Properties of Electrospun Nanofibers of Multi-Block Copolymers of [Poly-ε-caprolactone-b-poly(tetrahydrofuran-co-ε-caprolactone)]m Synthesized by Janus Polymerization.
ABSTRACT: Novel biodegradable multiblock copolymers of [PCL-b-P(THF-co-CL)]m with PCL fractions of 53.3 and 88.4 wt % were prepared by Janus polymerization of ε-caprolactone (CL) and tetrahydrofuran (THF). Their electrospun mats were obtained with optimized parameters containing bead-free nanofibers whose diameters were between 290 and 520 nm. The mechanical properties of the nanofiber scaffolds were measured showing the tensile strength and strain at break of 8⁻10 MPa and 123⁻161%, respectively. Annealing improved their mechanical properties and their tensile strength and strain at break of the samples increased to 10⁻13 MPa and 267⁻338%, respectively. Due to the porous structure and crystallization in nanoscale confinement, the mechanical properties of the nanofiber scaffolds appeared as plastics, rather than as the elastomers observed in bulk thermal-molded film.
Project description:The broad application of electrospun nanofibrous scaffolds in tissue engineering is limited by their small pore size, which has a negative influence on cell migration. This disadvantage could be significantly improved through the combination of nano- and microfibrous structure. To accomplish this, different nano/microfibrous scaffolds were produced by hybrid electrospinning, combining solution electrospinning with melt electrospinning, while varying the content of the nanofiber. The morphology of the silk fibroin (SF)/poly(?-caprolactone) (PCL) nano/microfibrous composite scaffolds was investigated with field-emission scanning electron microscopy, while the mechanical and pore properties were assessed by measurement of tensile strength and mercury porosimetry. To assay cell proliferation, cell viability, and infiltration ability, human mesenchymal stem cells were seeded on the SF/PCL nano/microfibrous composite scaffolds. From in vivo tests, it was found that the bone-regenerating ability of SF/PCL nano/microfibrous composite scaffolds was closely associated with the nanofiber content in the composite scaffolds. In conclusion, this approach of controlling the nanofiber content in SF/PCL nano/microfibrous composite scaffolds could be useful in the design of novel scaffolds for tissue engineering.
Project description:In recent years, poly(lactic acid) (PLA) has attracted more and more attention as one of the most promising biobased and biodegradable polymers. However, the inherent brittleness significantly limits its wide application. Here, ternary blends of PLA, poly(ε-caprolactone) (PCL) with various amounts of ethylene-methyl acrylate-glycidyl methacrylate (EMA-GMA) terpolymer were fabricated through reactive melt blending in order to improve the toughness of PLA. The effect of different addition amounts of EMA-GMA on the mechanical properties, interfacial compatibility and phase morphology of PLA/PCL blends were studied. The reactions between the epoxy groups of EMA-GMA and carboxyl and hydroxyl end groups of PLA and PCL were investigated thorough a Fourier transform infrared (FT-IR). The miscibility and thermal behavior of the blends were studied through a dynamic mechanical analysis (DMA), differential scanning calorimetric (DSC) and X-ray diffraction (XRD). The phase morphology and impact fracture surface of the blends were also investigated through a scanning electron microscope (SEM). With the addition of 8 phr EMA-GMA, a PLA/PCL (90 wt %:10 wt %)/EMA-GMA ternary blend presenting a suitable multiple stacked phase structure with an optimum interfacial adhesion exhibited an elongation at break of 500.94% and a notched impact strength of 64.31 kJ/m2 with a partial break impact behavior. Finally, the toughening mechanism of the supertough PLA based polymers have been established based on the above analysis.
Project description:The crystallization behavior of poly(ε-caprolactone) (PCL) in a poly(vinylidene fluoride) (PVDF)/PCL blend as well as on a highly orientated PVDF substrate was studied by means of POM, DSC and TEM. The results show that the miscibility of the PVDF/PCL blend and the spherulitic morphology of PVDF varies with the blend ratio. For all the compositions, the pre-existing PVDF crystals accelerated the crystallization of PCL because the PVDF exhibits very strong nucleation ability toward PCL as reflected by the occurrence of heteroepitaxy and the transcrystallization of PBA on the PVDF substrate. This is associated with the perfect lattice matching between the PBA and PVDF crystals.
Project description:Polymeric nanofibers are of great interest in biomedical applications, such as tissue engineering, drug delivery and wound healing, due to their ability to mimic and restore the function of natural extracellular matrix (ECM) found in tissues. Electrospinning has been heavily used to fabricate nanofibers because of its reliability and effectiveness. In our research, we fabricated poly(ε-caprolactone)-(PCL), magnesium oxide-(MgO) and keratin (K)-based composite nanofibers by electrospinning a blend solution of PCL, MgO and/or K. The electrospun nanofibers were analyzed by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), mechanical tensile testing and inductively-coupled plasma optical emission spectroscopy (ICP-OES). Nanofibers with diameters in the range of 0.2-2.2 µm were produced by using different ratios of PCL/MgO and PCL-K/MgO. These fibers showed a uniform morphology with suitable mechanical properties; ultimate tensile strength up to 3 MPa and Young's modulus 10 MPa. The structural integrity of nanofiber mats was retained in aqueous and phosphate buffer saline (PBS) medium. This study provides a new composite material with structural and material properties suitable for potential application in tissue engineering.
Project description:The objective of this study was to produce antibacterial poly(?-caprolactone) (PCL)-gelatin (GEL) electrospun nanofiber mats containing clove essential oil (CLV) using glacial acetic acid (GAA) as a "benign" (non-toxic) solvent. The addition of CLV increased the fiber diameter from 241 ± 96 to 305 ± 82 nm. Aside from this, the wettability of PCL-GEL nanofiber mats was increased by the addition of CLV. Fourier-transform infrared spectroscopy (FTIR) analysis confirmed the presence of CLV, and the actual content of CLV was determined by gas chromatography-mass spectrometry (GC-MS). Our investigations showed that CLV-loaded PCL-GEL nanofiber mats did not have cytotoxic effects on normal human dermal fibroblast (NHDF) cells. On the other hand, the fibers exhibited antibacterial activity against Staphylococcus aureus and Escherichia coli. Consequently, PCL-GEL/CLV nanofiber mats are potential candidates for antibiotic-free wound healing applications.
Project description:Electrospinning has been widely used to fabricate scaffolds imitating the structure of natural extracellular matrix (ECM). However, conventional electrospinning produces tightly compacted nanofiber layers with only small superficial pores and a lack of bioactivity, which limit the usefulness of electrospinning in biomedical applications. Thus, a porous poly(?-caprolactone) (PCL)/gelatin composite electrospun scaffold with crater-like structures was developed. Porous crater-like structures were created on the scaffold by a gas foaming/salt leaching process; this unique fiber structure had more large pore areas and higher porosity than the conventional electrospun fiber network. Various ratios of PCL/gelatin (concentration ratios: 100/0, 75/25, and 50/50) composite electrospun scaffolds with and without crater-like structures were characterized by their microstructures, surface chemistry, degradation, mechanical properties, and ability to facilitate cell growth and infiltration. The combination of PCL and gelatin endowed the scaffold with both structural stability of PCL and bioactivity of gelatin. All ratios of scaffolds with crater-like structures showed fairly similar surface chemistry, degradation rates, and mechanical properties to equivalent scaffolds without crater-like structures; however, craterized scaffolds displayed higher human mesenchymal stem cell (hMSC) proliferation and infiltration throughout the scaffolds after 7-day culture. Therefore, these results demonstrated that PCL/gelatin composite electrospun scaffolds with crater-like structures can provide a structurally and biochemically improved three-dimensional ECM-mimicking microenvironment.
Project description:The regeneration of functional tissue in osseous defects is a formidable challenge in orthopedic surgery. In the present study, a novel biomimetic composite scaffold, here called nano-hydroxyapatite (HA)/poly-?-caprolactone (PCL) was fabricated using a selective laser sintering technique. The macrostructure, morphology, and mechanical strength of the scaffolds were characterized. Scanning electronic microscopy (SEM) showed that the nano-HA/PCL scaffolds exhibited predesigned, well-ordered macropores and interconnected micropores. The scaffolds have a range of porosity from 78.54% to 70.31%, and a corresponding compressive strength of 1.38 MPa to 3.17 MPa. Human bone marrow stromal cells were seeded onto the nano-HA/PCL or PCL scaffolds and cultured for 28 days in vitro. As indicated by the level of cell attachment and proliferation, the nano-HA/PCL showed excellent biocompatibility, comparable to that of PCL scaffolds. The hydrophilicity, mineralization, alkaline phosphatase activity, and Alizarin Red S staining indicated that the nano-HA/PCL scaffolds are more bioactive than the PCL scaffolds in vitro. Measurements of recombinant human bone morphogenetic protein-2 (rhBMP-2) release kinetics showed that after nano-HA was added, the material increased the rate of rhBMP-2 release. To investigate the in vivo biocompatibility and osteogenesis of the composite scaffolds, both nano-HA/PCL scaffolds and PCL scaffolds were implanted in rabbit femur defects for 3, 6, and 9 weeks. The wounds were studied radiographically and histologically. The in vivo results showed that both nano-HA/PCL composite scaffolds and PCL scaffolds exhibited good biocompatibility. However, the nano-HA/PCL scaffolds enhanced the efficiency of new bone formation more than PCL scaffolds and fulfilled all the basic requirements of bone tissue engineering scaffolds. Thus, they show large potential for use in orthopedic and reconstructive surgery.
Project description:3D-printed bone scaffolds hold great promise for the individualized treatment of critical-size bone defects. Among the resorbable polymers available for use as 3D-printable scaffold materials, poly(?-caprolactone) (PCL) has many benefits. However, its relatively low stiffness and lack of bioactivity limit its use in load-bearing bone scaffolds. This study tests the hypothesis that surface-oxidized cellulose nanocrystals (SO-CNCs), decorated with carboxyl groups, can act as multi-functional scaffold additives that (1) improve the mechanical properties of PCL and (2) induce biomineral formation upon PCL resorption. To this end, an <i>in vitro</i> biomineralization study was performed to assess the ability of SO-CNCs to induce the formation of calcium phosphate minerals. In addition, PCL nanocomposites containing different amounts of SO-CNCs (1, 2, 3, 5, and 10 wt%) were prepared using melt compounding extrusion and characterized in terms of Young's modulus, ultimate tensile strength, crystallinity, thermal transitions, and water contact angle. Neither sulfuric acid-hydrolyzed CNCs (SH-CNCs) nor SO-CNCs were toxic to MC3T3 preosteoblasts during a 24 h exposure at concentrations ranging from 0.25 to 3.0 mg/mL. SO-CNCs were more effective at inducing mineral formation than SH-CNCs in simulated body fluid (1x). An SO-CNC content of 10 wt% in the PCL matrix caused a more than 2-fold increase in Young's modulus (stiffness) and a more than 60% increase in ultimate tensile strength. The matrix glass transition and melting temperatures were not affected by the SO-CNCs but the crystallization temperature increased by about 5.5°C upon addition of 10 wt% SO-CNCs, the matrix crystallinity decreased from about 43 to about 40%, and the water contact angle decreased from 87 to 82.6°. The abilities of SO-CNCs to induce calcium phosphate mineral formation and increase the Young's modulus of PCL render them attractive for applications as multi-functional nanoscale additives in PCL-based bone scaffolds.
Project description:Reactive extrusion of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/poly(?-caprolactone) (PHBV/PCL) blends was performed in the presence of cross-linker 1,3,5-tri-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TAIC) and peroxide. The compatibility between the two biodegradable polymers was significantly improved only when TAIC and peroxide work together, as evidenced by the decreased PCL particle size and blurred interfacial gap between the PHBV and PCL. The mechanical, thermal, morphological, and rheological properties of the compatibilized blends were studied and compared to the blends without TAIC and peroxide. At the optimal TAIC content (1 phr), the elongation at break of the compatibilized blends was 380% that of the PHBV/PCL blend without any additives and 700% that of neat PHBV. The improved interfacial compatibility, decreased PCL particle size, and uniform PHBV crystals are all factors that contribute to improving the toughness of the blend. Through Fourier transform infrared (FTIR) and rheological studies, the reaction mechanism is discussed. The study shows that PHBV and PCL are cross-linked by TAIC, resulting in the formation of a PHBV–PCL co-polymer, which improves the compatibility of the blend. The biodegradable polymer blends with high crystallinity and improved toughness prepared in this study are proposed to be used in sustainable packaging or other applications.
Project description:This study aims to develop biodegradable and biocompatible polymer-based nanofibers that continuously monitor pH within microenvironments of cultured cells in real-time. In the future, these fibers will provide a scaffold for tissue growth while simultaneously monitoring the extracellular environment.Sensors to monitor pH were created by directly electrospinning the sensor components within a polymeric matrix. Specifically, the entire fiber structure is composed of the optical equivalent of an electrode, a pH-sensitive fluorophore, an ionic additive, a plasticizer, and a polymer to impart mechanical stability. The resulting poly(?-caprolactone) (PCL) and poly(lactic-co-glycolic acid) (PLGA) based sensors were characterized by morphology, dynamic range, reversibility and stability. Since PCL-based nanofibers delivered the most desirable analytical response, this matrix was used for cellular studies.Electrospun nanofiber scaffolds (NFSs) were created directly out of optode material. The resulting NFS sensors respond to pH changes with a dynamic range centered at 7.8?±?0.1 and 9.6?±?0.2, for PCL and PLGA respectively. NFSs exhibited multiple cycles of reversibility with a lifetime of at least 15 days with preservation of response characteristics. By comparing the two NFSs, we found PCL-NFSs are more suitable for pH sensing due to their dynamic range and superior reversibility.The proposed sensing platform successfully exhibits a response to pH and compatibility with cultured cells. NSFs will be a useful tool for creating 3D cellular scaffolds that can monitor the cellular environment with applications in fields such as drug discovery and tissue engineering.