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The modification of epoxy composites through the construction of nanostructures via self-organization of block copolymers has become a hot topic. In this research, high toughness epoxy thermoset was prepared through constructing wormlike-nanostructure by incorporating amphiphilic polydimethylsiloxane-block-poly(ε-caprolactone) block copolymer. The fracture toughness of subsequent epoxy thermosets increased nearly 355% comparing with neat epoxy with the addition of 40 wt % wormlike nanostructure, which was higher than that of thermosets with spherical nanostructure (142%). There was obviously plastic deformation in fractured surfaces of thermosets with wormlike nanostructure, it is believed that a combination of several toughening mechanisms leads to the improvement in fracture toughness. The morphologies transition, dynamic mechanical properties and wetting behavior of the thermoset containing spherical/wormlike nanostructures are also reported.
Burns on human skin often leads to slow recovery because of continuous wound infections caused by the loss of skin protection. In this study, a seed-free soaking method is put forward to prepare PCL@ZIF-8/εPL nanofibers as a dressing for burn wounds. This ZIF-8-coated polycaprolactone (PCL) fiber exhibits increased specific surface area, significantly increasing the polypeptide loading of epsilon polylysine (εPL) from 12 to 20 wt.%. The antibacterial experiment found that ZIF-8 and εPL exhibited dual antibacterial properties, and after εPL was loaded to ZIF-8, the nanofiber demonstrated stronger antibacterial properties that can better kill the remaining tenacious bacteria. This high-efficiency bactericidal property, combined with the ability to protect wounds from common infections by bacteria in the air, would promote wound healing, shortening the healing time period from 24 to 17 days. Further tissue sections confirm that the shielding effect and dual antibacterial properties of the composite fiber membrane are the reasons behind the acceleration of the healing of burns and scalds. Shielding and antibacterial material are helpful for the treatment of burns and scalds, and it may also guide the treatment of other types of wounds.
Mesoporous bioactive glass (MBG) is a potential biomedical material in bone defect repairment because of its bioactivity, biocompatibility, and osteoinduction properties. Here we report that Mg-doped MBG scaffold with 3:1 Ca/Mg ratio (MBG-Ca/Mg-3) is good for MC3T3-E1 osteoblast differentiation and mineralization. Mimicking bone extracellular matrix structure by electrospinning, we used MBG-Ca/Mg-3 adsorbed with Osteocalcin-Osteopontin-Biglycan (OOB), a new unique matrix fusion protein, to form [email protected] /Mg-3 scaffold, which has multifunctional ability in calvarial bone defect repairment in vivo . Intriguingly, we found that [email protected] /Mg-3 scaffold increases the expression of osteoblastic marker genes, including bone morphogenetic protein ( Bmp2 ), osteopontin ( Opn ), Osterix , Runx2 through activation of ERK1/2. We concluded that [email protected] /Mg-3 scaffold promotes osteoblast differentiation and mineralization through ERK1/2 pathway and it can also enhance bone formation in vivo , which provides a new biomaterial in bone tissue engineering.
Electrospun nanofiber membranes have been widely used for guided bone regeneration (GBR). For assistance in bone healing, photothermal therapy which renders moderate heat stimulation to defect regions by near-infrared (NIR) light irradiation has attracted much attention in recent years. Combined with photothermal therapy, novel electrospun poly(ε-caprolactone)/molybdenum disulfide (PCL/MoS 2 ) nanofiber membranes are innovatively synthesized as GBR for bone therapy, wherein the exfoliated MoS 2 nanosheets served as osteogenic enhancers and NIR photothermal agents. With the doping of MoS 2 , the mechanical properties of nanofiber membranes got improved with the degradation unaffected. The composite PCL/MoS 2 membranes show enhanced cell growth and osteogenic performance compared with PCL alone. Under NIR-triggered mild photothermal therapy, osteogenesis and bone healing are accelerated by using PCL/MoS 2 nanofiber membranes for growth of bone mesenchymal stem cells in vitro and repair of rat tibia bone defect in vivo. The novel nanofiber membranes may be developed as intelligent GBR in the therapy of bone defects.
Making artificial bile ducts in vitro for repairing and replacing diseased bile ducts is an important concept in tissue engineering. This study printed a tubular composite scaffold using polycaprolactone (PCL) through the current 3D printing method. It served as a matrix for the organoid cells of the bile duct to proliferation, migration, and differentiation. The PCL scaffold full of bile duct-like organ cells can achieve the effect of bionics, replacing the original bile duct to perform its proper function. In order to enrich the performance of the tubular scaffold, hydrogels were also used in this study. Applying a layer of gelatin methacryloyl (GelMA) hydrogel with an appropriate thickness on the outer layer of the PCL scaffold not only protects and supports the scaffold, but also improves the biocompatibility of the printed bile duct. In addition, ultrasmall superparamagnetic iron oxide (USPIO) nanoparticles dispersed in GelMA served as the contrast agent to monitor the repair of the lesion site and the degradation of the bile duct in real time by magnetic resonance imaging (MRI). In this study, a tubular composite scaffold that could reconstruct bile duct function and possess a real-time MRI imaging property was constructed by 3D printing. After 13 days of the co-culture of bone marrow derived stem cells (BMSCs), the survival rate of the BMSCs was greater than 95%, and the coverage of the BMSCs was as high as 90%. At the same time, the compression modulus of the stent could reach 17.41 kPa and the Young's modulus could reach 5.03 kPa. Thus, the mechanical properties of it can meet the needs of human implantation. USPIO can achieve MRI imaging in situ and nondestructively monitor the degradation of the stent in the body. In summary, PCL/GelMA/USPIO bile duct scaffolds are beneficial to the proliferation of cells on the scaffolds and can be used to construct biologically active artificial bile ducts.
6-Gingerol, an active herbal ingredient of ginger has various bioactivities such as anti-neurodegenerative disease, anti-inflammatory and so on. The aim of the present study was to enhance the oral bioavailability and brain distribution of 6-Gingerol via polymeric micelles. A polymeric micelles drug delivery system of 6-Gingerol consisting of D-α-Tocopheryl polyethylene glycol 1000 succinate (TPGS) and Poly (ethylene glycol)-poly (ε-caprolactone) (PEG-PCL) was prepared via solvent injection method. The developed 6-Gingerol-loaded TPGS/PEG-PCL micelles (6-GTPMs) were characterized based on particle size, polydispersity index (PDI), zeta potential, encapsulation efficiency (EE), drug loading (DL) and in vitro release profile. The pharmacokinetics and tissue distribution studies were also evaluated. The nanoformulation produced a particle size of 73.24 ± 2.84 nm with acceptable PDI (0.129 ± 0.03), zeta potential (−2.74 ± 0.92 mV), DL (4.64%) and EE (79.68%). The in vitro release profile showed that the 6-GTPMs enhanced the solubility of 6-Gingerol, while the pharmaceutical analysis in rats indicated that 6-GTPMs significantly improved the oral bioavailability of 6-Gingerol (about 3 folds) in circulation. The 6-GTPMs exhibited remarkable brain targetability in the tissue distribution analysis. Collectively, a 6-Gingerol polymeric micelle with enhanced oral bioavailability coupled with excellent brain distribution was successfully developed.
The application of a three-dimensional (3D)-printed biological functional scaffold in the repair of bone defects is a promising strategy. In this study, strontium-containing hydroxyapatite (SrHA) powder was synthesized by the hydrothermal method, and then poly(ε-caprolactone) (PCL)/HA and PCL/SrHA composite scaffolds were prepared by the high-temperature melt extrusion 3D printing technology. The basic physical and chemical properties, in vitro biological properties, osteogenesis, and angiogenesis abilities of the scaffold were studied. The results showed that HA and SrHA were uniformly embedded in the composite scaffold, and the scaffold exhibited a 3D interconnected porous structure and rough microsurface. The in vitro release curve showed that Sr2+ and Ca2+ were continuously released from the PCL/SrHA scaffold. In order to verify the performance of the composite scaffold in bone regeneration, the proliferation and osteogenic differentiation of mouse embryonic osteoblasts (MC3T3E1) grown on the scaffold were evaluated. The experimental results showed that the incorporation of SrHA significantly promoted cell proliferation. Compared with the PCL/HA scaffold, the PCL/SrHA scaffold could better promote cell osteogenic differentiation. Deferoxamine (DFO) was loaded on the surface of the PCL/SrHA scaffold. By studying the proliferation, angiogenesis, and expression of osteogenesis and angiogenesis-related genes of human umbilical vein endothelial cells (HUVECs) on PCL/SrHA@DFO scaffold, it was verified that DFO had the ability to promote angiogenesis. It could induce angiogenesis in vitro in combination with Sr2+. Therefore, we believe that the composite scaffold has potential application prospects in the field of bone tissue engineering.
Biodegradable composites from starch and hydrophobic polymer usually show poor compatibility. A novel p -phthaloyl chloride-based prepolymer (PCP) compatibilizer based on p -phthaloyl chloride and polycaprolactone (PCL) diol (2000) was synthesized successfully and the chemical structure was characterized by Fourier transform infrared spectra and 1 H nuclear magnetic resonance (NMR). The PCP compatiblizer was mixed with starch granules to form a coating layer, and then the coated starch granules were melt-compounded with PCL plastic to prepare compatible starch-PCL composites with enhanced properties. The structural, mechanical, thermal properties, and water absorption of the composites were then investigated. It was found that the composites containing the PCP compatibilizer showed better interfacial interaction and compatibility between starch and PCL domains compared to the pure starch-PCL composite, which led to the improved mechanical properties of the composites. The results were attributed to the ester linkage between the PCP compatibilizer and starch as well as the strong physical crosslinking between the PCP compatibilizer and PCL plastic through PCL-PCL crystallinity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45400.
Constructing biomimetic structure and incorporating bioactive molecules is an effective strategy to achieve a more favorable cell response. To explore the effect of electrospinning (ES) nanofibrous architecture and collagen I (COL I)-incorporated modification on tuning osteoblast response, a resorbable membrane composed of poly(lactic-co-glycolic acid)/poly(caprolactone) (PLGA/PCL; 7:3 w/w) was developed via ES. COL I was blended into PLGA/PCL solution to prepare composite ES membrane. Notably, relatively better cell response was delivered by the bioactive ES-based membrane which was fabricated by modification of 3,4-dihydroxyphenylalanine and COL I. After investigation by field emission scanning electron microscopy, Fourier transform infrared spectroscopy, contact angle measurement, and mechanical test, polyporous three-dimensional nanofibrous structure with low tensile force and the successful integration of COL I was obtained by the ES method. Compared with traditional PLGA/PCL membrane, the surface hydrophilicity of collagen-incorporated membranes was largely enhanced. The behavior of mouse preosteoblast MC3T3-E1 cell infiltration and proliferation on membranes was studied at 24 and 48 hours. The negative control was fabricated by solvent casting. Evaluation of cell adhesion and morphology demonstrated that all the ES membranes were more favorable for promoting the cell adhesion and spreading than the casting membrane. Cell Counting Kit-8 assays revealed that biomimetic architecture, surface topography, and bioactive properties of membranes were favorable for cell growth. Analysis of β1 integrin expression level by immunofluorescence indicated that such biomimetic architecture, especially COL I-grafted surface, plays a key role in cell adhesion and proliferation. The real-time polymerase chain reaction suggested that both surface topography and bioactive properties could facilitate the cell adhesion. The combined effect of biomimetic architecture with enhanced surface activity by 3,4-dihydroxyphenylalanine-assisted modification and COL I incorporation of PLGA/PCL electrospun membranes could successfully fill osteogenic defects and allow for better cell proliferation and differentiation.
Fluorescent block amphiphilic copolymers are one of the most important bioimaging materials which are highly desirable for early stage cancer diagnosis and treatment. However, sometimes the application of the fluorescent block copolymers is severely limited because of the aggregation-caused quenching (ACQ) effect. In this study, new aggregation induced emission polymer dots (AIE Pdots) were prepared through a self-assembly process by using an AIE-conjugated block copolymer containing an AIE fluorophore, 9,10-bis(4-hydroxystyryl)anthracene, hydrophobic poly(ε-caprolactone) segments, hydrophilic poly(ethylene glycol) segments and folate groups. The AIE Pdots are monodispersed in H2O with an average diameter of 15 nm, and possess strong emission and high solid state fluorescence quantum efficiency (Φ = 27.0%). Furthermore, the AIE Pdots show good stability and little toxicity to living cells and thus can be utilized for targeted HeLa cell imaging. Biological imaging investigation indicated that the folic acid functionalized AIE Pdots can be applied for targeted HeLa intracellular imaging.
Fresh pork is easily contaminated by microorganisms, leading to spoilage. Dielectric barrier discharge (DBD) cold plasma technology has shown significant advantages in the preservation of meat. However, severe lipid oxidation of pork resulting from DBD treatment greatly limits its development. Herein, the antibacterial D@MSNs-P/PCL nanofiber membranes were prepared by modification polycaprolactone (PCL) with pre-reported nanomaterials (D@MSNs-P) through electrostatic spinning. Compared with the PCL membranes, the D@MSNs-P/PCL membranes showed better water stability, lower water vapor transmission rate, stronger hydrophobicity, and potent antibacterial activity. The D@MSNs-P/PCL membranes can be used for wrapping fresh pork before treatment with DBD plasma, which can not only improve the antibacterial efficiency but effectively inhibit the lipid oxidation and color change of fresh pork, extending the shelf life for 2 days. The developed D@MSNs-P/PCL membranes can also be used alone to preserve other fresh meat or oily food, with a wide range of application prospects.
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