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Dynamic materials (DMs) or dynamers have potential applications across a broad range of material science challenges. These applications include sustainable materials as a part of the circular plastics economy, advanced materials with tailored high stress properties and biomedical agents. DMs are comprised of polymers that crosslinked through reversible covalent and noncovalent linking groups. This group provides reversible bonds, which impart properties such as (re)healing, adaptability, toughness into a material. The nature of the linker dictates the dynamer's stability and dynamic properties, although for many applications one linker alone cannot give materials with complex multiresponsive functions. The combination of multiple dynamic linkers can introduce complementary functionalities into a single material. This combination of linkers enhances the collective material properties by matching their strengths and offsetting the weaknesses, or by selecting linkers for specific functions, such as one linker for rapid exchange and the other to respond to external stimuli. This contribution highlights the possibilities and unique features of materials containing multiple dynamic linkers, reviewing both fundamental discoveries of materials possessing multiple dynamic bonds and applications facilitated by the presence of multiple linking group chemistry. [ABSTRACT FROM AUTHOR]

A multistimuli-responsive transient supramolecular polymerization of β-sheet-encoded dendritic peptide monomers in water is presented. The amphiphiles, which contain glutamic acid and methionine, undergo a glucose oxidase catalyzed, glucose-fueled transient hydrogelation in response to an interplay of pH and oxidation stimuli, promoted by the production of reactive oxygen species (ROS). Adjusting the enzyme and glucose concentration allows tuning of the assembly and the disassembly rates of the supramolecular polymers, which dictate the stiffness and transient stability of the hydrogels. The incorporation of triethylene glycol chains introduces thermoresponsive properties to the materials. We further show that repair enzymes are able to reverse the oxidative damage in the methionine-based thioether side chains. Since ROS play an important role in signal transduction cascades, our strategy offers great potential for applications of these dynamic biomaterials in redox microenvironments. [ABSTRACT FROM AUTHOR]

Chemistry, pure and applied, is a science and an industry. By its power over the expressions of matter, it also displays the creativity of art. It has expanded from molecular to supramolecular chemistry and then, by way of constitutional dynamic chemistry, towards adaptive chemistry. Constitutional dynamics allow for adaptation, through component exchange and selection in response to physical stimuli (e.g. light, photoselection), to chemical effectors (e.g. metal ions, metalloselection) or to environmental effects (e.g. phase change) in equilibrium or out-of-equilibrium conditions, towards the generation of the best-adapted/fittest constituent(s) in a dynamic set. Such dynamic systems can be represented by two-dimensional or three-dimensional dynamic networks that define the agonistic and antagonistic relationships between the different constituents linked through component exchange. The introduction of constitutional dynamics into materials science opens perspectives towards adaptive materials and technologies, presenting attractive behavioral features (such as self-healing). In particular, dynamic polymers may undergo modification of their properties (mechanical, optical, etc.) through component exchange and recombination in response to physical or chemical agents. Constitutional adaptive materials open towards a systems materials science and offer numerous opportunities for soft-matter technologies. [ABSTRACT FROM AUTHOR]

The importance of noncovalent interactions in the realm of biological materials continues to inspire efforts to create artificial supramolecular polymeric architectures. These types of self-assembled materials hold great promise as environmentally stimuli-responsive materials because they are capable of adjusting their various structural parameters, such as chain length, architecture, conformation, and dynamics, to new surrounding environments upon exposure to appropriate external stimuli. Nevertheless, in spite of considerable advances in the area of responsive materials, it has proved challenging to create synthetic self-assembled materials that respond to highly disparate analytes and whose environmentally induced changes in structure can be followed directly through both various spectroscopic and X-ray diffraction analyses. Herein, we report a new set of artificial self-assembled materials obtained by simply mixing two appropriately chosen, heterocomplementary macrocyclic receptors, namely a tetrathiafulvalene-functionalized calix[4]pyrrole and a bis(dinitrophenyl)-meso-substituted calix[4]pyrrole. The resulting polymeric materials, stabilized by combination of donor-acceptor and hydrogen bonding interactions, undergo dynamic, reversible dual guest-dependent structural transformations upon exposure to two very different types of external chemical inputs, namely chloride anion and trinitrobenzene. The structure and dynamics of the copolymers and their analyte-dependent responsive behavior was established via single crystal X-ray crystallography, SEM, heterocomplementary isodesmic analysis, 1- and 2D NMR, and dynamic light scattering spectroscopies. Our results demonstrate the benefit of using designed heterocomplementary interactions of two functional macrocyclic receptors to create synthetic, self-assembled materials for the development of "smart" sensory materials that mimic the key biological attributes of multianalyte recognition and substrate-dependent multisignaling. [ABSTRACT FROM AUTHOR]

Abstract: Dynamers may be defined as constitutional dynamic polymers, i.e. polymeric entities whose monomeric components are linked through reversible connections and have therefore the capacity to modify their constitution by exchange and reshuffling of their components. They may be either of molecular or supramolecular nature depending on whether the connections are reversible covalent bonds or non-covalent interactions. They are formed, respectively, either by polycondensation with functional recognition or by polyassociation with interactional recognition between the connecting subunits. Both types are illustrated by specific examples implementing hydrogen bonding on one hand and acylhydrazone formation on the other. The dynamic properties confer to dynamers the ability to undergo adaptation and driven evolution under the effect of external chemical or physical triggers. Dynamers thus are constitutional dynamic materials resulting from the application of the principles of constitutional dynamic chemistry to polymer science. [Copyright &y& Elsevier]