Ethylene Oxide Terephthalate Research Articles

The influences of polyethylene glycol molecular weight on thermal stability, nonisothermal crystallization behavior, and morphology of poly(trimethylene terephthalate)/poly(ethylene oxide terephthalate) copolymers

A series of poly(trimethylene terephthalate)/poly(ethylene oxide terephthalate) copolymers with approximately 25 wt% PEG content were synthesized and investigated. The results showed that the thermal stability of copolymers increased with increasing Mn, PEG from 1000 to 4000 g/mol. However, the thermal stability of the copolymer with Mn, PEG = 300 g/mol was better than the copolymer with Mn, PEG = 600 g/mol. The nonisothermal crystallization kinetics of the copolymers was analyzed using Ozawa and Mo models, and only the Mo method was satisfactory in describing this system. Polarized optical microscopy revealed that all copolymers could form ring banded spherulites and the temperature window for their formation was basically identical for all copolymers. In addition, the spherulitic growth rate curves of copolymers exhibited a bell shape, and both the maximum growth rate and the crystallization temperature corresponding to the maximum growth rate increased with the increase in Mn, PEG.

Tissue-engineered constructs: the effect of scaffold architecture in osteochondral repair

Cartilage has a poor regenerative capacity. Tissue-engineering approaches using porous scaffolds seeded with chondrocytes may improve cartilage repair. The aim of this study was to examine the effect of pore size and pore interconnectivity on cartilage repair in osteochondral defects treated with different scaffolds seeded with allogenic chondrocytes. Scaffolds consisting of 55 wt% poly(ethylene oxide terephthalate) and 45 wt% poly(butylene terephthalate) (PEOT/PBT) with different pore sizes and interconnectivities were made, using a compression moulding (CM) and a three-dimensional fibre (3DF) deposition technique. In these scaffolds, allogenic chondrocytes were seeded, cultured for 3 weeks and implanted in osteochondral defects of skeletally mature rabbits. At 3 weeks no difference in cartilage repair between an empty osteochondral defect, CM or 3DF scaffolds was found. Three months post-implantation, cartilage repair was significantly improved after implantation of a 3DF scaffold compared to a CM scaffold. Although not significant, Mankin scores for osteoarthritis (OA) indicated less OA in the 3DF scaffold group compared to empty defects and CM-treated defects. It is concluded that scaffold pore size and pore interconnectivity influences osteochondral repair and a decreased pore interconnectivity seems to impair osteochondral repair.

Crystallization, and morphology of poly(trimethylene terephthalate)/poly(ethylene oxide terephthalate) segmented block copolymers

A new type of poly(ether–ester) based on poly(trimethylene terephthalate) as rigid segments and poly(ethylene oxide terephthalate) as soft segments was synthesized and its crystallization behavior and morphology were investigated. Differential Scanning Calorimetry revealed that the copolymer containing 57 wt% soft segments presented a low glass transition temperature (−46.4 °C) and a high melting temperature (201.8 °C), suggesting that it had the typical characteristic of thermoplastic elastomer. With increasing soft segment content from 35 to 57 wt%, the crystallization morphology transformed from banded spherulites to compact seaweed morphology at a certain film thickness, which was due to the change of surface tension and diffusivity caused by increasing the soft segment content. Moreover, with the decrease of film thickness from 15 to 2 μm, the crystallization morphology of the copolymer (57 wt% soft segment) changed from wheatear-like, compact seaweed to dendritic. Scanning Electron Microscopy revealed that some flower-like crystals presenting in the bulk, which had been surprisingly found in the poly(ether–ester) segmented block copolymers for the first time. Possible mechanism was discussed in the text.

Crystallization‐induced aging in poly(trimethylene terephthalate)/ poly(ethylene oxide terephthalate) segmented block copolymers

AbstractA new type poly(ether–ester) based on poly(trimethylene terephthalate) as rigid segments and poly(ethylene oxide terephthalate) as soft segments was synthesized and its aging behavior were investigated. Different from other polymer, the segmented block copolymers exhibited a unique aging mechanism. That is, the degradation of mechanical property within short term annealing was due to the overgrown crystals and dramatically increased crystallinity, which was proved by field emission scanning electron microscope (FE‐SEM) and differential scanning calorimetry (DSC), respectively. The deterioration in mechanical property after long term annealing was the results of both the increase in crystallinity and the decrease in molecular weight. Moreover, FE‐SEM showed many interesting flower‐like crystals presented on the surface of annealed sample. The flower‐like crystals consist of several radialized petal‐like arms and a more densely packed center, which has been seldom found in polymer bulk. Wide‐angle x‐ray diffraction results showed that the copolymer has the same crystal structure as PTT. Such poly(ether–ester) or its blends with other polymer could be suitable for rapid degradable products, such as package and vessel. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 411–416, 2010

Calcium Phosphate Coated Electrospun Fiber Matrices as Scaffolds for Bone Tissue Engineering

Electrospun polymeric scaffolds are used for various tissue engineering applications. In this study, we applied a biomimetic coating method to provide electrospun scaffolds from a block copolymer-poly(ethylene oxide terephthalate)-poly(buthylene terephthalate), with a calcium phosphate layer to improve their bioactivity in bone tissue engineering. The in vitro studies with human mesenchymal stem cells demonstrated cell proliferation on both uncoated and coated samples. No significant effect of calcium phosphate coating was observed on the expression of alkaline phosphatase in vitro. Implantation of scaffold-goat mesenchymal stem cells constructs subcutaneously in nude mice resulted in bone formation in the calcium phosphate coated samples, in contrast to the uncoated ones, where no new bone formation was observed. The results of this study showed that the biomimetic method can successfully be used to coat electrospun scaffolds with a calcium phosphate layer, which improved the in vivo bioactivity of the polymer.

PEOT/PBT based scaffolds with low mechanical properties improve cartilage repair tissue formation in osteochondral defects

The aim of our study was to compare the healing response of biomechanically and biochemically different scaffolds in osteochondral defects created in rabbit medial femoral condyles. A block copolymer comprised of poly(ethylene oxide terephthalate) and poly(butylene terephthalate) was used to prepare porous scaffolds. The 70/30 scaffold (70 wt % poly(ethylene oxide terephthalate)) was compared to the stiffer 55/45 (55 wt % poly(ethylene oxide terephthalate)) scaffold. Nine 6-month-old rabbits were used. Osteochondral defects were filled with 55/45 scaffolds (n = 6); 70/30 scaffolds (n = 6); or left empty (n = 6). Defect sites were allowed to heal for 12 weeks. Condyles were macroscopically evaluated and analysed histologically using the O'Driscoll score for evaluating repair of osteochondral defects. Repair tissue in 70/30 scaffolds consisted of cartilage-like tissue on top of trabecular bone, whereas the tissue within the 55/45 scaffolds consisted predominantly of trabecular bone. O'Driscoll scores for 70/30 scaffolds were significantly better (p = 0.024) in comparison to untreated osteochondral defects and 55/45 scaffolds. This study reveals that the biomechanical and biochemical properties of the scaffold play an important role by themselves, and can affect the healing response of osteochondral defects. Scaffolds with low mechanical properties were superior in cartilage repair tissue formation.

Fiber diameter and texture of electrospun PEOT/PBT scaffolds influence human mesenchymal stem cell proliferation and morphology, and the release of incorporated compounds

Electrospinning (ESP) has lately shown a great potential as a novel scaffold fabrication technique for tissue engineering. Scaffolds are produced by spinning a polymeric solution in fibers through a spinneret connected to a high-voltage electric field. The fibers are then collected on a support, where the scaffold is created. Scaffolds can be of different shapes, depending on the collector geometry, and have high porosity and high surface per volume ratio, since the deposited fibers vary from the microscale to the nanoscale range. Such fibers are quite effective in terms of tissue regeneration, as cells can bridge the scaffold pores and fibers, resulting in a fast and homogeneous tissue growth. Furthermore, fibers can display a nanoporous ultrastructure due to solvent evaporation. The aim of this study was to characterize electrospun scaffolds from poly(ethylene oxide terephthalate)-poly(butylene terephthalate) (PEOT/PBT) copolymers and to unravel the mechanism of pore formation on the fibers. The effect of different fiber diameters and of their surface nanotopology on cell seeding, attachment, and proliferation was studied. Smooth fibers with diameter of 10microm were found to support an optimal cell seeding and attachment within the micrometer range analyzed. Moreover, a nanoporous surface significantly enhanced cell proliferation and cells spreading on the fibers. The fabrication of ESP scaffolds with incorporated dyes with different molecular dimensions is also reported and their release measured. These findings contribute to the field of cell-material interaction and lead to the fabrication of "smart" scaffolds which can direct cells morphology and proliferation, and eventually release biological signals to properly conduct tissue formation.

Dynamic mechanical properties of 3D fiber‐deposited PEOT/PBT scaffolds: An experimental and numerical analysis

Mechanical properties of three-dimensional (3D) scaffolds can be appropriately modulated through novel fabrication techniques like 3D fiber deposition (3DF), by varying scaffold's pore size and shape. Dynamic stiffness, in particular, can be considered as an important property to optimize the scaffold structure for its ultimate in vivo application to regenerate a natural tissue. Experimental data from dynamic mechanical analysis (DMA) reveal a dependence of the dynamic stiffness of the scaffold on the intrinsic mechanical and physicochemical properties of the material used, and on the overall porosity and architecture of the construct. The aim of this study was to assess the relationship between the aforementioned parameters, through a mathematical model, which was derived from the experimental mechanical data. As an example of how mechanical properties can be tailored to match the natural tissue to be replaced, articular bovine cartilage and porcine knee meniscus cartilage dynamic stiffness were measured and related to the modeled 3DF scaffolds dynamic stiffness. The dynamic stiffness of 3DF scaffolds from poly(ethylene oxide terephthalate)-poly(butylene terephthalate) (PEOT/PBT) copolymers was measured with DMA. With increasing porosity, the dynamic stiffness was found to decrease in an exponential manner. The influence of the scaffold architecture (or pore shape) and of the molecular network properties of the copolymers was expressed as a scaffold characteristic coefficient alpha, which modulates the porosity effect. This model was validated through an FEA numerical simulation performed on the structures that were experimentally tested. The relative deviation between the experimental and the finite element model was less than 15% for all of the constructs with a dynamic stiffness higher than 1 MPa. Therefore, we conclude that the mathematical model introduced can be used to predict the dynamic stiffness of a porous PEOT/PBT scaffold, and to choose the biomechanically optimal structure for tissue engineering applications.

Three‐dimensional fiber‐deposited PEOT/PBT copolymer scaffolds for tissue engineering: Influence of porosity, molecular network mesh size, and swelling in aqueous media on dynamic mechanical properties

Among novel scaffold fabrication techniques, 3D fiber deposition (3DF) has recently emerged as a means to fabricate well-defined and custom-made scaffolds for tissue regeneration, with 100% interconnected pores. The mechanical behavior of these constructs is dependent not only on different three-dimensional architectural and geometric features, but also on the intrinsic chemical properties of the material used. These affect the mechanics of the solid material and eventually of 3D porous constructs derived from them. For instance, poly(ethylene oxide terephthalate)-poly(butylene terephthalate) (PEOT/PBT) block copolymers are known to have mechanical properties, depending on the PEOT/PBT weight ratio in block form and on the molecular weight of the initial poly(ethylene glycol) (PEG) blocks. These differences are enhanced even more by their different swelling properties in aqueous media. Therefore, this article examines the influence of copolymer compositions in terms of their swelling on dynamic mechanical properties of solid material and porous 3DF scaffolds. The molecular weight of the starting PEG blocks used in the copolymer synthesis varied from 300 to 1000 g/mol. The PEOT/PBT weight ratio in the blocks used varied from 55/45 to 80/20. This corresponded to an increase of the swelling ratio Q from 1.06 to 2.46, and of the mesh size xi from approximately 9 Angstrom to approximately 47 Angstrom. With increased swelling, dynamic mechanical analysis (DMA) revealed a decrease in elastic response and an increase of viscoelasticity. Thus, by coupling structural and chemical characteristics, the viscoelastic properties of PEOT/PBT 3DF scaffolds may be fine tuned to achieve mechanical requirements for a variety of engineered tissues. Ultimately, the combination of 3DF and DMA may be useful to validate the hypothesis that mimicking the biomechanical behavior of a specific tissue for its optimal replacement is an important issue for at least some tissue-engineering applications.