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.

Fabrication and characterization of self-doped poly (aniline-co-anthranilic acid) nanorods in bundles

Poly (aniline-co-anthranilic acid) (PANANA) nanorods in bundles was prepared successfully in an alcohol/aqueous media without assistance of an), other kinds of acids. Anthranilic acid played all roles of monomer, acid-media provider, and dopant in the reaction system, and ammonium persulfate (APS) served as the oxidant. The morphologies of PANANA nanorods in bundles were investigated by scanning electron microscopy (SEM). Influences of the monomer molar ratio on the resulting morphology were investigated. Moreover the formation mechanism of the nanostructured copolymer was proposed. FT-IR. UV-vis and X-ray diffraction (XRD) measurements were used to confirm the molecular and electrical structure of the self-doped PANANA. The intrinsic properties, such as conductivity, electrochemical redox activity and room-temperature solubility of the resulting copolymer were explored.

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.

Mesoporous acid solid as a carrier for metallocene catalyst in ethylene polymerization and a catalyst in catalytic degradation of polyethylene

The possibility of mesoporous acid solid as a carrier for metallocene catalyst in ethylene polymerization and catalyst for polyethylene (PE) catalytic degradation was investigated. Here, HMCM- 41 and AIMCM-41, and mesoporous silicoaluminophosphate molecular sieves (SAPO1 and SAPO2) were synthesized and used as acid solid. Much more gases were produced during catalytic degradation in PE/acid solid mixtures via in situ polymerization than those via physical mixing. The particle size distribution results exhibited that the particle size of SAPO1 in the PE/SAPO1 mixture via in situ polymerization was about 1/14 times of that of the original SAPO1 or SAPO1-supported metallocene catalyst. This work shows a novel technology for chemical recycling of polyolefin.

Polyelectrolyte complexes based on chitosan and poly(L-glutamic acid)

Polyelectrolyte complexes (PECs) were prepared by mixing aqueous solutions of chitosan (CS) and poly(L-glutamic acid) (PLGA) at various pH. It was found that the stoichiometry of the PECs depends on pH.An investigation of the PECs using Fourier transform infrared spectroscopy proved that the formation of the complexes is due to electrostatic interaction between –NH3 + groups of CS and –COO− groups of PLGA. The solid PECs were characterized using wide-angle X-ray diffraction, which suggested that a strong interaction occurs between the two polymers at pH = 4 or 5 and relatively weak interaction at pH = 3. These results were further confirmed by thermogravimetric analysis data. Transmission electron microscopy showed that the complexes have a spherical shape. The effect of ionic strength on the size of the PECs was also studied using dynamic light scattering. It was found that the size of the PECs is dependent on pH.

Synthesis and characterization of hyperbranched poly(ester-amide)s based on gallic acid and DL-2-aminobutyric acid

A novel AB(3)-type monomer was prepared from gallic acid and DL-2-aminobutyric acid, and used for the synthesis of the biocompatible hyperbranched poly(ester-amide)s by self-polycondensation. The polymers were characterized via FTIR and NMR spectroscopy and thermal analysis, and the average degree of branching of the polymers was estimated to be 0.75. The polymers with abundant acetyl end groups were found to be amorphous with lower intrinsic viscosity, better thermal stability and excellent solubility.

Assemble of poly(aniline-co-o-aminobenzenesulfonic acid) three-dimensional tubal net-works onto ITO electrode and its application for the direct electrochemistry and electrocatalytic behavior of cytochrome c

Stable electroactive film of poly(aniline-co-o-aminobenzenesulfonic acid) three-dimensional tubal net-works was assembled on indium oxide glass (ITO) successfully, and the cytochrome c was immobilized on the matrix by the electrostatic interactions. The adsorbed cytochrome c showed a good electrochemical activity with a pair of well-defined redox waves in pH 6.2 phosphate buffer solution, and the adsorbed protein showed more faster electron transfer rate (12.9 s(-1)) on the net-works matrix than those of on inorganic porous or even nano-materials reported recently. The immobilized cytochrome c exhibited a good electrocatalytic activity and amperometric response (2 s) for the reduction of hydrogen peroxide (H2O2). The detection limit for H2O2 was 1.5 mu M, and the linear range was from 3 mu M to 1 mM. Poly(aniline-co-o-aminobenzenesulfonic acid) three-dimensional tubal net-works was proved to be a good matrix for protein immobilization and biosensor preparation.

The direct synthesis of wholly aromatic poly(p-phenylene)s bearing sulfobenzoyl side groups as proton exchange membranes

Sulfonated poly(p-phenylene)s (SPPs) containing sulfonic acid groups in their side chains had been directly synthesized by Ni(0) catalytic coupling of sodium 3-(2,5-dichlorobenzoyl)benzenesulfonate and 2,5-dichlorobenzophenone. The synthesized copolymers possessed high molecular weights revealed by their high viscosity, and the formation of tough and flexible membranes by casting from DMAc solution. The copolymers exhibited excellent oxidative stability and mechanical properties due to their fully aromatic structure extending through the backbone and pendent groups. Transmission electron microscopic (TEM) analysis revealed that these side-chain type SPP membranes have a microphase-separated structure composed of hydrophilic side-chain domains and hydrophobic polyphenylene main chain domains. The proton conductivities of copolymer membranes increased with the increase of IEC and temperature, reaching values above 3.4 x 10(-1) S/cm at 120 degrees C, which are almost 2-3 times higher than that of Nafion 117 at the same measurement conditions. Consequently, these materials proved to be promising as proton exchange membranes.

Preparation and properties of sulfonated poly(ether ether ketone)s (SPEEK)/polypyrrole composite membranes for direct methanol fuel cells

Polypyrrole (Ppy) was successfully introduced into methyl substituted sulfonated poly(ether ether ketone) (SPEEK) membranes by polymerization in SPEEK solutions to improve their methanol resistance. Uniform polypyrrole (Ppy) distributed composite membranes were formed by this method by the interaction between SPEEK and Ppy. The properties of the composite membranes were characterized in detail. The composite membranes show very good proton conductive capability (25 degrees C: 0.05-0.06s cm(-1)) and good methanol resistance (25 degrees C: 5.3 x 10(-7) 1.1 x 10(-6) cm(2) s(-1)). The methanol diffusion coefficients of composite membranes are much lower than that of pure SPEEK membranes (1.5 x 10(-6) cm(2) s(-1)). The composite membranes show very good potential usage in direct methanol fuel cells (DMFCs).

Dispersion copolymerization of acrylamide with acrylic acid in an aqueous solution of ammonium sulfate: Synthesis and characterization

Dispersion copolymerization of acrylamide with acrylic acid in an aqueous solution of ammonium sulfate using poly(2-acrylamido-2-methylpropanesulfonic acid sodium) as the stabilizer and ammonium persulfate (APS) as the initiator was investigated. The influence of initiator concentration, stabilizer concentration, ammonium sulfate concentration, chain-transfer agent concentration, and polymerization temperature on the copolymerization was discussed. The results showed that varying the ammonium sulfate concentration could affect the particle size and the intrinsic viscosity of the copolymer significantly. With increasing the stabilizer concentration, the particle size of the copolymer decreased first, and then increased, meanwhile the intrinsic viscosity of the copolymer decreased. The increase of initiator concentration, chain-transfer agent concentration, and polymerization temperature resulted in the increase in the particle size. Polydisperse spherical particles were formed in the system, and the kinetics for the dispersion copolymerization were discussed.

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.

A novel route for the preparation of CdS nanocrystal-poly(acrylic acid) composites using gamma-radiation

CdS nanocrystals were synthesized through AOT/heptane/H2O reverse micelles. New stable reverse mikelles were obtained by adding an appropriate amount of acrylic. acid monomer, CdS nanocrystal-poly(acrylic acid) composites were synthesized by gamma-radiation with a reverse mi'celle route at room temperature. The US nanocrystals with narrow size distribution were, found to be dispersed homogeneously in the poly(acrylic acid) matrix. (C) 2002 Elsevier Science B.V. All rights reserved.

Effect of the compatibilization of linear low-density polyethylene-g-acrylic acid on the morphology and mechanical properties of poly(butylene terephthalate)/linear low-density polyethylene blends

A poly(butylene terephthalate) (PBT)/linear low-density polyethylene (LLDPE) alloy was prepared with a reactive extrusion method, For improved compatibility of the blending system, LLDPE grafted with acrylic acid (LLDPE-g-AA) by radiation was adopted in place of plain LLDPE. The toughness and extensibility of the PBT/LLDPE-g-AA blends, as characterized by the impact strengths and elongations at break, were much improved in comparison with the toughness and extensibility of the PBT/LLDPE blends at the same compositions. However, there was not much difference in their tensile (or flexural) strengths and moduli. Scanning electron microscopy photographs showed that the domains of PBT/LLDPE-g-AA were much smaller and their dispersions were more homogeneous than the domains and dispersions of the PBT/ T,T PE blends. Compared with the related values of the PBT/LLDPE blends, the contents and melting temperatures of the usual spherulites of PBT in PBT/LLDPE-g-AA decreased.