Aggregation and thermal gelation of N-isopropylacrylamide based cucurbit[7]uril side-chain polypseudorotaxanes with low pseudorotaxane content

Chen, Hao; Ma, Haili; Chieng, Yu Yuan; Hou, Shengzhen; Xu, Liang; Tan, Yebang

doi:10.1039/c4ra17140c

Cited by 10 publications

(6 citation statements)

References 51 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In an interesting example of three-dimensional structure, aggregation of N -isopropylacrylamide (NIPAAM) thermogels has been controlled by introducing CB[7] as polypseudorotaxane side chains. Such inclusion results in semirigid polymer segments that induce transition from a globular to porous morphology that could be observed by optical microscopy in a hydrated state . Control of physical structure on these length scales holds great promise for the cell biology and biomaterials fields, as dynamic self-assembly of these structures may best recapitulate the natural processes that drive cell behavior.…”

Section: Structure Of Self-assemblymentioning

confidence: 99%

Supramolecular Guest–Host Interactions for the Preparation of Biomedical Materials

2015

View full text Add to dashboard Cite

Supramolecular chemistry has emerged as an important technique for the formation of biomaterials, including nano- and microparticles and hydrogels. One specific class of supramolecular chemistry is the direct association of guest-host pairs, which involves host macrocycles such as cyclodextrins and cucurbit[n]urils and a wide range of guest molecules, where association is typically driven by molecule size and hydrophobicity. These systems are of particular interest in the biomedical field due to their dynamic nature, chemical diversity, relative ease of synthesis, and ability to interact with biological or synthetic molecules. In this review, we discuss aspects of polymeric material assembly mediated by guest-host interactions, including the fundamentals of assembly into functional biomedical materials. Additionally, applications of biomaterials that utilize guest-host interactions are discussed with a focus on injectable material formulations, the sequestration and delivery of encapsulated cargo (i.e., drugs, biomolecules), and the investigation of cell-material interactions (i.e., adhesion, differentiation, and delivery). While methodologies for guest-host mediated assembly and biological interaction have rapidly evolved in recent years, they remain far from realizing their full potential in the biomaterials field.

show abstract

Section: Structure Of Self-assemblymentioning

confidence: 99%

Supramolecular Guest–Host Interactions for the Preparation of Biomedical Materials

2015

View full text Add to dashboard Cite

show abstract

“…21 Experimentally, recent reports have indicated that bulk physical hydrogels can form heterogeneous structures, including those formed through macrocyclic assembly. 22-26 Despite this work, there remains a lack of experimental investigation to bridge the gap between directed polymeric self-assembly and supramolecular microstructures.…”

Section: Introductionmentioning

confidence: 99%

Evolution of hierarchical porous structures in supramolecular guest–host hydrogels

et al. 2016

View full text Add to dashboard Cite

Macromolecular interactions are used to form supramolecular assemblies, including through the interaction of guest-host chemical pairs. Microstructural heterogeneity has been observed within such physical hydrogels; yet, systematic investigation of the microstructure and its determining inputs are lacking. Herein, we investigated the hierarchical self-assembly of hyaluronic acid (HA) modified by the guest-host pair adamantane (Ad-HA, guest) and β-cyclodextrin (CD-HA, host), as well as with methacrylate groups to both tether fluorescent agents and to covalently stabilize the material structure. We observed microporous materials in the hydrated state, which temporally arose from initially homogenous hydrogels composed of the two polymers. Independent fluorescent labeling of Ad-HA and CD-HA demonstrated spatiotemporal co-localization, indicative of guest-host polymer condensation on the microscale. The hydrogel void fractions and pore diameters were independently tuned through incubation time (0-7 days), polymer concentration (1.25-10 wt%), and polymer modification (25-50% Ad-HA modification). Void fractions as great as 93.3±2.4% were achieved and pore diameters ranged from 2.1±0.5 to 1025.4±209.4 μm. The segregation of discrete solid and solute phases was measured with both atomic force microscopy and diffusive microparticle tracking analysis, where the solute phase contained only dilute polymer. The study represents a systematic investigation of hierarchical self-assembly in binary associating hydrogels, and provides insights on mechanisms that control microstructure within supramolecular hydrogels.

show abstract

“…Many applications such as the development of injectable and printable hydrogels are closely linked to this characteristic 1 2 3 . In order to meet this goal, gelation mechanisms that are based on physical changes including temperature 4 5 , ionic strength 6 7 , pH value 8 , shear force 9 , and chemical reactions such as the Schiff base formation 10 11 , disulfide bond formation 12 , Michael addition 13 and photopolymerization 14 15 16 have been explored 17 . However, it remains a challenge to have effective control over gelation kinetics without compromising the structure and other properties of hydrogels.…”

mentioning

confidence: 99%

“…However, it remains a challenge to have effective control over gelation kinetics without compromising the structure and other properties of hydrogels. Although the gelation of hydrogels based on physical changes is triggered by external stimuli, their gelation usually proceeds through a sharp transition when the corresponding external stimuli are applied 4 5 6 7 8 . Control over the gelation kinetics of hydrogels based on chemical reactions is plausible.…”

mentioning

confidence: 99%

Controlled gelation kinetics of cucurbit[7]uril-adamantane cross-linked supramolecular hydrogels with competing guest molecules

Chen

Hou

et al. 2016

Sci Rep

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Aggregation and thermal gelation of N-isopropylacrylamide based cucurbit[7]uril side-chain polypseudorotaxanes with low pseudorotaxane content

Abstract: Low pseudorotaxane content (≤3 mol%) endows N-isopropylacrylamide based cucurbit[7]uril polypseudorotaxanes unique aggregation and thermal gelation properties.

Cited by 10 publications

References 51 publications

Supramolecular Guest–Host Interactions for the Preparation of Biomedical Materials

Supramolecular Guest–Host Interactions for the Preparation of Biomedical Materials

Evolution of hierarchical porous structures in supramolecular guest–host hydrogels

Controlled gelation kinetics of cucurbit[7]uril-adamantane cross-linked supramolecular hydrogels with competing guest molecules

Contact Info

Product

Resources

About