When one brings "polymeric materials" and "mechanical action" into the same conversation, the topic of this discussion might naturally focus on everyday circumstances such as failure of fibers, fatigue of composites, abrasion of coatings, etc. This intuitive viewpoint reflects the historic consensus in both academia and industry that mechanically induced chemical changes are destructive, leading to polymer degradation that limits materials lifetime on both macroscopic and molecular levels. In the 1930s, Staudinger observed mechanical degradation of polymers, and Melville later discovered that polymer chain scission caused the degradation. Inspired by these historical observations, we sought to redirect the destructive mechanical energy to a productive form that enables mechanoresponsive functions. In this Account, we provide a personal perspective on the origin, barriers, developments, and key advancements of polymer mechanochemistry. We revisit the seminal events that offered molecular-level insights into the mechanochemical behavior of polymers and influenced our thinking. We also highlight the milestones achieved by our group along with the contributions from key comrades at the frontier of this field. We present a workflow for the design, evaluation, and development of new "mechanophores", a term that has come to mean a molecular unit that chemically responds in a selective manner to a mechanical perturbation. We discuss the significance of computation in identifying pairs of points on the mechanophore that promote stretch-induced activation. Attaching polymer chains to the mechanophore at the most sensitive pair and locating the mechanophore near the center of a linear polymer are thought to maximize the efficiency of mechanical-to-chemical energy transduction. We also emphasize the importance of control experiments to validate mechanochemical transformations, both in solution and in the solid state, to differentiate "mechanical" from "thermal" activation. This Account offers our first-hand perspective of the change-in-thinking in polymer mechanochemistry from "destructive" to "productive" and looks at future advances that will stimulate this growing field.
Stimuli-responsive polymers are arguably the most widely considered systems for a variety of applications in biomedical arena. We report here a novel triple stimuli sensitive block copolymer assembly that responds to changes in temperature, pH and redox potential. Our block copolymer design constitutes an acid-sensitive THP-protected HEMA as the hydrophobic part and a temperature-sensitive PNIPAM as the hydrophilic part with an intervening disulfide bond. The micellar properties and the release kinetics of the encapsulated guest molecule in response to one stimulus as well as combinations of stimuli have been evaluated. Responsiveness to combination of stimuli not only allows for fine-tuning the guest molecule release kinetics, but also provides the possibility of achieving location-specific delivery.
The generation of acid under mechanical force is potentially useful for initiating proton-catalyzed changes in polymeric materials. Here we demonstrate that oxime sulfonates-known photoacid generators-are also acid generators when activated mechanically. NMR analysis of products suggests that the ultrasound-induced mechanochemical scission of the oxime sulfonate mechanophore also generates a ketone functional moiety, in addition to acid. Both acid and ketone moieties are useful for developing stress-responsive polymeric materials for autonomous self-healing applications.
Proton transport (PT) plays an important role in many biological processes as well as in materials for renewable energy devices. Gaining insights into functional group requirements for PT would aid the design of new materials that provide enhanced proton conduction. In this report, we outline our efforts to understand the most probable proton conduction pathway in 1H-1,2,3-triazole systems. In triazole-based systems, both imidazole-and pyrazole-like pathways are possible. By systematically comparing structurally analogous polymers based on Nheterocycles and benz-N-heterocycles, we find that the imida-zole-like pathway makes a significant contribution to the proton transfer in 1H-1,2,3-triazole systems, while the contribution from pyrazole-like pathway is negligible.
The dynamic nature of hydrogen bonds in phenolic polymers, where the hydrogen bond donor/acceptor reorientation can occur in a single site, presents lower barriers for proton transport.
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