Branched Amino Acid Based Poly(ester urea)s with Tunable Thermal and Water Uptake Properties

A series of amino-acid based poly­(ester urea)­s (PEU) with controlled amounts of branching was synthesized and characterized. The mechanical properties, thermal characteristics and water absorptions varied widely with the extent of branch unit incorporation. Herein, the details of the synthesis of a linear bis­(l-phenylalanine)-hexane 1,6-diester monomer, a branch tri-<i>O</i>-benzyl-l-tyrosine-1,1,1-trimethylethane triester monomer and a series of copolymers are described. The extent of branching was varied by adjusting the molar ratio of linear to branched monomer during the interfacial polymerization. The elastic moduli span a range of values (1.0–3.1 GPa) that overlaps with several clinically available degradable polymers. Increasing the amount of branching monomers reduces the molecular entanglement, which results in a decrease in elastic modulus values and an increase in values of elongation at break. The l<i>-</i>phenylalanine-based poly­(ester urea)­s also exhibited a branch density dependent water uptake ability that varied between 2 and 3% after 24 h of immersion in water. Nanofibers incorporating 8% branching were able to maintain their morphology at elevated temperature, in hydrated conditions, and during ethylene oxide sterilization which are critical to efforts to translate these materials to clinical soft tissue applications

Poly(ester urea)-Based Adhesives: Improved Deployment and Adhesion by Incorporation of Poly(propylene glycol) Segments

The adhesive nature of mussels arises from the catechol moiety in the 3,4-dihydroxyphenylalanine (DOPA) amino acid, one of the many proteins that contribute to the unique adhesion properties of mussels. Inspired by these properties, many biomimetic adhesives have been developed over the past few years in an attempt to replace adhesives such as fibrin, cyanoacrylate, and epoxy glues. In the present work, we synthesized ethanol soluble but water insoluble catechol functionalized poly­(ester urea) random copolymers that help facilitate delivery and adhesion in wet environments. Poly­(propylene glycol) units incorporated into the polymer backbone impart ethanol solubility to these polymers, making them clinically relevant. A catechol to cross-linker ratio of 10:1 with a curing time of 4 h exceeded the performance of commercial fibrin glue (4.8 ± 1.4 kPa) with adhesion strength of 10.6 ± 2.1 kPa. These adhesion strengths are significant with the consideration that the adhesion studies were performed under wet conditions

Versatile Ring-Opening Copolymerization and Postprinting Functionalization of Lactone and Poly(propylene fumarate) Block Copolymers: Resorbable Building Blocks for Additive Manufacturing

Additive manufacturing has the potential to change medicine, but clinical applications are limited by a lack of resorbable, printable materials. Herein, we report the first synthesis of polylactone and poly­(propylene fumarate) (PPF) block copolymers with well-defined molecular masses and molecular mass distributions using sequential, ring-opening polymerization and ring-opening copolymerization methods. These new copolymers represent a diverse platform of resorbable printable materials. Furthermore, these polymers open a previously unexplored range of accessible properties among stereolithographically printable materials, which we demonstrate by printing a polymer with a molecular mass nearly 4 times that of the largest PPF homopolymer previously printed. To further demonstrate the potential of these materials in regenerative medicine, we report the postprinting “click” functionalization of the material using a copper-mediated azide–alkyne cycloaddition

l‑Leucine-Based Poly(ester urea)s for Vascular Tissue Engineering

Poly­(ester urea)­s (PEUs) derived from α-amino acids are promising for vascular tissue engineering applications. The objective of this work was to synthesize and characterize l-leucine-based PEUs and evaluate their suitability for vascular tissue engineering. Four different PEUs were prepared from di-<i>p</i>-toluenesulfonic acid salts of bis-l-leucine esters and triphosgene using interfacial condensation polymerizations. Mechanical testing indicated that the elastic moduli of the respective polymers were strongly dependent on the chain length of diols in the monomers. Three of the resulting PEUs showed elastic moduli that fall within the range of native blood vessels (0.16 to 12 MPa). The in vitro degradation assays over 6 months indicated that the polymers are surface eroding and no significant pH drop was observed during the degradation process. Human umbilical vein endothelial cells (HUVECs) and A-10 smooth muscle cells (A-10 SMCs) were cultured on PEU thin films. Protein adsorption studies showed the PEUs did not led to significant platelet adsorption in platelet rich plasma (PRP) after pretreatment with fibrinogen. Taken together, our data suggest that the l-leucine-based PEUs are viable candidate materials for use in vascular tissue engineering applications

α‑Amino Acid-Based Poly(Ester urea)s as Multishape Memory Polymers for Biomedical Applications

The thermal shape memory behavior of a series of α-amino acid-based poly­(ester urea)­s has been explored. We demonstrate that these materials exhibit excellent shape memory performance in dual- and triple-shape thermomechanical testing. Significant activation of chain mobility above the <i>T</i>_g as well as a hydrogen bonding network provide the basis for shape transformations and recovery. Additionally, we tuned the shape memory properties of these materials with polymer blending, enabling the demonstration of quadruple-shape memory cycles

Caddisfly Inspired Phosphorylated Poly(ester urea)-Based Degradable Bone Adhesives

Bone and tissue adhesives are essential in surgeries for wound healing, hemostasis, tissue reconstruction, and drug delivery. However, there are very few degradable materials with high adhesion strengths that degrade into bioresorbable byproducts. Caddisfly adhesive silk is interesting due to the presence of phosphoserines, which are thought to afford adhesive properties. In this work, phosphoserine–valine poly­(ester urea) copolymers with 2% and 5% phosphoserine content were synthesized to mimic caddisfly adhesive silk. Significantly, the materials are ethanol soluble and water insoluble, making them clinically relevant. Their physical properties were quantified, and the adhesion properties were studied on aluminum and bovine bone substrates before and after cross-linking with Ca²⁺ ions. The adhesive strength of the phosphorylated copolymer on a bone substrate after cross-linking with Ca²⁺ was 439 ± 203 kPa, comparable to commercially available PMMA bone cement (530 ± 133 kPa)

Ionomers for Tunable Softening of Thermoplastic Polyurethane

Thermoplastic polyurethane (TPU) sulfonate ionomers with quaternary ammonium cations were synthesized to achieve soft TPUs without using conventional low molecular weight plasticizers. The sulfonated monomer <i>N</i>,<i>N</i>-bis­(2-hydroxy­ethyl)-2-amino­ethane­sulfonic acid (BES) neutralized with bulky ammonium counterions was incorporated as a chain extender to internally plasticize the TPU. Increasing the steric bulk of the counterion and the concentration of the ionic species produced softer TPUs with improved melt processability. The incorporation of the sulfonate species suppressed crystallinity of the TPU hard block, which was mainly responsible for the softening of the polymer. The synthetic procedure developed allows for facile tuning of the mechanical properties of the TPU by simply switching the counterion and/or increasing the feed ratio of ionic monomer. The precursors in this study were synthesized and analyzed via ¹H NMR, and the thermomechanical properties of the resulting TPU ionomers were characterized by differential scanning calorimetry, dynamic mechanical analysis, Shore A hardness, and static mechanical testing

Tuning Energy Levels of Low Bandgap Semi-Random Two Acceptor Copolymers

A series of low bandgap semi-random copolymers incorporating various ratios of two acceptor unitsthienothiadiazole and benzothiadiazolewere synthesized by Pd-catalyzed Stille coupling. The polymer films exhibited broad and intense absorption spectra, covering the spectral range from 350 nm up to 1240 nm. The optical bandgaps and HOMO levels of the polymers were calculated from ultraviolet–visible spectroscopy and cyclic voltammetry measurements, respectively. By changing the ratio of the two acceptor monomers, the HOMO levels of the polymers were tuned from −4.42 to −5.28 eV and the optical bandgaps were varied from 1.00 to 1.14 eV. The results indicate our approach could be applied to the design and preparation of conjugated polymers with specifically desired energy levels and bandgaps for photovoltaic applications

Consequences of Water between Two Hydrophobic Surfaces on Adhesion and Wetting

The contact of two hydrophobic surfaces in water is of importance in biology, catalysis, material science, and geology. A tenet of hydrophobic attraction is the release of an ordered water layer, leading to a dry contact between two hydrophobic surfaces. Although the water-free contact has been inferred from numerous experimental and theoretical studies, this has not been directly measured. Here, we use surface sensitive sum frequency generation spectroscopy to directly probe the contact interface between hydrophobic poly­(dimethylsiloxane) (PDMS) and two hydrophobic surfaces (a self-assembled monolayer, OTS, and a polymer coating, PVNODC). We show that the interfacial structures for OTS and PVNODC are identical in dry contact but that they differ dramatically in wet contact. In water, the PVNODC surface partially rearranges at grain boundaries, trapping water at the contact interface leading to a 50% reduction in adhesion energy compared to OTS–PDMS contact. The Young–Dupré equation, used extensively to calculate the thermodynamic work of adhesion, predicts no differences between the adhesion energy for these two hydrophobic surfaces, indicating a failure of this well-known equation when there is a heterogeneous contact. This study exemplifies the importance of interstitial water in controlling adhesion and wetting

Post-Assembly Derivatization of Electrospun Nanofibers via Strain-Promoted Azide Alkyne Cycloaddition

A primary amine-derivatized 4-dibenzocyclooctynol (DIBO) was used to initiate the ring-opening polymerization of poly­(γ-benzyl-l-glutamate) (DIBO-PBLG). This initiator yields well-defined PBLG polymers functionalized with DIBO at the chain termini. The DIBO end group further survives an electrospinning process that yields nanofibers that were then derivatized post-assembly with azide-functionalized gold nanoparticles. The availability of DIBO on the surface of the fibers is substantiated by fluorescence, SEM, and TEM measurements. Post-assembly functionalization of nanofiber constructs with bioactive groups can be facilitated easily using this process