The biodegradable polymer demonstrates significant potential for addressing the critical environmental challenges associated with oil spills;however, the cellular film structure and hydrophobic characteristics of the ...The biodegradable polymer demonstrates significant potential for addressing the critical environmental challenges associated with oil spills;however, the cellular film structure and hydrophobic characteristics of the polymer restrict their efficacy. In this study, a biodegradable thin membrane composed of a blend of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly(caprolactone) (PCL) was fabricated utilizing the electrospinning technique. The membrane exhibited an adsorption capacity for cooking oil of 10.8 g/g, and Fourier-transform infrared spectroscopy (FTIR) analysis confirmed the anticipated chemical structures, revealing no evidence of chemical interactions between PHBV and PCL. This research presents an environmentally friendly and straightforward approach for fabricating biodegradable membrane structure with exceptional oil-water separation capabilities.展开更多
In this work,a degradable polyurethane composed of caprolactone(CL)and L-Lactide(LLA)as soft segments,and 4,40-methylenebis(cyclohexyl isocyanate)(H12 MDI)and polytetramethylene ether glycol(PTMEG)as hard segments,was...In this work,a degradable polyurethane composed of caprolactone(CL)and L-Lactide(LLA)as soft segments,and 4,40-methylenebis(cyclohexyl isocyanate)(H12 MDI)and polytetramethylene ether glycol(PTMEG)as hard segments,was prepared.Hydrolytic degradation experiment revealed that the degradable polyurethane(PU)could be degraded in artificial seawater.It also showed that caprolactone-copolyurethane(CL-PU)copolymer with higher crystallinity degraded much slower in artificial seawater.However,the introduction of LLA resulted in an increase in the hydrophilicity and reduction in the crystallinity of degradable PU,as demonstrated by the contact angle analysis.The result of the scanning electron microscope showed that the surface of degradable PU renewed under static condition.Moreover,degradable PU was able to be used as a carrier,and it controlled the release rate of 4,5-dichloro-2-octyl-isothiazolone(DCOIT).The anti-diatom(Navicula incerta)test demonstrated that the(caprolactone-co-L-lactide)-co-polyurethane 4(CL/LAx-PU4)with DCOIT contents prevented the adhesion of diatom Navicula incerta(88.37%reduction)due to their self-polishing and the release of antifoulants.Therefore,the degradable PU consisted of CL,LLA,and DCOIT could be a durable resin with good antifouling activity for the application in the marine anti-biofouling field.展开更多
Electron microscope and electron diffraction have been used to study epitaxial crystallization of poly(ε-caprolactone)(PCL).on highly oriented film of isotactic polypropylene(iPP).The results obtained from bright fie...Electron microscope and electron diffraction have been used to study epitaxial crystallization of poly(ε-caprolactone)(PCL).on highly oriented film of isotactic polypropylene(iPP).The results obtained from bright field(BF)electron micrograph and electron diffraction indicate that the PCL can epitaxially grow on iPP substrate and form cross-hatched lamellar texture.The c axes of PCL are ±500 apart from the c axes of iPP. The contact planes of the two kinds of crystals are(010)of iPP and(100) of PCL,respectively.展开更多
The miscibility of poly(ethylene terephthalate (ET)- caprolactone (CL) (TCL)/poly(ethylene terephthalate) (PET) blends were examined by Differential Scanning Calorimeter (DSC). In these blends, a miscibility limit spe...The miscibility of poly(ethylene terephthalate (ET)- caprolactone (CL) (TCL)/poly(ethylene terephthalate) (PET) blends were examined by Differential Scanning Calorimeter (DSC). In these blends, a miscibility limit specified by ET content in the TCL was found to be about 70 (wt%). In the blends of TCL/TCL with different ET contents, a miscibility window defined by ET content was also found to range from 82 to 58 (wt%). Based on the experimental miscibility limits and the mean field binary interaction model, the interaction parameter between monomeric units of ET and CL was obtained.展开更多
Two octaisobutyl-polyhedral oligomeric silsesquioxanes(oib-POSS)reinforced biodegradable poly(ε-caprolactone)(PCL)composites were prepared via two different methods,i.e.,melt compounding and solution casting,which we...Two octaisobutyl-polyhedral oligomeric silsesquioxanes(oib-POSS)reinforced biodegradable poly(ε-caprolactone)(PCL)composites were prepared via two different methods,i.e.,melt compounding and solution casting,which were named as m PCL/oib-POSS and s PCL/oibPOSS,respectively,in this work.Oib-POSS dispersed finely in both composites;moreover,oib-POSS aggregates were larger in m PCL/oib-POSS than in s PCL/oib-POSS.Despite the different preparation methods,oib-POSS obviously promoted the crystallization of PCL,especially in s PCL/oib-POSS,but did not modify the crystal structure of PCL.The storage moduli of PCL were improved significantly in both composites.PCL/oib-POSS composites with enhanced crystallization behavior and improved dynamic mechanical properties were successfully prepared through both methods;moreover,the solution casting method was more effective than the melt compounding method.展开更多
Reaction of (MeC 5H 4) 3Ln with HOCH 2CH 2NMe 2 in tetrahydrofuran(THF) gives the new complexes [(MeC 5H 4) 2Ln(μ OCH 2CH 2NMe 2)] 2 (Ln=Sm, Y, Nd) with nitrogen functionalized μ alkoxide ligand. The ...Reaction of (MeC 5H 4) 3Ln with HOCH 2CH 2NMe 2 in tetrahydrofuran(THF) gives the new complexes [(MeC 5H 4) 2Ln(μ OCH 2CH 2NMe 2)] 2 (Ln=Sm, Y, Nd) with nitrogen functionalized μ alkoxide ligand. The complexes were characterized by elemental analysis and IR, and [(MeC 5H 4) 2Sm(μ OCH 2CH 2NMe 2)] 2 was structurally characterized by the X ray diffraction to be a dimer formed by two unsymmetric oxygen bridges. The complex has a tricyclic skeleton with the additional two Sm-N bonds via intramolecular coordination of OCH 2CH 2NMe 2. The coordination number of the central metal Sm is nine. The title complexes show good catalytic activity for ring opening polymerization of ε caprolactone.展开更多
A series of zinc silylamido complexes based upon NNO tridentate enolic Schiff base framework have been synthesized and characterized. These complexes were tested for the ring opening polymerization of lactide and e-ca...A series of zinc silylamido complexes based upon NNO tridentate enolic Schiff base framework have been synthesized and characterized. These complexes were tested for the ring opening polymerization of lactide and e-caprolactone, exhibiting notably high activity at ambient temperature, The influence of imine bridge length and substituents of diketone over the course of polymerization was investigated in details. Remarkably, 4a was confirmed to be a rare example of exceedingly active and robust zinc catalysts, achieving major transformation of lactide under extremely low loading （0.025 mol%） within 18 rain. The influence of various monomers as well as the polymerization mechanism have also been discussed.展开更多
Mismatch in mechanical properties can induce intimal hyperplasia,which is one of the main reasons for the failure of small diameter artificial blood vessels. Electrospun small diameter tubes with tailored mechanical p...Mismatch in mechanical properties can induce intimal hyperplasia,which is one of the main reasons for the failure of small diameter artificial blood vessels. Electrospun small diameter tubes with tailored mechanical properties were fabricated through blending poly( L-lactide-co-ε-caprolactone)( PLCL) and silk fibroin( SF)with the mass ratios of 30 /70,50 /50,and 70 /30 in this study.Scanning electron microscopy( SEM) and mechanical testing were used to characterize morphological and mechanical properties of the tubes. Results showed that tensile strength of the tubes was higher than most of the native blood vessels,and elongations at break of them were improved greatly by blending PLCL. Compliances of the tubes were all higher than 1% /13. 33 kPa( 1% /100 mmHg).Particularly,tubes with blending mass ratio of 50 /50 showed similar compliance with human native femoral arteries,which provided a promising biomaterial that could be applied on small diameter vascular applications.展开更多
A series of nanocomposites based on poly（ε-caprolactone） （PCL） and graphene oxide （GO） were prepared by in situ polymerization. Scanning electron microscopy observation revealed not only a well dispersion of GO...A series of nanocomposites based on poly（ε-caprolactone） （PCL） and graphene oxide （GO） were prepared by in situ polymerization. Scanning electron microscopy observation revealed not only a well dispersion of GO but also a strong interfacial interaction between GO and the PCL matrix, as evidenced by the presence of some GO nanosheets embedded in the matrix. Effects of GO nanofillers on the crystal structure, crystallization behavior and spherulitic morphology of the PCL matrix were investigated in detail. The results showed that the crystallization temperature of PCL enhanced significantly due to the presence of GO in the nanocomposites, however, the addition of GO did not affect the crystal structure greatly. Thermal stability of PCL remarkably increased with the addition of GO nanosheets, compared with that of pure PCL. Incorporation of GO greatly improved the tensile strength and Young＇s modulus of PCL without a significant loss of the elongation at break.展开更多
Both four-ann star-shaped poly（ε-caprolactone） （4sPCL） and two-ann linear PCL （2LPCL） were synthesized and their inclusion complexation with α-cyclodextrin （α-CD） were studied. The inclusion complexes （ICs...Both four-ann star-shaped poly（ε-caprolactone） （4sPCL） and two-ann linear PCL （2LPCL） were synthesized and their inclusion complexation with α-cyclodextrin （α-CD） were studied. The inclusion complexes （ICs） formed between the PCL polymers and α-CD were characterized by ^1H-NMR, DSC, TGA, WAXD, and FT-1R, respectively. Both branch ann number and molecular weight of the PCL polymers have apparent effect on the stoichiometry （CL：CD, mol：mol） of these ICs. All these analytical results indicate that the branch arms of the PCL polymers are incorporated into the hydrophobic α-CD cavities and their original crystalline properties are completely suppressed. Moreover, the inclusion complexation between two-ann linear or four-ann star-shaped PCL polymers and α-CD not only enhances the thermal stability of the vip PCL polymers but also improves that of α-CD.展开更多
The ring-opening polymerization of e-caprolactone (CL) initiated by novel single lanthanide tris(4-tert-butylphenolate)s [Ln(OTBP)3] is reported. Single-component La(OTBP)3 can effectively prepare polycaprolactone (PC...The ring-opening polymerization of e-caprolactone (CL) initiated by novel single lanthanide tris(4-tert-butylphenolate)s [Ln(OTBP)3] is reported. Single-component La(OTBP)3 can effectively prepare polycaprolactone (PCL) with over 90% yield and viscosity average molecular weight about 60 x 10 under quite mild conditions: molar ratio of CL to initiator is 1000, 60 C, 2 h in toluene. Mechanism study indicates that the monomer inserts into the growing chain via the break of acyl-oxygen bond of CL.展开更多
Hydrophilic degraded gelatin was modified with hydrophobic poly(ε-caprolactone) (PCL) via a chemical grafting route.Firstly,PCL with one hydroxyl end group was prepared by the ring-opening polymerization of εcaprola...Hydrophilic degraded gelatin was modified with hydrophobic poly(ε-caprolactone) (PCL) via a chemical grafting route.Firstly,PCL with one hydroxyl end group was prepared by the ring-opening polymerization of εcaprolactone (ε-CL) with tin (Ⅱ) 2-ethylhexanoate as catalyst and n-butyl alcohol as initiator.Secondly,the PCL reacted with isophorone diisocyanate (IPDI) to prepare PCL with isocyanate functional group (PCL-NCO).Hydroxylamine was used to degrade gelatin by the cleavage between asparagine and glycine residues of gelatin.PCL-NCO reacted with the hydroxyl/amino groups of degraded gelatin in a homogeneous system and yielded the PCL modified gelatin copolymers.The gelatin grafted PCL copolymers were measured by means of XRD,FTIR,DSC and 1 H NMR.The results confirmed the conjugation of PCL onto gelatin chains.The PCL modified gelatin can be used as biomaterials owing to their biocompatibility and biodegradation.展开更多
The electrospinning process was applied to fabricate the nanofibers of biodegradable poly(ε-caprolactone)(PCL) in which different contents of multiwalled carbon nanotubes(MWCNTs) were embedded. Afterward,the electros...The electrospinning process was applied to fabricate the nanofibers of biodegradable poly(ε-caprolactone)(PCL) in which different contents of multiwalled carbon nanotubes(MWCNTs) were embedded. Afterward,the electrospun nanofibers were successfully decorated with shish-kebab structure via a self-induced crystallization technique. The topographical features and the mechanical properties of the composite scaffolds were characterized,and the biocompatibility of the material was assessed by using human osteogenic sarcoma osteoblasts(MG-63 cells). The carbon nanotube(CNT) concentration is found to affect the fiber diameter and mechanical properties of electrospun nanofibers and the periodic distance of the shish-kebab architecture. Cellular attachment and proliferation assays reveal that 0.5 wt% CNT-embedded PCL scaffold shows enhanced biocompatibility with MG-63 cells than their counterparts made of neat PCL, and the collagen-like nanotopology provided by the shish-kebab structure further facilitates the cell adhesion and proliferation. The superior interactions between cells and scaffolds demonstrate that the shish-kebab-structured CNTs/PCL nanofibers may be promising candidate for tissue engineering scaffold application.展开更多
Ring-opening polymerization of ε-caprolactone has been carried out by using rare earth Schiff base complexes： lanthanide tris（N-phenyl-3,5-di-t-butylsalicylaldiminato）s [Ln（OPBS）3] as single component catalyst f...Ring-opening polymerization of ε-caprolactone has been carried out by using rare earth Schiff base complexes： lanthanide tris（N-phenyl-3,5-di-t-butylsalicylaldiminato）s [Ln（OPBS）3] as single component catalyst for the first time. The influences of different rare earth elements, monomer and catalyst concentration as well as reaction time on the polymerization were investigated. Mechanism studies showed that monomer inserts into the active site with the acyl-oxygen bond scission rather than the break of alkyl-oxygen bond.展开更多
Hyperbranched polyamidoamines （HPAs） were directly employed as macroinitiators to initiate the Sn（Oct）2 catalyzed ring-opening polymerization of ε-caprolactone （CL）, resulting in multiarm star copolymers with p...Hyperbranched polyamidoamines （HPAs） were directly employed as macroinitiators to initiate the Sn（Oct）2 catalyzed ring-opening polymerization of ε-caprolactone （CL）, resulting in multiarm star copolymers with poly（6- caprolactone） （PCL） as shells and HPA as core （HPA-b-PCL）. From 1H-NMR characterization it was deduced that both the primary amines and the secondary amide groups of HPAs could initiate the CL polymerization, and the initiation efficiency increased when more CL monomers were fed. The average arm-numbers of the obtained stars were in the range of 115-353. Differential scanning calorimetry measurements demonstrated that the melting and crystallization temperatures, fusion and crystallization enthalpy and the degree of crystallinity of the star polymers increased as the PCL arm length increased. HPA- b-PCL stars could be used as nanocarriers to efficiently accommodate anionic dyes at acidic condition, while load cationic dyes at basic condition. Compared with the dye-loading behavior of multiarrn star PCL with the neutral hyperbranched polyglycerol as core, it was deduced that HPA-b-PCL nanocarriers accommodated anionic dyes using the HPA core, while loaded cationic dyes using both the HPA core and the PCL shell. Dynamic light scattering analyses also supported such deduction. Furthermore, HPA-b-PCL nanocarriers could selectively load the anionic Eosin Y or the cationic methylene blue from their mixture at pH = 6 or 9, respectively, realizing their separation.展开更多
Poly(ε-caprolactone) (PCL) with different molecular weights was synthesized and characterized by a gelpermeation chromatograph equipped with multiple detector. The melting behavior of PCL was also studied. It was fou...Poly(ε-caprolactone) (PCL) with different molecular weights was synthesized and characterized by a gelpermeation chromatograph equipped with multiple detector. The melting behavior of PCL was also studied. It was found thatthe equilibrium melting points (T_m^0) of PCL samples depend on their molecular weights. Wide angle X-ray diffractionmeasurements (WAXD) and DSC measurements showed that the crystals of the high molecular weight PCLs were moreperfect than those of the low molecular weigh ones. These results demonstrate that the concentration of the end groups ofPCL chains is the main factor that influences the melting behavior. The fusion enthalpy per repeating unit (ΔH_u) wasdetermined to be 11.3 kJ/mol for PCL.展开更多
Complexes of lanthanide trisborohydrides, formally Ln（BH4）3（THF）, （Ln=La, Ce, Sm, Yb）, were synthesized and their catalytic activity for polymerization of ε-caprolactone was studied. All the complexes can catal...Complexes of lanthanide trisborohydrides, formally Ln（BH4）3（THF）, （Ln=La, Ce, Sm, Yb）, were synthesized and their catalytic activity for polymerization of ε-caprolactone was studied. All the complexes can catalyze this polymerization. It was found that the catalytic activities decreased in the order of La〉Ce〉Sm〉Yb. The crystal structure of cerium trisborohydride was determined for the first time by single crystal X-ray diffraction analysis. It is an ionic pair complex of [Ce（BH4）E（THF）5][Ce（BH4）4（THF）2]. The cationic part involves two ηa-BH4 ligands, while the anionic part involves two η3-BH4 groups and two η2-BH4 groups.展开更多
The mechanical properties and water solubility of electrospinning SF films limit their use as biomaterials. In order to develop a tissue engineering biomaterial with both satisfying biological properties and sufficien...The mechanical properties and water solubility of electrospinning SF films limit their use as biomaterials. In order to develop a tissue engineering biomaterial with both satisfying biological properties and sufficient biomechanical properties,blended films composed of silk fibroin( SF) and poly( ε-caprolactone)( PCL) were fabricated by electrospinning in this study. Scanning electron microscope( SEM), X-ray diffraction( XRD),thermal analysis,Fourier transform-infrared( FT-IR),Raman spectra,mechanical testing,and water solubility were used to characterize the morphological, structural and mechanical properties of the blended electrospinning films. Results showed that the diameter of the blended fiber was distributed between 600 and1000 nm,and the fiber diameter increased as the PCL content increased. There is no obvious phase separation due to the similarity and intermiscibility,as well as the interactions( mainly hydrogen bonds), between the two polymers. Meanwhile, the secondary structures of SF changed from random coils and Silk I to Silk II because of the interactions between SF and PCL. For this reason,the tensile strength and elongation at break of the electrospinning films improved significantly,and the water solubility decreased. In conclusion,the blended electrospinning films fabricated in this study showed satisfying mechanical properties and water insolubilities,and they may be promising biomaterials for applications in tissue engineering for blood vessels,nerve conduits,tendons,ligaments and other tissues.展开更多
Tetrahydrosalen ligand was employed in the synthesis of gadolinium complex. The ligand was deprotoned by LiBu, and the afforded lithium salt was reacted with anhydrous GdCl3 to produce the gadolinium complex through s...Tetrahydrosalen ligand was employed in the synthesis of gadolinium complex. The ligand was deprotoned by LiBu, and the afforded lithium salt was reacted with anhydrous GdCl3 to produce the gadolinium complex through salt metathesis. This complex was successfully used to initiate the ring-opening polymerization of ε-caprolactone. The initiation conditions in different temperature, monomer-to-initiator ratio and time were investigated. Under the condition： [ε-caprolactone]：[catalyst] = 600, 56 ℃, toluene： 2 ml, poly（ε-caprolactone） （PCL） with Mw = 11,2782 and PDI = 1.96 was achieved.展开更多
文摘The biodegradable polymer demonstrates significant potential for addressing the critical environmental challenges associated with oil spills;however, the cellular film structure and hydrophobic characteristics of the polymer restrict their efficacy. In this study, a biodegradable thin membrane composed of a blend of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly(caprolactone) (PCL) was fabricated utilizing the electrospinning technique. The membrane exhibited an adsorption capacity for cooking oil of 10.8 g/g, and Fourier-transform infrared spectroscopy (FTIR) analysis confirmed the anticipated chemical structures, revealing no evidence of chemical interactions between PHBV and PCL. This research presents an environmentally friendly and straightforward approach for fabricating biodegradable membrane structure with exceptional oil-water separation capabilities.
基金supported by the National Natural Science Foundation of China(21776249,21878267,21576236)。
文摘In this work,a degradable polyurethane composed of caprolactone(CL)and L-Lactide(LLA)as soft segments,and 4,40-methylenebis(cyclohexyl isocyanate)(H12 MDI)and polytetramethylene ether glycol(PTMEG)as hard segments,was prepared.Hydrolytic degradation experiment revealed that the degradable polyurethane(PU)could be degraded in artificial seawater.It also showed that caprolactone-copolyurethane(CL-PU)copolymer with higher crystallinity degraded much slower in artificial seawater.However,the introduction of LLA resulted in an increase in the hydrophilicity and reduction in the crystallinity of degradable PU,as demonstrated by the contact angle analysis.The result of the scanning electron microscope showed that the surface of degradable PU renewed under static condition.Moreover,degradable PU was able to be used as a carrier,and it controlled the release rate of 4,5-dichloro-2-octyl-isothiazolone(DCOIT).The anti-diatom(Navicula incerta)test demonstrated that the(caprolactone-co-L-lactide)-co-polyurethane 4(CL/LAx-PU4)with DCOIT contents prevented the adhesion of diatom Navicula incerta(88.37%reduction)due to their self-polishing and the release of antifoulants.Therefore,the degradable PU consisted of CL,LLA,and DCOIT could be a durable resin with good antifouling activity for the application in the marine anti-biofouling field.
文摘Electron microscope and electron diffraction have been used to study epitaxial crystallization of poly(ε-caprolactone)(PCL).on highly oriented film of isotactic polypropylene(iPP).The results obtained from bright field(BF)electron micrograph and electron diffraction indicate that the PCL can epitaxially grow on iPP substrate and form cross-hatched lamellar texture.The c axes of PCL are ±500 apart from the c axes of iPP. The contact planes of the two kinds of crystals are(010)of iPP and(100) of PCL,respectively.
文摘The miscibility of poly(ethylene terephthalate (ET)- caprolactone (CL) (TCL)/poly(ethylene terephthalate) (PET) blends were examined by Differential Scanning Calorimeter (DSC). In these blends, a miscibility limit specified by ET content in the TCL was found to be about 70 (wt%). In the blends of TCL/TCL with different ET contents, a miscibility window defined by ET content was also found to range from 82 to 58 (wt%). Based on the experimental miscibility limits and the mean field binary interaction model, the interaction parameter between monomeric units of ET and CL was obtained.
基金financially supported by the National Natural Science Foundation of China (Nos. 51373020 and 51573016)
文摘Two octaisobutyl-polyhedral oligomeric silsesquioxanes(oib-POSS)reinforced biodegradable poly(ε-caprolactone)(PCL)composites were prepared via two different methods,i.e.,melt compounding and solution casting,which were named as m PCL/oib-POSS and s PCL/oibPOSS,respectively,in this work.Oib-POSS dispersed finely in both composites;moreover,oib-POSS aggregates were larger in m PCL/oib-POSS than in s PCL/oib-POSS.Despite the different preparation methods,oib-POSS obviously promoted the crystallization of PCL,especially in s PCL/oib-POSS,but did not modify the crystal structure of PCL.The storage moduli of PCL were improved significantly in both composites.PCL/oib-POSS composites with enhanced crystallization behavior and improved dynamic mechanical properties were successfully prepared through both methods;moreover,the solution casting method was more effective than the melt compounding method.
文摘Reaction of (MeC 5H 4) 3Ln with HOCH 2CH 2NMe 2 in tetrahydrofuran(THF) gives the new complexes [(MeC 5H 4) 2Ln(μ OCH 2CH 2NMe 2)] 2 (Ln=Sm, Y, Nd) with nitrogen functionalized μ alkoxide ligand. The complexes were characterized by elemental analysis and IR, and [(MeC 5H 4) 2Sm(μ OCH 2CH 2NMe 2)] 2 was structurally characterized by the X ray diffraction to be a dimer formed by two unsymmetric oxygen bridges. The complex has a tricyclic skeleton with the additional two Sm-N bonds via intramolecular coordination of OCH 2CH 2NMe 2. The coordination number of the central metal Sm is nine. The title complexes show good catalytic activity for ring opening polymerization of ε caprolactone.
基金financially supported by the National Natural Science Foundation of China(Nos.21574124,51503203 and51233004)
文摘A series of zinc silylamido complexes based upon NNO tridentate enolic Schiff base framework have been synthesized and characterized. These complexes were tested for the ring opening polymerization of lactide and e-caprolactone, exhibiting notably high activity at ambient temperature, The influence of imine bridge length and substituents of diketone over the course of polymerization was investigated in details. Remarkably, 4a was confirmed to be a rare example of exceedingly active and robust zinc catalysts, achieving major transformation of lactide under extremely low loading （0.025 mol%） within 18 rain. The influence of various monomers as well as the polymerization mechanism have also been discussed.
基金National Natural Science Foundation of China(No.51103092)Natural Science Foundation of Jiangsu Province,China(No.BK2012634)
文摘Mismatch in mechanical properties can induce intimal hyperplasia,which is one of the main reasons for the failure of small diameter artificial blood vessels. Electrospun small diameter tubes with tailored mechanical properties were fabricated through blending poly( L-lactide-co-ε-caprolactone)( PLCL) and silk fibroin( SF)with the mass ratios of 30 /70,50 /50,and 70 /30 in this study.Scanning electron microscopy( SEM) and mechanical testing were used to characterize morphological and mechanical properties of the tubes. Results showed that tensile strength of the tubes was higher than most of the native blood vessels,and elongations at break of them were improved greatly by blending PLCL. Compliances of the tubes were all higher than 1% /13. 33 kPa( 1% /100 mmHg).Particularly,tubes with blending mass ratio of 50 /50 showed similar compliance with human native femoral arteries,which provided a promising biomaterial that could be applied on small diameter vascular applications.
基金financially supported by the National Natural Science Foundation of China(No.31000427)the Fundamental Research Funds for the Central Universities(DUT12JB09)
文摘A series of nanocomposites based on poly（ε-caprolactone） （PCL） and graphene oxide （GO） were prepared by in situ polymerization. Scanning electron microscopy observation revealed not only a well dispersion of GO but also a strong interfacial interaction between GO and the PCL matrix, as evidenced by the presence of some GO nanosheets embedded in the matrix. Effects of GO nanofillers on the crystal structure, crystallization behavior and spherulitic morphology of the PCL matrix were investigated in detail. The results showed that the crystallization temperature of PCL enhanced significantly due to the presence of GO in the nanocomposites, however, the addition of GO did not affect the crystal structure greatly. Thermal stability of PCL remarkably increased with the addition of GO nanosheets, compared with that of pure PCL. Incorporation of GO greatly improved the tensile strength and Young＇s modulus of PCL without a significant loss of the elongation at break.
基金This work was supported by the National Natural Science Foundation of China (No. 20404007).
文摘Both four-ann star-shaped poly（ε-caprolactone） （4sPCL） and two-ann linear PCL （2LPCL） were synthesized and their inclusion complexation with α-cyclodextrin （α-CD） were studied. The inclusion complexes （ICs） formed between the PCL polymers and α-CD were characterized by ^1H-NMR, DSC, TGA, WAXD, and FT-1R, respectively. Both branch ann number and molecular weight of the PCL polymers have apparent effect on the stoichiometry （CL：CD, mol：mol） of these ICs. All these analytical results indicate that the branch arms of the PCL polymers are incorporated into the hydrophobic α-CD cavities and their original crystalline properties are completely suppressed. Moreover, the inclusion complexation between two-ann linear or four-ann star-shaped PCL polymers and α-CD not only enhances the thermal stability of the vip PCL polymers but also improves that of α-CD.
基金supported by the National Natural Science Foundation of China.(Grant No.20174033 and 20254001)the Special Found for Major State Basic Research Project(Grant No.G1999064801)the Committee of Science and Technology of Zhejiang Province.
文摘The ring-opening polymerization of e-caprolactone (CL) initiated by novel single lanthanide tris(4-tert-butylphenolate)s [Ln(OTBP)3] is reported. Single-component La(OTBP)3 can effectively prepare polycaprolactone (PCL) with over 90% yield and viscosity average molecular weight about 60 x 10 under quite mild conditions: molar ratio of CL to initiator is 1000, 60 C, 2 h in toluene. Mechanism study indicates that the monomer inserts into the growing chain via the break of acyl-oxygen bond of CL.
基金Supported by International Cooperation from Ministry of Science and Technology of China(No.2008DFA51170)
文摘Hydrophilic degraded gelatin was modified with hydrophobic poly(ε-caprolactone) (PCL) via a chemical grafting route.Firstly,PCL with one hydroxyl end group was prepared by the ring-opening polymerization of εcaprolactone (ε-CL) with tin (Ⅱ) 2-ethylhexanoate as catalyst and n-butyl alcohol as initiator.Secondly,the PCL reacted with isophorone diisocyanate (IPDI) to prepare PCL with isocyanate functional group (PCL-NCO).Hydroxylamine was used to degrade gelatin by the cleavage between asparagine and glycine residues of gelatin.PCL-NCO reacted with the hydroxyl/amino groups of degraded gelatin in a homogeneous system and yielded the PCL modified gelatin copolymers.The gelatin grafted PCL copolymers were measured by means of XRD,FTIR,DSC and 1 H NMR.The results confirmed the conjugation of PCL onto gelatin chains.The PCL modified gelatin can be used as biomaterials owing to their biocompatibility and biodegradation.
基金financially supported by the Fundamental Research Funds for the Central Universities (No. 22A201514030)China Postdoctoral Science Foundation (No. 2015M571504)+2 种基金the National Natural Science Foundation of China (Nos. 51503065 and 51273065)the Wisconsin Institute for Discovery in University of Wisconsin-MadisonChina Scholarship Council
文摘The electrospinning process was applied to fabricate the nanofibers of biodegradable poly(ε-caprolactone)(PCL) in which different contents of multiwalled carbon nanotubes(MWCNTs) were embedded. Afterward,the electrospun nanofibers were successfully decorated with shish-kebab structure via a self-induced crystallization technique. The topographical features and the mechanical properties of the composite scaffolds were characterized,and the biocompatibility of the material was assessed by using human osteogenic sarcoma osteoblasts(MG-63 cells). The carbon nanotube(CNT) concentration is found to affect the fiber diameter and mechanical properties of electrospun nanofibers and the periodic distance of the shish-kebab architecture. Cellular attachment and proliferation assays reveal that 0.5 wt% CNT-embedded PCL scaffold shows enhanced biocompatibility with MG-63 cells than their counterparts made of neat PCL, and the collagen-like nanotopology provided by the shish-kebab structure further facilitates the cell adhesion and proliferation. The superior interactions between cells and scaffolds demonstrate that the shish-kebab-structured CNTs/PCL nanofibers may be promising candidate for tissue engineering scaffold application.
基金This work was financially supported by the Key Program of National Natural Science Foundation of China(No.G 20434020)the Special Funds for Major Basic Research Projects(No.G 2005 CB623802)the Committee of Science and Technology of Zhejiang Province.
文摘Ring-opening polymerization of ε-caprolactone has been carried out by using rare earth Schiff base complexes： lanthanide tris（N-phenyl-3,5-di-t-butylsalicylaldiminato）s [Ln（OPBS）3] as single component catalyst for the first time. The influences of different rare earth elements, monomer and catalyst concentration as well as reaction time on the polymerization were investigated. Mechanism studies showed that monomer inserts into the active site with the acyl-oxygen bond scission rather than the break of alkyl-oxygen bond.
基金financially supported by the National Natural Science Foundation of China(Nos.21074088 and 31201426)
文摘Hyperbranched polyamidoamines （HPAs） were directly employed as macroinitiators to initiate the Sn（Oct）2 catalyzed ring-opening polymerization of ε-caprolactone （CL）, resulting in multiarm star copolymers with poly（6- caprolactone） （PCL） as shells and HPA as core （HPA-b-PCL）. From 1H-NMR characterization it was deduced that both the primary amines and the secondary amide groups of HPAs could initiate the CL polymerization, and the initiation efficiency increased when more CL monomers were fed. The average arm-numbers of the obtained stars were in the range of 115-353. Differential scanning calorimetry measurements demonstrated that the melting and crystallization temperatures, fusion and crystallization enthalpy and the degree of crystallinity of the star polymers increased as the PCL arm length increased. HPA- b-PCL stars could be used as nanocarriers to efficiently accommodate anionic dyes at acidic condition, while load cationic dyes at basic condition. Compared with the dye-loading behavior of multiarrn star PCL with the neutral hyperbranched polyglycerol as core, it was deduced that HPA-b-PCL nanocarriers accommodated anionic dyes using the HPA core, while loaded cationic dyes using both the HPA core and the PCL shell. Dynamic light scattering analyses also supported such deduction. Furthermore, HPA-b-PCL nanocarriers could selectively load the anionic Eosin Y or the cationic methylene blue from their mixture at pH = 6 or 9, respectively, realizing their separation.
文摘Poly(ε-caprolactone) (PCL) with different molecular weights was synthesized and characterized by a gelpermeation chromatograph equipped with multiple detector. The melting behavior of PCL was also studied. It was found thatthe equilibrium melting points (T_m^0) of PCL samples depend on their molecular weights. Wide angle X-ray diffractionmeasurements (WAXD) and DSC measurements showed that the crystals of the high molecular weight PCLs were moreperfect than those of the low molecular weigh ones. These results demonstrate that the concentration of the end groups ofPCL chains is the main factor that influences the melting behavior. The fusion enthalpy per repeating unit (ΔH_u) wasdetermined to be 11.3 kJ/mol for PCL.
基金Project supported by Jiangsu Key Laboratory for the Environment Functional Materialsthe Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)Innovation Program for Graduate Students of USTS(SKCX11S-058)
文摘Complexes of lanthanide trisborohydrides, formally Ln（BH4）3（THF）, （Ln=La, Ce, Sm, Yb）, were synthesized and their catalytic activity for polymerization of ε-caprolactone was studied. All the complexes can catalyze this polymerization. It was found that the catalytic activities decreased in the order of La〉Ce〉Sm〉Yb. The crystal structure of cerium trisborohydride was determined for the first time by single crystal X-ray diffraction analysis. It is an ionic pair complex of [Ce（BH4）E（THF）5][Ce（BH4）4（THF）2]. The cationic part involves two ηa-BH4 ligands, while the anionic part involves two η3-BH4 groups and two η2-BH4 groups.
基金National Natural Science Foundations of China(No.30970714,No.51103092)Natural Science Foundation of Jiangsu Province,China(No.BK2012634)+1 种基金College Natural Science Research Project of Jiangsu Province,China(No.12KJA430003)Priority Academic Program Development of Jiangsu Higher Education Institutions,China
文摘The mechanical properties and water solubility of electrospinning SF films limit their use as biomaterials. In order to develop a tissue engineering biomaterial with both satisfying biological properties and sufficient biomechanical properties,blended films composed of silk fibroin( SF) and poly( ε-caprolactone)( PCL) were fabricated by electrospinning in this study. Scanning electron microscope( SEM), X-ray diffraction( XRD),thermal analysis,Fourier transform-infrared( FT-IR),Raman spectra,mechanical testing,and water solubility were used to characterize the morphological, structural and mechanical properties of the blended electrospinning films. Results showed that the diameter of the blended fiber was distributed between 600 and1000 nm,and the fiber diameter increased as the PCL content increased. There is no obvious phase separation due to the similarity and intermiscibility,as well as the interactions( mainly hydrogen bonds), between the two polymers. Meanwhile, the secondary structures of SF changed from random coils and Silk I to Silk II because of the interactions between SF and PCL. For this reason,the tensile strength and elongation at break of the electrospinning films improved significantly,and the water solubility decreased. In conclusion,the blended electrospinning films fabricated in this study showed satisfying mechanical properties and water insolubilities,and they may be promising biomaterials for applications in tissue engineering for blood vessels,nerve conduits,tendons,ligaments and other tissues.
基金The authors acknowledge the financial supports from National Nature Science Foundation（Nos. 20674071, 20774078 and 20434020） ；the Special Funds for Major State Basic Research Projects （No.2005CB623802）.
文摘Tetrahydrosalen ligand was employed in the synthesis of gadolinium complex. The ligand was deprotoned by LiBu, and the afforded lithium salt was reacted with anhydrous GdCl3 to produce the gadolinium complex through salt metathesis. This complex was successfully used to initiate the ring-opening polymerization of ε-caprolactone. The initiation conditions in different temperature, monomer-to-initiator ratio and time were investigated. Under the condition： [ε-caprolactone]：[catalyst] = 600, 56 ℃, toluene： 2 ml, poly（ε-caprolactone） （PCL） with Mw = 11,2782 and PDI = 1.96 was achieved.
