Project description:In the field of polymer chemistry, tremendous efforts have been made over the lastdecade to replace petrochemical monomers with building blocks from renewable resources. In thisrespect, itaconic acid has been used as an alternative to acrylic acid or maleic acid in unsaturatedpolyesters for thermal or UV-curing applications. However, examples of poly(ester amide)s fromitaconic acid are scarce. Under standard polycondensation reactions, the presence of free aminesleads to aza-Michael addition reactions at the α,β-unsaturated double bond of the itaconic acid andisomerization reactions to mesaconic acid. Both reactions make the resulting materials useless asUV-curing polymer resins. To avoid these undesired side reactions, we herein report the use ofpreformed, well-defined diols containing internal amide bonds. The resulting unsaturatedpoly(ester amide) resins were analyzed before and after UV-induced crosslinking. Viscositymeasurements revealed a strong thixotropic behavior induced by the amide groups, which isusually not detected in structurally similar polyester resins.
Project description:Currently available synthetic biodegradable elastomers are primarily composed of crosslinked aliphatic polyesters, which suffer from deficiencies including (1) high crosslink densities, which results in exceedingly high stiffness, (2) rapid degradation upon implantation, or (3) limited chemical moieties for chemical modification. Herein, we have developed poly(1,3-diamino-2-hydroxypropane-co-polyol sebacate)s, a new class of synthetic, biodegradable elastomeric poly(ester amide)s composed of crosslinked networks based on an amino alcohol. These crosslinked networks feature tensile Young's modulus on the order of 1MPa and reversable elongations up to 92%. These polymers exhibit in vitro and in vivo biocompatibility. These polymers have projected degradation half-lives up to 20 months in vivo.
Project description:α-Amino acid based polyester amides (PEAs) are promising candidates for additive manufacturing (AM), as they unite the flexibility and degradability of polyesters and good thermomechanical properties of polyamides in one structure. Introducing α-amino acids in the PEA structure brings additional advantages such as (i) good cytocompatibility and biodegradability, (ii) providing strong amide bonds, enhancing the hydrogen-bonding network, (iii) the introduction of pendant reactive functional groups, and (iv) providing good cell-polymer interactions. However, the application of α-amino acid based PEAs for AM via fused deposition modeling (FDM), an important manufacturing technique with unique processing characteristics and requirements, is still lacking. With the aim to exploit the combination of these advantages in the creation, design, and function of additively manufactured scaffolds using FDM, we report the structure-function relationship of a series of α-amino acid based PEAs. The PEAs with three different molecular weights were synthesized via the active solution polycondensation, and their performance for AM applications was studied in comparison with a commercial biomedical grade copolymer of l-lactide and glycolide (PLGA). The PEAs, in addition to good thermal stability, showed semicrystalline behavior with proper mechanical properties, which were different depending on their molecular weight and crystallinity. They showed more ductility due to their lower glass transition temperature (Tg; 18-20 °C) compared with PLGA (57 °C). The rheology studies revealed that the end-capping of PEAs is of high importance for preventing cross-linking and further polymerization during the melt extrusion and for the steadiness and reproducibility of FDM. Furthermore, our data regarding the steady 3D printing performance, good polymer-cell interactions, and low cytotoxicity suggest that α-amino acid based PEAs can be introduced as favorable polymers for future AM applications in tissue engineering. In addition, their ability for formation of bonelike apatite in the simulated body fluid (SBF) indicates their potential for bone tissue engineering applications.
Project description:Wound healing dressing is increasingly needed in clinical owing to the large quantity of skin damage annually. Excessive reactive oxygen species (ROS) produced through internal or external environmental influences can lead to lipid peroxidation, protein denaturation, and even DNA damage, and ultimately have harmful effects on cells. Aiming to sufficiently contact with the wound microenvironment and scavenge ROS, superabsorbent poly (acrylic acid) and antioxidant poly (ester amide) (PAA/PEA) hybrid hydrogel has been developed to enhance wound healing. The physical and chemical properties of hybrid hydrogels were studied by Fourier-transform infrared (FTIR) absorption spectrum, compression, swelling, degradation, etc. Besides, the antioxidant properties of hybrid hydrogels can be investigated through the free radical scavenging experiment, and corresponding antioxidant indicators have been tested at the cellular level. Hybrid hydrogel scaffolds supported the proliferation of human umbilical vein endothelial cells and fibroblasts, as well as accelerated angiogenesis and skin regeneration in wounds. The healing properties of wounds in vivo were further assessed on mouse skin wounds. Results showed that PAA/PEA hybrid hydrogel scaffolds significantly accelerated the wound healing process through enhancing granulation formation and re-epithelialization. In summary, these superabsorbent and antioxidative hybrid hydrogels could be served as an excellent wound dressing for full-thickness wound healing.
Project description:This study reports the synthesis of polymeric matrices based on N-isopropylacrylamide and itaconic acid and its application for immobilization of lipase from Candida rugosa. The lipase was immobilized by entrapment method. Free and immobilized lipase activities, pH and temperature optima, and storage stability were investigated. The optimum temperature for free and entrapped lipase was found to be 40 and 45 °C, while the optimum pH was observed at pH 7 and 8, respectively. Both hydrolytic activity in an aqueous medium and esterolytic activity in an organic medium have been evaluated. Maximum reaction rate (V max) and Michaelis-Menten constants (K m ) were also determined for immobilized lipase. Storage stability of lipase was increased as a result of immobilization process. Furthermore, the operational stability and reusability of the immobilized lipase in esterification reaction have been studied, and it was observed that after 10 cycles, the residual activity for entrapped lipase was as high as 50%, implying that the developed hydrogel and immobilized system could provide a promising solution for the flavor ester synthesis at the industrial scale.
Project description:Stereolithography is a useful additive manufacturing technique for the production of scaffolds for tissue engineering. Here we present a tuneable, easy-to-manufacture, photocurable resin for use in stereolithography, based on the widely used biomaterial, poly(caprolactone) (PCL). PCL triol was methacrylated to varying degrees and mixed with photoinitiator to produce a photocurable prepolymer resin, which cured under UV light to produce a cytocompatible material. This study demonstrates that poly(caprolactone) methacrylate (PCLMA) can be produced with a range of mechanical properties and degradation rates. By increasing the degree of methacrylation (DM) of the prepolymer, the Young's modulus of the crosslinked PCLMA could be varied from 0.12-3.51 MPa. The accelerated degradation rate was also reduced from complete degradation in 17 days to non-significant degradation in 21 days. The additive manufacturing capabilities of the resin were demonstrated by the production of a variety of different 3D structures using micro-stereolithography. Here, β-carotene was used as a novel, cytocompatible photoabsorber and enabled the production of complex geometries by giving control over cure depth. The PCLMA presented here offers an attractive, tuneable biomaterial for the production of tissue engineering scaffolds for a wide range of applications.
Project description:In this work, electrospun membranes of α-amino acid based poly(ester amide)s (AAA-PEAs) from L-alanine (PEA_ala) or L-phenylalanine (PEA_phe) were successfully prepared to be used as physical barriers in the orthopedic field. Also, blends of these two polymers were used in different weight ratios (25:75, 50:50 and 75:25) to obtain physical barriers with different properties. All membranes had a suitable pore size to prevent fibroblast infiltration, and their porosity and permeability values were in a range that allowed the passage of nutrients. The membrane made from a blend of 25%wt of PEA_ala and 75% wt of PEA_phe showed the highest value of swelling capacity, suggesting a higher lubricant feature. The same membrane suffered a more pronounced degradation, as evidenced by the in vitro enzymatic degradation tests. All membranes showed suitable toughness values, a crucial property with regard to application. In vitro cytotoxicity tests performed with a NIH3T3 fibroblast cell line revealed decreased cell viability after 7 days, suggesting that these membranes are not ideal substrates to promote fibroblast adhesion and proliferation. These membranes as physical barriers represent a significant advance in the field given the limited literature on electrospun AAA-PEAs and their use to prevent tendon adhesion.
Project description:Poly(ester amide)s are attracting attention because they potentially have excellent thermal and mechanical properties as well as biodegradability. In this study, we synthesized a series of novel poly(ester amide)s by introducing γ-aminobutyric acid (GABA) regularly into polyesters, and investigated their properties and biodegradabilities. GABA is the monomer unit of biodegradable polyamide 4 (PA4). The new poly(ester amide)s were synthesized from the reaction of ammonium tosylate derivatives of alkylene bis(γ-aminobutylate) and p-nitrophenyl esters of dicarboxylic acids. All the obtained polymers showed relatively high melting temperatures (Tm). Their thermal decomposition temperatures were improved in comparison with that of PA4 and higher enough than their Tm. The poly(ester amide)s exhibited higher biodegradability in seawater than the corresponding homopolyesters. Their biodegradabilities in activated sludge were also studied.
Project description:Paper used for packaging applications is often coated with thin polymer coatings to improve the properties, like printability and barrier properties, respectively. Today, these coatings are still often based on petroleum-based polymers. In this study, the fabrication of biobased thin film coatings is described. Poly(itaconic acid ester)s, which are prepared by emulsion polymerization, are used as water-based coatings for paper. The thermal properties of the polymers are tuned by the side chain of the monomers (diethyl itaconate vs. dibutyl itaconate). Different formulations based on the polymer emulsion and additives, like rheology modifiers, are prepared and their film formation is studied. The usage of a rheology modifier results in excellent film formation. These polymer coatings feature an additional function - they are capable of self-healing. The healing ability is studied in scratch healing tests, in which almost complete recovery can be observed after healing at 100 °C. Moreover, the restoration of optical properties/aesthetics is studied. In gloss measurements before and after damage as well as after a healing time the complete recovery of the gloss can be observed. Furthermore, the barrier properties against fat are studied.