A biodegradable triblock copolymer poly(ethylene glycol)-b-poly(L-lactide)-b-poly(L-lysine): Synthesis, self-assembly and RGD peptide modification

A novel biodegradable triblock copolymer poly(ethylene glycol)-b-poly(L-lactide)-b-poly(L-lysine) (PEG-PLA-PLL) was synthesized by acidolysis of poly(ethylene glycol)-b-poly(L-lactide)-b-poly(F-benzyloxycarbonyl-L-lysine) (PEG-PLA-PZLL) obtained by the ring-opening polymerization (ROP) of epsilon-benzyloxycarbonyl-L-lysine N-carboxyanhydride (ZLys NCA) with amino-terminated PEG-PLA-NH2 as a macro-initiator, and the pendant amino groups of the lysine residues were modified with a peptide known to modulate cellular functions, Gly-Arg-Gly-Asp-Ser-Tyr (GRGDSY, abbreviated as RGD) in the presence of 1,1'-carbonyldiimidazole (CDI). The structures of PEG-PLA-PLL/RGD and its precursors were confirmed by H-1 NMR, FT-IR, amino acid analysis and XPS analysis. The cell adhesion and cell spread on the PEG-PLA-PLL/RGD film were enhanced compared to those on pure PLA film. Therefore, the novel RGD-grafted triblock copolymer is promising for cell or tissue engineering applications. Both copolymers PEG-PLA-PZLL and PEG-PLA-PLL showed an amphiphilic nature and could self-assemble into micelles of homogeneous spherical morphology. The micelles were determined by fluorescence technique, dynamic light scattering (DLS), and field emission scanning electron microscopy (ESEM) and could be expected to find application in drug and gene delivery systems.

Shape-memory and biocompatibility properties of segmented polyurethanes based on poly(L-lactide)

A series of segmented poly (L-lactide)-polyurethanes (PLA-PU) were synthesized by a two-step method, with oligo-poly(L-lactide) (PLA) as the soft segments and the reaction product of 2,4-toluene diisocyanate(TDI) and ethylene glycol(EG) as the hard segments. The shape memory properties of PLA-PUs were examined. The processed PLA-PUs could recover almost 100% to their original shape within 10 degrees C from the lowest recovery temperature. In the recovery process, the PLA-PUs showed a maximum contracting stress of shape change in the range of 1.5-4 MPa depending on the PLA segmental length and the hard-segmental content and higher than that of poly (e-caprolactone polyurethane) (PCL-PU). Besides, the influence of deforming and fixing temperatures on shape memory properties of PLA-PU was studied in detail. They could affect not only the recovery temperature but also the maximum contracting stress. The experiments of cell incubation were used to evaluate the biocompatibility of PLA-PU. The results show that the biocompatibility of PLA-PU is comparable to that of the pure PLA. This kind of polyurethane can be used as implanted medical devices with a shape memory property.

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.

Electro-assisted precipitation of electrolytes in poly(3,4-ethylenedioxythiophene) film

The electrolyte, NaBF4, can be enriched into the matrix of poly(3,4-ethylenedioxythiophene) (PEDOT) film during the p-doping potential cycling between 0.6 and -0.9 V. It has been demonstrated that this enrichment is originated from the mixed ion transfer between doping and dedoping, i.e. BF4- anion migrate into the PEDOT film during the oxidation process, the Ne cation insert into the film during the reduction process, and then, the electrolyte is accumulated into the film matrix after the multiple CV cycling. The quantitative analysis of energy-dispersive X-ray spectroscopy (EDX) confirmed the enrichment of NaBF4 in the PEDOT film.

The study of synthesis of poly(ethylene oxide)-b-poly(N,N-dimethylacrylamide) by atom transfer radical polymerization and self-assembly in selective solvents

Poly( ethylene oxide)-b-poly(N, N-dimethylacrylamide) (PEO-b-PDMA) was synthesized by successive atom transfer radical polymerization (ATRP) of N, N-dimethylacrylamide (DMA) monomer using PEO-Br macro initiators as initiator, CuBr and 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazamacrocyclotetra decane (Me-6[14] aneN(4)) as catalyst and ligand. PEO-Br macroinitiator was synthesized by esterification of PEO with 2-bromoisobutyryl bromide. GPC and H-1 NMR studies show that the plot of ln([DMA](0)/[ DMA]) against the reaction time is linear, and the molecular weight of the resulting PDMA increased linearly with the conversion. Within 3 h, the polymerization can reach almost 60% of conversion. PEO-b-PDMA copolymer with low polydispersity index (M-w/M-n approximate to 1.1) is obtained. Self-assembly of PEO-b-PDMA in selective solvents is also studied. It could self-assemble into micelles in methanol/acetone (1/10, v/v) solution. TEM analyses of the PEO-b-PDMA micelles with narrow size distribution revealed that their size and shape depend much on the copolymer composition.

Competition of lamellar orientation in thin films of a symmetric poly(styrene)-b-poly(L-lactide)diblock copolymer in melt state

We have studied the lamellar orientation in thin films of a model diblock copolymer, symmetric poly(styrene)-b-poly(L-lactide) (PS-PLLA), in the melt state on supported silicon wafer surface. In this system, while the PLLA block prefers to wet the polymer/substrate interface, the polymer/air as well as polymer/polymer interface is neutral for both blocks due to the similar surface energies of PS and PLLA in melt state. Our results demonstrate that the interplay of the interfaces during phase separation results in a series of structures before approaching the equilibrium state. Lamellar orientation of thin films with different initial film thicknesses at different annealing stages has been investigated using atomic force microscopy (AFM), transmission electronic microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). It is found that in the early stage (annealing time t < 10 min), the polymer/substrate interface dominates the structure evolution, leading to a parallel lamellar structure with holes or islands formed depending on the initial film thickness. Later on, the neutral air interface becomes important and leads to a transition of lamellar orientation from parallel to perpendicular. It is interesting to see that for films with thickness h > 2L, where L is the bulk lamellar period, the lamellar orientation transition can occur independently in different parallel lamellar domains due to the neutrality of polymer/polymer interface.

Properties of complex of Tb(III) and poly(N-isopropylacrylamide)-g-poly(N-isopropylacrylamide-co-styrene) core-shell nanoparticles

We successfully prepared a new kind of thermoresponsive and fluorescent complex of Tb(III) and PNIPAM-g-P(NIPAM-co-St) (PNNS) core-shell nanoparticle. It was found that Tb(III) mainly bonded to 0 of the carbonyl groups of PNNS, forming the novel (PNIPAM-g-P(NIPAM-co-St))-Tb(III) (PNNS-Tb(III)) complex. The maximum emission intensity of the complex at 545 nm is enhanced about 223 times comparing to that of the pure Tb(III). The intramolecular energy transfer efficiency from PNNS to Tb(III) reaches 50%. When the weight ratio of Tb(III) and the PNNS-Tb(III) complex is 1.2 wt.%, the enhancement of the emission fluorescence intensity at 545 nm is highest.

catena-Poly[[[di-mu-acetato-kappa O-4 : O '-bis[(acetato-kappa O-2,O ')manganese(II)]]-di-mu-4,4 '-bipyridine-kappa N-4 : N '] monohydrate

The title compound, {[Mn-2(CH3CO2)(4)(C10H8N2)(2)](H2O)-H-.}(n), is a one-dimensional coordination polymer with a ladder-like structure. Two Mn-II atoms, each coordinated by a chelating acetate ligand, are bridged by two bidentate acetate ligands to form a centrosymmetric [Mn-2(CH3CO2)(4)] unit. Two 4,4'-bipyridine ligands link the [Mn-2(CH3CO2)(4)] units through Mn-N bonds to generate a molecular ladder. The water O atom lies on a crystallographic twofold rotation axis.

Biodegradable poly(L-lactide)/poly(epsilon-caprolactone)-modified montmorillonite nanocomposites: Preparation and characterization

New nanocomposites were prepared by melt blending poly(L-lactide) (PLLA), poly(epsilon-caprolactone) (PCL), and organically modified montmorillonite (OMMT). The obtained nanocomposites showed enhanced tensile strength, modulus and elongation at break than that of PLLA/PCL blends. The dynamic mechanical analysis showed the increasing mechanical properties with temperature dependence of nanocomposites. Wide-angle X-ray diffraction analysis and transmission electron microscopy indicated that the material formed the nanostructure. Adding OMMT improved the thermal stability and crystalline abilities of nanocomposites. The morphology was investigated by environmental scanning electron microscopy, which showed that increasing content of OMMT reduces the domain size of phase-separated particles. The specific interaction between each polymer and OMMT was characterized by the Flory-Huggins interaction parameter, B, which was determined by the equilibrium melting point depression of nanocomposites. The final values of B showed that PLLA was more compatible with OMMT than PCL.

Structural characteristics and thermal properties of plasticized poly(L-lactide)-silica nanocomposites synthesized by sol-gel method

Plasticized poly(L-lactide)-silica nanocomposite materials have been successfully synthesized by sol-gel process. The resultant nanocomposites were characterized by infrared spectra (IR), X-ray diffraction (XRD), thermogravimetry (TG), Tensile testing and scanning electron microscope (SEM). IR measurements show that vibration of C-O-C group is confined by silica network. Also the crystallization of poly (L-lactide) is partly confined by silica network. The presence of even small amount of silica largely improves the tensile strength of the samples, TGA results reveal that the thermal stability of samples is improved with silica loading.

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.

A simple and effective route for the preparation of poly(vinylalcohol) (PVA) nanofibers containing gold nanoparticles by electrospinning method

Poly(vinyl alcohol) (PVA) nanofibers containing gold nanoparticles have been simply obtained by electrospinning a solution containing gold nanoparticles without the additional step of introducing other stabilizing agents. The optical property of gold nanoparticles in PVA aqueous solution was observed by UV-visible absorption spectra. Morphology of the Au/PVA nanofibers and distribution of the gold nanoparticles were characterized by transmission electron. microscopy (TEM). The structure transformation was characterized from PVA to PVA/Au composite by Fourier transform infrared spectroscopy (FTIR).

Synthesis and characterization of photo-cross-linked hydrogels based on biodegradable polyphosphoesters and poly(ethylene glycol) copolymers

Novel biodegradable hydrogels by photo-cross-linking macromers based on polyphosphoesters and poly(ethylene glycol) (PEG) are reported. Photo-cross-linkable macromers were synthesized by ring-opening polymerization of the cyclic phosphoester monomer 2-(2-oxo-1,3,2-dioxaphospholoyloxy) ethyl methacrylate (OPEMA) using PEG as the initiator and stannous octoate as the catalyst. The macrorners were characterized by H-1 NMR, Fourier transform infrared spectroscopy, and gel permeation chromatography measurements. The content of polyphosphoester in the macromer was controlled by varying the feed ratio of OPEMA to PEG. Hydrogels were fabricated by exposing aqueous solutions of macromers with 0.05% (w/w) photoinitiator to UV light irradiation, and their swelling kinetics as well as degradation behaviors were evaluated. The results demonstrated that cross-linking density and pH values strongly affected the degradation rates. The macromers was compatible to osteoblast cells, not exhibiting significant cytotoxicity up to 0.5 mg/mL. "Live/dead" cell staining assay also demonstrated that a large majority of the osteoblast cells remained viable after encapsulation into the hydrogel constructs, showing their potential as tissue engineering scaffolds.