Abstract
Mechanochemistry describes diverse phenomena in which mechanical load affects chemical reactivity. The fuzziness of this definition means that it includes processes as seemingly disparate as motor protein function, organic synthesis in a ball mill, reactions at a propagating crack, chemical actuation, and polymer fragmentation in fast solvent flows and in mastication. In chemistry, the rate of a reaction in a flask does not depend on how fast the flask moves in space. In mechanochemistry, the rate at which a material is deformed affects which and how many bonds break. In other words, in some manifestations of mechanochemistry, macroscopic motion powers otherwise endergonic reactions. In others, spontaneous chemical reactions drive mechanical motion. Neither requires thermal or electrostatic gradients. Distinct manifestations of mechanochemistry are conventionally treated as being conceptually independent, which slows the field in its transformation from being a collection of observations to a rigorous discipline. In this Review, we highlight observations suggesting that the unifying feature of mechanochemical phenomena may be the coupling between inertial motion at the microscale to macroscale and changes in chemical bonding enabled by transient build-up and relaxation of strains, from macroscopic to molecular. This dynamic coupling across multiple length scales and timescales also greatly complicates the conceptual understanding of mechanochemistry.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 digital issues and online access to articles
$119.00 per year
only $9.92 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Kaupp, G. Mechanochemistry: the varied applications of mechanical bond-breaking. CrystEngComm 11, 388–403 (2009). A comprehensive and thoughtful review of powder mechanochemistry and certain aspects of tribochemistry.
Boldyreva, E. Mechanochemistry of inorganic and organic systems: what is similar, what is different? Chem. Soc. Rev. 42, 7719–7738 (2013). A critical review of assumptions and misconceptions in powder mechanochemistry.
Horie, K. et al. Definitions of terms relating to reactions of polymers and to functional polymeric materials (IUPAC Recommendations 2003). Pure Appl. Chem. 76, 889–906 (2004).
Baláž, P. et al. Hallmarks of mechanochemistry: from nanoparticles to technology. Chem. Soc. Rev. 42, 7571–7637 (2013). A very detailed review of powder mechanochemistry with emphasis on extended solids and practical applications.
Cross, R. A. & McAinsh, A. Prime movers: the mechanochemistry of mitotic kinesins. Nat. Rev. Mol. Cell Biol. 15, 257–271 (2014).
Cross, R. A. Review: mechanochemistry of the kinesin-1 ATPase. Biopolymers 105, 476–482 (2016).
Hancock, W. O. The kinesin-1 chemomechanical cycle: stepping toward a consensus. Biophys. J. 110, 1216–1225 (2016).
Vogel, V. Unraveling the mechanobiology of extracellular matrix. Annu. Rev. Physiol. 80, 353–387 (2018).
Mohapatra, S., Lin, C.-T., Feng, X. A., Basu, A. & Ha, T. Single-molecule analysis and engineering of DNA motors. Chem. Rev. 120, 36–78 (2020).
Butler, P. J., Dey, K. K. & Sen, A. Impulsive enzymes: a new force in mechanobiology. Cell. Mol. Bioeng. 8, 106–118 (2015).
Stratigaki, M. & Göstl, R. Methods for exerting and sensing force in polymer materials using mechanophores. ChemPlusChem 85, 1095–1103 (2020).
Izak-Nau, E., Campagna, D., Baumann, C. & Göstl, R. Polymer mechanochemistry-enabled pericyclic reactions. Polym. Chem. 11, 2274–2299 (2020). A summary of a subclass of mechanochemical reactions from a mechanistic standpoint.
Bowser, B. H. & Craig, S. L. Empowering mechanochemistry with multi-mechanophore polymer architectures. Polym. Chem. 9, 3583–3593 (2018).
Anderson, L. & Boulatov, R. Polymer mechanochemistry: a new frontier for physical organic chemistry. Adv. Phys. Org. Chem. 52, 87–143 (2018).
Willis-Fox, N., Rognin, E., Aljohani, T. A. & Daly, R. Polymer mechanochemistry: manufacturing is now a force to be reckoned with. Chem 4, 2499–2537 (2018).
De Bo, G. Mechanochemistry of the mechanical bond. Chem. Sci. 9, 15–21 (2018).
Akbulatov, S. & Boulatov, R. Experimental polymer mechanochemistry and its interpretational frameworks. ChemPhysChem 18, 1422–1450 (2017). A critical review of the common approaches to interpreting experimental observations in polymer mechanochemistry, with emphasis on sonication.
Garcia-Manyes, S. & Beedle, A. E. M. Steering chemical reactions with force. Nat. Rev. Chem. 1, 0083 (2017).
Boulatov, R. (ed.) Polymer Mechanochemistry (Springer, 2015).
Schönfelder, J., Alonso-Caballero, A., De Sancho, D. & Perez-Jimenez, R. The life of proteins under mechanical force. Chem. Soc. Rev. 47, 3558–3573 (2018).
Lancellotti, S., Sacco, M., Basso, M. & De Cristofaro, R. Mechanochemistry of von Willebrand factor. Biomol. Concepts 10, 194–208 (2019).
Zhou, Y. et al. Controlling optical and catalytic activity of genetically engineered proteins by ultrasound. Angew. Chem. Int. Ed. https://doi.org/10.1002/anie.202010324 (2020).
Suryanarayana, C. Mechanical alloying and milling. Prog. Mater. Sci. 46, 1–184 (2001). A comprehensive review of mechanochemistry of powders of metals and oxides.
Šepelák, V., Duevel, A., Wilkening, M., Becker, K.-D. & Heitjans, P. Mechanochemical reactions and syntheses of oxides. Chem. Soc. Rev. 42, 7507–7520 (2013).
Intasa-ard, S., Imwiset, K., Bureekaew, S. & Ogawa, M. Mechanochemical methods for the preparation of intercalation compounds, from intercalation to the formation of layered double hydroxides. Dalton Trans. 47, 2896–2916 (2018).
Muñoz-Batista, M. J., Rodriguez-Padron, D., Puente-Santiago, A. R. & Luque, R. Mechanochemistry: toward sustainable design of advanced nanomaterials for electrochemical energy storage and catalytic applications. ACS Sustain. Chem. Eng. 6, 9530–9544 (2018).
Prochowicz, D., Saski, M., Yadav, P., Grätzel, M. & Lewiński, J. Mechanoperovskites for photovoltaic applications: preparation, characterization, and device fabrication. Acc. Chem. Res. 52, 3233–3243 (2019).
Giannakoudakis, D. A., Chatel, G. & Colmenares, J. C. Mechanochemical forces as a synthetic tool for zero- and one-dimensional titanium oxide-based nano-photocatalysts. Top. Curr. Chem. 378, 2 (2020).
Palazon, F., El Ajjouri, Y. & Bolink, H. J. Making by grinding: mechanochemistry boosts the development of halide perovskites and other multinary metal halides. Adv. Energy Mater. 10, 1902499 (2020).
Beillard, A., Bantreil, X., Métro, T.-X., Martinez, J. & Lamaty, F. Alternative technologies that facilitate access to discrete metal complexes. Chem. Rev. 119, 7529–7609 (2019).
Chen, D., Zhao, J., Zhang, P. & Dai, S. Mechanochemical synthesis of metal–organic frameworks. Polyhedron 162, 59–64 (2019).
Zhao, L.-Y., Dong, X.-L. & Lu, A.-H. Mechanochemical synthesis of porous carbons and their applications in catalysis. ChemPlusChem 85, 866–875 (2020).
Tan, D. & García, F. Main group mechanochemistry: from curiosity to established protocols. Chem. Soc. Rev. 48, 2274–2292 (2019). A compilation of empirical observations in powder mechanochemistry, primarily of metal–organic molecules.
Hernández, J. G. & Bolm, C. Altering product selectivity by mechanochemistry. J. Org. Chem. 82, 4007–4019 (2017).
Bolm, C. & Hernández, J. G. From synthesis of amino acids and peptides to enzymatic catalysis: a bottom-up approach in mechanochemistry. ChemSusChem 11, 1410–1420 (2018).
Howard, J. L., Cao, Q. & Browne, D. L. Mechanochemistry as an emerging tool for molecular synthesis: what can it offer? Chem. Sci. 9, 3080–3094 (2018).
Leonardi, M., Villacampa, M. & Menéndez, J. C. Multicomponent mechanochemical synthesis. Chem. Sci. 9, 2042–2064 (2018).
Zhao, S., Li, Y., Liu, C. & Zhao, Y. Recent advances in mechanochemical C–H functionalization reactions. Tetrahedron Lett. 59, 317–324 (2018).
Avila-Ortiz, C. G., Pérez-Venegas, M., Vargas-Caporali, J. & Juaristi, E. Recent applications of mechanochemistry in enantioselective synthesis. Tetrahedron Lett. 60, 1749–1757 (2019).
Egorov, I. N. et al. Ball milling: an efficient and green approach for asymmetric organic syntheses. Green Chem. 22, 302–315 (2020).
Friščić, T., Mottillo, C. & Titi, H. M. Mechanochemistry for synthesis. Angew. Chem. Int. Ed. 59, 1018–1029 (2020).
Zhu, S.-E., Li, F. & Wang, G.-W. Mechanochemistry of fullerenes and related materials. Chem. Soc. Rev. 42, 7535–7570 (2013).
Isayev, A. I. Recycling of Natural and Synthetic Isoprene Rubbers (Woodhead Publishing, 2014).
Yin, S. et al. Mechanical reprocessing of polyolefin waste: a review. Polym. Eng. Sci. 55, 2899–2909 (2015).
Hsu, S. M., Zhang, J. & Yin, Z. The nature and origin of tribochemistry. Tribol. Lett. 13, 131–139 (2002).
Lussis, P. et al. A single synthetic small molecule that generates force against a load. Nat. Nanotechnol. 6, 553–557 (2011).
Eelkema, R. et al. Life-like motion driven by artificial molecular machines. Nat. Rev. Chem. 3, 536–551 (2019).
Sluysmans, D. et al. Synthetic oligorotaxanes exert high forces when folding under mechanical load. Nat. Nanotechnol. 13, 209–213 (2018).
Zhang, Q. M. & Serpe, M. J. Stimuli-responsive polymers for actuation. ChemPhysChem 18, 1451–1465 (2017).
White, T. J. & Broer, D. J. Programmable and adaptive mechanics with liquid crystal polymer networks and elastomers. Nat. Mater. 14, 1087–1098 (2015).
Chen, J. et al. Artificial muscle-like function from hierarchical supramolecular assembly of photoresponsive molecular motors. Nat. Chem. 10, 132–138 (2018).
Felts, J. R. et al. Direct mechanochemical cleavage of functional groups from graphene. Nat. Commun. 6, 6467 (2015).
Adams, H. L. et al. Shear-induced mechanochemistry: pushing molecules around. J. Phys. Chem. C 119, 7115–7123 (2015).
Zhang, Y., Wang, Y., Lü, J.-T., Brandbyge, M. & Berndt, R. Mechanochemistry induced using force exerted by a functionalized microscope tip. Angew. Chem. Int. Ed. 56, 11769–11773 (2017).
Qi, J. et al. Force-activated isomerization of a single molecule. J. Am. Chem. Soc. 142, 10673–10680 (2020).
Yan, H. et al. Sterically controlled mechanochemistry under hydrostatic pressure. Nature 554, 505–510 (2018).
Li, Y. & Sheiko, S. S. Molecular mechanochemistry: engineering and implications of inherently strained architectures. Top. Curr. Chem. 369, 1–36 (2015).
Milles, L. F., Schulten, K., Gaub, H. E. & Bernardi, R. C. Molecular mechanism of extreme mechanostability in a pathogen adhesin. Science 359, 1527–1533 (2018). A very rare example of a non-covalent molecular adduct with mechanochemical stability rivalling that of a covalent bond and an excellent illustration of the value of integrating computational and experimental approaches.
Chen, Z. et al. The cascade unzipping of ladderane reveals dynamic effects in mechanochemistry. Nat. Chem. 12, 302–309 (2020).
Tian, Y. et al. A polymer with mechanochemically active hidden length. J. Am. Chem. Soc. 142, 18687–18697 (2020).
Dopieralski, P., Ribas-Arino, J., Anjukandi, P., Krupicka, M. & Marx, D. Unexpected mechanochemical complexity in the mechanistic scenarios of disulfide bond reduction in alkaline solution. Nat. Chem. 9, 164–170 (2017).
Chakrabarti, S., Hinczewski, M. & Thirumalai, D. Phenomenological and microscopic theories for catch bonds. J. Struct. Biol. 197, 50–56 (2017).
Ardila-Fierro, K. J. et al. Direct visualization of a mechanochemically induced molecular rearrangement. Angew. Chem. Int. Ed. 59, 13458–13462 (2020).
Guo, Q. & Long, R. in Self-Healing and Self-Recovering Hydrogels (eds Creton, C. & Okay, O.) 127–164 (Springer, 2020).
Astumian, R. D. Huxley’s model for muscle contraction revisited: the importance of microscopic reversibility. Top. Curr. Chem. 369, 285–316 (2015).
Deneke, N., Rencheck, M. L. & Davis, C. S. An engineer’s introduction to mechanophores. Soft Matter 16, 6230–6252 (2020).
Binder, W. H. The “labile” chemical bond: a perspective on mechanochemistry in polymers. Polymer 202, 122639 (2020).
Zhang, H., Lin, Y., Xu, Y. & Weng, W. Mechanochemistry of topological complex polymer systems. Top. Curr. Chem. 369, 135–207 (2015).
Cintas, P., Cravotto, G., Barge, A. & Martina, K. Interplay between mechanochemistry and sonochemistry. Top. Curr. Chem. 369, 239–284 (2015).
Stolle, A. in Ball Milling Towards Green Synthesis: Applications, Projects, Challenges (eds Stolle, A. & Ranu. B.) 241–276 (Royal Society of Chemistry, 2015).
Burmeister, C. F. & Kwade, A. Process engineering with planetary ball mills. Chem. Soc. Rev. 42, 7660–7667 (2013).
Yang, B., Liu, Z., Liu, H. & Nash, M. A. Next generation methods for single-molecule force spectroscopy on polyproteins and receptor–ligand complexes. Front. Mol. Biosci. 7, 85 (2020).
Li, H. & Zheng, P. Single molecule force spectroscopy: a new tool for bioinorganic chemistry. Curr. Opin. Chem. Biol. 43, 58–67 (2018).
Stauch, T. & Dreuw, A. Quantum chemical strain analysis for mechanochemical processes. Acc. Chem. Res. 50, 1041–1048 (2017).
Kulik, H. J. Modeling mechanochemistry from first principles. Rev. Comput. Chem. 31, 265–311 (2019).
Kochhar, G. S., Heverly-Coulson, G. S. & Mosey, N. J. Theoretical approaches for understanding the interplay between stress and chemical reactivity. Top. Curr. Chem. 369, 37–96 (2015).
Bolm, C. & Hernández, J. G. Mechanochemistry of gaseous reactants. Angew. Chem. Int. Ed. 58, 3285–3299 (2019).
Ardila-Fierro, K. J., Bolm, C. & Hernández, J. G. Mechanosynthesis of odd-numbered tetraaryl[n]cumulenes. Angew. Chem. Int. Ed. 58, 12945–12949 (2019).
Crawford, D. E. & Casaban, J. Recent developments in mechanochemical materials synthesis by extrusion. Adv. Mater. 28, 5747–5754 (2016).
Huot, J. et al. Mechanochemical synthesis of hydrogen storage materials. Prog. Mater. Sci. 58, 30–75 (2013).
Ghanem, M. A. et al. The role of polymer mechanochemistry in responsive materials and additive manufacturing. Nat. Rev. Mater. https://doi.org/10.1038/s41578-020-00249-w (2020). The most up-to-date review of emerging applications of polymer mechanochemistry.
Traeger, H., Kiebala, D. J., Weder, C. & Schrettl, S. From molecules to polymers — harnessing inter- and intramolecular interactions to create mechanochromic materials. Macromol. Rapid Commun. https://doi.org/10.1002/marc.202000573 (2020).
Stirling, C. J. M. Evaluation of the effect of strain upon reactivity. Tetrahedron 41, 1613–1666 (1985).
Zhurkov, S. N. Kinetic concept of the strength of solids. Int. J. Fract. Mech. 1, 311–323 (1965).
Kausch, H.-H. (ed.) Polymer Fracture 2nd edn (Mir, 1981).
Leffler, J. E. & Grunwald, E. Rates and Equilibria of Organic Reactions: As Treated by Statistical, Thermodynamic and Extrathermodynamic Methods (Dover Publications, 1989).
Takacs, L. The historical development of mechanochemistry. Chem. Soc. Rev. 42, 7649–7659 (2013).
Boulatov, R. Reaction dynamics in the formidable gap. Pure Appl. Chem. 83, 25–41 (2010).
Huang, Z. & Boulatov, R. Chemomechanics: chemical kinetics for multiscale phenomena. Chem. Soc. Rev. 40, 2359–2384 (2011).
Ahmed, E. et al. From mechanical effects to mechanochemistry: softening and depression of the melting point of deformed plastic crystals. J. Am. Chem. Soc. 142, 11219–11231 (2020).
Zimmerman, J. A. et al. Calculation of stress in atomistic simulation. Model. Simul. Mater. Sci. Eng. 12, S319–S332 (2004).
Murdoch, A. I. A critique of atomistic definitions of the stress tensor. J. Elast. 88, 113–140 (2007).
Berry, R. S., Rice, S. A. & Ross, J. Physical and Chemical Kinetics 2nd edn Vol. 3 (Oxford Univ. Press, 2002).
Wilczek, F. Whence the force of F = ma? I: culture shock. Phys. Today 57, 11–12 (2004). An accessible and insightful summary of why force is an ambiguous construct.
Evans, E. & Ritchie, K. Dynamic strength of molecular adhesion bonds. Biophys. J. 72, 1541–1555 (1997).
Suzuki, Y. & Dudko, O. K. Single-molecule rupture dynamics on multidimensional landscapes. Phys. Rev. Lett. 104, 048101 (2010).
Ribas-Arino, J. & Marx, D. Covalent mechanochemistry: theoretical concepts and computational tools with applications to molecular nanomechanics. Chem. Rev. 112, 5412–5487 (2012). A review of computational methods in molecular mechanochemistry.
Kucharski, T. J. & Boulatov, R. The physical chemistry of mechanoresponsive polymers. J. Mater. Chem. 21, 8237–8255 (2011).
Jencks, W. P. A primer for the Bema Hapothle. An empirical approach to the characterization of changing transition-state structures. Chem. Rev. 85, 511–527 (1985).
Kucharski, T. J., Yang, Q.-Z., Tian, Y. & Boulatov, R. Strain-dependent acceleration of a paradigmatic SN2 reaction accurately predicted by the force formalism. J. Phys. Chem. Lett. 1, 2820–2825 (2010).
Hermes, M. & Boulatov, R. The entropic and enthalpic contributions to force-dependent dissociation kinetics of the pyrophosphate bond. J. Am. Chem. Soc. 133, 20044–20047 (2011).
Akbulatov, S. et al. Experimentally realized mechanochemistry distinct from force-accelerated scission of loaded bonds. Science 357, 299–303 (2017).
Akbulatov, S., Tian, Y. C. & Boulatov, R. Force–reactivity property of a single monomer is sufficient to predict the micromechanical behavior of its polymer. J. Am. Chem. Soc. 134, 7620–7623 (2012).
Wang, J., Kouznetsova, T. B., Boulatov, R. & Craig, S. L. Mechanical gating of a mechanochemical reaction cascade. Nat. Commun. 7, 13433 (2016).
Zhang, H. et al. Multi-modal mechanophores based on cinnamate dimers. Nat. Commun. 8, 1147 (2017).
Tian, Y. & Boulatov, R. Quantum-chemical validation of the local assumption of chemomechanics for a unimolecular reaction. ChemPhysChem 13, 2277–2281 (2012).
Tian, Y. & Boulatov, R. Comparison of the predictive performance of the Bell–Evans, Taylor-expansion and statistical-mechanics models of mechanochemistry. Chem. Commun. 49, 4187–4189 (2013).
Raman, S., Utzig, T., Baimpos, T., Ratna Shrestha, B. & Valtiner, M. Deciphering the scaling of single-molecule interactions using Jarzynski’s equality. Nat. Commun. 5, 5539 (2014).
Liphardt, J., Dumont, S., Smith, S. B., Tinoco, I. & Bustamante, C. Equilibrium information from nonequilibrium measurements in an experimental test of Jarzynski’s equality. Science 296, 1832–1835 (2002).
Lauterborn, W. & Kurz, T. Physics of bubble oscillations. Rep. Prog. Phys. 73, 106501 (2010). A detailed review of the state-of-the-knowledge of the physics underlying cavitation with relevance to polymer mechanochemistry in sonicated solutions.
Larson, R. G. The rheology of dilute solutions of flexible polymers: progress and problems. J. Rheol. 49, 1–70 (2005). An illuminating review of the complexities of the behaviour of polymers in elongational flows.
Moussatov, A., Granger, C. & Dubus, B. Cone-like bubble formation in ultrasonic cavitation field. Ultrason. Sonochem. 10, 191–195 (2003).
Fritze, U. F., Craig, S. L. & von Delius, M. Disulfide-centered poly(methyl acrylates): four different stimuli to cleave a polymer. J. Polym. Sci. A Polym. Chem. 56, 1404–1411 (2018).
Price, G. J. The use of ultrasound for the controlled degradation of polymer solutions. Adv. Sonochem. 1, 231–287 (1990).
Nguyen, T. Q. & Kausch, H.-H. Mechanochemical degradation in transient elongational flow. Adv. Polym. Sci. 100, 73–182 (1992).
Tyler, D. R. Mechanistic aspects of the effects of stress on the rates of photochemical degradation reactions in polymers. J. Macromol. Sci. Polym. Rev. 44, 351–388 (2004).
Vanapalli, S. A., Ceccio, S. L. & Solomon, M. J. Universal scaling for polymer chain scission in turbulence. Proc. Natl Acad. Sci. USA 103, 16660–16665 (2006).
Verstraeten, F., Göstl, R. & Sijbesma, R. P. Stress-induced colouration and crosslinking of polymeric materials by mechanochemical formation of triphenylimidazolyl radicals. Chem. Commun. 52, 8608–8611 (2016).
Sumi, T., Goseki, R. & Otsuka, H. Tetraarylsuccinonitriles as mechanochromophores to generate highly stable luminescent carbon-centered radicals. Chem. Commun. 53, 11885–11888 (2017).
Aoki, D., Yanagisawa, M. & Otsuka, H. Synthesis of well-defined mechanochromic polymers based on a radical-type mechanochromophore by RAFT polymerization: living radical polymerization from a polymerization inhibitor. Polym. Chem. 11, 4290–4296 (2020).
Nixon, R. & De Bo, G. Three concomitant C–C dissociation pathways during the mechanical activation of an N-heterocyclic carbene precursor. Nat. Chem. 12, 826–831 (2020).
Diesendruck, C. E. et al. Mechanically triggered heterolytic unzipping of a low-ceiling-temperature polymer. Nat. Chem. 6, 623–628 (2014).
Kersey, F. R., Yount, W. C. & Craig, S. L. Single-molecule force spectroscopy of bimolecular reactions: system homology in the mechanical activation of ligand substitution reactions. J. Am. Chem. Soc. 128, 3886–3887 (2006).
Sha, Y. et al. Generalizing metallocene mechanochemistry to ruthenocene mechanophores. Chem. Sci. 10, 4959–4965 (2019).
Paulusse, J. M. J. & Sijbesma, R. P. Reversible mechanochemistry of a PdII coordination polymer. Angew. Chem. Int. Ed. 43, 4460–4462 (2004).
Piermattei, A., Karthikeyan, S. & Sijbesma, R. P. Activating catalysts with mechanical force. Nat. Chem. 1, 133–137 (2009).
Karthikeyan, S., Potisek, S. L., Piermattei, A. & Sijbesma, R. P. Highly efficient mechanochemical scission of silver–carbene coordination polymers. J. Am. Chem. Soc. 130, 14968–14969 (2008).
Michael, P. & Binder, W. H. A mechanochemically triggered “click” catalyst. Angew. Chem. Int. Ed. 54, 13918–13922 (2015).
Clough, J. M., Balan, A. & Sijbesma, R. P. Mechanochemical reactions reporting and repairing bond scission in polymers. Top. Curr. Chem. 369, 209–238 (2015).
Clough, J. M., Balan, A., van Daal, T. L. J. & Sijbesma, R. P. Probing force with mechanobase-induced chemiluminescence. Angew. Chem. Int. Ed. 55, 1445–1449 (2016).
Lee, D. C., Kensy, V. K., Maroon, C. R., Long, B. K. & Boydston, A. J. The intrinsic mechanochemical reactivity of vinyl-addition polynorbornene. Angew. Chem. Int. Ed. 58, 5639–5642 (2019).
Jung, S. & Yoon, H. J. Mechanical force induces ylide-free cycloaddition of nonscissible aziridines. Angew. Chem. Int. Ed. 59, 4883–4887 (2020).
Wang, J., Kouznetsova, T. B. & Craig, S. L. Single-molecule observation of a mechanically activated cis-to-trans cyclopropane isomerization. J. Am. Chem. Soc. 138, 10410–10412 (2016).
Barbee, M. H., Wang, J., Kouznetsova, T., Lu, M. & Craig, S. L. Mechanochemical ring-opening of allylic epoxides. Macromolecules 52, 6234–6240 (2019).
Lenhardt, J. M. et al. Reactive cross-talk between adjacent tension-trapped transition states. J. Am. Chem. Soc. 133, 3222–3225 (2011).
Haehnel, A. P., Sagara, Y., Simon, Y. C. & Weder, C. Mechanochemistry in polymers with supramolecular mechanophores. Top. Curr. Chem. 369, 345–375 (2015).
Balkenende, D. W. R. et al. Mechanochemistry with metallosupramolecular polymers. J. Am. Chem. Soc. 136, 10493–10498 (2014).
Wang, J., Kouznetsova, T. B. & Craig, S. L. Reactivity and mechanism of a mechanically activated anti-Woodward–Hoffmann–DePuy reaction. J. Am. Chem. Soc. 137, 11554–11557 (2015).
Ramirez, A. L. B. et al. Mechanochemical strengthening of a synthetic polymer in response to typically destructive shear forces. Nat. Chem. 5, 757–761 (2013).
Wang, J. et al. Inducing and quantifying forbidden reactivity with single-molecule polymer mechanochemistry. Nat. Chem. 7, 323–327 (2015).
Li, J. et al. Mechanophore activation at heterointerfaces. J. Am. Chem. Soc. 136, 15925–15928 (2014).
Stevenson, R. & De Bo, G. Controlling reactivity by geometry in retro-Diels–Alder reactions under tension. J. Am. Chem. Soc. 139, 16768–16771 (2017).
Kean, Z. S., Gossweiler, G. R., Kouznetsova, T. B., Hewage, G. B. & Craig, S. L. A coumarin dimer probe of mechanochemical scission efficiency in the sonochemical activation of chain-centered mechanophore polymers. Chem. Commun. 51, 9157–9160 (2015).
Kan, L. et al. Anthracene dimer crosslinked polyurethanes as mechanoluminescent polymeric materials. New J. Chem. 43, 2658–2664 (2019).
Chen, Y. et al. Mechanically induced chemiluminescence from polymers incorporating a 1,2-dioxetane unit in the main chain. Nat. Chem. 4, 559–562 (2012).
Kean, Z. S., Niu, Z., Hewage, G. B., Rheingold, A. L. & Craig, S. L. Stress-responsive polymers containing cyclobutane core mechanophores: reactivity and mechanistic insights. J. Am. Chem. Soc. 135, 13598–13604 (2013).
Yang, J. et al. Benzoladderene mechanophores: synthesis, polymerization, and mechanochemical transformation. J. Am. Chem. Soc. 141, 6479–6483 (2019).
Yang, J. et al. Bicyclohexene-peri-naphthalenes: scalable synthesis, diverse functionalization, efficient polymerization, and facile mechanoactivation of their polymers. J. Am. Chem. Soc. 142, 14619–14626 (2020).
Thomas, III, S. W. Forcing ladderenes into plastic semiconductors with mechanochemistry. Angew. Chem. Int. Ed. 56, 15196–15198 (2017).
Chen, Z. et al. Mechanochemical unzipping of insulating polyladderene to semiconducting polyacetylene. Science 357, 475–479 (2017).
Larsen, M. B. & Boydston, A. J. Successive mechanochemical activation and small molecule release in an elastomeric material. J. Am. Chem. Soc. 136, 1276–1279 (2014).
Klukovich, H. M., Kouznetsova, T. B., Kean, Z. S., Lenhardt, J. M. & Craig, S. L. A backbone lever-arm effect enhances polymer mechanochemistry. Nat. Chem. 5, 110–114 (2013).
Wang, J. et al. A remote stereochemical lever arm effect in polymer mechanochemistry. J. Am. Chem. Soc. 136, 15162–15165 (2014).
Lin, Y., Kouznetsova, T. B. & Craig, S. L. A latent mechanoacid for time-stamped mechanochromism and chemical signaling in polymeric materials. J. Am. Chem. Soc. 142, 99–103 (2020).
Gossweiler, G. R., Kouznetsova, T. B. & Craig, S. L. Force-rate characterization of two spiropyran-based molecular force probes. J. Am. Chem. Soc. 137, 6148–6151 (2015).
Barbee, M. H. et al. Substituent effects and mechanism in a mechanochemical reaction. J. Am. Chem. Soc. 140, 12746–12750 (2018).
Zhang, H. et al. Mechanochromism and mechanical force-triggered cross-linking from a single reactive moiety incorporated into polymer chains. Angew. Chem. Int. Ed. 55, 3040–3044 (2016).
Pan, Y. et al. A mechanochemical reaction cascade for controlling load-strengthening of a mechanochromic polymer. Angew. Chem. Int. Ed. 59, 21980–21985 (2020).
Wollenhaupt, M., Krupička, M. & Marx, D. Should the Woodward–Hoffmann rules be applied to mechanochemical reactions? ChemPhysChem 16, 1593–1597 (2015).
Lee, C. K. et al. Force-induced redistribution of a chemical equilibrium. J. Am. Chem. Soc. 132, 16107–16111 (2010).
Sung, J., Robb, M. J., White, S. R., Moore, J. S. & Sottos, N. R. Interfacial mechanophore activation using laser-induced stress waves. J. Am. Chem. Soc. 140, 5000–5003 (2018).
Robb, M. J. et al. Regioisomer-specific mechanochromism of naphthopyran in polymeric materials. J. Am. Chem. Soc. 138, 12328–12331 (2016).
Wang, Z. et al. A novel mechanochromic and photochromic polymer film: when rhodamine joins polyurethane. Adv. Mater. 27, 6469–6474 (2015).
Willis-Fox, N. et al. Going with the flow: tunable flow-induced polymer mechanochemistry. Adv. Funct. Mater. 30, 2002372 (2020).
Peterson, G. I., Lee, J. & Choi, T.-L. Multimechanophore graft polymers: mechanochemical reactions at backbone–arm junctions. Macromolecules 52, 9561–9568 (2019).
Yildiz, D. et al. Anti-Stokes stress sensing: mechanochemical activation of triplet–triplet annihilation photon upconversion. Angew. Chem. Int. Ed. 58, 12919–12923 (2019).
Kida, J. et al. The photoregulation of a mechanochemical polymer scission. Nat. Commun. 9, 3504 (2018).
Zhang, M. & De Bo, G. Impact of a mechanical bond on the activation of a mechanophore. J. Am. Chem. Soc. 140, 12724–12727 (2018).
Hu, X., Zeng, T., Husic, C. C. & Robb, M. J. Mechanically triggered small molecule release from a masked furfuryl carbonate. J. Am. Chem. Soc. 141, 15018–15023 (2019).
Wang, Z. & Craig, S. L. Stereochemical effects on the mechanochemical scission of furan–maleimide Diels–Alder adducts. Chem. Commun. 55, 12263–12266 (2019).
Lyu, B. et al. Surface confined retro Diels–Alder reaction driven by the swelling of weak polyelectrolytes. ACS Appl. Mater. Interfaces 7, 6254–6259 (2015).
Hu, X., McFadden, M. E., Barber, R. W. & Robb, M. J. Mechanochemical regulation of a photochemical reaction. J. Am. Chem. Soc. 140, 14073–14077 (2018).
Kryger, M. J. et al. Masked cyanoacrylates unveiled by mechanical force. J. Am. Chem. Soc. 132, 4558–4559 (2010).
Klukovich, H. M., Kean, Z. S., Iacono, S. T. & Craig, S. L. Mechanically induced scission and subsequent thermal remending of perfluorocyclobutane polymers. J. Am. Chem. Soc. 133, 17882–17888 (2011).
Zhang, H. et al. Mechanochromism and optical remodeling of multi-network elastomers containing anthracene dimers. Chem. Sci. 10, 8367–8373 (2019).
Yang, F., Yuan, Y., Sijbesma, R. P. & Chen, Y. L. Sensitized mechanoluminescence design toward mechanically induced intense red emission from transparent polymer films. Macromolecules 53, 905–912 (2020).
Ducrot, E., Chen, Y., Bulters, M., Sijbesma, R. P. & Creton, C. Toughening elastomers with sacrificial bonds and watching them break. Science 344, 186–189 (2014).
Robb, M. J. & Moore, J. S. A retro-Staudinger cycloaddition: mechanochemical cycloelimination of a β-lactam mechanophore. J. Am. Chem. Soc. 137, 10946–10949 (2015).
Dopieralski, P., Ribas-Arino, J., Anjukandi, P., Krupicka, M. & Marx, D. Force-induced reversal of β-eliminations: stressed disulfide bonds in alkaline solution. Angew. Chem. Int. Ed. 55, 1304–1308 (2016).
Oka, H. et al. Enhancing mechanochemical activation in the bulk state by designing polymer architectures. ACS Macro Lett. 5, 1124–1127 (2016).
Lin, Y., Zhang, Y., Wang, Z. & Craig, S. L. Dynamic memory effects in the mechanochemistry of cyclic polymers. J. Am. Chem. Soc. 141, 10943–10947 (2019).
Peterson, G. I., Bang, K.-T. & Choi, T.-L. Mechanochemical degradation of denpols: synthesis and ultrasound-induced chain scission of polyphenylene-based dendronized polymers. J. Am. Chem. Soc. 140, 8599–8608 (2018).
Wang, J. & Klok, H.-A. Swelling-induced chain stretching enhances hydrolytic degrafting of hydrophobic polymer brushes in organic media. Angew. Chem. Int. Ed. 58, 9989–9993 (2019).
Dopieralski, P., Ribas-Arino, J. & Marx, D. Force-transformed free-energy surfaces and trajectory-shooting simulations reveal the mechano-stereochemistry of cyclopropane ring-opening reactions. Angew. Chem. Int. Ed. 50, 7105–7108 (2011).
Wang, J. P., Piskun, I. & Craig, S. L. Mechanochemical strengthening of a multi-mechanophore benzocyclobutene polymer. ACS Macro Lett. 4, 834–837 (2015).
Shi, Z., Wu, J., Song, Q., Göstl, R. & Herrmann, A. Toward drug release using polymer mechanochemical disulfide scission. J. Am. Chem. Soc. 142, 14725–14732 (2020).
White, J. L. & Sasaki, A. Free radical graft polymerization. Polym. Plast. Technol. Eng. 42, 711–735 (2003).
Matsuda, T., Kawakami, R., Namba, R., Nakajima, T. & Gong, J. P. Mechanoresponsive self-growing hydrogels inspired by muscle training. Science 363, 504–508 (2019).
Wang, Z., Ayarza, J. & Esser-Kahn, A. P. Mechanically initiated bulk-scale free-radical polymerization. Angew. Chem. Int. Ed. 58, 12023–12026 (2019).
Diesendruck, C. E. et al. Proton-coupled mechanochemical transduction: a mechanogenerated acid. J. Am. Chem. Soc. 134, 12446–12449 (2012).
Lin, Y., Kouznetsova, T. B. & Craig, S. L. Mechanically gated degradable polymers. J. Am. Chem. Soc. 142, 2105–2109 (2020).
Hsu, T.-G. et al. A polymer with “locked” degradability: superior backbone stability and accessible degradability enabled by mechanophore installation. J. Am. Chem. Soc. 142, 2100–2104 (2020).
Lin, Y., Kouznetsova, T. B., Chang, C.-C. & Craig, S. L. Enhanced polymer mechanical degradation through mechanochemically unveiled lactonization. Nat. Commun. 11, 4987 (2020).
Zhao, Y., Rocha, S. V. & Swager, T. M. Mechanochemical synthesis of extended iptycenes. J. Am. Chem. Soc. 138, 13834–13837 (2016).
Shi, Y. X. et al. The first synthesis of the sterically encumbered adamantoid phosphazane P4(NtBu)6: enabled by mechanochemistry. Angew. Chem. Int. Ed. 55, 12736–12740 (2016).
Koby, R. F., Hanusa, T. P. & Schley, N. D. Mechanochemically driven transformations in organotin chemistry: stereochemical rearrangement, redox behavior, and dispersion-stabilized complexes. J. Am. Chem. Soc. 140, 15934–15942 (2018).
Štrukil, V., Gracin, D., Magdysyuk, O. V., Dinnebier, R. E. & Friščić, T. Trapping reactive intermediates by mechanochemistry: elusive aryl N-thiocarbamoylbenzotriazoles as bench-stable reagents. Angew. Chem. Int. Ed. 54, 8440–8443 (2015).
Kulla, H. et al. In situ investigations of mechanochemical one-pot syntheses. Angew. Chem. Int. Ed. 57, 5930–5933 (2018).
Hutchings, B. P., Crawford, D. E., Gao, L., Hu, P. & James, S. L. Feedback kinetics in mechanochemistry: the importance of cohesive states. Angew. Chem. Int. Ed. 56, 15252–15256 (2017).
Rothenberg, G., Downie, A. P., Raston, C. L. & Scott, J. L. Understanding solid/solid organic reactions. J. Am. Chem. Soc. 123, 8701–8708 (2001).
Lukin, S. et al. Mechanochemical carbon–carbon bond formation that proceeds via a cocrystal intermediate. Chem. Commun. 54, 13216–13219 (2018).
Tricker, A. W., Samaras, G., Hebisch, K. L., Realff, M. J. & Sievers, C. Hot spot generation, reactivity, and decay in mechanochemical reactors. Chem. Eng. J. 382, 122954 (2020).
Kubota, K., Pang, Y., Miura, A. & Ito, H. Redox reactions of small organic molecules using ball milling and piezoelectric materials. Science 366, 1500–1504 (2019).
Michalchuk, A. A. L., Tumanov, I. A. & Boldyreva, E. V. Ball size or ball mass — what matters in organic mechanochemical synthesis? CrystEngComm 21, 2174–2179 (2019).
Colacino, E. et al. Processing and investigation methods in mechanochemical kinetics. ACS Omega 3, 9196–9209 (2018).
Delogu, F., Mulas, G., Schiffini, L. & Cocco, G. Mechanical work and conversion degree in mechanically induced processes. Mater. Sci. Eng. A 382, 280–287 (2004).
Urakaev, F. K. & Boldyrev, V. V. Mechanism and kinetics of mechanochemical processes in comminuting devices: 1. Theory. Powder Technol. 107, 93–107 (2000).
Kucharski, T. J. et al. Kinetics of thiol/disulfide exchange correlate weakly with the restoring force in the disulfide moiety. Angew. Chem. Int. Ed. 48, 7040–7043 (2009).
Yang, Q.-Z. et al. A molecular force probe. Nat. Nanotechnol. 4, 302–306 (2009).
Huang, Z. & Boulatov, R. Chemomechanics with molecular force probes. Pure Appl. Chem. 82, 931–951 (2010).
Akbulatov, S., Tian, Y., Kapustin, E. & Boulatov, R. Model studies of the kinetics of ester hydrolysis under stretching force. Angew. Chem. Int. Ed. 52, 6992–6995 (2013).
Tian, Y., Kucharski, T. J., Yang, Q.-Y. & Boulatov, R. Model studies of force-dependent kinetics of multi-barrier reactions. Nat. Commun. 4, 2538 (2013).
Prezhdo, O. & Pereverzev, Y. Theoretical aspects of the biological catch bond. Acc. Chem. Res. 42, 693–703 (2009).
Qiu, L. et al. High-pressure chemistry and the mechanochemical polymerization of [5]-cyclo-p-phenylene. Chem. Eur. J. 23, 16593–16604 (2017).
Van Quaethem, A., Lussis, P., Leigh, D. A., Duwez, A.-S. & Fustin, C.-A. Probing the mobility of catenane rings in single molecules. Chem. Sci. 5, 1449–1452 (2014).
McCullagh, M., Franco, I., Ratner, M. A. & Schatz, G. C. DNA-based optomechanical molecular motor. J. Am. Chem. Soc. 133, 3452–3459 (2011).
Astumian, R. D. Thermodynamics and kinetics of molecular motors. Biophys. J. 98, 2401–2409 (2010). A brief review of the models of mechanotransduction in motor proteins.
Fritch, B. et al. Origins of the mechanochemical coupling of peptide bond formation to protein synthesis. J. Am. Chem. Soc. 140, 5077–5087 (2018).
Rao, L., Berger, F., Nicholas, M. P. & Gennerich, A. Molecular mechanism of cytoplasmic dynein tension sensing. Nat. Commun. 10, 3332 (2019).
Acknowledgements
The authors thank the funders that supported their work in mechanochemistry in the past decade, particularly the US National Science Foundation, the US Air Force, the Petroleum Research Fund of the American Chemical Society, the UK Engineering and Physical Sciences Research Council, the Royal Society, the Newton Fund, the University of Liverpool and Michelin. They also thank their collaborators in mechanochemistry, especially S. L. Craig, W. Weng and W. Zhang.
Author information
Authors and Affiliations
Contributions
All authors contributed equally to the preparation of the manuscript.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
O’Neill, R.T., Boulatov, R. The many flavours of mechanochemistry and its plausible conceptual underpinnings. Nat Rev Chem 5, 148–167 (2021). https://doi.org/10.1038/s41570-020-00249-y
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41570-020-00249-y
This article is cited by
-
Mechanical scission of a knotted polymer
Nature Chemistry (2024)
-
Leveraging mechanochemistry for sustainable polymer degradation
Polymer Journal (2024)
-
Experimental quantitation of molecular conditions responsible for flow-induced polymer mechanochemistry
Nature Chemistry (2023)
-
Allosteric control of olefin isomerization kinetics via remote metal binding and its mechanochemical analysis
Nature Communications (2023)
-
Editing of polymer backbones
Nature Reviews Chemistry (2023)