Polymer Chemistry
Poly(propylene fumarate) Resins
We have developed an entire family of resorbable poly(propylene fumarate)-based copolyester resins with novel architectures and stoichiometries that can be 3D printed into complex geometries using photochemical methods and thiolpbased crosslinkers. Key to this innovation is the development of magnesium catalysts that afford a well-defined ring opening copolymerization method of epoxides and anhydrides. The methodology affords: (a) an inexpensive, scalable synthetic methods up to multi- kg batches, (b) highly accurate 3D printing, (c) reliable degradation kinetics, and (d) the reactive chain ends and side chain handles which afford post printing functionalization. We have also demonstrated a distinct molecular mass dependent resorption profile in vivo and the ability to utilize architecture to control viscosity and shape memory properties. Our latest synthetic methods address these challenges, including full resorption using degradable thiol-based crosslinkers. We are continuing to explore translationally relevant functionalization methods and strategies for hard and soft tissue repair.
Thiol-ene-Based 3D Printing of Bioresorbable Fumarate-Based ABA Triblock Copolyester Elastomers
TR Yeazel-Klein, AG Davis, ML Becker, Advanced Materials Technologies 2023.
Poly(propylene fumarate)-Based Materials: Synthesis, functionalization, properties, device fabrication and biomedical applications
Z Cai*, Y Wan, Y-Z Long, ML Becker, D Dean*. Biomaterials, 2019, 208, 45-71.
ROCOP of Maleic Anhydride with Functional Epoxides to Yield Poly(propylene fumarate) Analogues Capable of Post-polymerization Modification
Y Chen, JA Wilson, SR Petersen, S Sallam, J Mao, C Wesdemiotis, ML Becker*. Angew Chem, 2018, 57(39), 12759-12764.
Magnesium catalyzed polymerization of end functionalized poly(propylene maleate) and poly(propylene fumarate) for 3D Printing
JA Wilson, AP Kleinfehn, D Luong, S Sallam, C Wesdemiotis, ML Becker*. J. Amer. Chem. Soc., 2018, 140(1), 277–284. – Highlighted in Chemical & Engineering News.
Versatile Ring-Opening Copolymerization and Postprinting Functionalization of Lactone and Poly (propylene fumarate) Block Copolymers: Resorbable Building Blocks for Additive Manufacturing
SR Peterson, JA Wilson, ML Becker*. Macromolecules, 2018, 51 (16), 6202–6208.
Click Chemistry
Worch, J. C. et al. Chem Rev 2021
Resorbable Barrier Polymers for Flexible Bioelectronics
SM McDonald,Q Yang, Y-H Hsu, SP Nikam, Z Hu, Z Wang, D Asheghali, T Yen, AV Dobrynin, JA Rogers, ML Becker. Nature Communications, 2023.
Mechanochromism and Strain-Induced Crystallization in Thiol-yne-derived Stereoelastomers
VC. Ritter, SM McDonald, AV. Dobrynin, SL. Craig, ML. Becker. Advanced Materials, 2023.
SP. Nikam , YH Hsu, JR Marks, C Mateas, NC Brigham, SM McDonald, DS Guggenheim, D Ruppert, JI Everitt, H Levinson, ML Becker. Biomaterials 2022.
Ultra-Tough Elastomers from Stereochemistry-Directed Hydrogen Bonding in Isosorbide-Based Polymers
S. R. Petersen, H. Prydderch, J. C. Worch, C. J. Stubbs, Z. Wang, J. Yu, M. C. Arno, A. V. Dobrynin, M. L. Becker, A. P. Dove, Angew. Chem. Int. Ed. 2022.
Unsaturated Poly(ester-urethanes) with Stereochemically-dependent Thermomechanical Properties
CJ Stubbs, JC Worch, H Prydderch, ML Becker, AP Dove. Macromolecules, 2020, 53(1), 174-181..
Stereochemical enhancement of polymer properties
J Worch, H Prydderch, S Jimaja, P Bexis, ML Becker, AP Dove. Nature Chemistry Reviews, 2019, 3, 514–535.
Independent Control of Elastomer Properties through Stereocontrolled Synthesis
C Bell, J Yu, IA Barker, V Truong, Z Cao, AV Dobrynin, ML Becker*, AP Dove*. Angew Chem. Int. Ed., 2016, 55(42), 13076-13080.
Poly(ester urea)s
Amino acid-based poly(ester urea)s are a diverse library of materials which uniquely do not lead to acidosis upon degradation due to the presence of the conjugate base (urea) present in each repeat unit to neutralize the degrading ester linkages. The mechanical properties are three fold higher than the highest reported values for lactic acid. My team has developed a number or architectures and functionalization methods that further enhance the bioactivity, degradation and mechanical properties. In addition to developing (now patented) copolymer compositions, radiopacity compositions, and we have completed in vivo studies in rats (cranial implants, vascular grafts, hernia repair and bone-tendon interface healing), rabbits (growth hormone delivery), and sheep (segmental bone defect). The material properties can be tuned widely with chemical and structural modifications to the amino acid substituents and the architecture.
Branched Amino Acid Based Poly(ester urea)s with Tunable Thermal and Water Uptake Properties
J Yu, F Lin, ML Becker*. Macromolecules, 2015, 48(9), 2916–2924.
Radiopaque, Iodine Functionalized Phenylalanine-Based Poly(ester urea)s
S Li, J Yu, MB Wade, GM Policastro, ML Becker*. Biomacromolecules, 2015, 16(2), 615–624.
Brigham, N. C.et al. J Control Release 2021
Hydrogels
Mechanically tunable, PEG-Oxime Hydrogels with Invariant Composition, Concentration, and Stoichiometry
RA Dilla, CMM Motta, Y Xu, ZK Zander, N Bernard†, CG Weiner, BD Vogt, ML Becker*. Materials Today Chemistry, 2019, 11, 244-252.
Synthesis and 3D-printing of PEG-Poly(propylene fumarate) Diblock and Triblock Copolymer Hydrogels
RA Dilla, CMM Motta, SR Snyder, JA Wilson, C Wesdemiotis, ML Becker*. ACS Macro Letters, 2018, 7, 1254-1260.
Control of Mesh Size and Modulus by Kinetically Dependent Cross‐Linking in Hydrogels
Z Zander, G Hua, C Weiner, BD Vogt, ML Becker*. Advanced Materials, 2015, 27 (40), 6283-6288.
Bioconjugates
Concentration-Dependent hMSC Differentiation on Orthogonal Concentration Gradients of GRGDS and BMP-2 Peptides
Y Ma^, GM Policastro^, Q Li, J Zheng, R Jaquet, WJ Landis, ML Becker*. Biomacromolecules, 2016, 17, 1486−1495. (^co-first authors)
Bioactive Surface Modification of Metal Oxide via Catechol-Bearing Modular Peptides: Multivalent-Binding, Surface Retention, and Peptide Bioactivity
W Tang, GM Policastro, G Hua, K Guo, J Zhou, C Wesdemiotis, GL Doll, ML Becker*. J. Amer. Chem. Soc., 2014, 136, 16357-16367.
Reactions: a Versatile Toolbox for the Synthesis of Peptide-Conjugates
W Tang, ML Becker*. Chem. Soc. Rev., 2014 43(20), 7013-7039.
