Biodegradable elastic hydrogels for bioprinting
Inventors
Hong, Yi • DAI, Guohao • XU, Cancan • LEE, Wen-han
Assignees
Northeastern University Boston • University of Texas System
Publication Number
US-12187834-B2
Publication Date
2025-01-07
Expiration Date
2039-04-02
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Abstract
Disclosed herein are hydrogel compositions comprising a triblock copolymer having a formula A-B-A, wherein A is a polycaprolactone (PCL) block or a polyvalerolactone (PVL) block and B is a polyethylene glycol (PEG) block. Also disclosed are methods of making a hydrogel comprising providing a photoinitiator and a triblock copolymer having a formula A-B-A, wherein the triblock copolymer comprises one or more ethylenically unsaturated moieties; and photocrosslinking the triblock copolymer, thereby forming a hydrogel. Also disclosed are methods of printing a three-dimensional (3D) article comprising extruding a printing composition from a deposition nozzle moving relative to a substrate, the printing composition comprising a photoinitiator and any herein disclosed triblock copolymer, wherein the triblock copolymer comprises one or more ethylenically unsaturated moieties; depositing one or more layers comprising the printing composition on the substrate; and photocrosslinking the triblock copolymer to form the printed 3D article.
Core Innovation
The invention discloses hydrogel compositions comprising a triblock copolymer of the formula A-B-A, where 'A' is a polycaprolactone (PCL) or polyvalerolactone (PVL) block and 'B' is a polyethylene glycol (PEG) block. The triblock copolymer includes one or more ethylenically unsaturated moieties, which enable photocrosslinking upon exposure to visible light, resulting in a biodegradable and elastic hydrogel suitable for 3D bioprinting and cell culture applications.
The problem addressed by this invention is the lack of hydrogel materials for soft tissue bioprinting that combine biodegradability, elasticity, and mechanical strength with ease of preparation and cell compatibility. Existing hydrogels are typically brittle and lack stretchability, making them unsuitable for mimicking the properties of soft tissues like skin and muscle. Furthermore, dual-network systems or multi-step crosslinking approaches are complex and difficult to implement for cell printing, often requiring multiple precursors or external stimuli.
The disclosed invention provides a solution through a single-component triblock copolymer hydrogel that can be photocrosslinked by exposure to visible light, greatly simplifying preparation and handling for bioprinting. The hydrogels are printable, elastic, and customizable in mechanical properties, permitting direct encapsulation and printing of viable cells for tissue engineering and cell culture. Methods for making the hydrogel and for printing 3D articles are included, facilitating applications that require resilience and biodegradability similar to native soft tissues.
Claims Coverage
The patent claims cover two main inventive features related to the method of making biodegradable and elastic hydrogels and to the method of printing three-dimensional (3D) articles from these hydrogels.
Method of making a hydrogel with a photocrosslinkable triblock copolymer
A method comprising: - Providing a composition with a photoinitiator and a triblock copolymer of formula A-B-A, where 'A' is a polycaprolactone (PCL) or polyvalerolactone (PVL) block and 'B' is a polyethylene glycol (PEG) block of molecular weight 2,000 Da to 100,000 Da, and the triblock copolymer includes one or more ethylenically unsaturated moieties (M). - Photocrosslinking the triblock copolymer to form a hydrogel.
Method of printing a 3D article using a photocrosslinkable hydrogel composition
A method comprising: 1. Extruding a printing composition from a deposition nozzle relative to a substrate, wherein the composition contains: - A photoinitiator - A triblock copolymer having the formula A-B-A, with 'A' as a PCL or PVL block, 'B' as a PEG block (molecular weight 2,000–100,000 Da), and one or more ethylenically unsaturated moieties (M). 2. Depositing one or more layers comprising the composition on the substrate. 3. Photocrosslinking the triblock copolymer to form the printed 3D article.
The claims broadly cover methods for creating and printing elastic, biodegradable hydrogels using a triblock copolymer system that can be photocrosslinked by visible light, enabling the formation of cell-compatible, mechanically robust 3D structures.
Stated Advantages
The system employs a single crosslinking mechanism, increasing control and significantly simplifying the hydrogel preparation process.
Crosslinking can use visible light, avoiding exposure of cells to DNA-damaging ultraviolet light and maintaining high cell viability.
The hydrogel is comprised of biodegradable and biocompatible FDA-approved components, facilitating its use in in vivo applications.
Hydrogels produced exhibit high and tunable elasticity, flexibility, and strength, closely mimicking the mechanical behavior of human soft tissues.
The hydrogels support encapsulation and printing of a wide array of viable cells, enabling applications in soft tissue engineering and cell culture.
The hydrogel preparation process is simple, does not require multiple external stimuli, and can be performed as a single-step reaction.
The hydrogels are compatible with other biomaterials and additives, allowing further modification for specific applications.
Documented Applications
3D bioprinting of cell-laden constructs for tissue engineering and cell culture.
Printing of hydrogels as scaffolds to support the growth and culture of viable cells for patient transplants, transfusions, injections, or other medical procedures.
Fabrication of soft tissue constructs mimicking the elasticity, flexibility, and strength of human tissues such as skin, skeletal muscle, blood vessels, and heart muscle.
Use as a support matrix for culturing eukaryotic or prokaryotic cells in vitro, including applications in single cell analysis, drug screening, and stem cell differentiation.
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