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1.
The mechanical strength of polymer scaffold is closely related to its crystallinity. In this work, cellulose nanocrystals (CNC) were incorporated into poly-l-lactide (PLLA) scaffold which was fabricated by selective laser sintering, aiming to improve the mechanical properties. CNC possesses numerous hydroxyl groups which might form hydrogen bond with PLLA molecular chains. The hydrogen bond induces the ordered arrangement of PLLA chain by using CNC as heterogeneous nucleating agent, thereby increasing crystallization rate and crystallinity. Results showed that PLLA scaffolds with 3 wt% CNC resulted in 191%, 351%, 34%, 83.5%, 56% increase in compressive strength, compressive modulus, tensile strength, tensile modulus and Vickers hardness, respectively. Encouragingly, with the incorporation of hydrophilic CNC, the PLLA/CNC scaffolds showed not only better hydrophilicity, but also faster degradation than PLLA. In vitro cell culture studies proved that the PLLA/CNC scaffolds were biocompatible and capable of supporting cell adhesion, proliferation and differentiation. The above results indicated that the PLLA/CNC scaffolds may therefore be a potential replacement in bone repair.  相似文献   

2.
A hybrid hydrogel composed of solid lipid nanoparticles (LNPs) entrapped within chemically cross‐linked carboxymethylcellulose (CMC) is developed to achieve localized and sustained release of lipophilic drugs. The analysis of LNP stability as well as the hydrogel swelling and mechanical properties confirm the successful incorporation of particles up to a concentration of 50% w/wCMC. The initial LNP release rate can be prolonged by increasing the particle diameter from 50 to 120 nm, while the amount of long‐term release can be adjusted by tailoring the particle surface charge or the cross‐linking density of the polymer. After 30 d, 58% of 50 nm diameter negatively charged LNPs escape from the matrix while only 17% of positively charged nanoparticles are released from materials with intermediate cross‐linking density. A mathematical diffusion model based on Fick's second law is efficient to predict the diffusion of the particles from the hydrogels.  相似文献   

3.
Current therapeutic interventions in bone defects are mainly focused on finding the best bioactive materials for inducing bone regeneration via activating the related intracellular signaling pathways. Integrins are trans‐membrane receptors that facilitate cell‐extracellular matrix (ECM) interactions and activate signal transduction. To develop a suitable platform for supporting human bone marrow mesenchymal stem cells (hBM‐MSCs) differentiation into bone tissue, electrospun poly L‐lactide (PLLA) nanofiber scaffolds were coated with nano‐hydroxyapatite (PLLA/nHa group), gelatin nanoparticles (PLLA/Gel group), and nHa/Gel nanoparticles (PLLA/nHa/Gel group) and their impacts on cell proliferation, expression of osteoblastic biomarkers, and bone differentiation were examined and compared. MTT data showed that proliferation of hBM‐MSCs on PLLA/nHa/Gel scaffolds was significantly higher than other groups (P < .05). Alkaline phosphatase activity was also more increased in hBM‐MSCs cultured under osteogenic media on PLLA/nHa/Gel scaffolds compared to others. Gene expression evaluation confirmed up‐regulation of integrin α2β1 as well as the osteogenic genes BGLAP, COL1A1, and RUNX2. Following use of integrin α2β1 blocker antibody, the protein level of integrin α2β1 in cells seeded on PLLA/nHa/Gel scaffolds was decreased compared to control, which confirmed that most of the integrin receptors were bound to gelatin molecules on scaffolds and could activate the integrin α2β1/ERK axis. Collectively, PLLA/nHa/Gel scaffold is a suitable platform for hBM‐MSCs adhesion, proliferation, and osteogenic differentiation in less time via activating integrin α2β1/ERK axis, and thus it might be applicable in bone tissue engineering.  相似文献   

4.
We described the curcumin‐loaded biodegradable polyurethane (PU) scaffolds modified with gelatin based on three‐dimensional (3D) printing technology for potential application of cartilage regeneration. The printing solution of poly(ε‐caprolactone) (PCL) triol (polyol) and hexamethylene diisocyanate (HMDI) in 2,2,2‐trifluoroethanol was printed through a nozzle in dimethyl sulfoxide phase with or without gelatin. The weight ratio of HMDI against PCL triol was varied as 3, 5, and 7 in order to evaluate its effect on the mechanical properties and biodegradation rate. A higher ratio of HMDI resulted in higher mechanical properties and a lower biodegradation rate. The use of gelatin increased the mechanical properties, biodegradation rate, and curcumin release due to the surface cross‐linking, nanoporous structure, and surface hydrophilicity of the scaffolds. In vitro study revealed that the released curcumin enhanced the proliferation and differentiation of chondrocyte. The 3D‐printed biodegradable PU scaffold modified with gelatin should thus be considered as a potential candidate for cartilage regeneration.  相似文献   

5.
A three‐layered fibrous scaffold composed of fibers of different diameters in each layer was fabricated in correspondence with the structure of the blood vessels. Effect of solution and electrospinning parameters on morphology and diameters of the fibers were investigated by scanning electron microscopy (SEM), for each layer. The SEM images showed that 18% poly (lactic‐co‐glycolic acid) (PLGA)‐gelatin‐chitosan in 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP)/acid acetic solution resulted in bead‐free fibers for the outer layer. For the middle layer, 18% PLGA‐gelatin in HFIP at 13 kV with 13 cm needle to collector distance was chosen as the optimum condition. SEM imaging demonstrated that by increasing graphene content from 0.5 to 2 wt% in the inner layer (as an electrically conductive/platelet anti‐adhesion material), the fiber diameter decreased from 324.01 ± 58.90 to 288.59 ± 70.77 nm. The effect of gelatin crosslinking on the microstructure of the fibers was also examined. Shrinkage ratio decreased from 57 to below 21% upon crosslinking of the three‐layered scaffold in exposure to vapor of 50% glutaraldehyde solution for 2 hours. Mechanical test showed that tensile strength of the crosslinked three‐layer scaffold in the longitudinal direction was 2.90 MPa which is comparable to that of the vein and artery. The MTT [3‐(4,5‐Dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide] assay displayed cell viability of above 96% for the PLGA‐gelatin containing 2 wt% graphene. SEM analysis revealed that the addition of graphene to PLGA‐gelatin (up to 2%) causes a remarkable improvement in cell adhesion.  相似文献   

6.
Self‐healing hydrogels have been studied by many researchers via multiple cross‐linking approaches including physical and chemical interactions. It is an interesting project in multifunctional hydrogel exploration that a water soluble polymer matrix is cross‐linked by combining the ionic coordination and the multiple hydrogen bonds to fabricate self‐healing hydrogels with injectable property. This study introduces a general procedure of preparing the hydrogels (termed gelatin‐UPy‐Fe) cross‐linked by both ionic coordination of Fe3+ and carboxyl group from the gelatin and the quadruple hydrogen bonding interaction from the ureido‐pyrimidinone (UPy) dimers. The gelatin‐UPy‐Fe hydrogels possess an excellent self‐healing property. The effects of the ionic coordination of Fe3+ and quadruple hydrogen bonding of UPy on the formation and mechanical behavior of the prepared hydrogels are investigated. In vitro drug release of the gelatin‐UPy‐Fe hydrogels is also observed, giving an intriguing glimpse into possible biological applications.

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7.
The dynamic covalent characteristics of oxime and boronate ester bonds have been explored. A small excess of a competing aldehyde under acidic conditions resulted in oxime polymer degradation from high molecular weights (30 kDa) to low molecular weight oligomers (2.2 kDa). The dynamic nature of oxime bonds imparts oxime cross‐linked hydrogels with self‐healing properties and the incorporation of phenyl boronic acid groups into the hydrogel network provides a platform for hydrogel functionalization. The addition of a polyphenol (tannic acid) proves a facile means to incorporate a second, dynamic covalent cross‐linking network through boronate ester formation which, owing to the increase in the degree of cross‐linking, is found to be nearly double the hydrogel strength (storage modulus increased from 4.6 to 8.5 kPa). Finally, the tannic acid cross‐linking network is selectively degraded returning the hydrogel storage modulus to its initial value and providing a means for the synthesis of materials with tunable mechanical properties.

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8.
Sugarcane bagasse was used as a cellulose resource, and the transparent cellulose hydrogel films were obtained from the purified cellulose by phase inversion process without chemical cross‐linking, when the dissolved cellulose in lithium chloride/N,N‐dimethyl acetamide was transformed into the solid film. On these processes, bagasse was pre‐treated by 10 wt% sodium hydroxide in the absence and presence of bleaching of 10 vol% sodium hypochlorite (NaOCl) solution in order to obtain cellulose fibers. Here, the bleaching temperature was varied from 40 to 50°C. The effect of pre‐treatment conditions on the resultant cellulose solution and hydrogel films was investigated. It was seen that strong bleaching removed most of lignin component from the bagasse. However, viscosity and size exclusion chromatogram of the cellulose indicated that this operation decreased average molecular weight of the cellulose fibers from 2.1 × 106 to 4.8 × 105. These property changes of fibers also caused increase of water content and weakening of mechanical strength of the resultant hydrogels. In addition, scanning probe microscopy in wet state revealed that the porous fiber network structure in the hydrogel was greatly influenced by bleaching with NaOCl. The average pore size of fiber network was decreased from 8.1 to 5.9 nm as the NaOCl treatment was at 50°C, because of expanded fibers in the swollen hydrogel. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

9.
Self‐healing hydrogel such as polyacrylic acid (PAA) hydrogel has attracted increasing attention based on its promising potential applications. However, it usually suffers from low strength especially as mechanical device. Herein, a commercial microcrystalline cellulose (MCC) was modified with acrylamide to graft polyacrylamide (PAM) chains on the particle surface. The acrylamide‐modified MCC (AM‐MCC) was then dispersed in monomer solution of acrylic acid to prepare composite hydrogel. The mechanical properties of the obtained composite hydrogels and the self‐healed hydrogels were carefully measured by compressive and tensile tests, and by dynamic mechanical analysis. Our results demonstrate that introduction of a small amount of AM‐MCC such as 3 wt% can not only reinforce the original hydrogel and the healed hydrogel markedly, but also improve self‐healing efficiency obviously. The analyses indicate that in addition to the reversible multi‐interactions such as hydrogen bonding and ionic interactions, the entanglements between the PAA chains of the hydrogel matrix and the PAM chains grafted on the MCC particles have also played an important role on the improvement in mechanical performances and the healing ability of the hydrogel. Moreover, the responsiveness to exterior ion has been tested to indicate potential application of the composite hydrogel as self‐healable sensor.  相似文献   

10.
Starburst triblock copolymers consisting of 8‐arm poly(ethylene glycol) (8‐arm PEG) and biodegradable poly(L ‐lactide) (PLLA) or its enantiomer poly(D ‐lactide) (PDLA), 8‐arm PEG‐b‐PLLA‐b‐PEG ( Stri‐L ), and 8‐arm PEG‐b‐PDLA‐b‐PEG ( Stri‐D ) were synthesized. An aqueous solution of a 1:1 mixture ( Stri‐Mix ) of Stri‐L and Stri‐D assumed a sol state at room temperature, but instantaneously formed a physically crosslinked hydrogel in response to increasing temperature. The resulting hydrogel exhibited a high‐storage modulus (9.8 kPa) at 37 °C. Interestingly, once formed at the transition temperature, the hydrogel was stable even after cooling below the transition temperature. The hydrogel formation process was irreversible because of the formation of stable stereocomplexes. In aqueous solution, gradual hydrolytic erosion was observed because of degradation of the hydrogel. The combination of rapid temperature‐triggered irreversible hydrogel formation, high‐mechanical strength, and degradation behavior render this polymer mixture system suitable for use in injectable biomedical materials, for example, as a drug delivery system for bioactive reagents or a biodegradable scaffold for tissue engineering. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6317–6332, 2008  相似文献   

11.
Current materials used for bone regeneration are usually bioactive ceramics or glasses. Although they bond to bone, they are brittle. There is a need for new materials that can combine bioactivity with toughness and controlled biodegradation. Sol‐gel hybrids have the potential to do this through their nanoscale interpenetrating networks (IPN) of inorganic and organic components. Poly(γ‐glutamic acid) (γ‐PGA) was introduced into the sol‐gel process to produce a hybrid of γ‐PGA and bioactive silica. Calcium is an important element for bone regeneration but calcium sources that are used traditionally in the sol‐gel process, such as Ca salts, do not allow Ca incorporation into the silicate network during low‐temperature processing. The hypothesis for this study was that using calcium methoxyethoxide (CME) as the Ca source would allow Ca incorporation into the silicate component of the hybrid at room temperature. The produced hybrids would have improved mechanical properties and controlled degradation compared with hybrids of calcium chloride (CaCl2), in which the Ca is not incorporated into the silicate network. Class II hybrids, with covalent bonds between the inorganic and organic species, were synthesised by using organosilane. Calcium incorporation in both the organic and inorganic IPNs of the hybrid was improved when CME was used. This was clearly observed by using FTIR and solid‐state NMR spectroscopy, which showed ionic cross‐linking of γ‐PGA by Ca and a lower degree of condensation of the Si species compared with the hybrids made with CaCl2 as the Ca source. The ionic cross‐linking of γ‐PGA by Ca resulted in excellent compressive strength and reduced elastic modulus as measured by compressive testing and nanoindentation, respectively. All hybrids showed bioactivity as hydroxyapatite (HA) was formed after immersion in simulated body fluid (SBF).  相似文献   

12.
Development of high‐strength hydrogels has recently attracted ever‐increasing attention. In this work, a new design strategy has been proposed to prepare graphene oxide (GO)/polyacrylamide (PAM)/aluminum ion (Al3+)‐cross‐linked carboxymethyl hemicellulose (Al‐CMH) nanocomposite hydrogels with very tough and elastic properties. GO/PAM/Al‐CMH hydrogels were synthesized by introducing graphene oxide (GO) into PAM/CMH hydrogel, followed by ionic cross‐linking of Al3+. The nanocomposite hydrogels were characterized by means of FTIR, X‐ray diffraction (XRD), and scanning electron microscopy/energy‐dispersive X‐ray analysis (SEM‐EDX) along with their swelling and mechanical properties. The maximum compressive strength and the Young's modulus of GO3.5/PAM/Al‐CMH0.45 hydrogel achieved values of up to 1.12 and 13.27 MPa, increased by approximately 6488 and 18330 % relative to the PAM hydrogel (0.017 and 0.072 MPa). The as‐prepared GO/PAM/Al‐CMH nanocomposite hydrogels possess high strength and great elasticity giving them potential in bioengineering and drug‐delivery system applications.  相似文献   

13.
We present a novel approach to the fabrication of advanced polymeric nanocomposite hydrogels from polyacrylamide (PAAm) by incorporation of graphene‐silver‐polyethylenedioxythiophene‐polystyrene sulfonate (rGO‐Ag‐PEDOT/PSS) by photopolymerization method. Infrared spectroscopy was employed to characterize the structure of the hydrogels. The internal network structure of nanocomposite hydrogels was investigated by scanning electron microscope. Swelling, deswelling, and mechanical properties of the hydrogels were investigated. The compressive strength of nanocomposite hydrogels reaches maximum of 1.71 MPa when the ratio of rGO‐Ag‐PEDOT/PSS to PAAm was 0.3 wt%, which is 1.57 times higher than that of PAAm hydrogels (1.09 MPa). The electrical conductivity of the PAAm‐rGO‐Ag‐PEDOT/PSS hydrogel was found to be 3.91 × 10?5 S cm?1. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

14.
《先进技术聚合物》2018,29(4):1322-1333
This work aims to develop novel composites from a poly(L ‐lactide‐co‐trimethylene carbonate‐co‐glycolide) (PLTG) terpolymer and mesoporous silica (SBA‐15) nanofillers surface modified by post‐synthetic functionalization. SBA‐15 first reacts with a silane coupling agent, γ‐aminopropyl‐trimethoxysilane to introduce ammonium group. PLLA chains were then grafted on the surface of SBA‐15 through ammonium initiated ring‐opening polymerization of L ‐lactide. Composites were prepared via solution mixing of PLTG terpolymer and surface modified SBA‐15. The structures and properties of pure SBA‐15, γ‐aminopropyl‐trimethoxysilane modified SBA‐15 (H2N‐SBA‐15), PLLA modified SBA‐15 (PLLA‐NH‐SBA‐15), and PLTG/PLLA‐NH‐SBA‐15 composites were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, X‐ray diffraction, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, transmission electron microscopy, N2 adsorption‐desorption, differential scanning calorimetry, contact angle measurement, and mechanical testing. The results demonstrated that PLLA chains were successfully grafted onto the surface of SBA‐15 with grafting amounts up to 16 wt.%. The PLTG/PLLA‐NH‐SBA‐15 composites exhibit good mechanical properties. The tensile strength, Young's modulus, and elongation at break of the composite containing 5 wt.% of PLLA‐NH‐SBA‐15 were 39.9 MPa, 1.3 GPa, and 273.6%, respectively, which were all higher than those of neat PLTG or of the composite containing 5 wt.% of pure SBA‐15. Cytocompatibility tests showed that the composites present very low cytotoxicity.  相似文献   

15.
Nanocomposite hydrogels based on carbon nanotubes (CNTs) are known to possess remarkable stiffness, electrical, and thermal conductivity. However, they often make use of CNTs as fillers in covalently cross‐linked hydrogel networks or involve direct cross‐linking between CNTs and polymer chains, limiting processability properties. Herein, nanocomposite hydrogels are developed, in which CNTs are fillers in a physically cross‐linked hydrogel. Supramolecular nanocomposites are prepared at various CNT concentrations, ranging from 0.5 to 6 wt%. Incorporation of 3 wt% of CNTs leads to an increase of the material's toughness by over 80%, and it enhances electrical conductivity by 358%, compared to CNT‐free hydrogel. Meanwhile, the nanocomposite hydrogels maintain thixotropy and processability, typical of the parent hydrogel. The study also demonstrates that these materials display remarkable cytocompatibility and support cell growth and proliferation, while preserving their functional activities. These supramolecular nanocomposite hydrogels are therefore promising candidates for biomedical applications, in which both toughness and electrical conductivity are important parameters.  相似文献   

16.
Reverse osmosis (RO) membrane technology is widely employed to address the demands for freshwater. In this study, fabrication and performance evaluation of customized RO membranes comprised of Matrimid and polyacrylonitrile (PAN) is carried out. While exploring adoption of slip coating procedure, the effects of various modification techniques including incorporation of TiO2 nanoparticles and polyethylene glycol (PEG) into the skin layer as well as cross‐linking were investigated. The individual and combined effects of parameters on membrane morphology, surface characteristics and performance were also examined. Despite the distinctive characteristics of involved materials, delamination‐free composite membranes were successfully formed with an intimate contact at the interface of two layers. The results also indicated that increasing concentration of Matrimid in dope solution led to increase in membrane thickness and consequently decline in water flux. In the best case, membrane prepared using 1 wt.% Matrimid in dope exhibited water flux of 0.98 LMH and NaCl rejection of 95.7%. Also, incorporation of 3 wt.% TiO2 nanoparticles offered membranes with improved water flux of 1.37 LMH and salt rejection of 95.8%. On the other hand, water flux and salt rejection in membranes containing 5 wt.% PEG were 1.18 LMH and 96.2%, respectively. The co‐presence of both nanoparticles and PEG provided more insights about the contributing factors in tuned membranes. Modification of skin layer by cross‐linking significantly improved salt rejection at the expense of water flux. The results are scientifically interpreted and compared to the values reported in literature.  相似文献   

17.
Bone‐derived extracellular matrix (ECM) is widely used in studies on bone regeneration because of its ability to provide a microenvironment of native bone tissue. However, a hydrogel, which is a main type of ECM application, is limited to use for bone graft substitutes due to relative lack of mechanical properties. The present study aims to fabricate a scaffold for guiding effective bone regeneration. A polycaprolactone (PCL)/beta‐tricalcium phosphate (β‐TCP)/bone decellularized extracellular matrix (dECM) scaffold capable of providing physical and physiological environment are fabricated using 3D printing technology and decoration method. PCL/β‐TCP/bone dECM scaffolds exhibit excellent cell seeding efficiency, proliferation, and early and late osteogenic differentiation capacity in vitro. In addition, outstanding results of bone regeneration are observed in PCL/β‐TCP/bone dECM scaffold group in the rabbit calvarial defect model in vivo. These results indicate that PCL/β‐TCP/bone dECM scaffolds have an outstanding potential as bone graft substitutes for effective bone regeneration.  相似文献   

18.
A blend of two biodegradable and semi‐crystalline polymers, poly (L‐lactic acid) (PLLA; 70 wt%) and poly (butylene succinate‐co‐L‐lactate) (PBSL; 30 wt%), was prepared in the presence of various polyethylene oxide‐polypropylene oxide‐polyethylene oxide (PEO‐PPO‐PEO) triblock copolymer contents (0.5, 1, 2 wt%). Mechanical, thermal properties, and Fourier transform infrared (FTIR) analysis of the blends were investigated. It was found that the addition of copolymer to PLLA/PBSL improved the fracture toughness of the blends as shown by mode I fracture energies. It was supported by morphological analysis where the brittle deformation behavior of PLLA changed to ductile deformation with the presence of elongated fibril structure in the blend with copolymer system. The glass transition temperature (Tg), melting temperature (Tm) of PLLA, and PBSL shift‐closed together indicated that some compatibility exists in the blends. In short, PEO‐PPO‐PEO could be used as compatibilizer to improve the toughness and compatibility of the PLLA/PBSL blends. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

19.
Natural and synthetic cross‐linked polymers allow the improvement of cytocompatibility and mechanical properties of the individual polymers. In osteochondral lesions of big size it will be required the use of scaffolds to repair the lesion. In this work a borax cross‐linked scaffold based on fumarate‐vinyl acetate copolymer and chitosan directed to osteochondrondral tissue engineering is developed. The cross‐linked scaffolds and physical blends of the polymers are analyzed in based on their morphology, glass transition temperature, and mechanical properties. In addition, the stability, degradation behavior, and the swelling kinetics are studied. The results demonstrate that the borax cross‐linked scaffold exhibits hydrogel behavior with appropriated mechanical properties for bone and cartilage tissue regeneration. Bone marrow progenitor cells and primary chondrocytes are used to demonstrate its osteo‐ and chondrogenic properties, respectively, assessing the osteo‐ and chondroblastic growth and maturation, without evident signs of cytotoxicity as it is evaluated in an in vitro system.

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20.
A binary poly(L ‐lactide)/poly(ε‐caprolactone) (PLLA/PCL) (70/30 w/w) blend and a ternary PLLA/PCL/PLLA‐PCL‐PLLA blend of the same composition which contains 4 wt.‐% of a triblock PLLA‐PCL‐PLLA copolyester as compatibilizing agent were prepared by melt mixing at 200°C. Investigation of the thermal and mechanical properties of the blends and scanning electron microscopy of their fracture surfaces showed in the case of the ternary blend a better state of dispersion of PCL in the PLLA matrix and an improved toughness.  相似文献   

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