Polymer Mechanochemistry

Mechanical activation of chemical bonds is usually achieved by applying external forces. However, nearly all molecules exhibit inherent strain of their chemical bonds and angles as a result of constraints imposed by covalent bonding and interactions with the surrounding environment. Particularly strong deformation of bonds and angles is observed in hyperbranched macromolecules caused by steric repulsion of densely grafted polymer branches. In addition to the tension amplification, macromolecular architecture allows for accurate control of strain distribution, which enables focusing of the internal mechanical tension to specific chemical bonds and angles. As such, chemically identical bonds in self-strained macromolecules become physically distinct because the difference in bond tension leads to the corresponding difference in the electronic structure and chemical reactivity of individual bonds within the same macromolecule. In this review, we outline different approaches to the design of strained macromolecules along with physical principles of tension management, including generation, amplification, and focusing of mechanical tension at specific chemical bonds.

The use of mechanical stresses to induce chemical reactions has attracted significant interest in recent years. Computational modeling can play a significant role in developing a comprehensive understanding of the interplay between stresses and chemical reactivity. In this review, we discuss techniques for simulating chemical reactions occurring under mechanochemical conditions. The methods described are broadly divided into techniques that are appropriate for studying molecular mechanochemistry and those suited to modeling bulk mechanochemistry. In both cases, several different approaches are described and compared. Methods for examining molecular mechanochemistry are based on exploring the force-modified potential energy surface on which a molecule subjected to an external force moves. Meanwhile, it is suggested that condensed phase simulation methods typically used to study tribochemical reactions, i.e., those occurring in sliding contacts, can be adapted to study bulk mechanochemistry.

Atomic force spectroscopy (AFM)-based single-molecule force spectroscopy (SMFS) was invented in the 1990s. Since then, SMFS has been developed into a powerful tool to study the inter- and intra-molecular interactions of macromolecules. Using SMFS, a number of problems in the field of supramolecular chemistry and mechanochemistry have been studied at the single-molecule level, which are not accessible by traditional ensemble characterization methods. In this review, the principles of SMFS are introduced, followed by the discussion of several problems of contemporary interest at the interface of supramolecular chemistry and mechanochemistry of macromolecules, including single-chain elasticity of macromolecules, interactions between water and macromolecules, interactions between macromolecules and solid surface, and the interactions in supramolecular polymers.

Although existing since the concept of macromolecules, polymer mechanochemistry is a burgeoning field which attracts great scientific interest in its ability to bias conventional reaction pathways and its potential to fabricate mechanoresponsive materials. We review here the effect of topology on the mechanical degradation of polymer chains and the activation of mechanophores in polymer backbones. The chapter focuses on both experimental and theoretical work carried out in the past 70 years. After a general introduction (Sect. 1), where the concept, the history, and the application of polymer mechanochemistry are briefly described, flow fields to study polymer mechanochemistry are discussed (Sect. 2), results of mechanochemistry study are presented for linear polymers (Sect. 3), cyclic polymers (Sect. 4), graft polymers (Sect. 5), star-shaped polymers (Sect. 6), hyperbranched polymers and dendrimers (Sect. 7), and systems with dynamic topology (Sect. 8). Here we focus on (1) experimental results involving the topological effect on the coil-to-stretch transition and the fracture of the polymer chains, (2) the underlying mechanisms and the key factor that determines the mechanical stability of the macromolecules, (3) theoretical models that relate to the experimental observations, and (4) rational design of mechanophores in complex topology to achieve multiple activations according to the existing results observed in chain degradation.

The past 10 years have seen a resurgence of interest in the field of polymer mechanochemistry. Whilst the destructive effects of mechanical force on polymer chains have been known for decades, it was only recently that researchers tapped into these forces to realize more useful chemical transformations. The current review discusses the strategic incorporation of weak covalent bonds in polymers to create materials with stress-sensing and damage-repairing properties. Firstly, the development of mechanochromism and mechanoluminescence as stress reporters is considered. The second half focuses on the net formation of covalent bonds as a response to mechanical force, via mechanocatalysis and mechanically unmasked chemical reactivity, and concludes with perspectives for the field.

Ultrasonic irradiation-based mechanochemical strategies have recently been the subject of intensive investigation because of the advantages they offer. These include simplicity, energy savings and wide applicability. Traditional areas of sonoprocessing such as cleaning, efficient mixing and solid activation have been extended to both macromolecular and micro/nanostructures, some of which are biologically significant, ultrasound-responsive actuators and crystal design, among others. Unlike conventional mechanochemical protocols, which require little solvent usage if any at all, mechanical (and chemical) effects promoted by ultrasound are observed in a liquid medium. Tensile forces, which share similarities with solid mechanochemistry, are generated by virtue of nonlinear effects, notably cavitation, when high-amplitude waves propagate in a fluid. This work aims to provide insight into some recent developments in the multifaceted field of sono-mechanochemistry using various examples that illustrate the role of ultrasonic activation, which is capable of boosting hitherto sterile transformations and inventing new crafts in applied chemistry. After a preliminary discussion of acoustics, which is intended to provide a mechanistic background, we mainly focus on experimental developments, while we often mention emerging science and occasionally delve into theoretical models and force simulations.

Andrew Huxley’s model for muscle contraction is the first mechanistic description of how an energy-providing chemical reaction, ATP hydrolysis, can be coupled by a molecule (myosin) to do work in the environment in a cyclic process. The model was originally used to fit experimentally obtained force vs velocity curves, and has served as a paradigm for understanding mechanochemical coupling ever since. Despite the remarkable success in fitting kinetic data, Huxley’s model is thermodynamically inconsistent in several regards, most notably in its failure to include thermal noise in the description of the mechanical transitions by which motion occurs. This inconsistency has led subsequent workers to incorrect conclusions regarding the importance of mechanical transitions for determining the direction of motion, the efficiency of energy conversion, the ratio of forward to backward steps, and the applied force necessary to stop the motion of chemically driven molecular motors. In this chapter an extension of Huxley’s model is described where the principle of microscopic reversibility provides a framework for developing a thermodynamically consistent description of a molecular machine. The results show clearly that mechanical strain and the so-called “power stroke” are irrelevant for determining the directionality and thermodynamic properties of any chemically driven molecular motor. Instead these properties are controlled entirely by the chemical specificity that describes how the relative rates of the ATP hydrolysis reaction depend, by allosteric interactions, on the mechanical state of the molecule. This mechanism has been termed an “information ratchet” in the literature. In contrast to the results for chemical driving, a power stroke can be a key component for the operation of an optically driven motor, the transitions of which do not obey microscopic reversibility.

The behavior of chemical bonding under various mechanical loadings is an intriguing mechanochemical property of biological materials, and the property plays a critical role in determining their deformation and failure mechanisms. Because of their astonishing mechanical properties and roles in constituting the basis of a variety of physiologically relevant materials, biological protein materials have been intensively studied. Understanding the relation between chemical bond networks (structures) and their mechanical properties offers great possibilities to enable new materials design in nanotechnology and new medical treatments for human diseases. Here we focus on how the chemical bonds in biological systems affect mechanical properties and how they change during mechanical deformation and failure. Three representative cases of biomaterials related to the human diseases are discussed in case studies, including: amyloids, intermediate filaments, and collagen, each describing mechanochemical features and how they relate to the pathological conditions at multiple scales.

Mechanochemistry is a burgeoning field of materials science. Inspired by nature, many scientists have looked at different ways to introduce weak bonds into polymeric materials to impart them with function and in particular mechano-responsiveness. In the following sections, the incorporation of some of the weakest bonds, i.e. non-covalent bonds, into polymeric solids is being surveyed. This review covers sequentially π–π interactions, H-bonding and metal-ligand coordination bonds and tries to highlight some of the advantages and limitations of such systems, while providing some key perspective of what may come next in this tantalizing field.

Responsive polymer-based materials can adapt to their surrounding environment by expanding and shrinking. This swelling and shrinking (mechanotransduction) can result in a number of functions. For example, the response can be used to lift masses, move objects, and can be used for sensing certain species in a system. Furthermore, responsive polymers can also yield materials capable of self-healing any damage affecting their mechanical properties. In this chapter we detail many examples of how mechanical responses can be triggered by external electric and/or magnetic fields, hygroscopicity, pH, temperature, and many other stimuli. We highlight how the specific responses can be used for artificial muscles, self-healing materials, and sensors, with particular focus on detailing the polymer response yielding desired effects.