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1.
Chitosan‐graft‐poly(ϵ‐caprolactone) was prepared via the ring‐opening graft polymerization of ϵ‐caprolactone (CL) through chitosan with 4‐dimethylaminopyridine as a catalyst and water as a swelling agent. The graft content of PCL within the graft copolymer was adjusted by the feed ratio of CL to chitosan, and the highest grafting concentration of PCL was up to about 400%. Fourier transform infrared, 1H NMR, and two‐dimensional heteronuclear single quantum coherence analyses indicated that the amino group (NH2 CH‐2) of chitosan initiated the graft polymerization of CL through the backbone of chitosan, and the hydroxyl group (HO CH2–6) of chitosan did not participate in initiating the graft polymerization. The percentage of amino groups initiating the graft polymerization decreased with an increasing molar ratio of CL to chitosan in the feed, and this was attributed to the fact that the graft polymerization system increasingly became heterogeneous with an increasing feed ratio of CL to chitosan. The physical properties of the graft copolymers were characterized by thermogravimetric analysis and wide‐angle X‐ray diffraction, respectively. These suggested that the introduction of PCL grafts through the chitosan backbone would to some extent destroy the crystalline structure of chitosan, and the PCL grafts existed in an amorphous structure. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5353–5361, 2006  相似文献   

2.
In this study, a three layered poly (ε‐caprolactone) (PCL) graft (tPCL) was fabricated by electrospinning PCL and electrospraying poly (ethylene oxide) (PEO), which has a thin dense inner layer, a loose middle layer, and a dense outer layer. Regular PCL grafts (rPCL) with only a dense layer were used as control. In vivo evaluation was performed in rabbit carotid artery. Enhanced cell infiltration, rapid regeneration of endothelium and smooth muscle layers, and increased elastin deposition were observed within the tPCL graft wall. After 3 months, tPCL grafts showed faster PCL degradation than the rPCL grafts. Infiltrated macrophages in the tPCL grafts secreted higher level of monocyte chemoattractant protein‐1 (MCP‐1) and vascular endothelial growth factor (VEGF) which enhanced vascular regeneration. In conclusion, the tPCL graft may be a useful vascular prosthesis and worth for further investigation.

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3.
Magnesium‐based implants present several advantages for clinical applications, in particular due to their biocompatibility and degradability. However, degradation products can affect negatively the cell activity. In this work, a combined coating strategy to control the implant degradation and cell regulation processes is evaluated, including plasma electrolytic oxidation (PEO) that produces a 13 µm‐thick Ca, P, and Si containing ceramic coating with surface porosity, and breath figures (BF) approach that produces a porous polymeric poly(ε‐caprolactone) surface. The degradation of PCL‐PEO‐coated Mg hierarchical scaffold can be tailored to promote cell adhesion and proliferation into the porous structure. As a result, cell culture can colonize the inner PEO‐ceramic coating structure where higher amount of bioelements are present. The Mg/PEO/PCL/BF scaffolds exhibit equally good or better premyoblast cell adhesion and proliferation compared with Ti CP control. The biological behavior of this new hierarchical functionalized scaffold can improve the implantation success in bone and cardiovascular clinical applications.  相似文献   

4.
Aiming to construct small diameter (ID <6 mm) off‐the‐shelf tissue‐engineered vascular grafts, the end‐group heparinizd poly(ε‐caprolactone) (PCL) is synthesized by a three‐step process and then electrospun into an inner layer of double‐layer vascular scaffolds (DLVSs) showing a hierarchical double distribution of nano‐ and microfibers. Afterward, PCL without the end‐group heparinization is electrospun into an outer layer. A steady release of grafted heparin and the existence of a glycocalyx structure give the grafts anticoagulation activity and the conjugation of heparin also improves hydrophilicity and accelerates degradation of the scaffolds. The DLVSs are evaluated in six rabbits via a carotid artery interpositional model for a period of three months. All the grafts are patent until explantation, and meanwhile smooth endothelialization and fine revascularization are observed in the grafts. The composition of the outer layer of scaffolds exhibits a significant effect on the aneurysm dilation after implantation. Only one aneurysm dilation is detected at two months and no calcification is formed in the follow‐up term. How to prevent aneurysms remains a challenging topic.  相似文献   

5.
The present study was aimed at designing a novel porous hydroxyapatite/poly(ε-caprolactone) (nHAp/PCL) hybrid nanocomposite matrix on a magnesium substrate with high and low porosity. The coated samples were prepared using a dip-coating technique in order to enhance the bioactivity and biocompatibility of the implant and to control the degradation rate of magnesium alloys. The mechanical and biocompatible properties of the coated and uncoated samples were investigated and an in vitro test for corrosion was conducted by electrochemical polarization and measurement of weight loss. The corrosion test results demonstrated that both the pristine PCL and nHAp/PCL composites showed good corrosion resistance in SBF. However, during the extended incubation time, the composite coatings exhibited more uniform and superior resistance to corrosion attack than pristine PCL, and were able to survive severe localized corrosion in physiological solution. Furthermore, the bioactivity of the composite film was determined by the rapid formation of uniform CaP nanoparticles on the sample surfaces during immersion in SBF. The mechanical integrity of the composite coatings displayed better performance (∼34% higher) than the uncoated samples. Finally, our results suggest that the nHAp incorporated with novel PCL composite membranes on magnesium substrates may serve as an excellent 3-D platform for cell attachment, proliferation, migration, and growth in bone tissue. This novel as-synthesized nHAp/PCL membrane on magnesium implants could be used as a potential material for orthopedic applications in the future.  相似文献   

6.
Hydrophilicity improvement and bioactive surface design of poly(?-caprolactone) (PCL) grafts are of key importance for their application in tissue engineering. Herein, we develop a convenient approach for achieving stable hydrophilic surfaces by modifying electrospun PCL grafts with a class II hydrophobin (HFBI) coating. Static water contact angles (WCA) demonstrated the conversion of the PCL grafts from hydrophobic to hydrophilic after the introduction of amphiphilic HFBI. ATR-FTIR and XPS confirmed the presence of self-assembled HFBI films on the surface of the PCL nanofibers. The biocompatibility of the HFBI-modified PCL grafts was evaluated by cell proliferation in vitro, and by arteriovenous shunt (AV shunt) experiments ex vivo. Anti-CD31 antibody, which is specific for endothelial cells (ECs), was subsequently immobilized on the HFBI-coated PCL scaffolds through protein-protein interactions. This bioactive PCL graft was found to promote the attachment and retention of endothelial cells. These results suggest that this stepwise strategy for introducing cell-specific binding molecules into PCL scaffolds may have potential for development of vascular grafts that can endothelialize rapidly in vivo.  相似文献   

7.
Poly(ε‐caprolactone)‐based graft copolymers were prepared via a “grafting from” technique derived from iodine transfer polymerization. This copolymerization was done thanks to a poly(ε‐caprolactone‐co‐α‐iodo‐ε‐caprolactone) (PCL‐I), which was used as a multisite transfer agent. Styrene (Sty) and n‐butyl acrylate (n‐BuA) were firstly used as model monomers to establish the feasibility of using PCL‐I as multisite transfer agent, and investigate some general properties of the polymerization. The formation of PCL‐g‐PSty and PCL‐g‐P(n‐BuA) copolymers was confirmed by SEC and NMR analyzes of the copolymers before and after degradation of the PCL backbone. This method was extended to an acrylamide monomer, namely (N,N‐dimethyl) acrylamide (DMA), to prepare original amphiphilic copolymers with PCL as hydrophobic backbone and amido‐functionalized hydrophilic grafted chains. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5006–5016, 2009  相似文献   

8.
Biodegradable polymers provide an attractive solution to reduce environmental pollution caused by the accumulation of plastic waste in landfills. In this study, the effect of polyethylene‐graft‐glycidyl methacrylate (PE‐g‐GMA) on the biodegradation of blends of poly(ε‐caprolactone) (PCL) and cellulose acetate (CA) (80/20, 60/40, 40/60, and 20/80 PCL/CA, w/w) was assessed by mass retention, tensile strength, and morphological properties. The principal fungal strains present in the soil after biodegradation were also identified. PCL and the blends containing 60% and 80% PCL showed greater mass loss and superficial change in simulated soil. PE‐g‐GMA increased the tensile strength retention during 3 months of aging in simulated soil. Scanning electron microscopy (SEM) indicated that pure PCL was more porous, which enhanced the hydrolysis and biodegradation of PCL. PE‐g‐GMA decreased the mass loss of the polymers, possibly by enhancing the interaction between PCL and CA, with the formation of hydrogen bonds between the carbonyl groups of PCL and the hydroxyl groups of CA. This effect was marked in blends with >40% PCL. Microbiological analysis revealed the presence of several species of fungi in the soil. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

9.
In prostate cancer, hormone therapy via leuprolide acetate drug (LUP) is used to lower the level of testosterone down to castration level to effectively control the development of prostate cancer. The objective of this study was to evaluate the effective parameters in degradation and controlled release of an injectable in situ formed polymeric implant, loaded with leuprolide acetate, in order to achieve an optimum formulation for sustained drug release for 90 days with minimum burst release. The main problem associating with such implants is their high burst release. Designing an injectable implant with sustained and minimum burst release has thus become an attractive challenge in drug delivery field. Effects of type of poly(lactic‐co‐glycolic acid) 75:25 copolymers (RG752, RG756) and addition of nano‐hydroxyapatite (HA) particles on degradation rates of the implants and release profiles were examined in vitro and in vivo in a rabbit animal model. Results showed that implants containing polymers with higher molecular weights had significantly lower weight loss and molecular weight reduction. Adding nanoparticles of hydroxyapatite into poly(lactic‐co‐glycolic acid) implants caused further reduction in degradation rates, leading to a more sustained drug release in vivo, with reduced burst release. Different conventional kinetic models were applied to drug release and degradation data. The degradation data fit well to the first‐order degradation model. Higuchi model was the best kinetic release model fitted to the experimental in vitro release data. This study led to an optimum formulation (RG756:RG752 3:1 + 5% HA) with sustained leuprolide release and testosterone suppression over a 90‐day period with significant decrease of burst release phase (50%, p < 0.001) compared with the conventional Eligard formulation. The histopathology test showed that the formulated implant had no effects of toxicity or tissue necrosis in organs of the animal model. Copyright © 2017 John Wiley & Sons, Ltd.  相似文献   

10.
The various morphology and structure microspheres were fabricated via one‐step single‐solvent electrospraying of hydrophilic and hydrophobic block modified copolymer of polycaprolactone (PCL). A honeycomb‐like hierarchical structure microspheres of PCL‐b‐PTFOA(4h) and abundant nanometer pores of PCL‐b‐PEG400 microspheres were obtained due to the solvent evaporation, thermally and polymer diffusion‐induced phase separation effect. Furthermore, a superhydrophobic coatings and robust superhydrophobic‐coated cotton woven fabric surfaces were prepared by using PCL‐b‐PTFOA(4h) microspheres with hierarchical structure and low surface energy. The contact angle (CA) and sliding angle (SA) of PCL‐b‐PTFOA(4h) microspheres‐coated cotton woven fabric surfaces reached 164.4 ± 5.5° and 6.8 ± 0.5°, respectively, which allows for self‐cleaning. The self‐cleaning test demonstrated that the coated superhydrophobic surface could shed aqueous dyes and dust without any trace. The superhydrophobic‐coated fabric shows good soaping fastness against mechanical abrasion without significant reduction of CA. This electrospraying coating of block copolymers can provide a simple, facile, and promising technique for producing multifunctional textiles.  相似文献   

11.
Biodegradable and biocompatible PCL‐g‐PEG amphiphilic graft copolymers were prepared by combination of ROP and “click” chemistry via “graft onto” method under mild conditions. First, chloro‐functionalized poly(ε‐caprolactone) (PCL‐Cl) was synthesized by the ring‐opening copolymerization of ε‐caprolactone (CL) and α‐chloro‐ε‐caprolactone (CCL) employing scandium triflate as high‐efficient catalyst with near 100% monomer conversion. Second, the chloro groups of PCL‐Cl were quantitatively converted into azide form by NaN3. Finally, copper(I)‐catalyzed cycloaddition reaction was carried out between azide‐functionalized PCL (PCL‐N3) and alkyne‐terminated poly(ethylene glycol) (A‐PEG) to give PCL‐g‐PEG amphiphilic graft copolymers. The composition and the graft architecture of the copolymers were characterized by 1H NMR, FTIR, and GPC analyses. These amphiphilic graft copolymers could self‐assemble into sphere‐like aggregates in aqueous solution with diverse diameters, which decreased with the increasing of grafting density. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

12.
Well‐defined in‐chain norbornene‐functionalized poly(ethylene oxide)‐b‐poly(?‐caprolactone) copolymers (NB‐PEO‐b‐PCL) were synthesized from a dual clickable containing both hydroxyl‐ and alkyne‐reactive groups, namely heterofunctional norbornene 3‐exo‐(2‐exo‐(hydroxymethyl)norborn‐5‐enyl)methyl hexynoate. A range of NB‐PEO‐b‐PCL copolymers were obtained using a combination of orthogonal organocatalyzed ring‐opening polymerization (ROP) and click copper‐catalyzed azide–alkyne cycloaddition (CuAAC). Ring‐opening metathesis polymerization (ROMP) of NB‐PEO‐b‐PCL macromonomers using ruthenium‐based Grubbs’ catalysts provides comb‐like and umbrella‐like graft copolymers bearing both PEO and PCL grafts on each monomer unit. Mikto‐arm star A2B2 copolymers were obtained through a new strategy based on thiol–norbornene photoinitiated click chemistry between 1,3‐propanedithiol and NB‐PEO‐b‐PCL. The results demonstrate that in‐chain NB‐PEO‐b‐PCL copolymers can be used as a platform to prepare mikto‐arm star, umbrella‐, and comb‐like graft copolymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 4051–4061  相似文献   

13.
Herein, a bilayer cylindrical conduit (P‐CA) is presented consisting of electrospun polycaprolactone (PCL) nanofibers and sodium alginate hydrogel covalently cross‐linked with N,N′‐disuccinimidyl carbonate (DSC). The bilayer P‐CA conduit is developed by combining the electrospinning and outer–inner layer methods. Using DSC, as a covalent crosslinker, increases the degradation time of the sodium alginate hydrogel up to 2 months. The swelling ratio of the hydrogel is also 503% during the first 8 h. The DSC cross‐linked sodium alginate in the inner layer of the conduit promotes the adhesion and proliferation of nerve cells, while the electrospun PCL nanofibers in the outer layer provide maximum tensile strength of the conduit during surgery. P‐CA conduit promotes the migration of Schwann cells along the axon in a rat model based on functional and histological evidences. In conclusion, P‐CA conduit will be a promising construct for repairing sciatic nerves in a rat model.  相似文献   

14.
Well‐defined AB3‐type miktoarm star‐shaped polymers with cholic acid (CA) core were fabricated with a combination of “click” chemistry and ring opening polymerization (ROP) methods. Firstly, azide end‐functional poly(ethylene glycol) (mPEG), poly(methyl methacrylate) (PMMA), polystyrene (PS), and poly(ε‐caprolactone) (PCL) polymers were prepared via controlled polymerization and chemical modification methods. Then, CA moieties containing three OH groups were introduced to these polymers as the end groups via Cu(I)‐catalyzed click reaction between azide end‐functional groups of the polymers ( mPEG‐N3 , PMMA‐N3 , PS‐N3 , and PCL‐N3 ) and ethynyl‐functional CA under ambient conditions, yielding CA end‐functional polymers ( mPEG‐Cholic , PMMA‐Cholic , PS‐Cholic , and PCL‐Cholic ). Finally, the obtained CA end‐capped polymers were employed as the macroinitiators in the ROP of ε‐caprolactone (ε‐CL) yielding AB3‐type miktoarm star polymers ( mPEG‐Cholic‐PCL3 , PMMA‐Cholic‐PCL3 , and PS‐Cholic‐PCL3 ) and asymmetric star polymer [ Cholic‐(PCL)4 ]. The chemical structures of the obtained intermediates and polymers were confirmed via Fourier transform infrared and 1H nuclear magnetic resonance spectroscopic techniques. Thermal decomposition behaviors and phase transitions were studied in detail using thermogravimetric analysis and differential scanning calorimetry experiments. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3390–3399  相似文献   

15.
Poly(ethylene‐co‐vinyl acetate) (EVA) powders containing 10 and 20 wt % of vinyl acetate (VAc) units was saponified in ethanol/KOH solution in a heterogeneous manner. Intermolecular interaction between vinyl alcohol(VOH) units in the produced poly(ethylene‐co‐vinyl alcohol) (EVOH) promoted the crystallization of intervening segments composed of ethylene units. Ring opening polymerization of caprolactone (CL) in the presence of EVOH gave EVOH‐g‐PCL graft copolymers with relatively short chain branches. Even though the graft copolymerization was carried out in a homogeneous solution, all the VOH units were not equally reactive for the PCL grafting. And the unreacted VOH units decreased very slowly with the graft copolymerization time. EVOH‐g‐PCL decreased the domain size of the dispersed phase in low density polyethylene (PE)/biodegradable master batch (MB) blends, and thus increased their tensile properties significantly. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2561–2569, 2002  相似文献   

16.

Multi‐block copolymers of PLLA and PCL were prepared by a coupling reaction between PLLA and PCL prepolymers with –NCO end groups. FTIR proved that the products were PLLA‐PCL copolymers. The weight‐average molecular weight of the copolymers was up to 180,000 at a composition of 60% PLLA and 40% PCL. The degradation properties of PLLA and PLLA‐PCL copolymers were studied by a soil burial test and a hydrolysis test in a phosphate‐buffer solution. The degradation rate was estimated by the mass loss, molecular weight reduction, pH value changes and swelling index; the degradation rates of the copolymers were a function of the composition of PLLA and PCL. Increasing PCL content in the copolymers resulted in lower degradation rate.  相似文献   

17.
Resorbable poly(ester anhydride) networks based on ε‐caprolactone, L ‐lactide, and D,L ‐lactide oligomers were synthesized. The ring‐opening polymerization of the monomers yielded hydroxyl telechelic oligomers, which were end‐functionalized with succinic anhydride and reacted with methacrylic anhydride to yield dimethacrylated oligomers containing anhydride bonds. The degree of substitution, determined by 13C NMR, was over 85% for acid functionalization and over 90% for methacrylation. The crosslinking of the oligomers was carried out thermally with dibenzoyl peroxide at 120 °C, leading to polymer networks with glass‐transition temperatures about 10 °C higher than those of the constituent oligomers. In vitro degradation tests, in a phosphate buffer solution (pH 7.0) at 37 °C, revealed a rapid degradation of the networks. Crosslinked polymers based on lactides exhibited high water absorption and complete mass loss in 4 days. In ε‐caprolactone‐based networks, the length of the constituent oligomer determined the degradation: PCL5‐AH, formed from longer poly(ε‐caprolactone) (PCL) blocks, lost only 40% of its mass in 2 weeks, whereas PCL10‐AH, composed of shorter PCL blocks, completely degraded in 2 days. The degradation of PCL10‐AH showed characteristics of surface erosion, as the dimensions of the specimens decreased steadily and, according to Fourier transform infrared, labile anhydride bonds were still present after 90% mass loss. © 2003 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3788–3797, 2003  相似文献   

18.
A novel synthetic approach was developed for the controllable modification of chitosan (CS) with poly(ϵ-caprolactone) (PCL). 6-O-Triphenylmethyl-chitosan (TMCS) was synthesized as a highly soluble intermediate in organic solvents to facilitate an efficient grafting reaction of PCL onto CS in a homogeneous reaction medium. Subsequently, the syntheses of CS-g-PCL copolymers with different degrees of substitution (ds) and various chain lengths of PCL (number-average molecular weight = 1200–11,000) were carried out by a coupling reaction between the carboxylic terminal groups of PCL chains and the amino groups of TMCS. The successful grafting reaction was confirmed by GPC measurements, which indicated that the products were graft copolymers rather than physical blends. The ds, defined as the number of PCL chains per saccharide unit, of the graft copolymers could be adjusted simply by changes in the molar feed ratios of PCL to CS, and graft copolymers with different ds values ranging from 0.28 to 0.49 were synthesized, as calculated by 1H NMR and elemental analysis. DSC and X-ray measurements showed that the melting temperature and enthalpy of the PCL grafts of these graft copolymers could be adjusted by the ds and the chains length of PCL, respectively. Meanwhile, the CS-g-PCL copolymers exhibited better solubility in various solvents, such as in chloroform for some of the resultant graft copolymers, than the original CS. Finally, nanoparticles of 100–200 nm, having hydrophobic PCL domains and cationic hydrophilic surfaces, were obtained through the self-assembly of the copolymers in selective solvents. These types of graft copolymers have great potential in various applications, such as targeted drug and gene delivery as well as tissue engineering. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2556–2568, 2007  相似文献   

19.
Fabrication of tissue engineering scaffolds with the use of novel 3D printing has gained lot of attention, however systematic investigation of biomaterials for 3D printing have not been widely explored. In this report, well‐defined structures of polycaprolactone (PCL) and PCL‐ carbon nanotube (PCL‐CNT) composite scaffolds have been designed and fabricated using a 3D printer. Conditions for 3D printing has been optimized while the effects of varying CNT percentages with PCL matrix on the thermal, mechanical and biological properties of the printed scaffolds are studied. Raman spectroscopy is used to characterise the functionalized CNTs and its interactions with PCL matrix. Mechanical properties of the composites are characterised using nanoindentation. Maximum peak load, elastic modulus and hardness increases with increasing CNT content. Differential scanning calorimetry (DSC) studies reveal the thermal and crystalline behaviour of PCL and its CNT composites. Biodegradation studies are performed in Pseudomonas Lipase enzymatic media, showing its specificity and effect on degradation rate. Cell imaging and viability studies of H9c2 cells from rat origin on the scaffolds are performed using fluorescence imaging and MTT assay, respectively. PCL and its CNT composites are able to show cell proliferation and have the potential to be used in cardiac tissue engineering.

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20.
Polycaprolactone (PCL) is a bioresorbable and biocompatible polymer that has been widely used in long-term implants and controlled drug release applications. However, when it comes to tissue engineering, PCL suffers from some shortcomings such as slow degradation rate, poor mechanical properties, and low cell adhesion. The incorporation of calcium phosphate-based ceramics and bioactive glasses into PCL has yielded a class of hybrid biomaterials with remarkably improved mechanical properties, controllable degradation rates, and enhanced bioactivity that are suitable for bone tissue engineering. This review presents a comprehensive study on recent advances in the fabrication and properties of PCL-based composite scaffolds containing calcium phosphate-based ceramics and bioglasses in terms of porosity, degradation rate, mechanical properties, in vitro and in vivo biocompatibility and bioactivity for bone regeneration applications. The fabrication routes range from traditional methods such as solvent casting and particulate leaching to novel approaches including solid free-form techniques.  相似文献   

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