolecular chromophores,80 are believed to derive from intramolecular electron overlap of closely clustered amines and amides. Stretching this material resulted in a linear increase of fluorescence intensity at the same wavelength, which could be activated and deactivated reversibly. The applicability of this class of mechanophores to different systems may be limited by the close proximity, and therefore high concentration, of these groups that is required for fluorescence. Additionally, a fluorescent background is present prior to activation and no significant shift in excitation wavelength is observed; so the fluorescent signal is only meaningful when it can be compared to the initial state of the material. Nevertheless, this unique approach may lead to the development of more generally applicable, highly sensitive mechanofluorophores as well as a better understanding of this unusual photophysical response.
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Fig. 9 Structures of mobility-based photoluminescent mechanophores. (a) A hyperbranched network containing amide groups and tertiary amines in close proximity show enhanced fluorescence emission upon increasing strain.79 (b) Phosphorescent copper(I)-pyridinophanes ligated to an N-heterocyclic carbenes undergo a rapid ligand exchange, which is hindered by mechanical tension, thereby increasing the photoluminescent response.81 For R = i-Pr, a shift in emission spectrum is also observed.83 |
Filonenko and co-workers have described a chemically different, yet mechanistically similar approach for force detection in polymers with a Cu(I)–pyridinophane complex (Fig. 9).81,82 This complex contains a tetradentate ligand that binds to the metal in a tridentate fashion, leaving one tertiary amine available that can exchange rapidly with an identical copper-bound ligand. The complex displays a phosphorescent photoluminescent response; however, the dynamic ligand exchange provides a pathway for non-radiative decay, resulting in a low phosphorescence intensity. When the exchangeable ligands are mechanically activated by tensile strain in polyurethane materials, the reduced dynamicity of the system leads to a higher probability of phosphorescent emission occurring before non-radiative decay, thereby enhancing the phosphorescent signal. This normally does not produce a shift in emission wavelength, limiting its use in materials to intensity-based detection. A derivative with a more sterically-hindered co-ligand was reported that did show a hypochromic emission shift upon mechanical activation in a comparable material.83 The origin of this shift was explained by the interaction between the Cu+ center and the non-coordinating PF6− or BF4− counterions. This shift also occurred due to different stimuli that affect the ion-pair distance, such as solvent polarity or temperature changes. The reason for a change in ion-pair distance was thought to be related to the change in free volume of the polymer material. Because of the shift in emission wavelength, a ratiometric response could be measured, in contrast to other mobility-based mechanophores. However, the color change is highly dependent on the environment, and it is difficult to predict its behavior in other materials.
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Fig. 10 (a) Dioxetane mechanophore is activated by force and emits blue light. (b) Dioxetane mechanophore was incorporated into filler network of multiple-network elastomers, and the elastomers presented blue light in uniaxial extension.86 (c) Different dye acceptors were physically blended into poly(methacrylate) materials, and materials showed different light during elongation.84 (b) is reprinted with permission from ref. 86, (published under a Creative Commons license, CC BY-NC), Copyright 2014 AAAS. (c) is reprinted with permission from ref. 84, Copyright 2012 Springer Nature. |
When the dioxetane mechanophore was integrated into the center of a PMA polymer backbone or used as a crosslinker in an acrylate polymer network, emission of blue light with a maximum at 420 nm85,87 was observed during extension or sonication in polymer solution (Fig. 10b). The sensitivity and color of light emission was tuned by energy transfer to suitable acceptor dyes84 (Fig. 10c). Dioxetane luminescence has been used as a highly sensitive molecular probe to evaluate failure mechanisms,86,88 stress distribution, and stress evolution86 in polymer materials, which is discussed in Sections 3 and 4.
In an attempt to reduce the activation threshold, a cascade strategy was developed in which a Pd–NHC complex49–90 was incorporated into a (PTHF) backbone, and release of a strongly basic NHC ligand upon mechanochemical activation was used to deprotonate a precursor 1,2-dioxetane chemiluminescent probe.89 Subsequently, the 1,2-dioxetane was activated and emitted light. The cascade strategy decreases the force threshold of the dioxetane mechanophore, and elevates the sensitivity and effectivity of mechanical activation of mechanophores.
Diarylbibenzofuranone (DABBF) is a homodimer of arylbenzofuranone connected by a central C–C bond as shown in Fig. 11a. The C–C bond with a length of 1.586 Å and a bond dissociation energy of 95.5 kJ mol−191 is longer and weaker than a normal C–C bond. Using heat or light, these motifs can dissociate into two highly stable carbon-centered radicals – a process which is accompanied by a large shift in absorbance from 346 nm to 650 nm (Fig. 11b).91,92 Interestingly, arylbenzofuranones are not oxygen-sensitive, and DABBF can easily dissociate and recombine reversibly under ambient conditions.91,93 Mechanically, the threshold force has been calculated using CoGEF to be 3.5 nN.33
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Fig. 11 (a) Activation of DABBF by force. (b) Strain-induced color change of polyurethane with DABBF incorporated in the main chain.92 (c) Activation of TASN by force. (d) Color change from colorless to pink upon uniaxial extension of a poly(hexyl methacrylate) network containing TASN.100 (e) Activation of DBBT by force (f) strain induced color change of block polymer of poly(styrene)–poly(methyl acrylate)–poly(styrene) with DBBT incorporated into the soft domain.97 (b) is reprinted with permission from ref. 92, Copyright 2015 American Chemical Society. (d) is adapted with permission from ref. 100, Copyright 2020 American Chemical Society. (f) is reprinted with permission from ref. 97, Copyright 2018 American Chemical Society. |
Tetraarylsuccinonintrile (TASN) is a similar dimer in which the lactone group is replaced with a nitrile substituent (Fig. 11c). In this mechanophore the central C–C bond is slightly longer at 1.608 Å, but the bond dissociation energy increases to 26.2 kcal mol−191 resulting in a larger overall threshold force at 4.5 nN.33 Cleaved TASN exhibits an absorption maximum at 550 nm (Fig. 11d) as well as strong yellow light emission upon excitation with UV light (λ = 356 nm).94 It retains the remarkable reversibility of DABBF both in solution and in polymer networks even in the presence of oxygen.91,95
Diarylbibenzothiophenonyl (DABBT) is another dimer that undergoes homolytic cleavage of a C–C bond by light or mechanical activation into two arylbibenzothiophenonyl radicals as shown in Fig. 11e. It has an equilibrium bond length of 1.574 Å, a dissociation energy of 96 kJ mol−1,96 and a threshold force of 4.4 nN.33 These radicals display a broad absorbance peak around λ = 450 nm (Fig. 11f). These homodimers can be modified to adjust their dissociation energy and presumably also the threshold force, although the latter has not been demonstrated. For instance, when the phenyl rings are functionalized with a p-bromo substituent, the dissociation energy is lowered to 86 kJ mol−1.96
The DABBT mechanophore was first applied in a polymer material by Otsuka's group in 2018.97,98 A block copolymer was synthesized to contain soft domains with inbuilt DABBT as a damage sensor, and hard domains with another TASN mechanophore integrated within the polymer backbone. Due to the different colors of the two dissociated mechanophores, the color of polymers in response to mechanical stimulus enables discrimination between force concentration in the hard and in the soft phase, which could be actuated by stretching and grinding, respectively. However, recent research focusing on DABBT as a mechanophore is rare. Application of radicals generated from DABBT has been limited to mechanochromic force detection rather than other possibilities unlocked using these stable yet active radicals. Possible further application could lie in the initiation of a local chemical reaction in a network; for instance, a polymerization to strengthen the material.99 For now, the unique color change from light yellow to green in mechanochemistry possesses high potential for mechanochromic applications when, for instance, multiple independent color changes are required.
When two mechanoradical dimers were separately integrated into the backbone of polymer chains,92,98,101,102 the materials showed both thermal and stress sensitivity. They exhibited color change before and after extension or grinding due to the dissociation of dimers (Fig. 11b and d). The color change is different due to the different absorption of the two radicals after dissociation. Materials labelled with DABBF show a color switch from colorless to blue (Fig. 11b),92 and the color of materials with TASN changes from colorless to pink (Fig. 11d).98 The threshold force of DABBF is lower than that of TASN; and thus, DABBF is activated by force before TASN. The dissociation of DABBF in various polymer architectures was investigated by Otsuka's group102 who found more effective activation of mechanophores in longer polymer chains. Additionally, it was found that these mechanophores are more sensitive to mechanical stress in star polymers than linear polymers in bulk materials.102 Further details are presented in Section 3.
Carbon-centered radicals have also been formed by scission of two carbon–heteroatom bonds in diazo-functionalized polymers. A well-known thermal initiator for radical reactions, 4,4′-azobis(4-cyanovaleric acid), was coupled to polymers and found to be mechanically-active.103 Nitrogen gas was liberated upon sonication and two stabilized radicals were formed. A threshold force of 3.7 nN was calculated using CoGEF.33
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Fig. 12 (a) Mechanism of HABI activation by force or heat (b) HABI was incorporated into poly(urethane), and the materials showed color change after freezing.104 (b) is adapted with permission from the authors of ref. 104. |
Weakly polarized bonds involving heteroatoms often break homolytically without requiring extensive conjugation to stabilize the formed radical. In the group of chalcogenides, S–S and Se–Se bonds are mechanically-active and have been incorporated into polymer materials. Diselenide bonds in polystyrene chains were activated by sonication and allowed for selective cleavage of the polymers.106 In addition, the radicals that were formed reacted with a diselenide bond of an added small molecule in a metathesis reaction. Mechanically-induced diselenide metathesis reactions were also used in force-responsive amphiphilic vesicles, that responded to an increase in osmotic pressure.107 The formation of selenide radicals has so far been primarily followed by its characteristic reactivity, and because of this diselenides may become important mechanophores for use in responsive materials.
Disulfide bonds are more established mechanophores and have been more thoroughly characterized and applied in polymers. In the presence of nucleophiles disulfides may react in a force-dependent SN2 reaction, in which no radicals are formed.108 At higher forces the reaction proceeds with a more radical-like character – partially due to the higher energy, and partially due to conformational changes resulting in steric hindrance.109,110 For homolytic cleavage, a threshold force of 3.6 nN was calculated for alkyl-substituted disulfides.33 The formation of radicals can be established using spin traps, allowing for a colorimetric response.111 Different responses to mechanical liberation of thiol radicals or anions allow for applications other than sensing. For instance, recently, Göstl and Herrmann et al. visualized the mechanical cleavage of disulfides with a secondary reaction that could also be potentially useful for controlled drug release applications.112 In this work, mechanically generated thiols reacted with a Michael acceptor that underwent a retro-Diels–Alder reaction to liberate a furan derivative. Upon re-aromatization, this furan derivative spontaneously dissociated to release a small molecule, in this case a fluorescent dye or a prodrug.
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Fig. 13 Mechanocatalysts (a) Ag(I)–NHC incorporated in poly(tetrahydrofuran) releases a N-heterocyclic carbene upon activation by ultrasound in solution, which catalyzes transesterification.114 (b) Activation of Ru(II)-NHCs incorporated in poly(tetrahydrofuran) produces a Ru(II) metal centre that catalyzes alkene metathesis reactions.114 (c) Mechanical activation of Cu(I)–NHC in a polymer leads to the formation of a Cu(I) metal centre that catalyzes an azide–acetylene cycloaddition (“click” reaction).116 |
Mechanophores derived from cyclopropane, cyclobutene, or epoxides that undergo bond rearrangement in response to a mechanical stimulus have been shown to dramatically elevate mechanical properties or conductivity of polymer materials. Mechanical activation leads to electrocyclic ring opening and rearrangement of the structure. Upon rearrangement, cyclopropane and cyclobutene mechanophores produce double bonds in the polymer backbone (Fig. 15). For instance, gem-dihalocyclopropane mechanophores, reported by Craig's group,123–127 generate a 2,3-dihaloalkene sequence after activation as shown in Fig. 15a. Threshold forces for activation of gem-dihalocyclopropanes have been calculated by CoGEF,33 and the results are consistent with measurements by single-molecular force spectroscopy techniques. While the mechanochemical reaction does not give an optical signal or catalysis, it generates a double bond. The double bond generated upon mechanochemical ring opening of this type of mechanophore is a potential crosslinker and this feature has been used to strengthen a polymer with a mechanical stimulus.128 Epoxide mechanophores generate carbonyl ylides upon ring opening, which facilitates force-induced cross-linking by reaction with an alcohol (Fig. 15a).128 A different strategy offering high potential to strengthen polymer materials was reported by Weng's group.129 Multiple macrocyclic cinnamate dimers were integrated into a polyester. Stretching a polymer of the dimers above a critical force of 1–2 nN more than doubled its contour length and increased the strain energy that the chain absorbed before fragmenting by at least 2500kJ per mole of monomer (Fig. 15b).
A completely different type of functionality is unveiled in polyladderene mechanophores: soluble, non-conjugated polymers that convert to conjugated polyacetylenes upon mechanical activation. In seminal work from the group of Xia, a ladderene mechanophore consisting of four fused cyclobutene rings was used as monomer in a ring-opening metathesis polymerization to give a poly-ladderene. Upon sonication in solution, a conjugated polymer was formed (Fig. 15b), which self-assembled into semiconducting nanowires.130,131
The most described system is based on PMA.35,56,62,63,67,84,137–142 Following a suitable functionalization, the mechanophore is covalently incorporated in the polymer as an initiator using controlled radical polymerization techniques (Fig. 16). The group of Moore described the incorporation of SP and benzocyclobutene (BCB) in PMA for the first time.35,138 In this study, an α-bromo-α-methylpropionyloxy bifunctionalized SP or BCB was used to initiate the single electron transfer living radical polymerization (SET-LRP) of the methyl acrylate (MA) monomer to produce linear PMA polymers containing a SP or BCB moiety near its chain midpoint, respectively (Fig. 16). The study showed that the molar mass could be easily tuned (from 18 kDa to 287 kDa) while maintaining a low dispersity (PDI ≤ 1.3). Similarly, other mechanosensitive molecules were incorporated in the center of PMA polymer chains; namely, azobenzene,139 maleimide-anthracene Diels–Alder adduct,56,62,63,142 coumarin,67 1,2-dioxetane,84 and platinum–acetylide complex.141 This technique (Fig. 16) is not limited to the preparation of mechanophore-containing PMA. Several studies reported the use of similar procedures to incorporate mechanosensitive molecules in other linear polymers chains: poly(methyl methacrylate) (PMMA),143 and other polyacrylates,144 – including poly(ethyl acrylate) (PEA), poly(n-butyl acrylate) (PnBA), poly(iso-butyl acrylate) (PiBA) and poly(tert-butyl acrylate) (PtBA) and polystyrenes (PS).145
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Fig. 16 General procedure for the preparation of mechanophore-linked PMA based on SET-LRP route using α-bromo-α-methylpropionyloxy bifunctionalized mechanophore as an initiator. |
Similarly, using the mechanophore as an initiator in a ring opening polymerization (ROP) process resulted in a mechanoresponsive polyester.146,147 As an example, O’Bryan et al.146 reported the use of indolinospiropyran diol as an initiator in ROP of ε-caprolactone leading to photo- and mechanochromic polymers. Later, Peterson et al.147 extended the preparation methods of SP-containing poly(ε-caprolactone) (PCL) to 3D printing techniques. This technology allowed, in particular, the preparation of multicomponent materials with spatially-varying mechanoresponsive properties (Fig. 17).
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Fig. 17 Preparation of a 3D-printed multicomponent mechanoresponsive sample: (a) CAD representation, (b) Pre-elongation sample, (c) Post-elongation sample, (d) Post-elongation sample after 365 nm UV irradiation. Scale bars = 20 nm.147Fig. 17 is reprinted with permission from ref. 52, Copyright 2015 American Chemical Society. |
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Fig. 18 Chemical structure unsegmented PU containing multiple SP (1) units in its chain.154Fig. 18 is reprinted with permission from ref. 154, Copyright 2010 American Chemical Society. |
Many mechanosensitive molecules – including azobenzene,152 SP,149–151,153,154,159,160 1,2-dioxetane,148 DABBF,92 rhodamine,50 STP,43 and HABI104 – have been incorporated in PU chains by using the same chemistry (i.e. functionalization of a diol-terminated mechanophore with functions followed by step-growth polymerization), independently of the mechanophore responsiveness.
Interestingly, using a similar synthetic approach, i.e. step growth polymerization, mechanophores were incorporated into other thermoplastic polymers such as polyamides (PA) and polyesters (PES) by polyamidation or polyesterification, respectively, starting from the diol-functional mechanophore.43,70,148 Chen and Sijbesma reported the straightforward synthesis of PU, PES and PA with a tunable amount of the mechanoluminescent bis(adamantyl)dioxetane, starting from the same dihydroxyl-functionalized mechanophore precursor. The subsequent reaction of the latter with an excess of suberic acid and hydroxyl-terminated poly(tetramethylene glycol) or bis(3-aminopropyl)-terminated poly(tetrahydrofuran) lead to a mechanoresponsive PES or PA, respectively (Fig. 19).148
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Fig. 19 Synthetic scheme for SP-containing thermoplastic elastomers.148Fig. 19 is reprinted with permission from ref. 148, Copyright 2014 American Chemical Society. |
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Fig. 20 Synthetic route for the preparation of (a) PnBA-b-PAA containing a maleimide–anthracene Diels–Alder adduct mechanophore at the block junction58 and (b) Ag–NHC polymer complexes.113 (a) is reprinted with permission from ref. 58, Copyright 2016 American Chemical Society. (b) is reprinted with permission from ref. 113, Copyright 2011 American Chemical Society. |
The same group reported a straightforward method based on RAFT polymerization for the preparation of a poly-mechanophore polymer system.171 Various copolymers made from cyclobutene carboxylates (CBCs) and nBA were synthesized with Mn varying from 8 to 127 kDa while maintaining a relatively low molecular weight dispersity (Đ ≤ 1.7).
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Fig. 21 Illustration of the incorporation of mechanophores into a polymer network through a bulk radical polymerization process, directly in the mold (1 mol% of cross-linker). Notes: without primary crosslinker, the crosslinks are purely composed of mechanophore crosslinkers (in yellow); the procedure can be performed without the pre-polymer step via the direct incorporation of all the reactants in the mold as described by Clough and coworkers.179 |
This preparation method was extended to the preparation of other polymeric networks. In particular, it was applied to polyacrylamides: recently, Kabb et al.57 reported the incorporation of maleimide–anthracene Diels–Alder adducts in a poly(N,N-dimethylacrylamide) (PDMAc) network by copolymerizing DMAc and the mechanophore crosslinker by bulk free radical photopolymerization. The network properties were tuned by adding di(ethylene glycol) diacrylate (DEGDA) as primary crosslinker to vary the crosslink density.57 Similarly, Stratigaki et al.187 incorporated Diels–Alder adducts of π-extended anthracenes into poly(N-isopropyl acrylamide) (PNIPAAm) hydrogel networks to study the bond scissions in the network using confocal laser scanning microscopy.
Not only is the chemical nature of the network tunable, but also its architecture. More complex structures were achieved through sequential free radical polymerization steps: the multiple networks elastomers,52,86 which are known to be particularly tough due to the presence of sacrificial bonds. To investigate the reinforcement mechanism based on these sacrificial bonds, Ducrot et al.86 incorporated a bis(adamantyl)-1,2-dioxetane bisacrylate crosslinker into a single network, and in the first network of double and triple networks made of EA.
From a global point of view, the crosslinking process, generally via a Pt catalyzed hydrosilylation reaction, is the typical strategy to covalently and randomly incorporate mechanophores in silicone elastomers.44,48,158,190–196 Based on this strategy, Craig's group reported the introduction of SP in commercial PDMS:44,194–196 SP was functionalized with two alkene groups and covalently incorporated as a crosslinker in the network via the Pt catalyzed hydrosilylation reaction (Fig. 22).
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Fig. 22 Schematic representation of SP-containing PDMS network: synthesis route.44Fig. 22 is reprinted with permission from ref. 44, Copyright 2014 American Chemical Society. |
Using a similar strategy, other mechanophores can be covalently incorporated in PDMS.48,190,191 As an example, to investigate the regiochemistry dependence of the mechanoresponsiveness, Robb et al.48 described the preparation of three naphthopyran regioisomers-containing PDMS networks: the mechanophore was first functionalized with 4-pentenoic anhydride, then mixed with the prepolymer solution and covalently incorporated during Pt cure hydrosilylation.
In the field of mechanochemistry of polymer composites, epoxy-based thermoset networks are also well-known.201–206,209 In these systems, the fillers are mechanophore nanoparticles which bring mechanosensitive properties to the matrix rather than reinforcement. To incorporate a dimeric anthracene-based mechanophore in an epoxy matrix, Koo et al.203 mixed the carboxylic acid functional dimer particles with epoxy resin and the hardener. Then, the homogenized mixture was poured into a mold and allowed to cure at room temperature. This simple curing process (with possible adjustments) is typical for the preparation of such thermoset composites networks.
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Fig. 23 Illustration of the preparation method of maleimide–anthracene Diels–Alder adduct mechanophore-anchored PMA brush – grafted nanoparticles.59Fig. 23 is reprinted with permission from ref. 59, Copyright 2014 American Chemical Society. |
Other strategies were described to incorporate mechanophores at heterointerfaces and design new composite materials. To prepare highly mechanosensitive composites, Kosuge et al.211 incorporated DABBF in rigid networks using a sol–gel method. Sagara et al.212 proposed a straightforward strategy based on the covalent attachment of Py derivative micelles on glass beads, polymer beads, or living cells to prepare various mechanoluminescent materials. Woodcock et al.213 introduced a silk fiber in an epoxy matrix putting Rhodamine at the heterointerface.
General characteristics | Polymers | ||
---|---|---|---|
Incorporation in the polymer chain | Chain-growth polym. | Process in solution | PMA,35,56,62,63,67,84,137–142 PMMA,143 PEA,144 PnBA,144 PiBA,144 PtBA,144 PS,145,167 copolymers,167,168,171 PCL,146,147 polybutadiene68,123,170 |
Controlled/living polym. (SET-LRP, ATRP, ROP, ROMP, RAFT, etc.…) | |||
Bifunctional mechanophore used as an initiator | |||
Well-defined polymers with controlled molar masses (9–300 kDa), tunable architectures, low dispersities) | |||
Step-growth polym. | Process in solution | PU,43,50,74,92,104,148–160 PES,43,70,148 PA148 | |
Bifunctional mechanophore used as monomer (functionalization with OH, NCO or COOH) | |||
Multiple mechanosensitive units throughout the backbone | |||
Versatile method | |||
Coupling | Synthesis of a functional polymers (generally using controlled/living polym.) | PEG,162 PMA,104 PS,98,102,164 copolymers,58,163,165 metal–NHC polymers complexes: PTHF;89,113,115,161,166 PS;89,113,115,161,166 PIB89,113,115,161,166 | |
Post-polymerization coupling steps (amidification, oxidation, Diels–Alder reaction, etc.…) | |||
Complex architectures | |||
Incorporation in a network | Free radical polym. | Process in bulk, solution or dispersed medium | PMMA,35,172–179 PMA,84,181 PHMA,142 PEA,52,86,181 PDEA,180 PDMAc,57 PNIPAAm,187 copolymers,182 |
Bifunctional mechanophore used as crosslinker (unique or secondary in a dual crosslinker system) | |||
Straightforward synthetic conditions | |||
Hydrosilylation react. | Bis-alkene functionalized mecanophore | PDMS44,48,158,188–196 | |
Pt-catalyzed hydrosilylation | |||
Typical strategy for the preparation of thermoset polymers | |||
Other strategies | Tin-catalyzed condensation, curing in mulberry leaf, Diels–Alder reaction, curing, etc… | PDMS,189,197 PEAA2M3,200 Epoxy201–206,209 | |
Incorporation at the interface | Surface funct. approach | Immobilization of the functional mechanophore on the surface | PMA59,61,64,210 |
Growing of the polymer chain using the immobilized mechanophore as initiator | |||
Other strategies | Sol–gel method, covalent attachment of dye micelles, etc.… | Rigid networks,211 PLA,212 Epoxy213 |
Based on this knowledge, the technique of ultrasonication has been widely employed in the field of polymer mechanochemistry to validate the activation of the molecule by force. In some particular cases, the method of activation is varied to be more suitable to the system; for example, the application of a vortex,212 and CO2-breathing activation.180 Depending on the chemistry of the mechanosensitive unit, various mechanical responses can be detected.
Scission reactions are generally not reversible (or hardly reversible), while isomerization reactions are generally fully reversible. This reversibility, and the generally better sensitivity to lower forces, is the reason why non-scissile-type mechanophores are used in polymer mechanochemistry. The best known and most efficient mechanophore based on an isomerization reaction is the SP. In 2007, Moore's group studied the ultrasound-induced ring-opening of SP in solution. Upon sonication, the colorless SP-centered PMA solution turned pink, revealing the SP-to-MC isomerization.138 The same group also reported the ultrasound-induced ring-opening reaction of BCB in PMA,138 and in PEG.162 The mechanically-induced ring-opening of STP was exploited by Zhang and coworkers, who incorporated the mechanophore in PES and reported load-induced addition reactions upon sonication of the solution in presence of N-ethylmaleimiede.43 The group of Craig used the non-scissile properties of gDCC mechanophore to quantify the strength of weak bonds.123,170 They designed a multimechanophore system in which gDCC and multiple scissile bonds were embedded in a polymer chain. Their approach relied on the competition between the ring-opening reaction of gDCC and the weak bonds scissions within the polymer chain triggered by ultrasound.
Some studies suggested other important parameters to describe mechanical responsiveness; namely, the polydispersity index (PDI),67 and the degree of polymerization.144 Craig's group investigated the mechanoactivation of coumarin-centered PMA upon sonication and highlighted that higher PDI promotes “off-center” mechanophore structure leading to less selective bond scission.67 By comparing five SP-centered polyacrylates (namely, PMA, PEA, PnBA, PiBA and PtBA), Moore's group investigated the impact of the polymer composition, the side-chain nature, and the chain length on the mechanical response.144 Interestingly, they demonstrated that the mechanical transduction kinetics are governed by the degree of polymerization, i.e. the number of C–C bonds, rather than the molecular weight (Fig. 24).
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Fig. 24 Rate constant of the SP activation as a function of degree of polymerization for various SP-containing polyacrylates.144Fig. 24 is reprinted with permission from ref. 144, Copyright 2016 American Chemical Society. |
The impact of the polymer architecture on the mechanical response was studied by Church et al.,56 who compared the bond scission mechanism of a linear PMA containing an anthracene–maleimide Diels–Alder adduct moiety and its three-arm counterpart (Fig. 25a). Both architectures demonstrated a high selectivity of the scission events; although, differences occurred in the chain scission rate. The study showed that the rate constant is defined by the number-average molar mass per arm rather than the global molar mass and the architecture. The specific case of the micellar structure was investigated by Wang et al.168 They demonstrated an increase by 5 of the reactivity of the SP-centered triblock copolymer made of tBA and NIPAAm. It self-assembled into micelles, in contrast to its linear counterpart (Fig. 25b). This enhancement was explained by the swelling of the micelle core and by the enhancement of the dielectric constant near SP units. Li et al.58 investigated the mechanical reactivity of the maleimide–anthracene Diels–Alder adduct mechanophores put at the interface between the hydrophobic core (PnBA) and the hydrophilic shell (PAA) of micelles. The study showed the scission of the centrally located mechanophore upon sonication when it was located at the interface between the hydrophobic core and hydrophilic shell in a micelle, but not when the polymer was in solution where the viscous drag is too low to transfer a sufficient force (Fig. 26).
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Fig. 25 (a) Sonochemical activation of a linear PMA containing an anthracene–maleimide Diels–Alder adduct moiety and its three-arm counterpart;56 (b) UV absorbance vs. ultrasonication duration for SP-centered triblock copolymers made of tBA and NIPAAm, self-assembled into micelles and its linear counterpart.168 (a) is reprinted with permission from ref. 56, Copyright 2014 American Chemical Society. (b) is reprinted with permission from ref. 168, Copyright 2015 American Chemical Society. |
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Fig. 26 Evolution of the emission intensity at λem = 420 nm as a function of sonication time of PBA-b-PAA dispersed in water (square) or in solution (triangle) and PAA-b-PAA in aqueous solution (circle).58Fig. 26 is reprinted with permission from ref. 58, Copyright 2016 American Chemical Society. |
In addition to intrinsic parameters, external parameters can also be important for the mechanically induced response. In particular, the concentration of mechanophore is a key point, as shown by Groote and coworkers who demonstrated an increase of the mechanocatalyst activity with concentration.161 One can imagine that the process used for the activation is determining the mechanosensitive response; but interestingly, Surampudi et al.139 showed comparable isomerization conversion and polymer chain scission rate for an azobenzene-centered PMA exposed to continuous or pulsed sonication. By comparing the mechanochemical response of waterborne PU in solution, dispersion, and emulsion, Zhang and coworkers pointed out the role of the environment.160 While no activation was observed in emulsion, mechanoluminescence was detected in solution and dispersion with an optimal water content estimated at 15 v%. The lack of activation in emulsion was explained by the aggregation state of PU chains: the strong coiling of the chains hinders the force transduction. The key question is then how is the force applied to the chemical bond to trigger activation?
The activation of the mechanophore inside the material requires the application of a macroscopic force on the sample that may (or may not) activate molecules inside the material. By far the most common way to do this are uniaxial tensile or compressive tests. If the sample is stretchable and fracture in the grips can be avoided, tensile tests are more severe and more representative of the actual toughness of the sample. In this case a strip or a dogbone-shaped sample (e.g.Fig. 27) is typically fixed into a standard tensile tester and stretched while an optical observation setup of the sample is used while it is being deformed. If tensile tests are not practical or the sample is brittle, compression tests are a viable alternative for a proof of concept but the friction between sample and plate exerting the compression is unknown so local stress is actually much more difficult to determine than in tension.
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Fig. 27 (a) Change in green intensity for SP-containing PMA and its inactive counterpart (control) as a function of plastic strain during cyclic testing.35 (b) Peak absorbance of SP-containing PU and its inactive counterpart (control) as a function of stretch ratio.154 (c) Optical images of DABBF-containing PU samples before and after being stretched manually.92 (a) is reprinted with permission from ref. 35, Copyright 2009 Springer Nature. (b) is reprinted with permission from ref. 154, Copyright 2010 American Chemical Society. (c) is reprinted with permission from ref. 92, Copyright 2015 American Chemical Society. |
Some early activation results were obtained by Rubner, who used visible spectrometry to investigate the optical properties of soft segmented PU containing reactive diacetylene groups in the hard segment.156 A shift and changes in shape of the absorption band were observed upon stretching a partially cross-polymerized thin film. In particular, the changes in the absorption spectrum highlighted the mechanisms involved in the deformation of the elastomer. Later, Kim and Reneker used UV-visible spectrometry to monitor the activation of the azo moiety in polyurethane copolymers upon uniaxial cyclic stretching.152 While no change in the UV-visible absorption spectrum was observed after three 100% tensile stretches, a relative increase of the amount of the trans-form was observed after three successive 200% tensile stretches. After three 300% tensile stretches, a quasi-total isomerization of the cis-form into the trans-form was observed. In a seminal paper in 2009, the group of Moore systematically studied the mechanical transduction of SP to MC in a polymer melt containing center-labeled PMA chains (Tg ∼ 15 °C) at room temperature during monotonic and cyclic tensile loading tests. A significant color change was observed upon plastically deforming these polymer melts up to failure, proving the SP to MC isomerization. Cyclic tests provided additional information: a red-green-blue (RGB) analysis of the digital images recorded by the color camera during the experiment showed a progressive decrease of the green intensity (i.e. increase of the activation) after reaching a plastic strain level of 200% until failure (Fig. 27a).35 By changing the polymer nature to a classical PU formulation, similar results were observed with a physically-crosslinked soft polymer (i.e. the increase of the SP to MC isomerization with stress (Fig. 27b).154 Activation kinetics within PU were studied using fluorescence imaging, showing in particular that the reversion from MC to SP after unloading the PU occurred in an hour, while no reversion was observed under constant strain.
The group of Otsuka introduced reversible scissile DABBF linkages in PU, and studied the time-dependent breakage of the bonds under tensile loading with EPR spectroscopy. Upon stretching, a blue coloration of the sample due to bond scissions occurred from 50% strain up, followed by a progressive increase of the cleavages with strain. After 5 h at RT, the linkages had recombined and the sample had almost recovered its shape, demonstrating the reversibility of the activation (Fig. 27c).92
In these uniaxial tensile tests, the degree of activation of the mechanophore typically increases monotonously with macroscopic uniaxial deformation (or stress), independent of the nature of the mechanophore and of the details of its incorporation (in linear chains,35,84 networks,84 physically cross-linked linear chains,92,152,156 or coatings made from emulsion);182 and activation starts to be detected at a threshold value of strain (dependent on the system properties).
These first activation studies in materials were clearly designed to address whether the molecule incorporated as a label in the material can be activated by a macroscopic stretch or compression, and concerned a variety of different polymer-based materials, including chemically-crosslinked elastomers52,84,86,142,190 and gels,180,184,187,195,219,220 glassy polymers,57,166,176–179 and physically crosslinked thermoplastic elastomers like polyurethanes,148–151,159 or triblock copolymers.167,168
In elastomeric polymers and gels, the forces along the backbone of the polymer chains can be orders of magnitude higher than between polymer chains. As a result, the force detected by the mechanophore can be quantitatively related to the macroscopic properties: stress, strain, or bond scission. However, in order to see widespread activation in the bulk, the material should not be too brittle. Therefore, unfilled, well-crosslinked elastomers far from their Tg were not used in these early studies. The two simple options were (1) the physically-crosslinked PU family of materials, where hydrogen bonds (hard segments) can dissipate energy and delay the nucleation and propagation of a crack; and (2) lightly crosslinked PMA with a Tg slightly below room temperature, where a high level of viscoelasticity also favors delayed crack propagation.221,222
In glassy polymers, the situation is very different since the chains are frozen in place, and the elastic properties are controlled by the van der Waals bonds between chains, i.e. enthalpic elasticity. In these conditions, it is very unlikely that any covalent bond activation occurs before actual yielding, i.e. before the van der Waals bonds start to fail. Hence, mechanophore activation can be used to detect localized yielding or bond scission after yielding, but is not a good measure of macroscopic stresses in the elastic regime, since the molecular forces are distributed over many more bonds and not only the backbone of the chain. This reasoning is key to the understanding and interpretation of all intermediate cases where the material is neither fully glassy nor fully elastomeric, such as in particle-filled composites, or polymers close to their Tg such as in some paints and coatings. In the following, we review in more detail the main findings obtained from this activation of mechanophores inside materials.
In their study on mechanoresponsive elastomeric acrylic latex coatings made of BA and MMA, Li et al.182 used vinyltriethoxysilane (VTES) as an interparticle crosslinker, and SP as an intra-particle crosslinker, and investigated the effect of intra- and interparticle crosslink density on the SP activation. They observed a higher stress sensitivity and lower stress activation threshold when increasing the intraparticle crosslink density (i.e. increasing the SP content); while the increase of the interparticle density did not impact the sensitivity but increased the activation threshold. This clear result suggests that the activation intensity is related to the concentration of activated SP molecules while the relation between macroscopic stress and concentration of activated molecules can be influenced by the material architecture. In other words, the interparticle crosslinking of the silane sustains a significant part of the stress and partially unloads the SP containing chains. As a result, activation of SP occurs at a higher macroscopic stress.
The introduction of physical crosslinks in the structure is a good way to improve mechanical activation of mechanophores in polymers.149–151,159,220 Weng's group incorporated a quadruple hydrogen bonding non-covalent 2-ureido-4-pyrimidone (UPy) motif into the SP-containing PU, thereby creating physical crosslinking through H-bonding between UPy.149,150 Upon stretching, organization in microdomains occurs and the fragmentation of the hard domains, as well as the dissociation of the UPy stacks and dimers, induced energy dissipation and delayed crack propagation.150 Further investigations showed that supramolecular interactions between UPy units promote chain orientation and strain-induced crystallization, which explained the improvement of the mechanical activation of SP (Fig. 28).149 Weng's group also reported the sensitive mechanoactivation of SP introduced into doubly-crosslinked PU: oligo-poly(lactic acid)-capped pentaerythritol (PTT–PLA) was chosen as a covalent cross-linker, and UPy dimer units played the role of physical crosslinks.159 Chen and Sijbesma highlighted the effect of the type of H-bonding on the activation by comparing rubbery materials made of segmented dioxetane-containing PU, PES, and PA. All dioxetane containing PU possessed similar molar mass (12 kDa) and were incorporated into PU of higher molar masses PU (42 kDa). A more densely-packed H-bond network favors the transduction of the force to the mechanophore (as revealed by a more intense light emission).148 In other words, the level of activation of the mechanophore can provide information on the internal relaxation of the polymer chains inside the material.
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Fig. 28 Mechanism of SP mechanical activation enhanced by H-bonding in SP-containing PU, proposed by Weng's group. The stretching axis is vertical. (a) Before stretching, (b) within strain-hardening region, (c) SIC of PTHF segments, and (d) mechanical activation of SP to MC.149Fig. 28 is reprinted with permission from ref. 149, Copyright 2014 American Chemical Society. |
Besides material design, external parameters like temperature,182 solvent,74 strain rate,148,159,182,224 and laser excitation140 impact the force at which the mechanophore activates; presumably by modifying activation barriers for the reaction. Such sensitivity to the environment should be kept in mind if a quantitative interpretation of the mechanochemical response is desired. An important example is the activation of mechanophores in hydrogels. Wang and coworkers incorporated a rhodamine-based mechanophore into a micellar hydrogel. As the gel is stretched to large strains, the micelles are deformed and exert a force on the mechanophore that activates optical visibility.225
As described above, the probability of mechanical activation of mechanophores in a polymer backbone is affected by several factors from the molecular structure of mechanophores to the structure of polymer materials themselves. In Section 1, we reported values of the threshold force for activation measured or calculated for specific mechanophores by SMFS or CoGEF. These values are for individual molecules. However, the stress to activate the mechanophores embedded in polymer materials reflects an average concentration of activated molecules inside the material and depends also on the molecule's environment. For polymer melts it may depend on molecular weight and strain rate, for networks it may depend on the composition, orientation, regiochemistry of the polymers, network architecture and of course temperature relative to the glass transition temperature. This last point is essential since It determines the elastic modulus and hence the share of the total load carried by the mechanophore relative to the rest of the bonds.
For example, in soft hydrogels the covalent bonds carry a much larger share of the load than in polymer glasses and this affects the relationship between macroscopic stress and mechanophore activation.
To put the activity of mechanophores within each respective polymer matrix in prospective, we list in Table 2 the critical stress of mechanophore activation, the Young's modulus of polymer materials and the glass transition temperature when such information is available from the original publication.
Matrix | Molar mass (kDa) | Young's modulus (MPa) | Critical stress of mechanophores (MPa) | T g (°C) | Ref. |
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a Estimated using stress–strain curve (tensile test experiment at RT). b Estimated using stress–strain curve (compression loading experiment at RT).Polymers: PMA: poly(methyl acrylate); PMMA: poly(methyl methacrylate); PU: polyurethane; PnBA: poly(n-butyl acrylate); PS: polystyrene; PDMS: polydimethylsiloxane; PEVA: poly(ethylene-vinyl acetate); PEOC: poly(ethylene octene copolymer); PEA: poly(ethyl acrylate); PHMA: poly(n-hexyl methacrylate); PDMA: poly(N,N-dimethylacrylamide). SN: single network; DN: double network elastomers; TN: triple network elastomers. | |||||
Linear PMA | 18 to 287 | — | 10a (dioxetane) 1.5a (SP) | 12–15 | 35, 84 and 140 |
PMA network | — | — | 100b (compound 24) | 10–15 | 84, 117, 119 and 120 |
150b (compound 23) | |||||
Linear PMMA | 260 | 800a | 128 | 35, 143 and 219 | |
Linear plasticized PMMA | 260 | 400a | 15a (SP at 90 °C) | Below room temperature | 143 |
Cross-linked PMMA beads | — | 300b | 50b (SP) | — | 35 |
PU | 50–70 | 2–13 | 40b (dioxetane) | −70 (soft segments) | 74, 92, 101, 148–150, 153, 154, 156, 159 and 160 |
5a (SP) | |||||
8a (rotaxane) | |||||
6a (BABBF) | |||||
PS–PnBA–PS triblock copolymers | 37–51 | 0.32 (24 wt% PS) to 240 (45 wt% PS) | −40 (PnBA); 80 (PS) | 167 | |
P(nBA-co-MMA) film (from crosslinked particles) | — | 2a | 2a (SP) | −4 (46 wt% BA) to 30 °C (51 wt% MMA) | 182 |
PDMS | — | 1.4 | 2a (SP) | −125 | 40, 48, 190, 192 and 193 |
2a (dioxetane) | |||||
PEVA, PEOC | — | 5a | −90 (semi-crystalline at room T) | 224 | |
PEA (multiple networks) | — | 0.9 to 2.1 (SN) | 1.5a (SP in TN) | −20 | 41, 52 and 86 |
1.2 to 2.3 (DN) | 1.5a (rhodamine in TN) | ||||
1.7 to 5.4 (TN) | 2.5a (rhodamine in DN) | ||||
2.5 a (dioxetane in TN) | |||||
5a (dioxetane in DN) | |||||
PHMA | — | — | 0.6 (TASN) | 0 | 100 |
PDMA | — | 1.5 (1 mol% cross-linker) | 150b (compound 13) | 120 | 57 |
6 (5 mol% cross-linker) | |||||
9 (10 mol% cross-linker) |
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Fig. 29 Activation of the mechanophore in maleimide–anthracene Diels–Alder adduct as a function of the force of compression for different crosslink densities.57Fig. 29 is reprinted with permission from ref. 57, Published by The Royal Society of Chemistry (https://creativecommons.org/licenses/by/3.0/). |
Another experiment that was carried out is the activation by solvent swelling. Since swelling by a solvent may cause polymer chain stretching, it is reasonable to believe that activation of a mechanophore would occur as a result. In this case different mechanophores reveal different features for the same experiment. The experiments of Clough et al. with the chemoluminescent bis(adamantyl)-1,2-dioxetane mechanophore reveal the early stages of PMMA swelling very well; where the solvent causes localized crazes, and covalent bonds are broken locally.179 The experiments of Lee et al. on SP cross-linked PMMA networks that focused on equilibrium swelling pointed to a crosslink density effect: an increase of the crosslinking density induces a longer equilibrium period and less activation (due to a lower degree of swelling and, presumably, of chain stretching).178
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Fig. 30 (a) Amount of dissociated DABBF as a function of the molecular weight for linear (blue bars) four- and eight-arm star (red bars) DABBF-centered PS.102 (b) “click” reaction conversion as a function of compression cycle for different Cu(I) bis(NHC) polymer complexes mechanocatalysts.166 (a) is reprinted with permission from ref. 102, Copyright 2016 American Chemical Society. (b) is reprinted with permission from ref. 166, Copyright 2018 Wiley-VCH. |
Michael et al.166 designed four mechanocatalysts based on Cu(I) bis(NHC) polymers of different architectures: a low molecular weight complex, linear complexes bearing either flexible PIB or stiffer PS chains (different chain length were explored), a chain-extended PS-based complex with multiple Cu(I) bis(NHC) moieties along the polymer backbone, and networks containing a number of Cu(I) bis(NHC)s as crosslinking points. The mechanically-induced catalysis of the fluorogenic “click” reaction of 3-azido-7-hydroxy-coumarin and phenylacetylene was investigated directly in bulk by compression test. The study highlighted that a chain-extended structure (multiple-mechanophore material) and the network architecture exhibited the highest mechanically-induced catalytic activation (Fig. 30b).
Independent of the structure (linear, chain, or network), increasing the temperature modifies the mechanical behavior of the glassy polymer; and the activation of the mechanophore reveals the change in the forces felt by the backbone chains in the polymer. Beiermann et al.143 tested an SP-labeled PMMA at different temperatures and in the presence or absence of solvent. The PMMA is glassy at room temperature and at 80 °C; and the SP only sees the load when plastic deformation is activated. In those conditions, activation only occurs very close to the propagating crack where a plastic zone exists,226 and was not detected by the authors because of lack of spatial resolution. At 90–105 °C, the PMMA is no longer brittle and plasticity occurs in the bulk, causing a spatially-homogeneous activation of the SP at an engineering stress of around 15–20 MPa. Finally, at 120 °C the linear chains of PMA relax too fast, and forces on the backbone never reach the value necessary for activation. Similarly, adding plasticizer (15–20 wt% of MeOH) to SP-containing PMMA network allowed a mechanical response at RT similar to those at 90 °C.
The solvent polarity also affects the mechanoactivation; in particular, in swelling-induced activation systems. Lee et al.178 showed that a solvent with an intermediate polarity is required to observe swelling-induced activation of SP in PMMA network. This may also be connected to the ability of the solvent to swell the network and hence to stretch the backbone chains.
The testing method, specifically the way the force is applied (stretching, compression, shear, torsional creep), is also important in the details of the mechanophore response. The comparison of three studies made on SP-containing crosslinked PMMA illustrates this idea. Davis et al.35 reported a quite constant threshold activation strain value (around 20%) with strain rate in uniaxial compression (Fig. 31a). Later, Kim et al.176 compared the mechanical response of crosslinked PMMA under compression and tension. The study showed that the threshold strain for activation was dependent on the strain rate; and although comparable trends are observed for both testing geometries, different threshold values were obtained (Fig. 31b). Shear experiments highlighted a near-constant threshold strain value at all tested shear rates, with a threshold value estimated around 45% strain (Fig. 31c).177 Consistent results were obtained by comparing monotonic and creep torsion experiments, revealing that large-scale polymer deformation and onset of flow and stress-induced mobility are needed to permit force transduction.174
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Fig. 31 Activation (strain or stress) threshold for SP-linked crosslinked PMMA as a function of strain rate: (a) Threshold (color) stress, yield stress and threshold strain as a function of strain rate reported by Davis et al.;35 (b) Yield- and activation strain as a function of strain rate in tension test and compression test as described by Kim et al.;176 (c) Activation strain as a function of shear rate, plotted using the values reported by Kingsbury et al.177 (a) is reprinted with permission from ref. 35, Copyright 2009 Springer Nature. (b) is reprinted with permission from ref. 176, Copyright 2015 American Chemical Society. (c) is reprinted with permission from ref. 177, Published by The Royal Society of Chemistry (https://creativecommons.org/licenses/by/3.0/). |
Performing mechanical tests at very high strain rate (shockwave conditions) has been tested to promote mechanophore activation by limiting relaxation.145,175 using a high spatial resolution technique, Hemmer and coworkers proposed the following high strain rate induced activation scenario: a fast loading and fast fracture induces plastic heating and subsequent thermal activation and creates localized craze zones, in which strong activation is detected175
The same interfacial activation has been studied in nanocomposites. In this case, because stresses are typically higher at soft–hard interfaces than in the bulk, the mechanophore is highly selective and reveals the heterogeneity of the composite.59,61 Activation can give detailed insight into molecular damage mechanisms in these more complex materials; but the particular structure of nanocomposites may also enhance the mechanophore activation, as was reported by Kim et al.210 who demonstrated a reduction of the activation threshold strain for SP at the heterointerface compared to one in bulk for silica-filled PMA materials. Otsuka's group studied the force-induced dissociation of DABBF in a complex polymer–inorganic composite structure comprised of a rigid silica network obtained by sol–gel, and embedded within a soft PBA matrix. They showed a significant increase of the sensitivity and a higher dissociation ratio of the mechanophore with increasing silica content. Moreover, the rigidity of the silica network (containing the grafted DABBF) hinders the deactivation of the mechanophore by recombination of the DA adduct.211 Generally speaking, if the mechanophore in a nanocomposite is grafted at the particle/matrix interface, it can be activated at a much lower macroscopic strain than the same mechanophore incorporated within the bulk of an unfilled soft polymer, which makes it possible to activate fluorescence or a change in absorption at a lower macroscopic strain and have a more sensitive strain probe.201,204,205,213
From a more general point of view, several parameters are important to enhance the sensitivity of the mechanophore to macroscopic strain, such as porosity of the structure,207 crosslink density and composition in polyurethane–silicone blends,227 strain rate,227 and pre-alignment of the mechanophore in the tensile direction.208
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Scheme 1 Schematic summary of the mechanophore activation in polymer materials and its interpretation. |
As already discussed previously for PMMA at room temperature, the crux of the matter is the localization of high stress regions leading to the propagation of a crack. A brittle material does not fail by plastic flow but by the propagation of a crack nucleated by an inherent flaw in the material. This propagation can be localized at the nm level (as in inorganic glass), or very delocalized at the 100 μm-level, as in the tearing of rubber. While modern tools of mechanics (such as digital image correlation) can be used to visualize propagating cracks and map the strains near a crack, the stresses and, even more so, the extent of molecular damage were impossible to detect until recently.
As an example of the use of mechanophores in mechanics, Craig's group reported the incorporation of weak, fast-exchanging supramolecular crosslinks, and was able to increase the maximum-achievable strain of an organogel made of P4VP under compression.119 To investigate the mechanism involved in the enhancement of the mechanical properties of the organogel bis(adamantyl)-1,2-dioxetane, a scissile chemoluminescent crosslinker was introduced into the network. During a compression test, the activation of the mechanophore occurred in a very localized way, and only upon rupture. By varying the content of supramolecular units, the onset of activation could be shifted with the strain at break, while keeping a constant intensity (Fig. 32). This suggested that the reversible interactions delay the nucleation and propagation of a crack to higher strains, but do not influence the extent of bond scission once the crack propagates.
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Fig. 32 Representative stress–strain curve and the corresponding emission intensity–strain plot of mechanoluminescent PN2·PdEt gels (P4VP networks with PdEt as physical crosslinker) as a function of [PdEt].220Fig. 32 is reprinted with permission from ref. 220, Copyright 2014 Wiley-VCH. |
In another example of space-resolved mapping, the color change of colorless SP into blue MC was used to map the stress distribution around crack tip in a polyurethane material by Weng's group.159 The SP was activated around the crack tip and revealed a loaded region via the blue color; whereas, due to the isomerization of MC, a second color switch (from blue to purple) was observed in the unloaded regions (Fig. 33a). In a different example, Craig et al.196 used the color change of SP to measure the continuous 3D spatial strain distribution in PDMS soft materials when they are hit by a projectile (Fig. 33d), and argued that this type of experiment could be used to simulate brain strain for traumatic brain injury applications. The fluorescence of MC was also used to map and localize the high stress distribution around the crack by Sprakel's,228 and Moore's group (as shown in Fig. 33b and c).172
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Fig. 33 SP was used to detect and map high stress regions. (a) SP was incorporated into polyurethane and the stress distribution around the crack tip was mapped from the color change before and after crack propagation.159 (b) SP was covalently crosslinked into poly(methyl methacrylate) network and was used as an indicator to measure the plastic deformation around crack tip by fluorescent feature of MC.172 (c) The strain distribution around the defect of a hole was mapped by photonic array reporting. The fluorescent region indicated by SP matched with the high strain distribution measured by photonic array.228 (d) The color change after SP activation was applied for mapping the strain deriving from the impact of projectile in PDMS.196 (a) is reprinted with permission from ref. 159, Copyright 2014 American Chemical Society. (b) is reprinted with permission from ref. 172, Copyright 2014 Elsevier. (c) is reprinted with permission from ref. 228, Copyright 2020 Wiley-VCH. (d) is reprinted with permission from ref. 196, Published by MDPI (https://creativecommons.org/licenses/by/4.0/). |
While in all these previous examples the degree of mechanophore activation could be measured by either fluorescence intensity or color change, the absolute value of the average stress (an important quantity in mechanics) could not be directly measured for lack of a calibration method that would work across sample geometries. A first attempt in that sense was made by Chen et al.42 who carefully calibrated the color change in uniaxial tension, and used the calibration data to directly obtain absolute values of engineering stress around an opening crack. The results were compared with a finite element simulation carried out without any adjustable parameters. The correspondence was remarkable as can be seen in Fig. 34.
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Fig. 34 Stress maps around crack tip are quantified by the color change of spiropyran and the simulation results by finite element simulation. (a) Experiment results of stress map for stiff materials; (b) experiment results of stress map for soft materials; (c) simulated stress map for stiff materials; (d) simulated stress map for stiff materials for soft materials.42Fig. 34 is reprinted with permission from ref. 42, (published under a Creative Commons license, CC BY-NC), Copyright 2020 AAAS. |
While spatial mapping of stress is clearly a useful tool to identify the highly loaded regions in the sample, of even greater use is the extent of molecular damage caused by the fracture. This has been done with two types of molecules.
Mechanoluminescent 1,2-dioxetane mechanophore was used as a time-resolved molecular damage probe to map the damage distribution in multiple network elastomers by Creton's and Sijbesma's groups.86 A 1,2-dioxetane derivative was crosslinked in the filler network of multiple network elastomers; and in fracture tests, single, double, and triple network elastomers showed a very different scale of molecular damage upon crack propagation, as is revealed by luminescence due to the bond scission of 1,2-dioxetane that is shown in Fig. 35a. The blue light regions gradually increased with the numbers of networks in elastomers, consistent with the increase of toughness of multiple network elastomers. The same molecule was also used as a damage sensor190 in a commercial PDMS elastomer containing nanoparticles. The luminescence resulting from the 1,2-dioxetane scission was quantified in step-cyclic tests, and showed unambiguously the early molecular damage taking place directionally in nanocomposites as a function of strain. Interestingly, the time-resolved information showed that some damage also took place upon unloading (Fig. 35b).
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Fig. 35 (a) 1,2-Dioxetane mechanophore as damage indicator showed the damaged region around crack tip for multiple network elastomers.86 (b) 1,2-Dioxetane mechanophore was integrated in polymer composite and the images show the luminescent intensity increase with strain and in relaxation luminescence gradually decrease.190 (c) SP was used as stress sensor to quantify the stress distribution around crack tip in multiple network elastomers. The regions and magnitude of stress around crack tip increase significantly with deformation.42 (a) is reprinted with permission from ref. 86, (published under a Creative Commons license, CC BY-NC), Copyright 2014 AAAS. (b) is reprinted with permission from ref. 190, Copyright 2016 Wiley-VCH and (c) is reprinted with permission from ref. 42, (published under a Creative Commons license, CC BY-NC), Copyright 2020 AAAS. |
Finally, it is important to mention the applications of a recently developed mechanofluorophore for damage detection. The Diels–Alder (DA) adduct of π-extended anthracene developed by Goestl and Sijbesma,63,142 emits a stable and high-yield fluorescent signal after scission of the DA bond. This new mechanofluorophore was used in particular to detect bond scission in hydrogels,187 and was used to devise a method to quantify bond scission in absolute terms by Slootman et al.181 By carrying out a series of fracture tests at different temperatures and stretch rates on pre-notched samples, they could demonstrate, for the first time, that bond scission during elastomer fracture increases up to 50 times with increasing stretch rate or decreasing temperature; it occurs over tens of microns near the crack tip, even in the absence of any sacrificial bonds; and it contributes significantly to the measured fracture energy, even at high strain rates, contradicting existing theories.229 An important point to validate the quantification of bond scission is the representativity of the mechanophore signal. In other words, although the mechanophore is a weaker bond than the normal C–C covalent bonds of the polymer backbone, is the fraction of broken DA bonds in the material equal to the fraction of broken strands? There is no absolute answer to this; but Slootman et al.181 compared the activation of a set of elastomers with the same total crosslinker concentration (and the same mechanical properties) but at different concentrations of mechanophores, and the activation was nearly proportional to the added concentration, as can be seen in Fig. 36.
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Fig. 36 Linear dependence of fluorescence intensity with mechanophore concentration in the same material.181Fig. 36 is reprinted with permission from ref. 181, Copyright 2020 American Physical Society. |
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Fig. 37 Mechanophores used as “locks” were integrated into the backbone of degradable polymer materials to control degradation of polymer materials. (a) The scheme of degradable polymer materials controlled by mechanophore activation.230 (b) The sequential degradation of polymer was initiated by the activation of mechanophores via sonication.231 (a) is reprinted with permission from ref. 230, Copyright 2020 American Chemical Society. (c) is reprinted with permission from ref. 231, Copyright 2020 American Chemical Society. |
Recently, Matsuda et al.99 achieved just that for double network hydrogels. They prepared tough double network hydrogels containing (in the water phase of the gel) ferrous ions, additional AMPS monomer, and crosslinker (Fig. 38c). Upon stretching the gel in an argon atmosphere, the scission of covalent bonds in the sacrificial network created radicals that, on the one hand, were detected by reacting with water to form hydrogen peroxide, which oxidized ferrous ions into ferric ions and changed the color of the solution to brown (Fig. 38b). On the other hand, when enough monomers were present in the water and monomers and crosslinkers were present in an equal ratio, the radicals formed upon scission triggered the polymerization and crosslinking, and reformed a sacrificial network that increased both stiffness (modulus) and stress at break (Fig. 38c). Despite the limitation of the argon atmosphere and relatively long polymerization time (12–24 hours), this clever proof-of-principle shows the potential of polymer mechanochemistry to repair even sophisticated materials, such as interpenetrated networks.
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Fig. 38 The radicals deriving from the bond scission were used to self-heal or strengthen the polymer materials. (a) The scheme of double network hydrogels strengthening via a mechanoradical initiated polymerization reaction due to bond scission. (b) The presence of mechanoradicals is indicated by a color change. Image (i to iii) shows the generation of mechanoradicals after stretching in the necked region. (c) Due to a new polymerization and crosslinking initiated by the mechanoradical, pre-stretched double network hydrogels reformed a sacrificial network and showed a significant strengthening of the mechanical properties.99Fig. 38 is adapted from ref. 99 (published under a Creative Commons license, CC BY-NC), Copyright 2019 AAAS. |
If the material is designed to be sensitive, the next hurdle is the calibration. Typically, uniaxial tension tests are carried out to match the optical signal with a value of stress or strain. This calibration curve can then in principle be used for an arbitrary geometry. There are however two main challenges:
– The relationship between macroscopic stress and fraction of activated molecules is going to depend on the 3D spatial organization of the mechanophore-containing polymer chains in the material, and will need to be established for any new material.
– Mechanophores can report on the intensity of the optical signal, reflecting the local concentration of activated molecules, but not on directionality. Yet, stress or strain are both tensors. Chen et al. have discussed this point, and proposed to use the maximum principal nominal stress as the activation criterion.40 This methodology makes it possible to apply the calibration curve obtained from uniaxial tension to more complex loading situations, and compare results with simulations.
Despite these difficulties mechanophores that activate with an optically-visible change in color may find many interesting applications and some examples are given below.
Mechanically-responsive polymer materials can also be used as a smart skin for soft robots207 or robot arms in order to detect the pressure or stress distribution in the operating process. In this case, a mechanochromic nanocomposite lowers the activation threshold in terms of strain; and the color change that occurs due to the mechanical response can then be used as input for other functions.
An interesting example is the application of mechanochromic polymer materials as an overcoat for a touch screen,233 combined with cross-aligned silver nanowire transparent conductive electrodes (AgNW TCE) layers, as shown in Fig. 39a. The SP functionalized PDMS overcoat changes color as a result of the application of a local pressure and the AnNW TCE layers detect the location of dynamic touch. Since different writing pressures lead to the different color intensities on the screen (as shown in Fig. 39a), the writing style can be quantified much more precisely by analyzing, with a spectrophotometer, the intensity of the color change. The local pressure can then be extracted from the representation of the color coordinating on the CIE 1931 color space. This technology is promising for personal information safety, since persons typically possess a unique writing habit and applied pressure on a pencil.
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Fig. 39 Mechanically responsive polymeric materials applied in electronic devices. (a) SP-containing PDMS was used as a tough screen where the writing force can be quantified by an optical technology.233 (b) A liquid metal wire was cast into the centre of an SP-containing PDMS elastomer and the material changed color in uniaxial tensile tests.234 (a) is adapted with permission from ref. 233, Copyright 2017 American Chemical Society. (b) is reprinted with permission from ref. 234, Copyright 2018 American Chemical Society. |
Another interesting example also came from Dickey and Craig's group.234 Liquid metal wires composed of a eutectic gallium indium alloy were embedded into the central section of the labelled PDMS materials as shown in Fig. 39b. Since the onset of color change can be tuned by adjusting the modulus of the silicone layering in the PDMS materials, the onset strain of color change can be matched with the maximum allowable deformation of the metal wires. This, therefore, gives the user a visual warning of the limiting stretch of these flexible electronics, as shown in Fig. 39b.
The SP-functionalized PDMS were also cured into a molded soft robot walker and gripper.235 In Fig. 40a, the color distribution reveals the spatial distribution of the maximum force during the actuation process of the gripper or walker – useful information for engineering design. Alternatively, rhodamine was integrated as a stress sensor into the filler network of multiple-network elastomers, and the materials used as robotic skin.52 The labelled elastomeric skin stuck on a finger, showed different colors during the action of making a fist (Fig. 40b). The skin became fluorescent when the finger bent, switching from blue to red, and then turning yellow as the finger straightened. These optical variations provide feedback loops, and open up a possibility of a feedback loop that is based on the optical information. In addition, similar mechanochromic polymer materials were also applied in biomimetic materials or devices by Craig,194 and Sprakel et al.228 For example, a biomimetic device was designed via electro-mechanochemically responsive elastomers to imitate the behavior of cephalopods, which can show various color patterns by selectively contracting muscles to reversibly activate chromophores (Fig. 40c).
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Fig. 40 Mechanical responsive polymer materials are applied in soft robots and biomimetic device. (a) SP-containing PDMS was casted into a gripper and worker. The two robots showed color change in actuation process and indicated the high stress location after actuation.235 (b) Multiple network elastomers coupled of rhodamine acted as skin of finger and exhibited different fluorescent colors during the bending and straightening of finger.52 (c) SP was incorporated into PDMS network. PDMS materials combining with other electronic device was assembled to be an electro-mechanochemically responsive elastomers. The schematic shows the mechanism of the elastomers actuation.194 (a) is reprinted with permission from ref. 235, Copyright 2015 American Chemical Society. (b) is reprinted with permission from ref. 52, Copyright 2017 American Chemical Society. (c) is reprinted with permission from ref. 194, Copyright 2014 Springer Nature. |
– With the development of extreme molecular force sensors, the road is now open towards application of synthetic mechanophores to the study of biological phenomena in vivo, such as cell adhesion, mechanotransduction and subcellular viscosity patterns.236 In mechanobiology, much progress can be made by combining the specificity of biological force sensors with the smaller size and versatility of fully synthetic mechanophores. The capability to release small molecules with a mechanical stimulus promises applications for targeted drug release.
– Optical mechanophores find increasing use in the study of failure of polymer materials. Although we reported multiple examples of mapping strains or bond scission in a given material, the main challenge now ahead is to be quantitative in an absolute way in order to be able to compare activation in different materials and compare experimental data with molecular models or simulations. Along this line there are two main challenges: absolute calibration of the signal with a reference sample as discussed in a recent work of Slootman et al.,181 and representativity of the data. Since mechanophores are typically weaker bonds than C–C covalent bonds, two questions need to be addressed: (1) is the mechanophore altering the properties of the material into which it is incorporated? and (2) is the mechanophore correctly reporting what is happening to C–C bonds? A second important current limitation is that optical mechanophores require transparent or translucent materials while many engineering polymeric materials are opaque. Infrared dyes, or the detection of radicals could be interesting options for the development of probes for opaque materials.
– A more sustainable economy requires durable and recyclable materials. There are ample opportunities for mechanochemistry to play a role in this area. Stress and damage sensors can help extend the service lifetime of polymer materials, provided that the sensors are robust and have a simple readout. Another exciting prospect is the use of mechanocatalysts and mechanoradical initiators to promote polymerization and crosslinking in self-healing materials. While proof-of-concept has been demonstrated with catalysts as well as radical initiators, much work needs to be done before such self-healing schemes will be practical for commercial materials.
Making these opportunities a reality will not only require creativity and imagination – characteristics that our colleagues in the field of polymer mechanochemistry have demonstrated to possess in abundance – but also sustained interdisciplinary work and close collaborations between organic chemists, physicists, and solid mechanics experts. We thank our community for the inspiring work that has greatly enriched the scientific literature.
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