Janus Cross-links in Supramolecular Networks

Mondal, Swagata; Lessard, Jacob J.; Meena, Chhuttan Lal; Sanjayan, Gangadhar J.; Sumerlin, Brent S.

doi:10.1021/jacs.1c10606

Cited by 34 publications

(51 citation statements)

References 68 publications

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“…While this feature precludes their recyclability and reprocessability, thermosets maintain their robust properties even at elevated temperatures or solvent exposure. Innovative approaches have been developed to enable cross-link reversibility to access materials that maintain their network structure while providing avenues for reprocessability. − …”

Section: Introductionmentioning

confidence: 99%

Controlling Dynamics of Associative Networks through Primary Chain Length

2022

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Dynamic networks couple the robust nature of thermosets with the shapeability and recyclability of thermoplastics. Though a wealth of exchange chemistries can be leveraged to fabricate dynamic networks, reversibly cross-linked systems that are comprised primarily of chains with nonexchangeable backbones increase the network complexity and render flow behavior difficult to predict. Here, we report the flow behavior of polymethacrylate-based vitrimers prepared by cross-linking β-ketoester-containing polymers with multifunctional amines and demonstrate that the molecular weight and dispersity of the primary chains can be tuned to actively tailor the dynamics of the resulting networks. Vitrimers of similar composition and cross-link density made from polymers below and well above the entanglement molecular weight exhibited distinct viscoelastic flow properties with energies of activation ranging from 93 to 264 kJ/mol. Resistance to creep increased dramatically with increasing primary chain length. Finally, blending of prepolymers to skew M n above/below M e was demonstrated, showing a distinguishable effect of prepolymer breadth and skewness on vitrimer flow. Our results suggest that tailoring the molecular weight and chain-length distribution of the primary chain polymers is a viable strategy to design materials with predictable viscoelastic properties and customizable vitrimer flow behavior.

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Section: Introductionmentioning

confidence: 99%

Controlling Dynamics of Associative Networks through Primary Chain Length

2022

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“… 19 Subsequently, with the development of various polymerization techniques, many efforts have been made toward the synthesis of nucleobase-containing polymers and to explore the effect of complementary nucleobase interactions on supramolecular assembly properties. 20 − 28 …”

Section: Nucleobase-interaction-mediated Hierarchical Organization Of...mentioning

confidence: 99%

“…Significant advances in the synthesis of nucleobase-functionalized polymers were made in the early 1990s with the preparation of methacrylate monomer analogues . Subsequently, with the development of various polymerization techniques, many efforts have been made toward the synthesis of nucleobase-containing polymers and to explore the effect of complementary nucleobase interactions on supramolecular assembly properties. − …”

Section: Nucleobase-interaction-mediated Hierarchical Organization Of...mentioning

confidence: 99%

Nucleobase-Interaction-Directed Biomimetic Supramolecular Self-Assembly

2022

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Conspectus The design and fabrication of synthetic self-assembled systems that can mimic some biological features require exquisitely sophisticated components that make use of supramolecular interactions to attain enhanced structural and functional complexity. In nature, nucleobase interactions play a key role in biological functions in living organisms, including transcription and translation processes. Inspired by nature, scientists are progressively exploring nucleobase synthons to create a diverse range of functional systems with a plethora of nanostructures by virtue of molecular-recognition-directed assembly and flexible programmability of the base-pairing interactions. To that end, nucleobase-functionalized molecules and macromolecules are attracting great attention because of their versatile structures with smart and adaptive material properties such as stimuli responsiveness, interaction with external agents, and ability to repair structural defects. In this regard, a range of nucleobase-interaction-mediated hierarchical self-assembled systems have been developed to obtain biomimetic materials with unique properties. For example, a new “grafting to” strategy utilizing complementary nucleobase interactions has been demonstrated to temporarily control the functional group display on micellar surfaces. In a different approach, complementary nucleobase interactions have been explored to enable morphological transitions in functionalized diblock copolymer assembly. It has been demonstrated that complementary nucleobase interactions can drive the morphological transformation to produce highly anisotropic nanoparticles by controlling the assembly processes at multiple length scales. Furthermore, nucleobase-functionalized bottle brush polymers have been employed to generate stimuli-responsive hierarchical assembly. Finally, such interactions have been exploited to induce biomimetic segregation in polymer self-assembly, which has been employed as a template to synthesize polymers with narrow polydispersity. It is evident from these examples that the optimal design of molecular building blocks and precise positioning of the nucleobase functionality are essential for fabrication of complex supramolecular assemblies. While a considerable amount of research remains to be explored, our studies have demonstrated the potential of nucleobase-interaction-mediated supramolecular assembly to be a promising field of research enabling the development of biomimetic materials. This Account summarizes recent examples that employ nucleobase interactions to generate functional biomaterials by judicious design of the building blocks. We begin by discussing the molecular recognition properties of different nucleobases, followed by different strategies to employ nucleobase interactions in polymeric systems in order to achieve self-assembled nanomaterials with versatile properties. Moreover, some of their prospective biological/material applications such as enhanced drug encapsulation, superior adhesion,...

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“…Multiple noncovalent interactions between polymer termini or side chains have recently been used to achieve the cross-linking of polymer chains to create a network structure, thereby increasing the mechanical properties of polymers more than in the case of conventional linearly linked polymers. [1][2][3][4][5][6][7][8][9]12,13 Another interesting prospect in the design of terminal groups is the possibility of inducing the controlled assembly of polymers into a higher-order hierarchical structure. [1][2][3][4][5][6][7][8][9] Such ordered polymer assemblies could lead to applications in nanopatterning and directional materials transport.…”

Section: Introductionmentioning

confidence: 99%