Hyperbranched poly (amine‐ester)‐poly (lactide‐co‐glycolide) copolymer and their nanoparticles as paclitaxel delivery system

A new hyperbranched poly (amine‐ester)‐poly (lactide‐co‐glycolide) copolymer (HPAE‐co‐PLGA) was synthesized by ring‐opening polymerization of D , L ‐lactide (DLLA) glycolid and branched poly (amine‐ester) (HPAE‐OHs) with Sn(Oct)₂ as catalyst. The chemical structures of copolymers were determined by FT‐IR, ¹H‐NMR(¹³C NMR), TGA and their molecular weights were determined by gel permeation chromatography (GPC). Paclitaxel‐loaded copolymer nanoparticles were prepared by the nanoprecipitation method. Their physicochemical characteristics, e.g. morphology and nanoparticles size distribution were then evaluated by means of fluorescence spectroscopy, environmental scanning electron microscopy (ESEM), and dynamic light scattering (DLS). Paclitaxel‐loaded nanoparticles assumed a spherical shape and have unimodal size distribution. It was found that the chemical composition of the nanoparticles was a key factor in controlling nanoparticles size, drug‐loading content, and drug release behavior. As the molar ratio of DL ‐lactide/glycolide to HPAE increased, the nanoparticles size and drug‐loading content increased, and the drug release rate decreased. The antitumor activity of the paclitaxel‐loaded HPAE‐co‐PLGA nanoparticles against human liver cancer H7402 cells was evaluated by 3‐(4, 5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl tetrazolium bromide (MTT) method. The paclitaxel‐loaded HPAE‐co‐PLGA nanoparticles showed comparable anticancer efficacy with the free drug. Copyright © 2010 John Wiley & Sons, Ltd.     

Biocompatibility evaluation of self‐assembled micelles prepared from poly(lactide‐co‐glycolide)‐poly(ethylene glycol) diblock copolymers

In this work, a series of PLGA‐PEG diblock copolymers were synthesized by ring‐opening polymerization of L‐lactide and glycolide using mPEG as macroinitiator and stannous octoate as catalyst. Spherical micelles were obtained from the various copolymers by using co‐solvent evaporation method. The biocompatibility of micelles was evaluated with the aim of assessing their potential in the development of drug delivery systems. Various aspects of biocompatibility were considered, including MTT assay, agar diffusion test, release of cytokines, hemolytic test, dynamic clotting time, protein adsorption in vitro, and zebrafish embryonic compatibility in vivo. The combined results revealed that the micelles present good cytocompatibility and hemocompatibility in vitro. Moreover, the cumulative effects of micelles throughout embryos developing stages have no toxicity in vivo. It is thus concluded that micelles prepared from PLGA‐PEG copolymers present good biocompatibility as potential drug carrier.     

Thermosensitive polylactide‐glycolide delivery systems for treatment of narcotic addictions

Environmental switches may be fabricated for the controlled release of pharmaceutical drug using a thermally responsive polymer with the intrinsic chemical and physical nature of stimuli‐sensitive smart materials. Particularly, much attention has been paid to the biomedical applications of poly(N‐isopropyl acrylamide) (PNIPAAm) because of its unique reversible transition at a specific lower critical solution temperature (LCST).Thermally sensitive block copolymers, poly(N‐isopropyl acrylamide‐b‐poly(L ‐lactide‐co‐glycolide) (PNIPAAm‐b‐PLGA), and polyethylene glycol‐poly (lactide‐co‐glycolide) (PEG‐PLGA) triblock copolymers with different compositions and length of PLGA block were synthesized via ring‐opening polymerization of lactide and glycolide in the presence of OH‐terminated PNIPAAm or PEG. The composition and structure of the polymer were determined by NMR and FTIR. The effect of important factors, such as ionic strength, pH, and polymer concentration on the phase transition behavior of temperature‐sensitive polymers, were investigated by cloud point measurements. The resulting thermosensitive polymers were used for the entrapment of a narcotic antagonist drug, naltrexone, as the model drug. The loading efficiency and drug release behavior of naltrexone‐loaded hydrogels were investigated. The naltrexone loaded thermosensitive polymers were able to sustain the release of naltrexone for different periods of time, depending on the polymer composition, and concentration. In vitro release studies showed that these thermosensitive polymers are able to deliver naltrexone in biologically active forms at a controlled rate for 3–8 weeks. Copyright © 2009 John Wiley & Sons, Ltd.     

Emulsion copolymerization of D,L‐lactide and glycolide in supercritical carbon dioxide

Biodegradable polyesters were synthesized via an emulsion polymerization in supercritical carbon dioxide (SC‐CO₂). Copolymers of lactide and glycolide were synthesized in SC‐CO₂ with stannous octoate as the ring‐opening catalyst and a fluorocarbon polymer surfactant as an emulsifying agent. The conversion of lactide and glycolide was monitored with respect to the reaction time and temperature with ¹H NMR spectroscopy. The conversion of glycolide surpassed 99% within 72 h for an SC‐CO₂ phase maintained at 200 bar and 70 °C. Under the same conditions, lactide conversion reached 65% after 72 h of polymerization. Unpolymerized monomer was removed after the reaction by extraction with an SC‐CO₂ mobile phase. The molecular weights of all the copolymers were measured by gel permeation chromatography. Weight‐average molecular weights (M_w) ranged between 2500 and 30,200 g/mol and polydispersity indices ranged from 1.4 to 2.3 for polymerization times of 6 and 48 h, respectively. Although the molecular weight increased significantly during the first 48 h of reaction, there was no significant difference in the M_w for polymerization times of 48 and 72 h. Emulsion polymerization within the benign solvent SC‐CO₂ demonstrated improved conversion and molecular weight versus polymers synthesized without surfactant. The emulsion polymerization of lactide and glycolide copolymers in SC‐CO₂ is proposed as a novel production technique for high‐purity, biodegradable polymers. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 562–570, 2001     

Highly porous poly(lactide‐co‐glycolide) microparticles for sustained tiotropium release

In this study, porous poly(lactide‐co‐glycolide) (PLGA) microparticles with low mass density and large particle size were developed for chronic obstructive pulmonary disease treatment using anticholinergic drug (tiotropium). The porous PLGA microparticles were prepared by the water‐in‐oil‐in‐water (W₁/O/W₂) multi‐emulsion method using PLGA polymer and ammonium bicarbonate (as a porogen). Herein, soluble starch was incorporated in porous PLGA microparticles for long‐term tiotropium release. In vitro drug release studies determined that the rapid release of tiotropium from porous PLGA microparticles was reduced because of the high viscosity of the incorporated starch. Tiotropium release from porous PLGA microparticles continued up to 3 days. Furthermore, the inhaled microparticles showed longer drug residence in in vivo lung epithelium. Copyright © 2013 John Wiley & Sons, Ltd.     

Polyurethanes with separately tunable biodegradation behavior and mechanical properties for tissue engineering

Two series (random and block) poly(glycolide‐co‐ε‐caprolactone) macrodiols with various glycolide to ε‐caprolactone ratios (50/50 and 30/70, R‐PG50C, R‐PG30C, B‐PG50C, and B‐PG30C) were synthesized. Next, segmented polyurethanes (PUs) were synthesized based on the synthesized macrodiols, 1,6‐hexamethylene diisocyanate and 1,4‐butanediol (PU‐R30, PU‐R50, PU‐B30, and PU‐B50). Effect of glycolide (G) and ε‐caprolactone (C) monomers arrangement (random or block) on the PUs properties were investigated via FTIR, ¹H NMR, DSC, TGA, DMA, SEM, and mechanical tests. All PUs illustrated T_g (−33°C to −48°C) and T_m (102°C to 139°C) corresponding to the soft and the hard segments, respectively. Polymers based on block macrodiols also showed T_m related to the soft segments. While PUs underwent a two‐step thermal degradation, the PUs based on block macrodiols indicated higher degradation temperature. Dynamic mechanical analysis results evidenced development of a well‐defined microphase separated structure in PU‐R30. Contact angle (about 70°‐80°) and water uptake (around 20% after 24 hours) of the PU films are close to those suitable for tissue engineering materials. The PU based on R‐PG30C (PU‐R30) exhibited the highest tensile strength (2.87 MPa) followed by PU‐B50 and PU‐R50. Over a 63‐day in vitro degradation study in phosphate buffered saline, the PUs showed variable weight loss (up to 40%) depending on their soft segments composition and arrangement. Also, the PUs showed no cytotoxicity. Thus, these PUs with tunable biodegradation rate and mechanical properties are suitable candidates for tissue engineering.     

Mechanical properties and degradation studies of poly(D,L‐lactide‐co‐glycolide) 50:50/graphene oxide nanocomposite films

Poly(D,L‐lactide‐co‐glycolide) 50:50 (PLGA)/graphene oxide (GO) nanocomposite films were prepared with various GO weight fractions. A significant enhancement of mechanical properties of the PLGA/GO nanocomposite films was obtained with GO weight fractions. The incorporation of only 5 wt% of GO resulted in an ~2.5‐fold and ~4.7‐fold increase in the tensile strength and Young's modulus of PLGA, respectively. The thermomechanical behaviors of composite films were investigated by dynamic mechanical analysis. Results indicated that the values of T_g and storage moduli of the PLGA/GO composites were higher than those of the pristine PLGA. The improvement in oxygen barrier properties of composites was presumably attributed to the filler effect of the randomly dispersed GO throughout the PLGA matrix. In this work, we also studied in vitro biodegradation behavior. PLGA/GO composite films were hydrolyzed at 37°C for periods up to 49 days. Because of the presence of GO nanosheets, degradation of composite films took place more slowly with increasing GO amounts. Copyright © 2013 John Wiley & Sons, Ltd.     

Nanofibrosis of uncrystallizable poly(lactide‐co‐glycolide) via phase separation

Poly(lactide‐co‐glycolide) (PLGA) copolymers are a kind of biocompatible and biodegradable materials being widely used in tissue engineering. However, phase separation had not been reported successfully in fabricating these amorphous polymers into nanofibrous matrix, although this technique had shown advantages over electrospinning in producing a nanofiber network. In this study, tetrahydrofuran (THF)/H₂O solvent pairs were found suitable solvents to induce the formation of uniform PLGA gel at selected gelation temperatures. The results indicated that fine nanofibrous structures with fiber diameter around 40–60 nm could be obtained following the steps of gel formation, solvent extraction, and freeze‐drying, by controlling the concentration of PLGA/THF/H₂O solution, THF/H₂O ratio, and gelation temperature. Copyright © 2009 John Wiley & Sons, Ltd.     

Pyrogallic acid‐PLGA conjugate as new biodegradable material suitable for final sterilization by irradiation

This paper reports the feasibility to prepare a biodegradable material stable to γ‐irradiation by grafting of poly(lactide‐co‐glycolide) with pyrogallic acid (PLGA‐g‐PA) and ferulic acid (PLGA‐g‐FA) in mild condition. Only the grafting procedure with PA did not modify molecular weight (Mw) of the starting polymer and PLGA‐g‐PA showed antioxidant properties. The polymer degradation in pH 7.4 phosphate buffer saline (PBS) was mainly governed by a random chain scission mechanism according to a first‐order reaction. The irradiation at the dose of 25 kGy caused only a very slight decrease of Mw and the degradation patterns of the non‐irradiated and irradiated material were superimposable. PLGA‐g‐PA resulted a promising material to develop biodegradable drug delivery systems which would be sterilizable in the final container. Copyright © 2010 John Wiley & Sons, Ltd.     

The effect of additives on naltrexone hydrochloride release and solvent removal rate from an injectable in situ forming PLGA implant

Biodegradable in situ forming drug delivery systems for naltrexone release are promising for post‐treatment of drug addicts. The effect of two different additives, glycerol and ethyl heptanoate, on the naltrexone hydrochloride release and solvent removal from a poly(DL ‐lactide‐co‐glycolide) (PLGA) injectable implant is presented in this article. The experimental results showed that the in vitro initial release of the drug was decreased in the presence of these additives. Ethyl heptanoate was, however, more effective than glycerol and increasing the amount of additives in PLGA solution up to 5% (w/w) resulted in a decrease of initial naltrexone release rate up to 50%. The morphological evaluation of implants using scanning electron microscopy indicated that the additives generated a less porous structure together with a finger‐like to sponge‐like transition. The solvent removal profiles of injectable implants, which can be well described by thermogravimetric and morphological analysis, were in good agreement with drug release profiles. Copyright © 2006 John Wiley & Sons, Ltd.     

Synthesis and characterization of poly(vinyl alcohol)‐graft‐[poly(D,L‐lactide)/poly(D,L‐lactide‐co‐glycolide)] hydrogels

Poly(D ,L ‐lactide) and poly(D ,L ‐lactide‐co‐glycolide) with various composition and with one methacrylate and one carboxylate end group were synthesized and grafted onto poly(vinyl alcohol) (PVA) via the carboxylate group. The graft copolymers were crosslinked via the methacrylate groups using a free radical initiator. The polymer networks were characterized by means of NMR and studied qualitatively by means of IR spectroscopy. The influence of the glycolide content in the polyester grafts and of the number of ester units in the grafts on thermal properties and swellability were studied as well. The high swellability in water is characteristic of all hydrogels. Differential scanning calorimetry (DSC) showed a single glass transition temperature that occurs in the range between 51 and 69 °C. Thermogravimetric analysis (TGA) of the networks showed the main loss in weight in the temperature range between 290 and 370 °C. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4536–4544, 2007     

Synthesis of biodegradable copolymers with low‐toxicity zirconium compounds. III. Synthesis and chain‐microstructure analysis of terpolymer obtained from L‐lactide,glycolide, and ϵ‐caprolactone initiated by zirconium(IV) acetylacetonate

Zirconium(IV) acetylacetonate [Zr(acac)₄] is a very good initiator for the terpolymerization of glycolide with L‐lactide and ?‐caprolactone. The microstructure of the obtained terpolymer was determined by NMR spectroscopy and then compared with terpolymers obtained in the presence of stanous(II) octoate [Sn(oct)₂]. Samples obtained with Zr(acac)₄ were characterized by a segmental‐chain microstructure. Apart from relatively long lactidyl microblocks, there were also segments made of random copolymer of glycolide with lactide. Such a structure is formed as a result of strong transesterification caused by active caproyl chain endings attacking the glycolidyl groups. Domination of this type of transestrification is shown. The growth of terpolymer chains and the influence of transesterification on gradual changes of the microstructure of the forming terpolymer chain were examined. Significant differences among glycolide, lactide, and the least reactive caprolactone were observed. The results of differential scanning calorimetric examinations of the obtained terpolymers are presented. Differences between the structures of random terpolymers obtained during terpolymerization initiated by Sn(oct)₂ and those obtained by Zr(acac)₄ influence their thermal properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3129–3143, 2002     

Effect of comonomer on thermal/mechanical and shape memory property of L‐lactide‐based shape‐memory copolymers

In this study, three kinds of L ‐lactide‐based copolymers, poly(lactide‐co‐glycolide) (PLGA), poly(lactide‐co‐p‐dioxanone) (PLDON) and poly(lactide‐co‐caprolactone) (PLC), were synthesized by the copolymerization of L ‐lactide (L) with glycolide (G), or p‐dioxanone (DON) or ε‐caprolactone (CL), respectively. The copolymers were easily soluble in common organic solvents. The compositions of the copolymers were determined by ¹H‐NMR. Thermal/mechanical and shape‐memory properties of the copolymers with different comonomers were compared. Moreover, the effect of the chain flexibility of the comonomers on thermal/mechanical and shape‐memory properties of the copolymers were investigated. The copolymers with appropriate lactyl content showed good shape‐memory properties where both the shape fixity rate (R_f)and the shape recovery rate (R_r) could exceed 95%. It was found that the comonomers with different flexible molecular chain have different effects on their thermal/mechanical and shape‐memory properties. Among them, PLGA has the highest mechanical strength and recovery rate while PLC copolymer has high recovery rate when the lactyl content exceeded 85% and the lowest transition temperature (T_trans). Copyright © 2007 John Wiley & Sons, Ltd.     

Fabrication and characterization of composites composed of a bioresorbable polyester matrix and surface modified calcium carbonate whisker for bone regeneration

This work aims to evaluate the potential of a bioresorbable composite as material for bone regeneration. Surface‐modified calcium carbonate whiskers (CCWs) were prepared by grafting of ethylene glycol (EG) using 1,6‐hexamethylene diisocyanate as coupling agent, followed by ring‐opening polymerization of l ‐lactide initiated by the hydroxyl group of EG. The resulting PLLA‐EG‐g‐CCW was used as filler to reinforce a bioresorbable terpolymer, poly(l ‐lactide‐co‐trimethylene carbonate‐co‐glycolide) (PLTG). The mechanical properties and thermal stability of the PLTG/PLLA‐EG‐g‐CCW composites were greatly improved. Compared with neat PLTG, a 39.3% increase in tensile strength and 26.7% increase in elongation at break were obtained for the composite with 2 wt% PLLA‐EG‐g‐CCW filler. This was assigned to the reinforcement effect of evenly dispersed PLLA‐EG‐g‐CCW in the polymeric matrix. In fact, entanglement of PLLA grafts at the surface of PLLA‐EG‐g‐CCW with PLTG chains results in a homogeneous distribution of the filler in the matrix. Thus, the composites are simultaneously strengthened and toughened. The cytocompatibility of the materials was evaluated from cell morphology and 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay using L929 mouse fibroblast cell line. The results indicate that the composite presents very low cytotoxicity. Copyright © 2017 John Wiley & Sons, Ltd.     

Synthesis and characterization of polytulipalin‐g‐polylactide copolymers

Graft copolymers of poly(tulipalin A) (PT) and poly(DL‐lactide) (PDLLA) (PT‐g‐PDLLA) having various graft lengths and ratios were synthesized by free‐radical copolymerization of α‐methylene‐γ‐butyrolactone (MBL) and PDLLA macromonomers (HEMA‐PDLLA) terminated by 2‐hydroxyethyl methacrylate (HEMA)‐terminated. HEMA‐PDLLA were synthesized by ring opening polymerization (ROP) of DL‐lactide in the presence of HEMA. Both HEMA‐PDLLA and the copolymers were characterized by NMR spectroscopy and gel permeation chromatography (GPC). The thermal properties of the graft copolymers were found to depend on the graft length and the ratio. The copolymers consisting of PDLLA side chains of M_n = 500 Da showed a single T_g between T_gs of the two component polymers, suggesting a miscible state of PT and PDLLA. In contrast, the copolymers consisting of PDLLA side chains of M_n = 1100, 2000, and 7000 Da showed two isolated T_g, suggesting two segregated domains. The AFM phase images of the copolymers supported the single and phase‐separated morphologies for the former and latter systems, respectively. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Complex phase behavior and state of miscibility in Poly(ethylene glycol)/Poly(l‐lactide‐co‐ε‐caprolactone) Blends

A miscibility and phase behavior study was conducted on poly(ethylene glycol) (PEG)/poly(l ‐lactide‐ε‐caprolactone) (PLA‐co‐CL) blends. A single glass transition evolution was determined by differential scanning calorimetry initially suggesting a miscible system; however, the unusual T_g bias and subsequent morphological study conducted by polarized light optical microscopy (PLOM) and atomic force microscopy (AFM) evidenced a phase separated system for the whole range of blend compositions. PEG spherulites were found in all blends except for the PEG/PLA‐co‐CL 20/80 composition, with no interference of the comonomer in the melting point of PEG (T_m = 64 °C) and only a small one in crystallinity fraction (X_c = 80% vs. 70%). However, a clear continuous decrease in PEG spherulites growth rate (G) with increasing PLA‐co‐CL content was determined in the blends isothermally crystallized at 37 °C, G being 37 µm/min for the neat PEG and 12 µm/min for the 20 wt % PLA‐co‐CL blend. The kinetics interference in crystal growth rate of PEG suggests a diluting effect of the PLA‐co‐CL in the blends; further, PLOM and AFM provided unequivocal evidence of the interfering effect of PLA‐co‐CL on PEG crystal morphology, demonstrating imperfect crystallization in blends with interfibrillar location of the diluting amorphous component. Significantly, AFM images provided also evidence of amorphous phase separation between PEG and PLA‐co‐CL. A true T_g vs. composition diagram is proposed on the basis of the AFM analysis for phase separated PEG/PLA‐co‐CL blends revealing the existence of a second PLA‐co‐CL rich phase. According to the partial miscibility established by AFM analysis, PEG and PLA‐co‐CL rich phases, depending on blend composition, contain respectively an amount of the minority component leading to a system presenting, for every composition, two T_g's that are different of those of pure components. © 2013 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys. 2014 , 52, 111–121     

Stabilizer‐Free Poly(lactide‐co‐glycolide) Nanoparticles Conjugated with Quantum Dots as a Potential Carrier Applied in Human Mesenchymal Stem Cells

We report that human mesenchymal stem cells (hMSCs) were successfully labeled with poly(lactide‐co‐glycolide) nanoparticles (PLGA NPs) surface‐conjugated quantum dots (QDs) (PLGA‐QD NPs) via endocytosis pathway. These NPs were not toxicity even treated with PLGA‐QD NPs at high concentrations for at least four weeks. Besides, PLGA‐QD NPs‐labeled hMSCs did not change their proliferation and differentiation capability toward the cell fates of adipocytes, osteocytes, and chrondrocytes. It's known that PLGA has been widely employed to act as delivery carrier which encapsulates drugs and releases them under a controlled way. Currently, we have also demonstrated that FITC‐loaded PLGA‐QD NPs degraded in hMSCs to achieve intracellular release of FITC. The aim of this research is to investigate viability, proliferation and differentiation capability and the potential for gene delivery of MSCs labeled with PLGA‐QD NPs. In addition to PLGA‐QD NPs, QDs alone were used to serve as a control set for comparison.     

Fabrication of poly(lactide‐co‐glycolide) scaffold embedded spatially with hydroxyapatite particles on pore walls for bone tissue engineering

Poly(lactide‐co‐glycolide) (PLGA) scaffolds embedded spatially with hydroxyapatite (HA) particles on the pore walls (PLGA/HA‐S) were fabricated by using HA‐coated paraffin spheres as porogens, which were prepared by Pickering emulsion. For comparisons, PLGA scaffolds loaded with same amount of HA particles (2%) in the matrix (PLGA/HA‐M) and pure PLGA scaffolds were prepared by using pure paraffin spheres as porogens. Although the three types of scaffolds had same pore size (450–600 µm) and similar porosity (90%–93%), the PLGA/HA‐S showed the highest compression modulus. The embedment of the HA particles on the pore walls endow the PLGA/HA‐S scaffold with a stronger ability of protein adsorption and mineralization as well as a larger mechanical strength against compression. In vitro culture of rat bone marrow stem cells revealed that cell morphology and proliferation ability were similar on all the scaffolds. However, the alkaline phosphatase activity was significantly improved for the cells cultured on the PLGA/HA‐S scaffolds. Therefore, the method for fabricating scaffolds with spatially embedded nanoparticles provides a new way to obtain the bioactive scaffolds for tissue engineering. Copyright © 2011 John Wiley & Sons, Ltd.     

Enhancing crystallization behavior for optimized performances of poly(TMC‐b‐(LLA‐ran‐GA)) by PDLA/PLLA stereocomplex crystallization

The blends of poly(1,3‐trimethylene carbonate‐b‐(l ‐lactide‐ran‐glycolide)) (PTLG) with poly(d ‐lactide) (PDLA) were prepared via solution‐casting method using CH₂Cl₂ as solvent. The poly(l ‐lactide) (PLLA) segments of PTLG with PDLA chain constructed as stereocomplex structures and growth stereocomplex crystals of PLA (sc‐PLA). The effects of sc‐PLA crystals on thermal behavior, mechanical properties, thermal decomposition of the PTLG/PDLA blends were investigated, respectively. The differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction (WAXD) results showed that the total crystallinity of the PTLG/PDLA blends was increased with the PDLA content increasing. Heterogeneous nucleation of sc‐PLA crystals induced crystallization of the PLLA segments in PTLG. The crystallization temperature of samples shifted to 107.5°C for the PTLG/PDLA‐20 blends compared with that of the PTLG matrix, and decreased the half‐time of crystallization. The mechanical measurement results indicated that the tensile strength of the PTLG/PDLA blends was improved from 21.1 MPa of the PTLG matrix to 39.5 MPa of PTLG/PDLA‐20 blends. The results of kinetics of thermal decomposition of the PTLG/PDLA blends by TGA showed that the apparent activation energy of the PTLG/PDLA blends was increased from 59.1 to 72.1 kJ/mol with the increasing of the PDLA content from 3 wt% to 20 wt%, which indicated the enhancement of thermal stability of the PTLG/PDLA blends by addition of PDLA. Furthermore, the biocompatibility of the PTLG/PDLA blends cultured with human adipose‐derived stem cells was evaluated by CCK‐8 and live/dead staining. The experiment results proved the PTLG/PDLA blends were a kind of biomaterial with excellent physical performances with very low cytotoxicity.     

Synthesis and characterization of biodegradable,amorphous, soft IPNs with shape‐memory effect

Star‐shaped oligo[(D ,L ‐lactide)‐co‐ε‐caprolactone]s (PCLA) with various number average molecular weights were synthesized via ring‐opening polymerization of D ,L ‐lactide (DLLA) and ε‐caprolactone (CL) with organic Sn as catalyst and pentaerythritol as an initiator. The elastic amorphous interpenetrating polymer networks (IPNs) of polyesterurethane/poly(ethylene glycol) dimethacrylate (PEGDMA) were synthesized in situ by UV‐photopolymerization of PEGDMA and thermal polymerization of PCLA with isophorone diisocyanate (IPDI). IPNs are transparent soft materials and the gel content of the IPNs is exceeding 87%. They are rubbery when PEGDMA content is above 10% at room temperature. IPNs show good shape‐memory properties. IPNs recover quickly its permanent form in 10 sec when the environment temperature is above its glass transition temperature (T_g). IPNs have only one single T_g between the T_g of PEGDMA and polyesterurethane. The strain recovery rate (R_r) and the strain fixity rate (R_f) are above 90%. No characteristic peaks of PEG crystallites in X‐ray diffraction pattern (XRD) demonstrate that they are amorphous polymer networks. The wettability, degradation rate, mechanical properties, and T_g of the IPNs could be conveniently adjusted by changing PEGDMA content in IPNs. The soft IPNs are promising suitable as potential soft substrates with tailored mechanical properties for potential clinical or medical use. Copyright © 2011 John Wiley & Sons, Ltd.