Herein, we propose a new method for promoting covalent polymerization by supramolecular catalysts. To this end, we employed cucurbit[8]uril (CB[8]) as a supramolecular catalyst, and successfully prepared polyelectrolytes in an aqueous solution by taking advantage of the CB[8]-enhanced photodimerization of Brooker merocyanine moieties. Interestingly, 10 mol % CB[8] is enough to effectively catalyze this polymerization, because CB[8] can be spontaneously replaced by terminal groups from photodimerized products. In addition, the molecular weights of the obtained polyelectrolytes can be varied by the irradiation time or the monomer. By combining supramolecular catalysis and polymer chemistry, this line of research may enrich the methodology of polymerization and open up new horizons for supramolecular polymer chemistry.
Depending on the dynamics of the crosslinks, polymer networks can have distinct bulk mechanical behaviors, from viscous liquids to tough solids. Here, by means of designing a crosslink with variable molecular dynamics, we show the control of viscoelasticity of polymer networks in a broad range quantitatively. The hexanoate‐isoquinoline@cucurbit[7]uril (HIQ@CB[7]) crosslink exhibits in a combination of protonated and deprotonated states of similar association affinity but distinct molecular dynamics. The molecular property of this crosslink is contributed by linear combination of the parameters at the two states, which is precisely tuned by pH. Using this crosslink, we achieve the quantitative control of viscoelasticity of quasi‐ideal networks in 5 orders of magnitude, and we show the reversible control of mechanical response, such as stiffness, strength and extensibility, of tough random polymer networks. This strategy offers a way to tailor the mechanical properties of polymer networks at the molecular level and paves the way for engineering “smart” responsive materials.
A method of controllable supramolecular polymerization through kinetic trapping is developed. To this end, two bifunctional monomers with cucurbit[7]uril (CB[7]) and adamantane end groups were synthesized. The CB[7]-containing monomer was presaturated with a pH-responsive competitive guest for kinetic control. Then, the kinetics of supramolecular polymerization of the two monomers was easily controlled through the modulation of pH. As a result, supramolecular polymerization was kinetically trapped at certain stages, and supramolecular polymers with different molecular weights were obtained. It is anticipated that this research will enrich the methods of controllable supramolecular polymerization.
Gelation kinetics of hydrogels is closely linked to many applications such as the development of injectable and printable hydrogels. However, the control of gelation kinetics without compromising the structure and other properties of the hydrogels, remains a challenge. Here, we demonstrate a method to control the gelation kinetics of cucurbit[7]uril-adamantane (CB[7]-AD) cross-linked supramolecular hydrogels by using competing guest molecules. The association between CB[7] and AD moieties on the polymer backbone was impeded by pre-occupying the CB[7] cavity with competing guest molecules. By using various guest molecules and concentrations, the gelation of the hydrogels could be varied from seconds to hours. The strong interaction of CB[7]-AD pair endue the hydrogels good mechanical properties and stability. Moreover, the binding of functionalized guest molecules of CB[7] moieties offers a facile approach for tailoring of the hydrogels’ scaffold. Combined with hydrogel injection and printing technology, this method offers an approach for the development of hydrogels with advanced temporal and spatial complexity.
Compared with conventional drug delivery systems (DDSs), DDSs based on host−guest interactions possess unique advantages, such as high selectivity, tunable binding ability, and controllable release of drugs. It is important to study the host−guest interactions between the carrier and drug under physiological conditions for constructing DDSs. In this work, we have studied the host−guest interaction between cucurbit[7]uril (CB[7]) and oxaliplatin (OxPt), a clinical antitumor drug, in the cell culture medium. The results show that amino acids such as phenylalanine in the 1640 culture medium can partially occupy the cavity of CB [7], which leads to the decrease of enthalpy changes of the host−guest interaction between OxPt and CB [7]. In addition, inorganic salts such as NaCl in the medium reduce the enthalpy change and increase the entropy change of the binding because of the preorganization of the portal of CB[7] and sodium cation. As a result, the binding constant of CB [7] with OxPt in the 1640 culture medium is 1/20 of that in pure water. When CB[7] is modified at the terminal of star-type PEG to construct the star-PEGylated CB [7], it is shown that the molecular weight and topological structure of the PEG polymer backbone exhibit little effect on the host−guest interactions between CB [7] and OxPt. This study enriches the host−guest chemistry of cucurbiturils and may provide guidance for constructing novel DDSs based on host−guest interactions with high loading and releasing efficiency.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.