The toughened poly(L-lactic acid)/poly(butylene succinate-butylene terephthalate)(PLLA/PBST) blend with enhanced melt strength and excellent low temperature toughness and strength was prepared by melt compounding thro...The toughened poly(L-lactic acid)/poly(butylene succinate-butylene terephthalate)(PLLA/PBST) blend with enhanced melt strength and excellent low temperature toughness and strength was prepared by melt compounding through in situ compatibilization reaction in presence of multifunctional epoxy compound(ADR).The PLLA/PBST blend was an immiscible system,and the compatibility of the PLLA/PBST blend was improved after adding ADR.FTIR and GPC curves confirmed the formation of the PLLA-g-PBST copolymer,which improved the interfacial bonding of the blend and therefore the PLLA/PBST/ADR blend showed excellent melt strength and mechanical properties.For the PLLA/PBST/ADR blend with 70/30 PLLA/PBST content,the complex viscosity increased significantly with increasing ADR content.Moreover,the tensile strength,elongation at break and impact strength all increased obviously with increasing the ADR content.The elongation at break of the blend reached the maximum value of 392.7%,which was 93.2 times that of neat PLLA.And the impact strength of the blend reached the maximum value of 74.7 k J/m~2,which was 21.3 times that of neat PLLA.Interestingly,the PLLA/PBST/ADR blend exhibited excellent lowtemperature toughness and strength.At –20 ℃,the elongation at break of the PLLA/PBST/ADR blend was as high as 93.2%,and the impact strength reached 18.8 k J/m~2.Meanwhile,the tensile strength of the blend at low temperature was also high(64.7 MPa),which was beneficial to the application of PLA in the low temperature field.In addition,the PLLA/PBST/ADR blend maintaind good biodegradability,which was of great significance to the wide application of PLLA.展开更多
The demand for injectable dermal filler has unde rgone significant growth with the rapid development of the beauty industry.Poly(lactic acid)(PLA) as a benefit of excellent biocompatibility and long-term promotion of ...The demand for injectable dermal filler has unde rgone significant growth with the rapid development of the beauty industry.Poly(lactic acid)(PLA) as a benefit of excellent biocompatibility and long-term promotion of collagen regeneration has been favored as a commonly used filler.However,the effects of chirality and particle size of PLA on the efficacy of dermal filler have not been studied.In this study,we prepared three kinds of microspheres(MSs) consisting of poly(D-lactic acid)(PDLA MS),poly(L-lactic acid)(PLLA MS),or meso-PLA(PDLLA MS)at 5,10 and 20 μmto reveal the different biological functions as dermal filler.Following intradermal injection into guinea pig,it was found that PLLA MS induced the slightest inflammation,and the level of pro-inflammatory cytokine IL-1β induced by PLLA MS is only 0.3 or 0.7-fold of that induced by PDLA or PDLLA MS,respectively.More importantly,PLLA MS significantly stimulated the regeneration of collagen,which was 1.4 or 1.1 times higher than those stimulated by PDLA MS or PDLLA MS,respectively.The size of PLA MSs did not affect the levels of inflammation and collagen regeneration.The results confirmed the superiority of PLLA as a dermal filler.展开更多
The morphologies of poly(L-lactic acid)(PLLA)spherulites,when crystallized within the pre-existed poly(oxymethylene)(POM)crystal frameworks,have been investigated.PLLA/POM blend is a melt-miscible crystalline/crystall...The morphologies of poly(L-lactic acid)(PLLA)spherulites,when crystallized within the pre-existed poly(oxymethylene)(POM)crystal frameworks,have been investigated.PLLA/POM blend is a melt-miscible crystalline/crystalline blend system.Owing to the lower melting point but much faster crystallization rate than PLEA,POM crystallized first upon cooling from the melt state and then melted first during the subsequent heating process in this blend system.Lamellar assembly of PLLA crystals within the pre-existed POM spherulitic frameworks was directly observed with the polarized light microscopy by selectively melting the POM frameworks.The investigation indicated that PLLA crystals fully replicated the spherulitic morphology and optical birefringence of the POM crystal frameworks,which was independent of T_(o).On the other hand,POM could also duplicate the pre-existed PLLA morphologies.The result obtained provides us a possibility to design the lamellar assembly and crystal structures of polymer crystals in miscible crystalline/crystalline polymer blends.展开更多
Poly(L-lactic acid)(PLLA)is a thermoplastic material with complete degradability,high biocompatibility and excellent mechanical properties.It can replace petroleum-based polymers are currently being used in the fields...Poly(L-lactic acid)(PLLA)is a thermoplastic material with complete degradability,high biocompatibility and excellent mechanical properties.It can replace petroleum-based polymers are currently being used in the fields of packaging,agriculture,textiles,medical and so on.However,PLLA’s extremely flammability greatly limits its wider application.An bio-based flame retardant L-APP/PLLA composites was prepared by melt blending of the L-APP and PLLA.The morphology,impact properties,thermal properties and flame retardant properties of composites were investigated by field emission scanning electron microscope(SEM),impact tester,differential scanning calorimeter(DSC),thermogravimetric analyzer(TGA),limiting oxygen indexer(LOI)and horizontalvertical burning tester.The results showed that the degree of crystallization(X_(c))and LOI of L-APP/PLLA composites increased as increasing of L-APP content.What’s more,the impact strength first increased and then decreased,the glass transition temperature(T_(g))and melting temperature(T_(m))do not changed significantly.The impact strength of composites was 9.1 kJ/m^(2) at a 5 wt%loading for L-APP,which was the highest level.When the content of L-APP was 20%,the LOI was 30.8%,the Xc was 42.3%and the UL-94 level was V-0.This research can promote the value-added utilization of lignin and the application of PLLA in the fields of flame retardant materials.展开更多
A novel poly（d, /-lactic acid） （PDLLA） based biomimetic polymer was synthesized by grafting maleic anhydride, butanediamine and arg-gly-asp-ser （RGDS） peptides onto the backbone of PDLLA, aiming to overcome the ...A novel poly（d, /-lactic acid） （PDLLA） based biomimetic polymer was synthesized by grafting maleic anhydride, butanediamine and arg-gly-asp-ser （RGDS） peptides onto the backbone of PDLLA, aiming to overcome the acidity and auto-accelerating degradation of PDLLA during degradation and to improve its biospecificity and biocompatibility. The synthetic copolymer was characterized by FTIR, ^13C NMR and amino acid analyzer （AAA）.展开更多
The effect of a novel active nucleating agent(TBC8-eb) on the isothermal crystallization of poly(L-lactic acid) (PLLA) was studied by differential scanning calorimetry(DSC) and Fourier transform infrared spectroscopy(...The effect of a novel active nucleating agent(TBC8-eb) on the isothermal crystallization of poly(L-lactic acid) (PLLA) was studied by differential scanning calorimetry(DSC) and Fourier transform infrared spectroscopy(FTIR) . The analysis on kinetics demonstrates that TBC8-eb can not only accelerate the crystallization rate but also transform most of the original spherulite crystals of PLLA into sheaf-like crystals. Furthermore,the free energy of folding(σe) of PLLA and PLLA with TBC8-eb is 0.15 and 0.06 J·m-2,respectively,which suggests that the addition of TBC8-eb favors the regular folding of molecule chains in the crystallization of PLLA,improv-ing its crystallization rate. The FTIR results show that TBC8-eb can accelerate the conformational ordering of PLLA in the isothermal crystallization. The conformational ordering of PLLA nucleated with TBC8-eb begins with the interchain interaction of CH3,and then a short helix emerges where a couple of CH3 groups interact.展开更多
PLLA/CA mixtures of different compositions were successfully electrospun to obtain composite nanofibrous membranes. The microstructures of the membrances changed from homogeneous to heterogeneous with the addition of ...PLLA/CA mixtures of different compositions were successfully electrospun to obtain composite nanofibrous membranes. The microstructures of the membrances changed from homogeneous to heterogeneous with the addition of CA, which was observed by FE-ESEM. The PLLA/CA fabric membranes were characterized by mechanical testing, DSC and contact angle measurements. The tensile stress of the composite fibrous membranes increased obviously with the increase of CA content. DSC results indicated that the CA component was the main factor for the changes of enthalpies in the composite fibers. Contact angle measurements showed the hydrophilicity of the electrospun nanofiber membranes was improved with the addition of CA.展开更多
Poly(L-lactic acid)(PLLA)-based composites exhibit wide applications in many fields.However,most of hydrophilic fillers usually accelerate the hydrolytic degradation of PLLA,which is unfavorable for the prolonging of ...Poly(L-lactic acid)(PLLA)-based composites exhibit wide applications in many fields.However,most of hydrophilic fillers usually accelerate the hydrolytic degradation of PLLA,which is unfavorable for the prolonging of the service life of the articles.In this work,a small quantity of poly(methyl methacrylate)(PMMA)(2 wt%-10 wt%)was incorporated into the PLLA/carbon nanotubes(CNTs)composites.The effects of PMMA content on the dispersion of CNTs as well as the microstructure and hydrolytic degradation behaviors of the composites were systematically investigated.The results showed that PMMA promoted the dispersion of CNTs in the composites.Amorphous PLLA was obtained in all the composites.Largely enhanced hydrolytic degradation resistance was achieved by incorporating PMMA,especially at relatively high PMMA content.Incorporating 10 wt%PMMA led to a dramatic decrease in the hydrolytic degradation rate from 0.19%/h of the PLLA/CNT composite sample to 0.059%/h of the PLLA/PMMA-10/CNT composite sample.The microstructure evolution of the composites was also detected,and the results showed that no crystallization occurred in the PLLA matrix.Further results based on the interfacial tension calculation showed that the enhanced hydrolytic degradation resistance of the PLLA matrix was mainly attributed to the relatively strong interfacial affinity between PMMA and CNTs,which prevented the occurrence of hydrolytic degradation at the interface between PLLA and CNTs.This work provides an alternative method for tailoring the hydrolytic degradation ability of the PLLA-based composites.展开更多
In this paper, the surface structure of poly(L-lactic acid) (PLLA) film modified with gelatin was investigated. ThePLLA film specimens were treated directly with aqueous alkali solution to provide their surfaces with ...In this paper, the surface structure of poly(L-lactic acid) (PLLA) film modified with gelatin was investigated. ThePLLA film specimens were treated directly with aqueous alkali solution to provide their surfaces with carboxyl groups, sothat these functional groups could become the reactive sites for gelatin immobilization. The functional groups of the PLLAfilms were identified by ATR-FTIR spectra and XPS spectra, the changes in surface morphology were observed by usingenvironmental scanning electron microscopy (ESEM), and the hydrophilicity of modified PLLA films was examined bywater contact angle measurement. Experimental results showed that the gelatin was immobilized with water-solublecarbodiimide (EDC) onto the PLLA film's surfaces, and the gelatin content on the polymer surface was related to carboxylicgroup formed in the controlled hydrolysis process. Rough surfaces caused by hydrolysis will predominantly favor the adhesion and growth of cell; and the hydrophilicity of these surfaces after the modification procedure is enhanced.展开更多
Biodegradable chitosan-g-poly (D, L-lactic acid) copolymers were prepared via two methods. (1) The lactide was grafted onto hydroxyl groups of chitosan by using macromolecular initiator sodium of trimethylsilyl-chit...Biodegradable chitosan-g-poly (D, L-lactic acid) copolymers were prepared via two methods. (1) The lactide was grafted onto hydroxyl groups of chitosan by using macromolecular initiator sodium of trimethylsilyl-chitosan, (2) poly (D,L-lactic acid)(PLA) with low molecular weight can be linked to the amino group by coupling activated PLA to trimethylsilyl-chitosan. Two graft copolymers had hydrophilic-hydrophobic character and can be applied as carriers for drug delivery.展开更多
A novel modified poly(dl-lactic acid) (PDLLA) was obtained by covalently grafting of maleic anhydride onto the backbone of PDLLA, attempting to improve PDLLA’s hydrophilicity and cell affinity and to provide reactive...A novel modified poly(dl-lactic acid) (PDLLA) was obtained by covalently grafting of maleic anhydride onto the backbone of PDLLA, attempting to improve PDLLA’s hydrophilicity and cell affinity and to provide reactive groups for further chemical modification. FTIR, 13C NMR and DSC were used to characterize the maleic anhydride-modified PDLLA.展开更多
Integrating poly（lactic acid） （PLA）, glycolic acid （GA） and ethylene glycol （EG） will hopefully result in a novel copolymer that combines such advantages as fastened and controllable release rate and improved ...Integrating poly（lactic acid） （PLA）, glycolic acid （GA） and ethylene glycol （EG） will hopefully result in a novel copolymer that combines such advantages as fastened and controllable release rate and improved flexibility together with good biocompatibility. In this study, p-dioxanone （PDO） was employed to copolymerize with DL-lactide （LA） via ring-opening melt polymerization using Sn（Oct）2 as an initiator and ethylene glycol as a co-initiator. The obtained degradable macrodiols （HO-P（LA-co-PDO）-OH） were just such a copolymer consisting of PLA, GA and EG. 1HNMR was employed to characterize the copolymers, and the effect of PDO/LA molar ratios in the feedstock on the molecular weights of HO-P（LA-co-PDO）-OH was investigated by means of endhydroxyl analysis, 1H NMR or GPC-MALLs. The results confirmed the successful synthesis of HO-P（LA-co-PDO）-OH and revealed that one end-hydroxyl of the micarodiols was donated by LA or PDO and the other one by the co-initiator EG. In addition, the molecular weights of HO-P（LA-co-PDO）-OH increased with decreasing PDO/LA ratios.展开更多
Inhibition of neurite growth, which is in large part mediated by the Nogo-66 receptor, affects neural regeneration following bone marrow mesenchymal stem cell transplantation. The tissue engineering scaffold poly（D,L...Inhibition of neurite growth, which is in large part mediated by the Nogo-66 receptor, affects neural regeneration following bone marrow mesenchymal stem cell transplantation. The tissue engineering scaffold poly（D,L-lactide-co-glycolic acid） has good histocompatibility and can promote the growth of regenerating nerve fibers. The present study used small interfering RNA to silence Nogo-66 receptor gene expression in bone marrow mesenchymal stem cells and Schwann cells, which were subsequently transplanted with poly（D,L-lactide-co-glycolic acid） into the spinal cord lesion regions in rats. Simultaneously, rats treated with scaffold only were taken as the control group. Hematoxylin-eosin staining and immunohistochemistry revealed that at 4 weeks after transplantation, rats had good motor function of the hind limb after treatment with Nogo-66 receptor gene-silenced ceils prus the poly（O,L-lactide-co-glycolic acid） scaffold compared with rats treated with scaffold only, and the number of bone marrow mesenchymal stem cells and neuron-like cells was also increased. At 8 weeks after transplantation, horseradish peroxidase tracing and transmission electron microscopy showed a large number of unmyelinated and myelinated nerve fibers, as well as intact regenerating axonal myelin sheath following spinal cord hemisection injury. These experimental findings indicate that transplantation of Nogo-66 receptor gene-silenced bone marrow mesenchymal stem cells and Schwann cells plus a poly（D,L-lactide-co-glycolic acid） scaffold can significantly enhance axonal regeneration of spinal cord neurons and improve motor function of the extremities in rats following spinal cord injury.展开更多
High molecular weight（Mw） poly（L-lactic acid）s（PLLAs） were synthesized using multifunctional epoxy compound（Joncryl-ADR4370） as chain extender. The products were characterized by gel permeation chromatography...High molecular weight（Mw） poly（L-lactic acid）s（PLLAs） were synthesized using multifunctional epoxy compound（Joncryl-ADR4370） as chain extender. The products were characterized by gel permeation chromatography（GPC） and spectroscopy（1HNMR and FTIR）. The results indicated that the Mw of PLLA increased with the increasing of the ratio of epoxy compound and the extending of reaction time. The highest Mw of PLLA reached 360 000 g/mol when the ratio of epoxy compound was 1.5 wt%. However, the reactants turned to cross-linking when the ratio of epoxy compound was over 1.5 wt%. Differential scanning calorimetry（DSC） measurements demonstrated that the glass transition（Tg） and melting temperatures（Tm） of products increased slightly as the increase of the molecular weight. Analysis of the hydrolytic degradation in vitro showed that the branched PLLA possessed the quicker degradability than that of the linear PLLA.展开更多
The biocomposite films were prepared from poly(L-lactic acid)and cellulose nanocrystals.To improve interfacial compatibility of hydrophilic cellulose nanocrystals with hydrophobic matrix polymer as well as to provide ...The biocomposite films were prepared from poly(L-lactic acid)and cellulose nanocrystals.To improve interfacial compatibility of hydrophilic cellulose nanocrystals with hydrophobic matrix polymer as well as to provide the osteoconductive properties,cellulose was functionalized with poly(glutamic acid).The modified cellulose nanocrystals were better distributed and less aggregated within the matrix,which was testified by scanning electron,optical and polarized light microscopy.According to mechanical tests,composites filled with nanocrystals modified with PGlu demonstrated higher values of Young’s modulus,elongation at break and tensile strength.Incubation of composite materials in model buffer solutions for 30 weeks followed with staining of Ca^(2+)deposits with Alizarin Red S assay testified better mineralization of materials containing PGlu-modified cellulose nanocrystals as filler.As the result of in vivo experiment,the developed composite materials showed less level of inflammation in comparison with pure polymer matrix and composites filled with non-functionalized cellulose nanocrystals.展开更多
Objective：To observe the changing of biomechanical features during the degradation course of poly-D,L-lactic acid （PDLLA） rods in vivo and in vitro and to evaluate its value as an internal fixation material. Metho...Objective：To observe the changing of biomechanical features during the degradation course of poly-D,L-lactic acid （PDLLA） rods in vivo and in vitro and to evaluate its value as an internal fixation material. Methods ：PDLLA rods were emerged into PBS simultaneous body fluid with constant temperature of 37℃ and the rods were embedded into muscle tissue of 20 rabbits for degradation in vitro and in vivo . The rods were taken out in 2, 4, 6, 8 and 12 weeks. Biomechanical features of bending, shearing and axial compression strength, rigidity and elastic modulus were observed during the degradation course. Statistical method was used to test the changes of biomechanical parameters. Results： （1）There was similar changes of bending, compressive, shearing strength and bending, compressive and shearing rigidity of the PDLLA rods between in vivo and in vitro. （2）Bending, compressive, shearing strength decreased 33%, 18 % and 43 % respectively within the first stage of the degradation, and after 6 weeks of degradation, they decreased slowly. （3）Elastic modulus, bending, compressive and shearing rigidity.decreased sharply during the 6 weeks of degradation, with a drop of 22%, 39% and 30% respectively, and after 8 weeks, they decreased slowly. Even after 12 weeks of degradation, the strength of the rods was still higher than that of sponge bone. Conclusion： During the degradation of the material, the strength and rigidity of PDLLA rods can meet the need of fracture fixation of cancellous bones.展开更多
Semicrystalline polymers can crystallize in the unique crystalline polymorph and show different phase behaviors under the high-pressure CO_(2) treatment.Understanding such unique crystallization and phase transition b...Semicrystalline polymers can crystallize in the unique crystalline polymorph and show different phase behaviors under the high-pressure CO_(2) treatment.Understanding such unique crystallization and phase transition behavior is of fundamental importance for the CO_(2)-assisited processing of semicrystalline polymers.Herein,we investigated the polymorphic crystalline structure,phase transition,and structure-property relationships of poly(L-lactic acid)(PLLA)treated by CO_(2) at different pressures(1-13 MPa)and crystallization temperatures(Tc's,10-110℃).PLLA crystallized in the PLLA/CO_(2) complex crystals under 7-13 MPa CO_(2) at TCS50℃but the common a crystals under the high-pressure CO_(2) at TC≥70℃.Solid-state nuclear magnetic resonance analysis indicated that the PLLA/CO_(2) complex crystals possessed weaker interactions between the PLLA chains than the common a crystals.The PLLA/CO_(2) complex crystals were metastable and transformed into the thermally stable a crystals via the solid-to-solid route during heating or annealing at the temperature above 50℃.The complex crystals of PLLA produced at low Tc was more ductile than the a crystals due to the lower crystallinity and the plasticizing effect of CO_(2).展开更多
Equilibrium sorption amount, desorption diffusion coefficients and sorption diffusion coefficients of CO2 in poly（l-lactic acid） （PLLA） films at elevated pressures were determined by the gravimetric method, in whi...Equilibrium sorption amount, desorption diffusion coefficients and sorption diffusion coefficients of CO2 in poly（l-lactic acid） （PLLA） films at elevated pressures were determined by the gravimetric method, in which the Fick＇s diffusion model was applied to analyze both the desorption and sorption processes. The equilibrium sorption amount of CO2 in PLLA increased with lowering temperature and elevating pressure at the temperature range from 40 to 60 ℃ and pressure from 10^4 to 2x10^4 kPa. Desorption diffusion coefficients were greatly influenced by the equilibrium sorption amount, and they were in the same order of magnitude as the sorption diffusion coefficients. The scan electron microscope （SEM） photos demonstrated that there was no foaming phenomenon of the PLLA film during desorption and sorption processes. The XRD spectra implied that the crystalline degree of PLLA film decreased after CO2 processing. It was concluded that PLLA polymer could be well swollen and plasticized by supercritical CO2.展开更多
Objective： The aim of this study was to formulate polymer-based artesunate nanoparticles for malaria treatment. Methods： Artesunate was loaded with poly（D,L-lactic-co-glycolic acid） （PLGA） by solvent evaporation...Objective： The aim of this study was to formulate polymer-based artesunate nanoparticles for malaria treatment. Methods： Artesunate was loaded with poly（D,L-lactic-co-glycolic acid） （PLGA） by solvent evaporation from an oil-in-water single emulsion. Nanoparticles were characterized by X-ray diffraction and differential scanning calo- rimetry analyses. In vivo antimalarial studies at 4 mg/kg were performed on Swiss male albino mice infected with Plasmodium berghei. Hematological and hepatic toxicity assays were performed. In vitro cytotoxicity of free and en- capsulated artesunate （Art-PLGA） to cell line RAW 264.7 was determined at concentrations of 7.8-1000 pg/ml. Re- sults： The particle size of the formulated drug was （329.3±21.7） nm and the entrapment efficiency was （38.4±10.1）%. Art-PLGA nanoparticles showed higher parasite suppression （62.6%） compared to free artesunate （58.2%, P〈0.05）. Platelet counts were significantly higher in controls （305 000.00±148 492.40） than in mice treated with free artesunate （139 500.00±20 506.10） or Art-PLGA （163 500.00±3535.53） （P〈0.05）. There was no sign of hepatic toxicity following use of the tested drugs. The half maximal inhibitory concentration （IC50） of Art-PLGA （468.0 pg/ml） was significantly higher （P〈0.05） than that of free artesunate （7.3 pg/ml） in the in vitro cytotoxicity assay. Conclusions： A simple treatment of PLGA-entrapped artesunate nanoparticles with dual advantages of low toxicity and better antiplasmodial efficacy has been developed.展开更多
基金financially supported by the Science and Technology Development Plan of Jilin Province (No. 20210203199SF)。
文摘The toughened poly(L-lactic acid)/poly(butylene succinate-butylene terephthalate)(PLLA/PBST) blend with enhanced melt strength and excellent low temperature toughness and strength was prepared by melt compounding through in situ compatibilization reaction in presence of multifunctional epoxy compound(ADR).The PLLA/PBST blend was an immiscible system,and the compatibility of the PLLA/PBST blend was improved after adding ADR.FTIR and GPC curves confirmed the formation of the PLLA-g-PBST copolymer,which improved the interfacial bonding of the blend and therefore the PLLA/PBST/ADR blend showed excellent melt strength and mechanical properties.For the PLLA/PBST/ADR blend with 70/30 PLLA/PBST content,the complex viscosity increased significantly with increasing ADR content.Moreover,the tensile strength,elongation at break and impact strength all increased obviously with increasing the ADR content.The elongation at break of the blend reached the maximum value of 392.7%,which was 93.2 times that of neat PLLA.And the impact strength of the blend reached the maximum value of 74.7 k J/m~2,which was 21.3 times that of neat PLLA.Interestingly,the PLLA/PBST/ADR blend exhibited excellent lowtemperature toughness and strength.At –20 ℃,the elongation at break of the PLLA/PBST/ADR blend was as high as 93.2%,and the impact strength reached 18.8 k J/m~2.Meanwhile,the tensile strength of the blend at low temperature was also high(64.7 MPa),which was beneficial to the application of PLA in the low temperature field.In addition,the PLLA/PBST/ADR blend maintaind good biodegradability,which was of great significance to the wide application of PLLA.
基金financially supported by the National Natural Science Foundation of China(Nos.51703012 and 51603204)the Science and Technology Development Program of Jilin Province(No.20190701004GH)。
文摘The demand for injectable dermal filler has unde rgone significant growth with the rapid development of the beauty industry.Poly(lactic acid)(PLA) as a benefit of excellent biocompatibility and long-term promotion of collagen regeneration has been favored as a commonly used filler.However,the effects of chirality and particle size of PLA on the efficacy of dermal filler have not been studied.In this study,we prepared three kinds of microspheres(MSs) consisting of poly(D-lactic acid)(PDLA MS),poly(L-lactic acid)(PLLA MS),or meso-PLA(PDLLA MS)at 5,10 and 20 μmto reveal the different biological functions as dermal filler.Following intradermal injection into guinea pig,it was found that PLLA MS induced the slightest inflammation,and the level of pro-inflammatory cytokine IL-1β induced by PLLA MS is only 0.3 or 0.7-fold of that induced by PDLA or PDLLA MS,respectively.More importantly,PLLA MS significantly stimulated the regeneration of collagen,which was 1.4 or 1.1 times higher than those stimulated by PDLA MS or PDLLA MS,respectively.The size of PLA MSs did not affect the levels of inflammation and collagen regeneration.The results confirmed the superiority of PLLA as a dermal filler.
基金financially supported by the National Natural Science Foundation of China(Nos.21674033,21374027)National Key R&D Program of China(No.2017YFB0307704)
文摘The morphologies of poly(L-lactic acid)(PLLA)spherulites,when crystallized within the pre-existed poly(oxymethylene)(POM)crystal frameworks,have been investigated.PLLA/POM blend is a melt-miscible crystalline/crystalline blend system.Owing to the lower melting point but much faster crystallization rate than PLEA,POM crystallized first upon cooling from the melt state and then melted first during the subsequent heating process in this blend system.Lamellar assembly of PLLA crystals within the pre-existed POM spherulitic frameworks was directly observed with the polarized light microscopy by selectively melting the POM frameworks.The investigation indicated that PLLA crystals fully replicated the spherulitic morphology and optical birefringence of the POM crystal frameworks,which was independent of T_(o).On the other hand,POM could also duplicate the pre-existed PLLA morphologies.The result obtained provides us a possibility to design the lamellar assembly and crystal structures of polymer crystals in miscible crystalline/crystalline polymer blends.
基金This work was financially supported by the following funds:Hunan Provincial Natural Foundation of China(2019JJ50472)Opening Fund of National&Local Joint Engineering Laboratory for New Petro-chemical Materials and Fine Utilization of Resources(KF201802)+4 种基金Hunan Province Key Field R&D Program Project(2019GK2246)Education Department of Hunan Province Key Project(19A391)Key scientific research project of Huaihua University(HHUY2019-04)Special Project of Innovative Provincial Construction in Hunan Province(2020RC1013)Huaihua Key Laboratory for Preparation of Ceramic Materials and Devices and Science and Technology Plan Project of Huaihua City(2020R3101).
文摘Poly(L-lactic acid)(PLLA)is a thermoplastic material with complete degradability,high biocompatibility and excellent mechanical properties.It can replace petroleum-based polymers are currently being used in the fields of packaging,agriculture,textiles,medical and so on.However,PLLA’s extremely flammability greatly limits its wider application.An bio-based flame retardant L-APP/PLLA composites was prepared by melt blending of the L-APP and PLLA.The morphology,impact properties,thermal properties and flame retardant properties of composites were investigated by field emission scanning electron microscope(SEM),impact tester,differential scanning calorimeter(DSC),thermogravimetric analyzer(TGA),limiting oxygen indexer(LOI)and horizontalvertical burning tester.The results showed that the degree of crystallization(X_(c))and LOI of L-APP/PLLA composites increased as increasing of L-APP content.What’s more,the impact strength first increased and then decreased,the glass transition temperature(T_(g))and melting temperature(T_(m))do not changed significantly.The impact strength of composites was 9.1 kJ/m^(2) at a 5 wt%loading for L-APP,which was the highest level.When the content of L-APP was 20%,the LOI was 30.8%,the Xc was 42.3%and the UL-94 level was V-0.This research can promote the value-added utilization of lignin and the application of PLLA in the fields of flame retardant materials.
基金This study was supported by the National Natural Science Foundation of China(No.30270395 and 30300084)the National"863"Project(No.2003AA32X210).
文摘A novel poly（d, /-lactic acid） （PDLLA） based biomimetic polymer was synthesized by grafting maleic anhydride, butanediamine and arg-gly-asp-ser （RGDS） peptides onto the backbone of PDLLA, aiming to overcome the acidity and auto-accelerating degradation of PDLLA during degradation and to improve its biospecificity and biocompatibility. The synthetic copolymer was characterized by FTIR, ^13C NMR and amino acid analyzer （AAA）.
基金Supported by the National Natural Science Foundation of China （20876042） Program of Shanghai Subject Chief Scientist （10XD1401500） Research Fund for the Doctoral Program of Higher Education of China
文摘The effect of a novel active nucleating agent(TBC8-eb) on the isothermal crystallization of poly(L-lactic acid) (PLLA) was studied by differential scanning calorimetry(DSC) and Fourier transform infrared spectroscopy(FTIR) . The analysis on kinetics demonstrates that TBC8-eb can not only accelerate the crystallization rate but also transform most of the original spherulite crystals of PLLA into sheaf-like crystals. Furthermore,the free energy of folding(σe) of PLLA and PLLA with TBC8-eb is 0.15 and 0.06 J·m-2,respectively,which suggests that the addition of TBC8-eb favors the regular folding of molecule chains in the crystallization of PLLA,improv-ing its crystallization rate. The FTIR results show that TBC8-eb can accelerate the conformational ordering of PLLA in the isothermal crystallization. The conformational ordering of PLLA nucleated with TBC8-eb begins with the interchain interaction of CH3,and then a short helix emerges where a couple of CH3 groups interact.
基金supported by the National Natural Science Foundation of China(No.51103058)the Youth Foundation of Jilin Province(No.201101059)Open Foundation of Key Laboratory of Automobile Materials(Jilin University),Ministry of Education(No.10-450060326014)
文摘PLLA/CA mixtures of different compositions were successfully electrospun to obtain composite nanofibrous membranes. The microstructures of the membrances changed from homogeneous to heterogeneous with the addition of CA, which was observed by FE-ESEM. The PLLA/CA fabric membranes were characterized by mechanical testing, DSC and contact angle measurements. The tensile stress of the composite fibrous membranes increased obviously with the increase of CA content. DSC results indicated that the CA component was the main factor for the changes of enthalpies in the composite fibers. Contact angle measurements showed the hydrophilicity of the electrospun nanofiber membranes was improved with the addition of CA.
基金financially supported by the National Natural Science Foundation of China (No. 51473137)the International Science and Technology Cooperation Project of Sichuan Province (No. 2017HH0066)+1 种基金the International Science and Technology Cooperation Project of Chengdu (No. 2016-GH0200097-HZ)the Fundamental Research Funds for the Central Universities (2682019JQ04)
文摘Poly(L-lactic acid)(PLLA)-based composites exhibit wide applications in many fields.However,most of hydrophilic fillers usually accelerate the hydrolytic degradation of PLLA,which is unfavorable for the prolonging of the service life of the articles.In this work,a small quantity of poly(methyl methacrylate)(PMMA)(2 wt%-10 wt%)was incorporated into the PLLA/carbon nanotubes(CNTs)composites.The effects of PMMA content on the dispersion of CNTs as well as the microstructure and hydrolytic degradation behaviors of the composites were systematically investigated.The results showed that PMMA promoted the dispersion of CNTs in the composites.Amorphous PLLA was obtained in all the composites.Largely enhanced hydrolytic degradation resistance was achieved by incorporating PMMA,especially at relatively high PMMA content.Incorporating 10 wt%PMMA led to a dramatic decrease in the hydrolytic degradation rate from 0.19%/h of the PLLA/CNT composite sample to 0.059%/h of the PLLA/PMMA-10/CNT composite sample.The microstructure evolution of the composites was also detected,and the results showed that no crystallization occurred in the PLLA matrix.Further results based on the interfacial tension calculation showed that the enhanced hydrolytic degradation resistance of the PLLA matrix was mainly attributed to the relatively strong interfacial affinity between PMMA and CNTs,which prevented the occurrence of hydrolytic degradation at the interface between PLLA and CNTs.This work provides an alternative method for tailoring the hydrolytic degradation ability of the PLLA-based composites.
基金The authors thank the Ministry of Science and Technology,the National Natural Science Foundation of China and the Ministry of Education of China for supporting of this research(Grant No.G199905305,59973014 and 98005620,respectively).
文摘In this paper, the surface structure of poly(L-lactic acid) (PLLA) film modified with gelatin was investigated. ThePLLA film specimens were treated directly with aqueous alkali solution to provide their surfaces with carboxyl groups, sothat these functional groups could become the reactive sites for gelatin immobilization. The functional groups of the PLLAfilms were identified by ATR-FTIR spectra and XPS spectra, the changes in surface morphology were observed by usingenvironmental scanning electron microscopy (ESEM), and the hydrophilicity of modified PLLA films was examined bywater contact angle measurement. Experimental results showed that the gelatin was immobilized with water-solublecarbodiimide (EDC) onto the PLLA film's surfaces, and the gelatin content on the polymer surface was related to carboxylicgroup formed in the controlled hydrolysis process. Rough surfaces caused by hydrolysis will predominantly favor the adhesion and growth of cell; and the hydrophilicity of these surfaces after the modification procedure is enhanced.
文摘Biodegradable chitosan-g-poly (D, L-lactic acid) copolymers were prepared via two methods. (1) The lactide was grafted onto hydroxyl groups of chitosan by using macromolecular initiator sodium of trimethylsilyl-chitosan, (2) poly (D,L-lactic acid)(PLA) with low molecular weight can be linked to the amino group by coupling activated PLA to trimethylsilyl-chitosan. Two graft copolymers had hydrophilic-hydrophobic character and can be applied as carriers for drug delivery.
文摘A novel modified poly(dl-lactic acid) (PDLLA) was obtained by covalently grafting of maleic anhydride onto the backbone of PDLLA, attempting to improve PDLLA’s hydrophilicity and cell affinity and to provide reactive groups for further chemical modification. FTIR, 13C NMR and DSC were used to characterize the maleic anhydride-modified PDLLA.
基金supported by the National Key Technologies R&D Program of China(No.2006BA103B04)the Natural Key Scientific and Technological Project of Chongqing(No.CSTC 2008AB0027)
文摘Integrating poly（lactic acid） （PLA）, glycolic acid （GA） and ethylene glycol （EG） will hopefully result in a novel copolymer that combines such advantages as fastened and controllable release rate and improved flexibility together with good biocompatibility. In this study, p-dioxanone （PDO） was employed to copolymerize with DL-lactide （LA） via ring-opening melt polymerization using Sn（Oct）2 as an initiator and ethylene glycol as a co-initiator. The obtained degradable macrodiols （HO-P（LA-co-PDO）-OH） were just such a copolymer consisting of PLA, GA and EG. 1HNMR was employed to characterize the copolymers, and the effect of PDO/LA molar ratios in the feedstock on the molecular weights of HO-P（LA-co-PDO）-OH was investigated by means of endhydroxyl analysis, 1H NMR or GPC-MALLs. The results confirmed the successful synthesis of HO-P（LA-co-PDO）-OH and revealed that one end-hydroxyl of the micarodiols was donated by LA or PDO and the other one by the co-initiator EG. In addition, the molecular weights of HO-P（LA-co-PDO）-OH increased with decreasing PDO/LA ratios.
基金sponsored by the Science and Technology Foundation of Tianjin Health Bureau,No. 2010ky04the Application Basis and Front Technology Projects of Tianjin (Science and Technology Foundation of Tianjin),No.12JCYBJC18000
文摘Inhibition of neurite growth, which is in large part mediated by the Nogo-66 receptor, affects neural regeneration following bone marrow mesenchymal stem cell transplantation. The tissue engineering scaffold poly（D,L-lactide-co-glycolic acid） has good histocompatibility and can promote the growth of regenerating nerve fibers. The present study used small interfering RNA to silence Nogo-66 receptor gene expression in bone marrow mesenchymal stem cells and Schwann cells, which were subsequently transplanted with poly（D,L-lactide-co-glycolic acid） into the spinal cord lesion regions in rats. Simultaneously, rats treated with scaffold only were taken as the control group. Hematoxylin-eosin staining and immunohistochemistry revealed that at 4 weeks after transplantation, rats had good motor function of the hind limb after treatment with Nogo-66 receptor gene-silenced ceils prus the poly（O,L-lactide-co-glycolic acid） scaffold compared with rats treated with scaffold only, and the number of bone marrow mesenchymal stem cells and neuron-like cells was also increased. At 8 weeks after transplantation, horseradish peroxidase tracing and transmission electron microscopy showed a large number of unmyelinated and myelinated nerve fibers, as well as intact regenerating axonal myelin sheath following spinal cord hemisection injury. These experimental findings indicate that transplantation of Nogo-66 receptor gene-silenced bone marrow mesenchymal stem cells and Schwann cells plus a poly（D,L-lactide-co-glycolic acid） scaffold can significantly enhance axonal regeneration of spinal cord neurons and improve motor function of the extremities in rats following spinal cord injury.
基金Funded by the National Natural Science Foundation of China (No.30870609)the Natural Science Foundation of Chongqing (Nos.2009BA4025 and CSTC2009BB4382)the Foundation of Chongqing Municipal Education Commission(No.KJ091415)
文摘High molecular weight（Mw） poly（L-lactic acid）s（PLLAs） were synthesized using multifunctional epoxy compound（Joncryl-ADR4370） as chain extender. The products were characterized by gel permeation chromatography（GPC） and spectroscopy（1HNMR and FTIR）. The results indicated that the Mw of PLLA increased with the increasing of the ratio of epoxy compound and the extending of reaction time. The highest Mw of PLLA reached 360 000 g/mol when the ratio of epoxy compound was 1.5 wt%. However, the reactants turned to cross-linking when the ratio of epoxy compound was over 1.5 wt%. Differential scanning calorimetry（DSC） measurements demonstrated that the glass transition（Tg） and melting temperatures（Tm） of products increased slightly as the increase of the molecular weight. Analysis of the hydrolytic degradation in vitro showed that the branched PLLA possessed the quicker degradability than that of the linear PLLA.
基金funded by the Russian Ministry of Education and Science(state contract no.14.W03.31.0014,MegaGrant).
文摘The biocomposite films were prepared from poly(L-lactic acid)and cellulose nanocrystals.To improve interfacial compatibility of hydrophilic cellulose nanocrystals with hydrophobic matrix polymer as well as to provide the osteoconductive properties,cellulose was functionalized with poly(glutamic acid).The modified cellulose nanocrystals were better distributed and less aggregated within the matrix,which was testified by scanning electron,optical and polarized light microscopy.According to mechanical tests,composites filled with nanocrystals modified with PGlu demonstrated higher values of Young’s modulus,elongation at break and tensile strength.Incubation of composite materials in model buffer solutions for 30 weeks followed with staining of Ca^(2+)deposits with Alizarin Red S assay testified better mineralization of materials containing PGlu-modified cellulose nanocrystals as filler.As the result of in vivo experiment,the developed composite materials showed less level of inflammation in comparison with pure polymer matrix and composites filled with non-functionalized cellulose nanocrystals.
文摘Objective：To observe the changing of biomechanical features during the degradation course of poly-D,L-lactic acid （PDLLA） rods in vivo and in vitro and to evaluate its value as an internal fixation material. Methods ：PDLLA rods were emerged into PBS simultaneous body fluid with constant temperature of 37℃ and the rods were embedded into muscle tissue of 20 rabbits for degradation in vitro and in vivo . The rods were taken out in 2, 4, 6, 8 and 12 weeks. Biomechanical features of bending, shearing and axial compression strength, rigidity and elastic modulus were observed during the degradation course. Statistical method was used to test the changes of biomechanical parameters. Results： （1）There was similar changes of bending, compressive, shearing strength and bending, compressive and shearing rigidity of the PDLLA rods between in vivo and in vitro. （2）Bending, compressive, shearing strength decreased 33%, 18 % and 43 % respectively within the first stage of the degradation, and after 6 weeks of degradation, they decreased slowly. （3）Elastic modulus, bending, compressive and shearing rigidity.decreased sharply during the 6 weeks of degradation, with a drop of 22%, 39% and 30% respectively, and after 8 weeks, they decreased slowly. Even after 12 weeks of degradation, the strength of the rods was still higher than that of sponge bone. Conclusion： During the degradation of the material, the strength and rigidity of PDLLA rods can meet the need of fracture fixation of cancellous bones.
基金supported by the National Key R&D Program of China(No.2016YFC1100801)the National Natural Science Foundation of China(No.21873083)State Key Laboratory of Chemical Engineering(No.SKLChE-16Z).
文摘Semicrystalline polymers can crystallize in the unique crystalline polymorph and show different phase behaviors under the high-pressure CO_(2) treatment.Understanding such unique crystallization and phase transition behavior is of fundamental importance for the CO_(2)-assisited processing of semicrystalline polymers.Herein,we investigated the polymorphic crystalline structure,phase transition,and structure-property relationships of poly(L-lactic acid)(PLLA)treated by CO_(2) at different pressures(1-13 MPa)and crystallization temperatures(Tc's,10-110℃).PLLA crystallized in the PLLA/CO_(2) complex crystals under 7-13 MPa CO_(2) at TCS50℃but the common a crystals under the high-pressure CO_(2) at TC≥70℃.Solid-state nuclear magnetic resonance analysis indicated that the PLLA/CO_(2) complex crystals possessed weaker interactions between the PLLA chains than the common a crystals.The PLLA/CO_(2) complex crystals were metastable and transformed into the thermally stable a crystals via the solid-to-solid route during heating or annealing at the temperature above 50℃.The complex crystals of PLLA produced at low Tc was more ductile than the a crystals due to the lower crystallinity and the plasticizing effect of CO_(2).
基金Supported by the National Natura Science Foundation of China （21076185）.
文摘Equilibrium sorption amount, desorption diffusion coefficients and sorption diffusion coefficients of CO2 in poly（l-lactic acid） （PLLA） films at elevated pressures were determined by the gravimetric method, in which the Fick＇s diffusion model was applied to analyze both the desorption and sorption processes. The equilibrium sorption amount of CO2 in PLLA increased with lowering temperature and elevating pressure at the temperature range from 40 to 60 ℃ and pressure from 10^4 to 2x10^4 kPa. Desorption diffusion coefficients were greatly influenced by the equilibrium sorption amount, and they were in the same order of magnitude as the sorption diffusion coefficients. The scan electron microscope （SEM） photos demonstrated that there was no foaming phenomenon of the PLLA film during desorption and sorption processes. The XRD spectra implied that the crystalline degree of PLLA film decreased after CO2 processing. It was concluded that PLLA polymer could be well swollen and plasticized by supercritical CO2.
文摘Objective： The aim of this study was to formulate polymer-based artesunate nanoparticles for malaria treatment. Methods： Artesunate was loaded with poly（D,L-lactic-co-glycolic acid） （PLGA） by solvent evaporation from an oil-in-water single emulsion. Nanoparticles were characterized by X-ray diffraction and differential scanning calo- rimetry analyses. In vivo antimalarial studies at 4 mg/kg were performed on Swiss male albino mice infected with Plasmodium berghei. Hematological and hepatic toxicity assays were performed. In vitro cytotoxicity of free and en- capsulated artesunate （Art-PLGA） to cell line RAW 264.7 was determined at concentrations of 7.8-1000 pg/ml. Re- sults： The particle size of the formulated drug was （329.3±21.7） nm and the entrapment efficiency was （38.4±10.1）%. Art-PLGA nanoparticles showed higher parasite suppression （62.6%） compared to free artesunate （58.2%, P〈0.05）. Platelet counts were significantly higher in controls （305 000.00±148 492.40） than in mice treated with free artesunate （139 500.00±20 506.10） or Art-PLGA （163 500.00±3535.53） （P〈0.05）. There was no sign of hepatic toxicity following use of the tested drugs. The half maximal inhibitory concentration （IC50） of Art-PLGA （468.0 pg/ml） was significantly higher （P〈0.05） than that of free artesunate （7.3 pg/ml） in the in vitro cytotoxicity assay. Conclusions： A simple treatment of PLGA-entrapped artesunate nanoparticles with dual advantages of low toxicity and better antiplasmodial efficacy has been developed.
