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Microstructural Evolution of Poly(?-Caprolactone), Its Immiscible Blend, and In Situ Generated Nanocomposites.

ABSTRACT: Polymer-polymer systems with special phase morphology were prepared, leading to an exceptional combination of strength, modulus, and ductility. Two immiscible polymers: poly(?-caprolactone) (PCL) and polyhydroxyalkanoate (PHA) were used as components for manufacturing a nanoblend and a nanocomposite characterized by nanodroplet-matrix and nanofibril-matrix morphologies, respectively. Nanofibrils were formed by high shear of nanodroplets at sufficiently low temperature to stabilize their fibrillar shape by shear-induced crystallization. The effects of nanodroplet vs. nanofiber morphology on the tensile mechanical behavior of the nanocomposites were elucidated with the help of in situ 2D small-angle X-ray scattering, microcalorimetry and 2D wide-angle X-ray diffraction. For neat PCL and a PCL/PHA blend, the evolution of the structure under uniaxial tension was accompanied by extensive fragmentation of crystalline lamellae with the onset at strain e = 0.1. Limited lamellae fragmentation in the PCL/PHA composite occurred continuously over a wide range of deformations (e = 0.1-1.1) and facilitated plastic flow of the composite and was associated with the presence of a PHA nanofiber network that transferred local stress to the PCL lamellae, enforcing their local deformation. The PHA nanofibers acted as crystallization nuclei for PCL during their strain-induced melting-recrystallization.

SUBMITTER: Vozniak I

PROVIDER: S-EPMC7694185 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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Microstructural Evolution of Poly(ε-Caprolactone), Its Immiscible Blend, and In Situ Generated Nanocomposites.

Vozniak Iurii I Hosseinnezhad Ramin R Morawiec Jerzy J Galeski Andrzej A

Polymers 20201104 11

Polymer-polymer systems with special phase morphology were prepared, leading to an exceptional combination of strength, modulus, and ductility. Two immiscible polymers: poly(ε-caprolactone) (PCL) and polyhydroxyalkanoate (PHA) were used as components for manufacturing a nanoblend and a nanocomposite characterized by nanodroplet-matrix and nanofibril-matrix morphologies, respectively. Nanofibrils were formed by high shear of nanodroplets at sufficiently low temperature to stabilize their fibrilla ...[more]

PMID: 33158123

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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(ε-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 in vitro 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:Vascular endothelial growth factor (VEGF) is the major regulating factor for the formation of new blood vessels, also known as angiogenesis. VEGF is often incorporated in synthetic scaffolds to promote vascularization and to enhance the survival of cells that have been seeded in these devices. Such applications require sustained local delivery of VEGF of around 4 weeks for stable blood vessel formation. Most delivery systems for VEGF only provide short-term release for a couple of days, followed by a release phase with very low VEGF release. We now have developed VEGF-loaded polymeric microspheres that provide sustained release of bioactive VEGF for 4 weeks. Blends of two swellable poly(ε-caprolactone)-poly(ethylene glycol)-poly(ε-caprolactone)-b-poly(l-lactide) ([PCL-PEG-PCL]-b-[PLLA])-based multiblock copolymers with different PEG content and PEG molecular weight were used to prepare the microspheres. Loading of the microspheres was established by a solvent evaporation-based membrane emulsification method. The resulting VEGF-loaded microspheres had average sizes of 40-50 μm and a narrow size distribution. Optimized formulations of a 50:50 blend of the two multiblock copolymers had an average VEGF loading of 0.79 ± 0.09%, representing a high average VEGF loading efficiency of 78 ± 16%. These microspheres released VEGF continuously over 4 weeks in phosphate-buffered saline pH 7.4 at 37 °C. This release profile was preserved after repeated and long-term storage at -20 °C for up to 9 months, thereby demonstrating excellent storage stability. VEGF release was governed by diffusion through the water-filled polymer matrix, depending on PEG molecular weight and PEG content of the polymers. The bioactivity of the released VEGF was retained within the experimental error in the 4-week release window, as demonstrated using a human umbilical vein endothelial cells proliferation assay. Thus, the microspheres prepared in this study are suitable for embedment in polymeric scaffolds with the aim of promoting their functional vascularization.

Project description:This research investigates the accelerated hydrolytic degradation process of both anatomically designed bone scaffolds with a pore size gradient and a rectangular shape (biomimetically designed scaffolds or bone bricks). The effect of material composition is investigated considering poly-ε-caprolactone (PCL) as the main scaffold material, reinforced with ceramics such as hydroxyapatite (HA), β-tricalcium phosphate (TCP) and bioglass at a concentration of 20 wt%. In the case of rectangular scaffolds, the effect of pore size (200 μm, 300 μm and 500 μm) is also investigated. The degradation process (accelerated degradation) was investigated during a period of 5 days in a sodium hydroxide (NaOH) medium. Degraded bone bricks and rectangular scaffolds were measured each day to evaluate the weight loss of the samples, which were also morphologically, thermally, chemically and mechanically assessed. The results show that the PCL/bioglass bone brick scaffolds exhibited faster degradation kinetics in comparison with the PCL, PCL/HA and PCL/TCP bone bricks. Furthermore, the degradation kinetics of rectangular scaffolds increased by increasing the pore size from 500 μm to 200 μm. The results also indicate that, for the same material composition, bone bricks degrade slower compared with rectangular scaffolds. The scanning electron microscopy (SEM) images show that the degradation process was faster on the external regions of the bone brick scaffolds (600 μm pore size) compared with the internal regions (200 μm pore size). The thermal gravimetric analysis (TGA) results show that the ceramic concentration remained constant throughout the degradation process, while differential scanning calorimetry (DSC) results show that all scaffolds exhibited a reduction in crystallinity (Xc), enthalpy (Δm) and melting temperature (Tm) throughout the degradation process, while the glass transition temperature (Tg) slightly increased. Finally, the compression results show that the mechanical properties decreased during the degradation process, with PCL/bioglass bone bricks and rectangular scaffolds presenting higher mechanical properties with the same design in comparison with the other materials.

Dataset Information

Microstructural Evolution of Poly(?-Caprolactone), Its Immiscible Blend, and In Situ Generated Nanocomposites.

Publications

Microstructural Evolution of Poly(ε-Caprolactone), Its Immiscible Blend, and In Situ Generated Nanocomposites.

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