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. IV. Copolymerization of glycolide with trimethylene carbonate and 2,2‐dimethyltrimethylene carbonate: Microstructure analysis of copolymer chains by high‐resolution nuclear magnetic resonance spectroscopy

The results of the copolymerization of glycolide with cyclic trimethylene carbonate and 2,2‐dimethyltrimethylene carbonate are described. The copolymerization was conducted in the presence of low‐toxicity zirconium(IV) acetylacetonate as an initiator. With this kind of initiator, the composition of the comonomer units in the copolymer chains was assumed to be obtained with high efficiency. Despite significant differences in the comonomer reactivity, in copolymers containing comparable amounts of glycolidyl and carbonate sequences, highly randomized chain structures were observed. This effect resulted from strong intermolecular transesterification that proceeded during the studied copolymerization and caused glycolidyl microblock randomization. The assignment of the spectral NMR lines to appropriate comonomer sequences of polymeric chains was performed in the region of methylene protons of glycolidyl units in ¹H NMR spectra of the copolymers and in the carbonyl region of carbon spectra. The equations were formulated for a detailed characterization of the obtained copolymer chains, the average lengths of the blocks, and the transesterification and randomization coefficients. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 98–114, 2006     

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.     

Synthesis and characterization of a novel terpolymer based on L‐lactide,glycolide, and trimethylene carbonate for specific medical applications

The bioresorbable new terpolymers of L ‐lactide, glycolide, and trimethylene carbonate were synthesized via ring‐opening polymerization reaction of the cyclic monomers using Stannous octoate as initiator. Glycolide and L ‐lactide were prepared from their parent acids and then purified by multiple re‐crystallization from ethyl acetate. The thermal and mechanical properties of this polymer were characterized by means of thermogravimetry, differential scanning calorimetry, stress–strain measurements, and dynamic mechanical analysis. The glass transition temperature of the terpolymers changed from 33 to 51°C with composition in a predictable manner. The rheological properties of copolymers and molecular weight of each copolymer were determined showing good processability for making fibers. Using a mini‐extruder, it was possible to produce some filaments. The filaments produced at 140°C had appropriate ductility. The in vitro measurements, specifying the biological properties were also carried out. The sample with monomer composition LLA:GA:TMC = 60:34:6 showed a slower degradation rate than the one with LLA:GA:TMC = 54:34:12. The low‐toxicity bioresorbable terpolymers with good rheological and in vitro properties are the promising new materials for biomedical applications specially a new suture formulation. Copyright © 2011 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.     

Composites of poly(L‐lactide‐trimethylene carbonate‐glycolide) and surface modified SBA‐15 as bone repair material

This work aims to develop novel composites from a poly(L ‐lactide‐co‐trimethylene carbonate‐co‐glycolide) (PLTG) terpolymer and mesoporous silica (SBA‐15) nanofillers surface modified by post‐synthetic functionalization. SBA‐15 first reacts with a silane coupling agent, γ‐aminopropyl‐trimethoxysilane to introduce ammonium group. PLLA chains were then grafted on the surface of SBA‐15 through ammonium initiated ring‐opening polymerization of L ‐lactide. Composites were prepared via solution mixing of PLTG terpolymer and surface modified SBA‐15. The structures and properties of pure SBA‐15, γ‐aminopropyl‐trimethoxysilane modified SBA‐15 (H₂N‐SBA‐15), PLLA modified SBA‐15 (PLLA‐NH‐SBA‐15), and PLTG/PLLA‐NH‐SBA‐15 composites were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, X‐ray diffraction, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, transmission electron microscopy, N₂ adsorption‐desorption, differential scanning calorimetry, contact angle measurement, and mechanical testing. The results demonstrated that PLLA chains were successfully grafted onto the surface of SBA‐15 with grafting amounts up to 16 wt.%. The PLTG/PLLA‐NH‐SBA‐15 composites exhibit good mechanical properties. The tensile strength, Young's modulus, and elongation at break of the composite containing 5 wt.% of PLLA‐NH‐SBA‐15 were 39.9 MPa, 1.3 GPa, and 273.6%, respectively, which were all higher than those of neat PLTG or of the composite containing 5 wt.% of pure SBA‐15. Cytocompatibility tests showed that the composites present very low cytotoxicity.     

Paclitaxel‐Loaded Stabilizer‐Free Poly(D,L‐lactide‐co‐glycolide) Nanoparticles Conjugated with Quantum Dots for Reversion of Anti‐Cancer Drug Resistance and Cancer Cellular Imaging

We prepared the PLGA‐loaded anti‐cancer drug and coated it with quantum dots to make it a dual‐function nanoparticles, and analyzed its potential use in cellular imaging and curing cancers. Two cancer cell lines, paclitaxel‐sensitive KB and paclitaxel‐resistant KB paclitaxel‐50 cervical carcinoma cells, were the relativistic models for analysis of the cytotoxicity of free paclitaxel and paclitaxel‐loaded PLGA conjugated with quantum‐dot nanoparticles. The paclitaxel‐loaded PLGA conjugated with quantum dots nanoparticles were significantly more cytotoxic than the free paclitaxel drug in paclitaxel‐resistant KB paclitaxel‐50 cells. This might have been because the cancer cells developed multi‐drug resistance (MDR), which hampered the action of free paclitaxel by pumping its molecules to extracellular areas. Addition of verapamil, a P‐glycoprotein inhibitor, reversed the MDR mechanism and significantly reduced KB paclitaxel‐50 cell viability. As a result, KB paclitaxel‐50 was highly associated with MDR on the cell membrane. The cytotoxicity results indicated that PLGA nanoparticles served as drug carriers and protected the drugs from MDR‐accelerated efflux. Combined quantum dots with PLGA nanoparticles allowed additional functionality for cellular imaging.     

Measurement of Monomer Reactivity Ratios of D,L-3-Methylglycolide with Glycolide or D,L-Lactide

Polylactides, polyglycolide and copolymers based on them, are still gaining interestbecause of the numerous applications in the biomedical and pharmaceutical fieldsl. Theyare usually prepared by bulk homo- and co-polymerizations of lactides, glycolideinitiated with stannous octoate (Snoot,) because Snoot, is a highly efficient commercialcatalyst and a permitted food additive in numerous countriesl-2. However, the propertiesof poly(D,L-lactic acid-co-glycolic acid) (D,L-PLGA) have widely va…     

Synthesis of L-Aspartic Acid and Lactone Copolymers

Recently,thesynthesisandapplications0fbiodegradablepolydepsipeptides,alternatingcopolymersofa-aminoacidanda-hydroxyacidwithfunctionalside-chaingroupshavedrawnmoreandmoreattentionl'2.Thisisbecausethefunctionalizedpendantgroups0fthep0lydepsipeptidesmakethemusefulf0rthepreparationofavarietyofpolymer-drugconjugates.However,thepolymerizati0nofdepsipeptideswithfuncti0nalgr0upsisratherdifficultduetotheirbigstructuresandsterichindrance.Furthermore,high-molecular-weightpr0ductsofsuitablephysicalpropert…