Blends of Poly(lactic acid) with Thermoplastic Acetylated Starch

Blends of poly(lactic acid)(PLA) and thermoplastic acetylated starch(ATPS) were prepared by means of the melt mixing method. The results show that PLA and ATPS were partially miscible, which was confirmed with the measurement of T-g by dynamic mechanical analysis(DMA) and differrential scanning calorimetry(DSC). The mechanical and thermal properties of the blends were improved. With increasing the ATPs content, the elongation at break and impact strength were increased. The elongation at break increased from 5% of neat PLA to 25% of the blend PLA/ATPS40. It was found that the cold crystallization behavior of PLA changed evidently by addition of ATPS. The cold crystallization temperature(T-cc) of each of PLA/ATPS blends was found to shift to a lower temperature and the width of exothermic peak became narrow compared with that of neat PLA.

The nanocomposite scaffold of poly(lactide-co-glycolide) and hydroxyapatite surface-grafted with L-lactic acid oligomer for bone repair

Nanohydroxyapatite (op-HA) surface-modified with L-lactic acid oligomer (LAc oligomer) was prepared by LAc oligomer grafted onto the hydroxyapatite (HA) surface. The nanocomposite of op-HA/PLGA with different op-HA contents of 5, 10, 20 and 40 wt.% in the composite was fabricated into three-dimensional scaffolds by the melt-molding and particulate leaching methods. PLGA and the nanocomposite of HA/PLGA with 10 wt.% of ungrafted hydroxyapatite were used as the controls. The scaffolds were highly porous with evenly distributed and interconnected pore structures, and the porosity was around 90%. Besides the macropores of 100-300 mu m created by the leaching of NaCl particles, the micropores (1-50 mu m) in the pore walls increased with increasing content of op-HA in the composites of op-HA/PLGA. The op-HA particles could disperse more uniformly than those of pure HA in PLGA matrix. The 20 wt.% op-HA/PLGA sample exhibited the maximum mechanical strength, including bending strength (4.14 MPa) and compressive strength (2.31 MPa). The cell viability and the areas of the attached osteoblasts on the films of 10 wt.% op-HA/PLGA and 20 wt.% op-HA/PLGA were evidently higher than those on the other composites.

Lamella reorientation in thin films of a symmetric poly(L-lactic acid)-block-polystyrene upon crystallization at different temperatures

The thin films of a symmetric crystalline-coil diblock copolymer of poly(L-lactic acid) and polystyrene (PLLA-b-PS) formed lamellae parallel to the substrate surface in melt. When annealed at temperatures well above the glass transition temperature of PLLA block (T-g(PLLA)), the PLLA chains started to crystallize, leading to reorientation of lamellae. Such reorientation behavior exhibited dependence on the correlation between the crystallization temperature (T-c), the glass transition temperature of PS (T-g(PS)), the peak melting point of PLLA crystals (T-m(PLLA)), and the end melting point of PLLA crystals (T-m,end(PLLA)). When annealed at (T-c =) 80 degrees C (T-c < T-g(PS) < T-ODT, order-disorder transition temperature), 123 degrees C (T-g(PS) < T-c < T-m(PLLA) < T-ODT). 165 degrees C (T-g(PS) < T-m(PLLA) < T-c < T-m,end(PLLA) < T-ODT), the parallel lamellae became perpendicular to the substrate surface, exclusively starting at the edge of surface relief patterns. Meanwhile, the corresponding lamellar spacing was significantly enhanced.

Isothermal Crystallization Behavior of Poly(L-lactic acid)/Organo-Montmorillonite Nanocomposites

The isothermal crystallization behavior of poly(L-lactic acid)/organo-montmorillonite nanocomposites (PLLA/OMMT) with different content of OMMT, using a kind of twice-functionalized organoclay (TFC), prepared by melt intercalation process has been investigated by optical depolarizer. In isothermal crystallization from melt, the induction periods (t(i)) and half times for overall PLLA crystallization (100 degrees C <= T-c <= 120 degrees C) were affected by the temperature and the content of TFC in nanocomposites. The kinetic of isothermal crystallization of PLLA/TFC nanocomposites was studied by Avrami theory. Also, polarized optical photomicrographs supplied a direct way to know the role of TFC in PLLA isothermal crystallization process. Wide angle X-ray diffraction (WAXD) patterns showed the nanostructure of PLLA/TFC material, and the PLLA crystalline integrality was changed as the presence of TFC. Adding TFC led to the decrease of equilibrium melting point of nanocomposites, indicating that the layered structure of clay restricted the full formation of crystalline structure of polymer.

Crystallization Behavior and Mechanical Properties of Crosslinked Plasticized Poly(L-lactic acid)

Enhancing the stability of plasticized poly(L-lactic acid) (PLLA) with poly (ethylene glycol) (PEG) is necessary for its practical application. In this study, plasticized PLLA (PLLA/PEG 80/20 wt/wt) was crosslinked under I-ray (Co-60) in the presence of triallyl isocyanurate (TALC) as crosslinking agent. FTIR analysis revealed that PLLA, PEG, and TALC formed a cocrosslinking structure. Crystallization behavior and mechanical properties of the crosslinked plasticized PLLA were investigated by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), scanning electron microscopy (SEM), and tensile tests. Experimental results indicated that the crystallization behaviors of both PEG and PLLA in the blends were restrained after irradiation. The melting peak of PEG in the crystallized samples disappeared at a low irradiation doses about 10 kGy. Although PLLA still owned the behavior of crystallize, its cold crystallization temperature and glass transition temperature shifted to higher temperature. Mechanical properties of the plasticized PLLA were strengthened through crosslinking. Both yield strength and elastic modulus of the samples increased after crosslinking.

Preparation and Bioactivity of the Composite of PLGA and Hydroxyapatite Nanocrystals Surface-grafted with L-lactic Acid Oligomer

The hydroxyapatite (HA) nanocrystals of 100-200 nm in length and 20-30 nm in width were hydrothermally synthesized by the reaction of phosphoric acid and calcium hydroxide. Lactic acid oligomer surface grafted HA(op-HA) nanoparticles were obtained by oligomeric lactic acid with a certain molecular weight grafting onto the HA surface to form a Ca carboxylate bond in the absence of any catalyst. The op-HA was further blended with poly(lactide-co-glycolide) (PLGA) to prepare the nanocomposite of op-HA/PLGA. FTIR, TGA, ESEM and EDX were used to analyze grafting reaction, the graft ratio of op-HA, surface topography and calcium deposition of the composites, respectively. The rabbit osteoblasts were seeded and cultured on the surface of composites in vitro. The cell morphology, adhesion, proliferation and gene expression were evaluated with FITC staining, NIH image J software and the analysis of real-time PCR, respectively. The results show that the graft ratio of op-HA is 8.3% (mass fraction). The op-HA/PLGA nanocomposite possessed more suitable surface properties, including roughness and plenty of calcium and phosphor. It exhibited better cell adhesion, spreading and proliferation of rabbit osteoblasts, compared to pure PLGA.

Crystalline morphology of poly(L-lactic acid) thin films

Crystalline morphologies of spin-coated poly(L-lactic acid) (PLLA) thin films under different conditions are investigated mainly with atomic force microscopy (AFM) technique. When PLLA concentration in chloroform is varied from 0.01 to 1% gradually, disordered structure, rod-shape and larger spheres aggregates are observed in thin films subsequently. Under different annealing temperature, such as at 78, 102, 122 degrees C, respectively, we can find most rod-like crystalline aggregates. Interestingly, we observed that nucleation sites locate at the edge of the holes at the original crystalline stage. Then, these holes developed to form chrysanthemum-like and rods subsequently with annealing time meanwhile the size and the shape of crystalline aggregate are changed. In addition. effect of substrate and solvent on morphology is also discussed. On the other hand, the possible mechanism of crystalline morphology evolution is proposed.

Preliminary study on melt-spinning, adhesion and adsorption properties of poly(lactic acid)

For the purpose of manufacturing cigarette filter tows and filter rods, the melt-spinning, adhesion and adsorption properties of poly(lactic acid) were studied. The rheological measurements were performed to examine the effects of various processing conditions on the melt flowability and spinnability, including those of residual moisture. The melt spinning and post-processings were followed by determining the molecular weight, thermal and mechanical properties of the fibers. The results obtained were useful to establishing the specification of the PLA resins for filter tows and filter rods manufacturing and to choosing proper melt-spinning and post-processing technologies.

Triblock poly(lactic acid)-b-poly(ethylene glycol)-b-poly(lactic acid)/paclitaxel conjugates: Synthesis, micellization, and cytotoxicity

A triblock poly(lactic acid)-b-poly(ethylene glycol)-b-poly(lactic acid) (PLA-PEG-PLA)/paclitaxel (PTX) conjugate was synthesized by the reaction of carboxyl-terminated copolymer PLA-PEG-PLA with PTX in the presence of dicyclohexylcarbodiimide and dimethylaminopyridine. Carboxyl-terminated copolymer PLA-PEG-PLA was prepared by the reaction of the hydroxyl end groups in copolymer PLA-PEG-PLA with succinic anhydride. Its structure was confirmed by NMR and gel permeation chromatography. The PLA-PEG-PLA/PTX conjugates could self-assemble into micelles in aqueous solutions with a low critical micelle concentration. Dynamic light scattering and environmental scanning electron microscopy analyses of the PLA-PEG-PLA/PTX micelles revealed their spherical structure and size of 220 nm. The antitumor activity of the conjugate against woman Hela cancer cells, evaluated by the 3-(4,5-dimethylthiazol2-yl)-2,5-diphenyl tetrazolium bromide method, showed that the conjugates had an antitumor activity similar to that of pure PTX. The obtained PLA-PEG-PLA/PTX conjugates are expected to be used in clinical practice.

Surface-grafted silica linked with L-lactic acid oligomer: A novel nanofiller to improve the performance of biodegradable poly(L-lactide)

A new surface modification method by grafting L-lactic acid oligomer onto the surface silanol groups of silica nanoparticles has been developed. The surface-grafting reaction is confirmed by IR and Si-29 MAS NMR analyses. TEM and SEM results show that grafted SiO2 (g-SiO2) nanoparticles can be comparatively uniformly dispersed in chloroform or PLLA matrix, while the unmodified SiO2 nanoparticles tend to aggregate. The loading of g-SiO2 nanoparticles in poly(L-lactide) (PLLA) matrix greatly improves the toughness and tensile strength of this material. In contrast, the incorporation of un-grafted SiO2 nanoparticles into PLLA leads to the deterioration of its mechanical properties. DSC analysis shows that g-SiO2 nanoparticles can serve as a nucleating agent for the crystallization of PLLA in the composites. SEM characterization shows the tough characteristics and great interfacial combination strength for g-SiO2 (5wt%)/PLLA nanocomposites.

Dynamic mechanical and thermal properties of plasticized poly(lactic acid)

The blends of low molecular weight triacetin (TAC) and oligomeric poly(1,3-butylene glycol adipate) (PBGA) were used as multiple plasticizers to lubricate poly(lactic acid) (PLA) in this study. The thermal and mechanical properties of plasticized polymers were investigated by means of dynamic mechanical analysis and differential scanning calorimetry. Atomic force microscopy (AFM) was used to analyze the morphologies of the blends. Multiple plasticizers were effective in lowering the glass transition temperature (T-g) and the melting temperature (T-m) of PLA. Moreover, crystallinity of PLA increased with increasing the con-tent of multiple plasticizers. Tensile strength of the blends decreased following the increasing of the plasticizers, but increased in elongation at break. AFM topographic images showed that the multiple plasticizers dispersed between interfibrillar regions. Moreover, the fibrillar crystallite formed the quasicrosslinkings, which is another cause for the increase in elongation at break.

Surface modification of poly(L-lactic acid) to improve its cytocompatibility via assembly of polyelectrolytes and gelatin

Poly(L-lactide) (PLLA) surface was modified via aminolysis by poly(allylamine hydrochloride) (PAH) at high pH and subsequent electrostatic self-assembly of poly(sodium styrenesulfonate) (PSS) and PAH, and the process was monitored by X-ray photoelectron spectroscopy (XPS) and contact angle measurement. These modified PLLAs were then used as charged substrates for further incorporation of gelatin to improve their cytocompatibility. The amphoteric nature of the gelatin was exploited and the gelatin was adsorbed to the negatively charged PLLA/PSS and positively charged PLLA/PAH at pH = 3.4 and 7.4, respectively. XPS and water contact angle data indicated that the gelatin adsorption at pH = 3.4 resulted in much higher surface coverage by gelatin than at pH = 7.4. All the modified PLLA surfaces became more hydrophilic than the virgin PLLA. Chondrocyte culture was used to test the cell attachment, cell morphology and cell viability on the modified PLLA substrates.

Stereocomplexed poly(lactic acid)-poly(ethylene glycol) nanoparticles with dual-emissive boron dyes for tumor accumulation.

Responsive biomaterials play important roles in imaging, diagnostics, and therapeutics. Polymeric nanoparticles (NPs) containing hydrophobic and hydrophilic segments are one class of biomaterial utilized for these purposes. The incorporation of luminescent molecules into NPs adds optical imaging and sensing capability to these vectors. Here we report on the synthesis of dual-emissive, pegylated NPs with "stealth"-like properties, delivered intravenously (IV), for the study of tumor accumulation. The NPs were created by means of stereocomplexation using a methoxy-terminated polyethylene glycol and poly(D-lactide) (mPEG-PDLA) block copolymer combined with iodide-substituted difluoroboron dibenzoylmethane-poly(L-lactide) (BF2dbm(I)PLLA). Boron nanoparticles (BNPs) were fabricated in two different solvent compositions to study the effects on BNP size distribution. The physical and photoluminescent properties of the BNPs were studied in vitro over time to determine stability. Finally, preliminary in vivo results show that stereocomplexed BNPs injected IV are taken up by tumors, an important prerequisite to their use as hypoxia imaging agents in preclinical studies.

Stereocomplexes Formed From Select Oligomers of Polymer d-lactic Acid (PDLA) and l-lactate May Inhibit Growth of Cancer Cells and Help Diagnose Aggressive Cancers-Applications of the Warburg Effect.

It is proposed that select oligomers of polymer d-lactic acid (PDLA) will form a stereocomplex with l-lactate in vivo, producing lactate deficiency in tumor cells. Those cancer cells that utilize transport of lactate to maintain electrical neutrality may cease to multiply or die because of lactate trapping, and those cancer cells that benefit from utilization of extracellular lactate may be impaired. Intracellular trapping of lactate produces a different physiology than inhibition of LDH because the cell loses the option of shuttling pyruvate to an alternative pathway to produce an anion. Conjugated with stains or fluorescent probes, PDLA oligomers may be an agent for the diagnosis of tissue lactate and possibly cell differentiation in biopsy specimens. Preliminary experimental evidence is presented confirming that PDLA in high concentrations is cytotoxic and that l-lactate forms a presumed stereocomplex with PDLA. Future work should be directed at isolation of biologically active oligomers of PDLA.

Electron-beam treatment of poly(lactic acid) to control degradation profiles

Bioresorbable polymers such as polylactide (PIA) and polylactide-co-glycolide (PLGA) have been used successfully as biomaterials in a wide range of medical applications. However, their slow degradation rates and propensity to lose strength before mass have caused problems. A central challenge for the development of these materials is the assurance of consistent and predictable in vivo degradation. Previous work has illustrated the potential to influence polymer degradation using electron beam (e-beam) radiation. The work addressed in this paper investigates further the utilisation of e-beam radiation in order to achieve a more surface specific effect. Variation of e-beam energy was studied as a means to control the effective penetrative depth in poly-L-lactide (PLEA). PLEA samples were exposed to e-beam radiation at individual energies of 0.5 MeV, 0.75 MeV and 1.5 MeV. The near-surface region of the PLEA samples was shown to be affected by e-beam irradiation with induced changes in molecular weight, morphology, flexural strength and degradation profile. Moreover, the depth to which the physical properties of the polymer were affected is dependent on the beam energy used. Computer modelling of the transmission of each e-beam energy level used corresponded well with these findings. (C) 2010 Elsevier Ltd. All rights reserved.