Supramolecular Polymer Materials: Chain Extension of Telechelic Polymers Using a Reactive Hydrogen-Bonding Synthon

Folmer, B. J. B.; Sijbesma, Rint P.; Versteegen, Ron M.; Rijt, J.A.J. van der; Meijer, E. W.

doi:10.1002/1521-4095(200006)12:12<874::aid-adma874>3.0.co;2-c

Cited by 636 publications

(223 citation statements)

References 6 publications

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“…These experiments suggest that individual sets of hydrogen-bonded dimers are the predominant source of network formationÐstacks or clusters of UP moieties would not be completely broken down by the presence of UP cap , and must therefore not be a significant source of crosslinking. [8,14,15] The clear, colorless appearance of the bulk copolymer further supports this assessment. While the solution properties of the copolymer are intriguing, the primary motivation for this research was to demonstrate that the bulk copolymer forms an amorphous network with elastomeric properties.…”

mentioning

confidence: 52%

Polymerization of Ureidopyrimidinone-Functionalized Olefins by Using Late-Transition Metal Ziegler-Natta Catalysts: Synthesis of Thermoplastic Elastomeric Polyolefins

Rieth

Eaton

Coates

2001

Angew. Chem. Int. Ed.

139

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mentioning

confidence: 52%

Polymerization of Ureidopyrimidinone-Functionalized Olefins by Using Late-Transition Metal Ziegler-Natta Catalysts: Synthesis of Thermoplastic Elastomeric Polyolefins

Rieth

Eaton

Coates

2001

Angew. Chem. Int. Ed.

139

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“…The synthesis of polycaprolactone containing quadruple hydrogen bond–forming units (UPy) at both ends, PCL1250(UPy) 2 , was carried out in two steps as described in the literature 40. For the coupling of UPy units to the hydroxyl groups on the surface of HAp particle, dry HAp (mean particle size 2 μm) was reacted with 2(6‐isocyanatohexylamino)‐6‐methyl‐4[1H]‐pyrimidinone in DMF for 20 h. The solid phase was separated and purified by successively washing in DMF, dimethylsulfoxide (DMSO), ethanol, and diethylether and dried.…”

Section: Methodsmentioning

confidence: 99%

“…Supramolecular polymers resulting from the self‐assembly 2‐ureido‐4[1 H ]‐pyrimidinone (UPy) end‐functionalized oligomers provide a unique opportunity for the synthesis of polymers with bulk properties comparable to their conventional covalent‐bond counterparts, but exhibiting a lower melt viscosity 39. This improves the processability of supramolecular polymers significantly, and it allows the tuning of polymer properties through simple mixing of the appropriate building blocks bearing functionalized end groups 40. Dankers et al first demonstrated the use of UPy‐functionalized supramolecular polycaprolactone (PCL1250(UPy) 2 ) as a bioactive scaffold for tissue engineering 41–43…”

Section: Introductionmentioning

confidence: 99%

Biological and mechanical properties of novel composites based on supramolecular polycaprolactone and functionalized hydroxyapatite

Shokrollahi

Mirzadeh

Scherman

et al. 2010

J Biomedical Materials Res

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Supramolecular polymers based on quadruple hydrogen-bonding ureido-pyrimidinone (UPy) moieties hold promise as dynamic/stimuli-responsive materials in applications such as tissue engineering. Here, a new class of materials is introduced: supramolecular polymer composites. We show that despite the highly ordered structure and tacticity-dependent nature of hydrogen-bonded supramolecular polymers, the bioactivity of these polymers can be tuned through composite preparation with bioceramics. These novel supramolecular composites combine the superior processability of supramolecular polymers with the excellent bioactivity and mechanical characteristics of bioceramics. In particular, the bioactive composites prepared from supramolecular polycaprolactone and UPy-grafted hydroxyapatite (HApUPy) are described that can be easily formed into microporous biomaterials. The compression moduli increased about 40 and 90% upon composite preparation with HAp and HApUPy, respectively, as an indication to improved mechanical properties. These new materials show excellent potential as microporous composite scaffolds for the adhesion and proliferation of rat mesenchymal stem cells (rMSCs) as a first step toward bone regeneration studies; rMSCs proliferate about 2 and 2.7 times faster on the conventional composite with HAp and the supramolecular composite with (HApUPy) than on the neat PCL1250(UPy)(2).

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“…Many experimental studies confirm Cates’ theory, especially those investigating polymers with self-complementary H-bonding motifs. 29, 30 …”

Section: Introductionmentioning

confidence: 99%

Oxidatively Responsive Chain Extension to Entangle Engineered Protein Hydrogels

Tang

Glassman

et al. 2014

Macromolecules

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Engineering artificial protein hydrogels for medical applications requires precise control over their mechanical properties, including stiffness, toughness, extensibility and stability in the physiological environment. Here we demonstrate topological entanglement as an effective strategy to robustly increase the mechanical tunability of a transient hydrogel network based on coiled-coil interactions. Chain extension and entanglement are achieved by coupling the cysteine residues near the N- and C- termini, and the resulting chain distribution is found to agree with the Jacobson-Stockmayer theory. By exploiting the reversible nature of the disulfide bonds, the entanglement effect can be switched on and off by redox stimuli. With the presence of entanglements, hydrogels exhibit a 7.2-fold enhanced creep resistance and a suppressed erosion rate by a factor of 5.8, making the gels more mechanically stable in a physiologically relevant open system. While hardly affecting material stiffness (only resulting in a 1.5-fold increase in the plateau modulus), the entanglements remarkably lead to hydrogels with a toughness of 65,000 J m-3 and extensibility to approximately 3,000% engineering strain, which enables the preparation of tough yet soft tissue simulants. This improvement in mechanical properties resembles that from double-network hydrogels, but is achieved with the use of a single associating network and topological entanglement. Therefore, redox-triggered chain entanglement offers an effective approach for constructing mechanically enhanced and responsive injectable hydrogels.

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Supramolecular Polymer Materials: Chain Extension of Telechelic Polymers Using a Reactive Hydrogen-Bonding Synthon

Cited by 636 publications

References 6 publications

Polymerization of Ureidopyrimidinone-Functionalized Olefins by Using Late-Transition Metal Ziegler-Natta Catalysts: Synthesis of Thermoplastic Elastomeric Polyolefins

Polymerization of Ureidopyrimidinone-Functionalized Olefins by Using Late-Transition Metal Ziegler-Natta Catalysts: Synthesis of Thermoplastic Elastomeric Polyolefins

Biological and mechanical properties of novel composites based on supramolecular polycaprolactone and functionalized hydroxyapatite

Oxidatively Responsive Chain Extension to Entangle Engineered Protein Hydrogels

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