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
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
D,L-lactide was prepared from D,L-lactic acid by means of polymerization and depolymerization at low vacuum level.Morpholine-2,5-dione(MD) was synthesized from the cyclization of chloroacetyl glycine which was made fr...D,L-lactide was prepared from D,L-lactic acid by means of polymerization and depolymerization at low vacuum level.Morpholine-2,5-dione(MD) was synthesized from the cyclization of chloroacetyl glycine which was made from chloroacetyl chloride and glycine in the basic condition.A novel copolymer(PLAMD) with D,L-lactide(D,L-LA) and morpholine-2,5-dione(MD) was synthesized using stannous octoate as initiator,and characterized with FT-IR and 1HNMR.The biocompatibility of PLAMD and PLA was investigated by MTT and microscope.The results show that amino acid is introduced into PDLLA main chain.PLAMD has better cell affinity than PLA,so it is a promising biomaterial.展开更多
Paclitaxel(PTX) is an effective anticancer drug with poor solubility in water.Recently,much effort has been devoted into alternative formulations of PTX for improving its aqueous solubility.In this study,PTX and poly(...Paclitaxel(PTX) is an effective anticancer drug with poor solubility in water.Recently,much effort has been devoted into alternative formulations of PTX for improving its aqueous solubility.In this study,PTX and poly(L-lactic acid)(PLLA) were co-precipitated by a supercritical antisolvent(SAS) process using dichloromethane(DCM) and the mixtures of DCM/ethanol(EtOH) or DCM/dimethyl sulfoxide(DMSO) as the solvent,with super-critical carbon dioxide as the antisolvent.The effects of solvent,solvent ratio,temperature,pressure,polymer con-centration and solution flow rate on particle morphology,mass median diameter(Dp50) and PTX loading were in-vestigated using single-factor method.The particle samples were characterized using X-ray diffraction(XRD),scanning electron microscopy(SEM),laser diffraction particle size analyzer and high pressure liquid chromatogra-phy(HPLC).XRD results indicate that the micronized PTX is dispersed into the PLLA matrix in an amorphous form.SEM indicates that the solvent and the solvent ratio have great effect on the particle morphologies,and particle morphology is good at the volume ratio of DCM/EtOH of 50/50.For the mixed DCM/EtOH solvent,Dp50 increases with the increase of the temperature,pressure,PLLA concentration and solution flow rate,and PTX loading in-creases with pressure.Suitable operating conditions for the experimental system are as follows:DCM/EtOH 50/50(by volume),35 ℃,10-12 MPa,PLLA concentration of 5 g·L-1 and solution flow rate of 0.5 ml·min-1.展开更多
The process of production of lactide from butyl lactate was investigated. The process consists of two stages: oligomerisation of butyl lactatean and depolymerisation of oligomers. The type catalysts of the series of ...The process of production of lactide from butyl lactate was investigated. The process consists of two stages: oligomerisation of butyl lactatean and depolymerisation of oligomers. The type catalysts of the series of Lewis acid were tested. It was found that SnCI4 is the most efficient catalyst for both stages.展开更多
A novel cyclodextrin-containing polymer was prepared by graftingβ-cyclodextrin onto the backbone of poly(D,L-lactic acid)(PLA).First,mono(6-(2-aminoethyl)amino-6-deoxy)-β-cyclodextrin(β-CD-6-en)was prepared by sulf...A novel cyclodextrin-containing polymer was prepared by graftingβ-cyclodextrin onto the backbone of poly(D,L-lactic acid)(PLA).First,mono(6-(2-aminoethyl)amino-6-deoxy)-β-cyclodextrin(β-CD-6-en)was prepared by sulfonylation and amination ofβ-cyclodextrin and modified poly(D,L-lactic acid)(MPLA)was prepared by free radical polymerization of maleic anhydride and PLA.Then,grafting ofβ-cyclodextrin derivative to MPLA backbone was carried out by N-acylation reaction of MPLA andβ-CD-6-en in dimethyl formamide.The...展开更多
A novel cloisite modified solid catalyst was prepared in a single step from commercially available starting materials for the first time. The ring opening polymerization of L-lactide and D-lactide using this cloisite ...A novel cloisite modified solid catalyst was prepared in a single step from commercially available starting materials for the first time. The ring opening polymerization of L-lactide and D-lactide using this cloisite modified solid catalyst resulted in homopolymers of 75,000 and PDI = 1.6 and the maximum molecular weight (Mw) i.e. 180,000 with PDI = 1.9 were obtained. The catalytic activity ofcloisite modified solid catalyst was compared with the conventional stannous octoate catalyst and found superior to stannous octoate in all respect such as conversion, molecular weight and molecular weight distribution etc.. Moreover, the maximum molecular weight i.e. 180,000 was obtained at 220 ℃, whereas, transesterification reaction predominate in presence of stannous octoate The linear structure was confirmed by quantitative ^13C NMR Spectroscopy. Blend films were obtained by casting mixed solutions of poly (D-lactide) and poly (L-lactide) at various compositions, and stereocomplex was formed at 50/50 composition with molecular weight of 75,000.展开更多
The aim of this work was to verify the potential of infrared (IR) spectroscopy in near and mid regions to detect the beginning of the malolactic fermentation (MLF) occurring in a model-wine and the further cells a...The aim of this work was to verify the potential of infrared (IR) spectroscopy in near and mid regions to detect the beginning of the malolactic fermentation (MLF) occurring in a model-wine and the further cells autolysis. MLF in wine is a secondary biotransformation due to lactic acid bacteria that usually occurs spontaneou,;ly or after starter inoculation at the end of alcoholic fermentation. Nowadays, it is desirable to supply winemakers with a new rapid and non-destructive approach to monitor MLF progress and 1R spectroscopy technology appears to be suitable for this purpose. The transformation of L-malic acid into L-lactic acid was carried out by inoculating a synthetic wine with an Oenococcus oeni culture and it was monitored through microbiological and chemical methods. At the same time, Fourier transform near infrared (FT-NIR) spectral data, in diffusive transflection mode using an optic probe, and FT-IR spectra, using an germanium crystal attenuated total reflectance (ATR) cell, were collected. Principal component analysis of the spectra was able to identify absorption bands related to the key molecular modifications that took place during the L-malic acid transformation. Thus, the samples were discriminated according to the fermentation phase. Although this study is a preliminary approach, results confirm that near infrared (NIR) and mid infrared (MIR) spectroscopy could be successfully applied to detect the start of MLF and the autolysis of the lactic acid bacteria (LAB) cells.展开更多
The crystal morphology of zinc lactate trihydrate in the absence or presence of impurities(viz.succinic acid,L-malic acid and D-malic acid)is investigated by molecular simulation based on surface docking model and COM...The crystal morphology of zinc lactate trihydrate in the absence or presence of impurities(viz.succinic acid,L-malic acid and D-malic acid)is investigated by molecular simulation based on surface docking model and COMPASS force field.Combing simulation results with our previous experimental results,it is found that the solvent mainly has an inhibition effect on the(0 0 2)surface,and succinic acid impurity will inhibit the growth of(0 0 2)and(0 1 1)surfaces while two enantiomers of malic acid impurity will inhibit the(0 0 2)and(1 0 0)surfaces,which are in good agreement with the experimental results.展开更多
Objective: To explore the method to repair bone defect with bone-morphogenetic-protein loaded hydroxyapatite/collagen-poly(L-lactic acid) composite. Methods: 18 adult beagle dogs were randomly divided into 3 groups. I...Objective: To explore the method to repair bone defect with bone-morphogenetic-protein loaded hydroxyapatite/collagen-poly(L-lactic acid) composite. Methods: 18 adult beagle dogs were randomly divided into 3 groups. In Group A, bone-morphogenetic-protein (BMP) loaded hydroxyapatite/collagen-poly(L-lactic acid) (HAC-PLA) scaffold was implanted in a 2 cm diaphyseal defect in the radius. In Group B, unloaded pure HAC-PLA scaffold was implanted in the defects. No material was implanted in Group C (control group). The dogs were sacrificed 6 months postoperatively. Features of biocompatibility, biodegradability and osteoinduction were evaluated with histological, radiological examinations and bone mineral density (BMD) measurements. Results: In Group A, the radius defect healed after the treatment with BMP loaded HAC-PLA. BMD at the site of the defect was higher than that of the contralateral radius. Fibrous union developed in the animals of the control group. Conclusions: BMP not only promotes osteogenesis but also accelerates degradation of the biomaterials. Optimized design parameters of a three-dimensional porous biomaterial would give full scope to the role of BMP as an osteoinductive growth factor.展开更多
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 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.
基金Project(21107032) supported by the National Natural Science Foundation of China Projects(Y406469, Y4110606) supported by the Natural Science Foundation of Zhejiang Province, China+1 种基金Projects(2008AY2018, 2011AY1048-5, 2011AY1030) supported by the Science Foundation of Jiaxing Science and Technology Bureau,ChinaProject(2009C21003) supported by the Science and Technology Department of Zhejiang Province,China
文摘D,L-lactide was prepared from D,L-lactic acid by means of polymerization and depolymerization at low vacuum level.Morpholine-2,5-dione(MD) was synthesized from the cyclization of chloroacetyl glycine which was made from chloroacetyl chloride and glycine in the basic condition.A novel copolymer(PLAMD) with D,L-lactide(D,L-LA) and morpholine-2,5-dione(MD) was synthesized using stannous octoate as initiator,and characterized with FT-IR and 1HNMR.The biocompatibility of PLAMD and PLA was investigated by MTT and microscope.The results show that amino acid is introduced into PDLLA main chain.PLAMD has better cell affinity than PLA,so it is a promising biomaterial.
基金Supported by the National Natural Science Foundation of China (21076084)the Fundamental Research Funds for the Central Universities (2011ZZ0006)the Open Project Program of Provincial Key Laboratory of Green Processing Technology and Product Safety of Natural Products
文摘Paclitaxel(PTX) is an effective anticancer drug with poor solubility in water.Recently,much effort has been devoted into alternative formulations of PTX for improving its aqueous solubility.In this study,PTX and poly(L-lactic acid)(PLLA) were co-precipitated by a supercritical antisolvent(SAS) process using dichloromethane(DCM) and the mixtures of DCM/ethanol(EtOH) or DCM/dimethyl sulfoxide(DMSO) as the solvent,with super-critical carbon dioxide as the antisolvent.The effects of solvent,solvent ratio,temperature,pressure,polymer con-centration and solution flow rate on particle morphology,mass median diameter(Dp50) and PTX loading were in-vestigated using single-factor method.The particle samples were characterized using X-ray diffraction(XRD),scanning electron microscopy(SEM),laser diffraction particle size analyzer and high pressure liquid chromatogra-phy(HPLC).XRD results indicate that the micronized PTX is dispersed into the PLLA matrix in an amorphous form.SEM indicates that the solvent and the solvent ratio have great effect on the particle morphologies,and particle morphology is good at the volume ratio of DCM/EtOH of 50/50.For the mixed DCM/EtOH solvent,Dp50 increases with the increase of the temperature,pressure,PLLA concentration and solution flow rate,and PTX loading in-creases with pressure.Suitable operating conditions for the experimental system are as follows:DCM/EtOH 50/50(by volume),35 ℃,10-12 MPa,PLLA concentration of 5 g·L-1 and solution flow rate of 0.5 ml·min-1.
文摘The process of production of lactide from butyl lactate was investigated. The process consists of two stages: oligomerisation of butyl lactatean and depolymerisation of oligomers. The type catalysts of the series of Lewis acid were tested. It was found that SnCI4 is the most efficient catalyst for both stages.
基金Funded by the Natural Science Foundation of China(No.50603032)Education Commission of Chongqing(No.KJ090617)the Science and Technology Plan Project of Jiulongpo District,Chongqing,China(No.2008Q95)
文摘A novel cyclodextrin-containing polymer was prepared by graftingβ-cyclodextrin onto the backbone of poly(D,L-lactic acid)(PLA).First,mono(6-(2-aminoethyl)amino-6-deoxy)-β-cyclodextrin(β-CD-6-en)was prepared by sulfonylation and amination ofβ-cyclodextrin and modified poly(D,L-lactic acid)(MPLA)was prepared by free radical polymerization of maleic anhydride and PLA.Then,grafting ofβ-cyclodextrin derivative to MPLA backbone was carried out by N-acylation reaction of MPLA andβ-CD-6-en in dimethyl formamide.The...
文摘A novel cloisite modified solid catalyst was prepared in a single step from commercially available starting materials for the first time. The ring opening polymerization of L-lactide and D-lactide using this cloisite modified solid catalyst resulted in homopolymers of 75,000 and PDI = 1.6 and the maximum molecular weight (Mw) i.e. 180,000 with PDI = 1.9 were obtained. The catalytic activity ofcloisite modified solid catalyst was compared with the conventional stannous octoate catalyst and found superior to stannous octoate in all respect such as conversion, molecular weight and molecular weight distribution etc.. Moreover, the maximum molecular weight i.e. 180,000 was obtained at 220 ℃, whereas, transesterification reaction predominate in presence of stannous octoate The linear structure was confirmed by quantitative ^13C NMR Spectroscopy. Blend films were obtained by casting mixed solutions of poly (D-lactide) and poly (L-lactide) at various compositions, and stereocomplex was formed at 50/50 composition with molecular weight of 75,000.
文摘The aim of this work was to verify the potential of infrared (IR) spectroscopy in near and mid regions to detect the beginning of the malolactic fermentation (MLF) occurring in a model-wine and the further cells autolysis. MLF in wine is a secondary biotransformation due to lactic acid bacteria that usually occurs spontaneou,;ly or after starter inoculation at the end of alcoholic fermentation. Nowadays, it is desirable to supply winemakers with a new rapid and non-destructive approach to monitor MLF progress and 1R spectroscopy technology appears to be suitable for this purpose. The transformation of L-malic acid into L-lactic acid was carried out by inoculating a synthetic wine with an Oenococcus oeni culture and it was monitored through microbiological and chemical methods. At the same time, Fourier transform near infrared (FT-NIR) spectral data, in diffusive transflection mode using an optic probe, and FT-IR spectra, using an germanium crystal attenuated total reflectance (ATR) cell, were collected. Principal component analysis of the spectra was able to identify absorption bands related to the key molecular modifications that took place during the L-malic acid transformation. Thus, the samples were discriminated according to the fermentation phase. Although this study is a preliminary approach, results confirm that near infrared (NIR) and mid infrared (MIR) spectroscopy could be successfully applied to detect the start of MLF and the autolysis of the lactic acid bacteria (LAB) cells.
基金Supported by the Shanghai Commission of Science and Technology(06SR07108)the OpenProject of State Key Laboratory of Chemical Engineering(08C08)
文摘The crystal morphology of zinc lactate trihydrate in the absence or presence of impurities(viz.succinic acid,L-malic acid and D-malic acid)is investigated by molecular simulation based on surface docking model and COMPASS force field.Combing simulation results with our previous experimental results,it is found that the solvent mainly has an inhibition effect on the(0 0 2)surface,and succinic acid impurity will inhibit the growth of(0 0 2)and(0 1 1)surfaces while two enantiomers of malic acid impurity will inhibit the(0 0 2)and(1 0 0)surfaces,which are in good agreement with the experimental results.
文摘Objective: To explore the method to repair bone defect with bone-morphogenetic-protein loaded hydroxyapatite/collagen-poly(L-lactic acid) composite. Methods: 18 adult beagle dogs were randomly divided into 3 groups. In Group A, bone-morphogenetic-protein (BMP) loaded hydroxyapatite/collagen-poly(L-lactic acid) (HAC-PLA) scaffold was implanted in a 2 cm diaphyseal defect in the radius. In Group B, unloaded pure HAC-PLA scaffold was implanted in the defects. No material was implanted in Group C (control group). The dogs were sacrificed 6 months postoperatively. Features of biocompatibility, biodegradability and osteoinduction were evaluated with histological, radiological examinations and bone mineral density (BMD) measurements. Results: In Group A, the radius defect healed after the treatment with BMP loaded HAC-PLA. BMD at the site of the defect was higher than that of the contralateral radius. Fibrous union developed in the animals of the control group. Conclusions: BMP not only promotes osteogenesis but also accelerates degradation of the biomaterials. Optimized design parameters of a three-dimensional porous biomaterial would give full scope to the role of BMP as an osteoinductive growth factor.