Novel aliphatic poly(ester-carhonate) with pendant allyl ester groups and its folic acid functionalization

A series of novel poly(ester-carbonate)s bearing pendant allyl ester groups P(LA-co-MAC)s were prepared by ring-opening copolymerization Of L-lactide (LA) and 5-methyl-5-allyloxycarbonyl-1,3-dioxan-2-one (MAC) with diethyl zinc (ZnEt2) as initiator. NMR analysis investigated the microstructure of the copolymer. DSC results indicated that the copolymers displayed a single glass-transition temperature (T-g), which was indicative of a random copolymer, and the Tg decreased with increasing carbonate content in the copolymer.

Aliphatic Poly(ester-carbonate)s Bearing Amino Groups and Its RGD Peptide Grafting

This article deals with (1) synthesis of novel cyclic carbonate monomer (2-oxo [1,3]dioxan-5-yl)carbamic acid benzyl ester (CAB) containing protected amino groups; (2) ring-opening copolymerization of the cyclic monomer with L-lactide (LA) to provide novel degradable poly(ester-carbonate)s with functional groups; (3) removal of the protective benzyloxycarbonyl (Cbz) groups by catalytic hydrogenation to afford the corresponding poly(ester-co-carbonate)s with free amino groups; (4) grafting of oligopeptide Gly-Arg-Gly-Asp-Ser-Tyr (GRGDSY, abbreviated as RGD) onto the copolymer pendant amino groups in the presence of 1,1'-carbonyldiimidazole (CDI).

Preparation and characterization of poly(piperazineamide) composite nanofiltration membrane by interfacial polymerization of 3,3 ',5,5 '-biphenyl tetraacyl chloride and piperazine

Most nanofiltration (NF) membranes are composite and have a polyamide thin film prepared by interfacial polymerization. Their performances mainly correlate the structure of the thin film and monomers used for its preparation. In this work, a novel thin-film composite (TFC) nanofiltration membrane was successfully prepared from 3,3',5,5'-biphenyl tetraacyl chloride (mm-BTEC) and piperazine (PIP) through interfacial polymerization. Attenuated reflectance infrared (ATR-IR) and X-ray photoelectronic spectroscopy (XPS) were used to characterize the chemical composition of the membrane surface. The membrane performance was optimized by studying preparation parameters including monomer concentration, reaction time, and pH of aqueous phase.

The Surface Modification of Hydroxyapatite Nanoparticles by the Ring Opening Polymerization of gamma-Benzyl-L-glutamate N-carboxyanhydride

The surface modification of hydroxyapatite (HA) nanoparticles by the ring opening polymerization (ROP) of gamma-benzyl-L-glutamate N-carboxyanhydride (BLG-NCA) was proposed to prepare the poly(gamma-benzyl-L-glutamate) (PBLG)-grafted HA nanoparticles (PBLG-g-HA) for the first time. HA nanoparticles were firstly treated by 3-aminopropylthriethoxysilane (APS) and then the terminal amino groups of the modified HA particles initiated the ROP of BLG-NCA to obtain PBLG-g-HA. The process was monitored by XPS and FT-IR. The surface grafting amounts of PBLG on HA ranging from 12.1 to 43.1% were characterized by thermal gravimetric analysis (TGA). The powder X-ray diffraction (XRD) analysis confirmed that the ROP only underwent on the surface of HA nanoparticles without changing its bulk properties. The SEM measurement showed that the PBLG-g-HA hybrid could form an interpenetrating net structure in the self-assembly process.

Cinnamate-Functionalized Poly(ester-carbonate): Synthesis and Its UV Irradiation-Induced Photo-Crosslinking

A functionalized. cyclic carbonate monomer containing a cinnamate moiety, 5-methyl-5-cinnamoyloxymethyl-1,3-dioxan-2-one (MC), was prepared for the first time with 1,1,1-tri(hydroxymethyl) ethane as a starting material. Subsequent polymerization of the new cyclic carbonate and its copolymerization with L-lactide (LA) were successfully performed with diethyl zinc (ZnEt2) as initiator/catalyst. NMR was used for microstructure identification of the obtained monomer and copolymers. Differential scanning calorimetry (DSC) was used to characterize the functionalized poly(ester-carbonate). The results indicated that the copolymers displayed a single glass transition temperature (T-g) and the T, decreased with increasing carbonate content and followed the Fox equation, indicative of a random microstructure of the copolymer. The photo-crosslinking of the cinnamate-carrying copolymer was also demonstrated.

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.

Narion/Poly(sodium 4-styrenesulfonate) mixed coating modified bismuth film electrode for the determination of trace metals by anodic stripping voltammetry

To improve the reproducibility, stability, and sensitivity of bismuth film electrode (BiFE), we studied the performances of a mixed coating of two cation-exchange polymers, Nafion (NA) and poly(sodium 4-styrenesulfonate) (PSS), modified glassy carbon BiFE (GC/NA-PSS/BiFE). The characteristics of GC/NA-PSS/BiFE were investigated by scanning electron microscopy and cyclic voltammetry. Various parameters were studied in terms of their effect on the anodic stripping voltarnmetry (ASV) signals. Under optimized conditions, the limits of detection were 71 ng L-1 for Cd(II) and 93 ng L-1 for Pb(II) with a 10 min preconcentration. The results exhibited that GC/NA-PSS/BiFE can be a reproducible and robust toot for monitor of trace metals by ASV rapidly and environmentally friendly, even in the presence of surface-active compounds.

Electrostatic assembly of polyaniline and platinum-poly(amidoamine) dendrimers hybrid nanocomposite multilayer, and its electrocatalysis towards CO and O-2

The electrostatic layer-by-layer assembly method was successfully used in a multilayer buildup of polyaniline (PANT) and platinum nanocrystals encapsulated in the carboxyl-terminated poly(amidoamine) dendrimers (generation 4.5 G4.5COOH) (Pt-G4.5COOH NPs) on solid substrates. Multilayer growth was monitored by ultraviolet-visible (UV-vis) absorption spectroscopy. The AFM observation revealed a molecularly smooth (PANI/Pt-G4.5COOH NPs) multilayer film which is rougher and thicker than the multilayer of PANT and G4.5COOH (G4.5COOH/PANI)(m). The PANI/Pt-G4.5COOH NPs multilayers show a fast surface-confined electron-exchange process at the Au electrode in an acid solution, and remains stable, reversible and electroactive, even in neutral solution. Furthermore, the multilayers show a strong elect rocatalytic response towards CO oxidation and O-2 reduction, and the catalytic capability can be easily tuned by the control of multilayer thickness.

Morphology of electrodeposited poly(3,4-ethylenedioxythiophene)/poly(4-styrene sulfonate) films

Poly(4-styrene sulfonate)-doped poly(3,4-ethylenedioxythiophene) (PEDOT/PSS) films with ring-, arrow-, and bubble-like microstructures have been electrochemically generated simply by a one-step cyclic voltammetry in an aqueous media. Influences of applied potentials and surfactant/dopant-PSS on morphology of the resulting film were investigated, and a gas bubble template mechanism has been proposed. The result confirmed a well-doping of PSS in the PEDOT film. Electrochemical property and conductivity of the micro-structured PEDOT/PSS film were investigated further. Similar preparation with potential applications in fabrication of microdevices and micro-sensors can be extended to other micro-structured conducting polymers.

A facile approach to biodegradable poly(epsilon-caprolactone)-poly(ethylene glycol)-based polyurethanes containing pendant amino groups

A novel biodegradable poly(epsilon-caprolactone)-poly(ethylene glycol)-based polyurethanes (PCL-PEG-PU) with pendant amino groups was synthesized by direct coupling of PEG ester of NH2-protected-(aspartic acid) (PEG-Asp-PEG diols) and poly(epsilon-caprolactone) (PCL) diols with hexamethylene dissocyanate (HDI) under mild reaction conditions and by subsequent deprotection of benzyloxycarbonyl (Cbz) groups. GPC, H-1 NMR, and C-13 NMR studies confirmed the polymer structures and the complete deprotection. DSC and WXRD results indicated that the crystallinity of the copolymer was enhanced with increasing PCL diols in the copolymer. The content of amino group in the polymer could be adjusted by changing the molar ratio of PEG-Asp-PEG diols to PCL diols. Thus the results of this study provide a good way to prepare polyurethanes bearing hydrophilic PEG segments and reactive amino groups without complicated synthesis.

Composites of poly(lactide-co-glycolide) and the surface modified carbonated hydroxyapatite nanoparticles

To improve the mechanical properties of the composites of poly(lactide-co-glycolide) (PLGA, LA/GA = 80/20) and the carbonate hydroxyapatite (CHAP) particles, the rice-form or claviform CHAP particles with 30-40 nm in diameter and 100-200 nm in length were prepared by precipitation method. The uncalcined CHAP particles have a coarse surface with a lot of global protuberances, which could be in favor of the interaction of the matrix polymer to the CHAP particles. The nanocomposites of PLGA and surface grafted CHAP particles (g-CHAP) were prepared by solution mixing method. The structure and properties of the composites were subsequently investigated by the emission scanning electron microscopy, the tensile strength testing, and the cell culture. When the contents of g-CHAP were in the range of 2-15 wt %, the PLGA/g-CHAP nanocomposites exhibited an improved elongation at break and tensile strength. At the 2 wt % content of g-CHAP, the fracture strain was increased to 20%) from 4-5% for neat PLGA samples. Especially at g-CHAP content of 15 wt %, the tensile strength of PLGA/g-CHAP composite was about 20% higher than that of neat PLGA materials. The tensile moduli of composites were increased with the increasing of filler contents, so that the g-CHAP particles had both reinforcing and toughening effects on the PLGA composites. The results of biocompatibility test showed that the higher g-CHAP contents in PLGA composite facilitated the adhesion and proliferation properties of osteoblasts on the PLGA/g-CHAP composite film.

Self-assembly of a polymer pair through poly(lactide) stereocomplexation

A polymer pair composed of poly( N-isopropylacrylamide-co-2-hydroxyethyl methacrylate terminated oligo( L-lactide)) ( poly( NIPAAm-co-HEMAOLLA)) graft random copolymer and poly( D-lactide) ( PDLA) homopolymer was self-assembled into micelles with a diameter around 100 nm through the stereocomplexation between the OLLA branches of the graft copolymer and the PDLA homopolymer. The specific intermolecular stereocomplexation was considered as the powerful ordered aggregation force in the micelle cores. The shell's component of poly( NIPAAm-co-HEMA) and its thermosensitivity were proved by H-1 nuclear magnetic resonance ( NMR) and dynamic light scattering ( DLS), respectively. The incorporation of PDLA homopolymer into the graft copolymer affected the micelle size and the critical micelle concentration ( CMC). The incorporation of even a small quantity ( 11 wt%) of PDLA into the graft copolymer micelles resulted in a great decrease of the micelle size. For the graft copolymer with low per cent grafting of 18%, the size of the corresponding micelles decreased slightly even if the PDLA content increased up to 33 wt%. For the graft copolymer with high per cent grafting of 58%, with the further increase of PDLA content, the size of the corresponding micelles at first decreased further and then began to increase. The molecular weight of the PDLA did not significantly affect the micelle size.

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.