Form‐stable resorbable networks are prepared by gamma irradiating trimethylene carbonate (TMC)‐ and ε‐caprolactone (CL)‐based (co)polymer films. To evaluate their suitability for biomedical applications, their physical properties and erosion behavior are investigated. Homopolymer and copolymer networks that are amorphous at room temperature are flexible and rubbery with elastic moduli ranging from 1.8 ± 0.3 to 5.2 ± 0.4 MPa and permanent set values as low as 0.9% strain. The elastic moduli of the semicrystalline networks are higher and range from 61 ± 3 to 484 ± 34 MPa. The erosion behavior of (co)polymer networks is investigated in vitro using macrophage cultures, and in vivo by subcutaneous implantation in rats. In macrophage cultures, as well as upon implantation, a surface erosion process is observed for the amorphous (co)polymer networks, while an abrupt decrease in the rate and a change in the nature of the erosion process are observed with increasing crystallinity. These resorbable and form‐stable networks with tuneable properties may find application in a broad range of biomedical applications.
Trimethylene carbonate (TMC) was copolymerized with D ,L ‐lactide (DLLA) or with ε‐caprolactone (CL), and the degradation of melt‐pressed solid copolymer films in phosphate‐buffered saline at pH 7.4 and 37 °C was followed for a period of over two years. The parent homopolymers were used as reference materials. The degradation profile of TMC‐DLLA‐ and TMC‐CL based copolymers was similar and was best described by autocatalyzed bulk hydrolysis, preferentially of ester bonds. The hydrolysis rates varied by two orders of magnitude, depending on polymer composition and physical characteristics under the degradation conditions. TMC‐DLLA copolymers degraded faster than the parent homopolymers. The copolymers lost their tensile strength in less than five months, after which mass loss occurred. Copolymers with 50 or 80 mol‐% of TMC underwent total degradation in eleven months. For TMC‐CL copolymers, a slow and gradual decrease in molecular weight and deterioration of the mechanical performance was observed. These copolymers maintained suitable mechanical properties for seventeen months or longer. Chain scission in the semicrystalline copolymers resulted in an increase in crystallinity. In comparison with the CL homopolymer, the introduction of a small amount of TMC (10 mol‐%) significantly reduced the increase in crystallinity during degradation. Poly(TMC) specimens were dimensionally stable and showed a negligible decrease in molecular weight. A 60% decrease in the initial tensile strength of the polymer samples was observed after two years.
3D porous and non-porous structures are designed and prepared by stereolithography using resins based on PTMC macromers. Tough, flexible network films prepared in this manner show E moduli of ≈3.8 MPa and high elongations at break >900%; tensile strengths are ≈4.2 MPa. These values increase with increasing PTMC macromer molecular weight. To reach suitable viscosities for processing, up to 45 wt% propylene carbonate is added as non-reactive diluent. The solid specimens have compression moduli of 3.1-4.2 MPa, similar to the values determined in tensile testing. The built porous structures show porosities of 53-66% and average pore sizes of 309-407 μm. The compression moduli of the porous structures are significantly lower than those of the solid structures. 相似文献
The present work was aimed at the development of functional polymeric materials to be used in the targeted delivery of proteic drug and tissue engineering fields. The adopted strategy was based on the design of special polymer classes whose structures and functionality could be easily modified by finely tuned synthetic procedures. Poly(ether ester)s containing H-bonding units were chosen as promising materials for the proposed applications. Commercially available precursors were successfully used for the synthesis of symmetrical diesters containing different H-bonding groups (amide, carbamate, and urea moieties). In all cases, pure products were obtained in good yields. Bulk polycondensation of the monomeric precursors with different mixtures of 1,4-butanediol and PEG 1000 diol afforded a variety of high molecular weight polymeric structures. Physical-chemical characterization of the polymers indicates that their thermal, mechanical, and swelling properties can be tailored by a proper selection of the H-bonding group and of the composition of the feed mixture. 相似文献
A novel method based on AFM was used to attach individual collagen fibrils between a glass surface and the AFM tip, to allow force spectroscopy studies of these. The fibrils were deposited on glass substrates that are partly coated with Teflon AF. A modified AFM tip was used to accurately deposit epoxy glue droplets on either end of the collagen fibril that cross the glass-Teflon AF interface, as to such attach it with one end to the glass and the other end to the AFM tip. Single collagen fibrils have been mechanically tested in ambient conditions and were found to behave reversibly up to stresses of 90 MPa. Within this regime a Young's modulus of 2-7 GPa was obtained. In aqueous media, the collagen fibrils could be tested reversibly up to about 15 MPa, revealing Young's moduli ranging from 0.2 to at most 0.8 GPa. 相似文献