The fabrication of injectable self-cross-linkable hyperbranched poly(e-caprolactone) (hyPCL) formulation using metal-free click chemistry was reported. The cross-linking between hyPCL32-(1R,8S,9s)-bicyclo[6.1.0]non-4-yn-9-ylmethanol (hyPCL32-BCN) and hyPCL32-azide (hyPCL32-N3) components was proceeded via strain-promoted alkyne–azide cycloaddition (SPAAC) click reaction. Cross-linking was tested to proceed effectively with the exclusion of any toxic cross-linking agents. Strong mechanical properties and excellent biocompatibility were demonstrated for the cross-linked substrates. These newly synthesized dendrimers may have broad applications in tissue engineering such as bone defect repair. In addition, the introduction of metal-free click chemistry to hydrophobic polymers provides an attractive new strategy for developing injectable stiff polymer formulations besides hydrogels for biomedical applications.
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