Abstract Electrospinning has been used to create scaffolds with tunable micro/nano architecture, stiffness, and porosity to mimic native extracellular matrix. This study investigated the effects of electrospinning parameters and hydrogel formulation (solvent and crosslinker type) on the architecture and properties of fibrous poly(ethylene glycol) (PEG) hydrogels formed from a photoclick thiol‐norbornene reaction. Fibrous hydrogels were prepared using hydrogel precursors (four‐arm PEG norbornene and multi‐thiol crosslinker), sacrificial poly(ethylene oxide) (PEO, 400 kDa), and photoinitiator (I2959) in either 2,2‐triflouroethanol (TFE) or water. Three thiol crosslinkers‐ 2,2′‐(ethylenedioxy)diethanethiol (EDT), pentaerythritol tetrakis(3mercaptopropionate) (PTMP), and PEG dithiol (PEGDT)‐ were investigated. Fibrous PEG networks with uniform fibers were produced at applied voltages of 10 or 12 kV for TFE and 16 kV for water. Fiber diameters of electrospun hydrogels were largely affected by the solvent when combined with PEO concentration and ranged from 0.5 to 3.5 mm in dry state. While the effect of crosslinker type on fiber diameter, morphology, and porosity of the fibrous hydrogel was minimal, it did modulate its shear modulus. To this end, this study provides the groundwork for selecting processing parameters to achieve desired properties of fibrous PEG thiol‐norbornene hydrogels for intended tissue engineering applications ranging from neural, cardiovascular to musculoskeletal.
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Time-dependent covalent network formation in extrudable hydrogels
The fabrication of hydrogel materials has gained increased attention for a broad range of biomedical and biotechnological applications. However, one longstanding challenge in the field is to develop hydrogels that can be easily processed into the desired form factor, while achieving the necessary final physical and biochemical properties. Herein, we report a shear-thinning hydrogel ink that can be photo-cured to create a stretchable, suturable hydrogel whose polymer network is formed via the combination of thiol-Michael addition and radical polymerization. A shear-thinning hydrogel based on bis-methacrylated Pluronic® F-127 was modified with varying equivalents of 2,2′-(ethylenedioxy)diethanethiol (EDT) as an additive. We observed that aging the hydrogel over time prior to extrusion allowed the relatively slow thiol-Michael addition to occur (between thiol and methacrylate) prior to UV initiated photopolymerization of the methacrylates. The viscoelastic properties of these hydrogels could be tuned based on the amount of EDT added, and the aging time of the hydrogel formulation. The changes to the physical properties of the hydrogels were attributed to the increased chain length between network junctions that resulted from the thiol-Michael addition reactions. The optimized hydrogel composition was then extruded from a coaxial nozzle to produce hydrogel tubes that, after curing, were resistant to tearing and were suturable. These extrudable synthetic hydrogels with tunable viscoelastic properties are promising for tissue engineering applications and as surgical training models for human vasculature.
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- Award ID(s):
- 1752972
- PAR ID:
- 10223082
- Date Published:
- Journal Name:
- Polymer Chemistry
- Volume:
- 11
- Issue:
- 43
- ISSN:
- 1759-9954
- Page Range / eLocation ID:
- 6910 to 6918
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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