Electrospun poly(L-lactide)-grafted hydroxyapatite/poly(L-lactide) nanocomposite fibers

Composite fibers composed of poly(L-lactide)-grafted hydroxyapatite (PLA-g-HAP) nanoparticles and polylactide (PLA) matrix were prepared by electro-spinning. Environmental scanning electron microscope (ESEM) and transmission electron microscopy (TEM) were employed to investigate the morphology of the composite fibers and the distribution of PLA-g-HAP nanoparticles in the fibers, respectively. At a low content (similar to 4 wt%) of PLA-g-HAP, the nanoparticles dispersed uniformly in the fibers and the composite fibrous mats exhibited higher strength properties, compared with the pristine PLA fiber mats and the simple hydroxyapatite/PLA blend fiber mats. But when the content of PLA-g-HAP further increased, the nanoparticles began to aggregate, which resulted in the deterioration of the mechanical properties of the composite fiber mats. The degradation behaviors of the composite fiber mats were closely related to the content of PLA-g-HAP. At a low PLA-g-HAP content, degradation may be delayed due to the reduction of autocatalytic degradation of PLA. When PLA-g-HAP content was high, degradation rate increased because of the enhanced wettability of the composite fibers and the escape of the nanoparticles from fiber surfaces during incubation.

Electroactive oligoaniline-containing self-assembled monolayers for tissue engineering applications

A novel electroactive silsesquioxane precursor, N-(4-aminophenyl)-M-(4'-(3-triethoxysilyl-propyl-ureido) phenyl-1,4-quinonenediimine) (ATQD), was successfully synthesized from the emeraldine form of amino-capped aniline trimers via a one-step coupling reaction and subsequent purification by column chromatography. The physicochemical properties of ATQD were characterized using mass spectrometry as well as by nuclear magnetic resonance and UV-vis spectroscopy. Analysis by cyclic voltammetry confirmed that the intrinsic electroactivity of ATQD was maintained upon protonic acid doping, exhibiting two distinct reversible oxidative states, similar to polyaniline. The aromatic amine terminals of self-assembled monolayers (SAMs) of ATQD on glass substrates were covalently modified with an adhesive oligopeptide, cyclic Arg-Gly-Asp (RGD) (ATQD-RGD). The mean height of the monolayer coating on the surfaces was similar to 3 nm, as measured by atomic force microscopy. The biocompatibility of the novel electroactive substrates was evaluated using PC12 pheochromocytoma cells, an established cell line of neural origin. The bioactive, derivatized electroactive scaffold material, ATQD-RGD, supported PC12 cell adhesion and proliferation, similar to control tissue-culture-treated polystyrene surfaces.

Large scale, templateless, surfactantless route to rapid synthesis of uniform poly(o-phenylenediamine) nanobelts

We reported the interesting finding that large scale uniform poly(o-phenylenediamine) nanobelts with several hundred micrometers in length, several hundred nanometers in width, and several ten nanometers in height can be rapidly yielded from an o-phenylenediamine-HAuCl4 aqueous solution without the additional introduction of other templates or surfactants at room temperature.

Preparation of a phosphopolyoxomolybdate P2Mo18O626- doped polypyrrole modified electrode and its catalytic properties

A phosphopolyoxomolybdate (P2Mo18) doped polypyrrole (PPy) modified electrode was prepared in aqueous solution by a one-step method. During the polymerization of PPy, P2Mo18 acted as both catalyst and dopant. The electrochemical behavior of the PPy/P2Mo18 modified electrode before and after the overoxidation of PPy was investigated. Both of these showed a catalytic effect toward bromate. The PPy/P2Mo18 composite film was characterized by chronoamperometry, cyclic voltammetry, the rotating disk electrode technique, X-ray photoelectron spectroscopy and Raman spectroscopy.

A method for cathodic polymerization of aniline by in situ electrogenerated intermediate at gold surface

Polyaniline (PANI) was cathodically synthesized at an evaporated gold electrode using an in situ electrogenerated intermediate as oxidant during reduction of the dissolved oxygen. The obtained PANI layer showed an electrochemical response similar to that synthesized by the conventionally anodic polymerization, and the average rate for the growth of PANI layer at polycrystalline gold electrode was 1.59 nm h(-1), while that at the Au (111) electrode was 4.93 nm h(-1). Based on these results, the thickness of the resulted layer can be easily controlled at molecular level for potential nanodevice applications. The obtained PANI layer showed morphology from an island-like nanostructure to an ultrathin film, depending on the crystal orientation of the electrode used.

Enzymatic degradation of poly(L-lactide) and poly (epsilon-caprolactone) electrospun fibers

Poly(L-lactide) (PLLA) and poly(epsilon-caprolactone) (PCL) ultrafine fibers were prepared by electrospinning. The influence of cationic and anionic surfactants on their enzymatic degradation behavior was investigated by measuring weight loss, molecular weight, crystallinity, and melting temperature of the fibers as a function of degradation time. Under the catalysis of proteinase K, the PLLA fibers containing the anionic surfactant sodium docecyl sulfate (SDS) exhibited a faster degradation rate than those containing cationic surfactant triethylbenzylammonium chloride (TEBAC), indicating that surface electric charge on the fibers is a critical factor for an enzymatic degradation. Similarly, TEBAC-containing PCL fibers exhibited a 47% weight loss within 8.5 h whereas SDS-containing PCL fibers showed little degradation in the presence of lipase PS. By analyzing the charge status of proteinase K and lipase PS under the experimental conditions, the importance of the surface charges of the fibers and their interactions with the charges on the enzymes were revealed. Consequently, a "two-step" degradation mechanism was proposed: (1) the enzyme approaches the fiber surface; (2) the enzyme initiates hydrolysis of the polymer.

Use of atomic force microscopy for imaging the initial stage of the nucleation of calcium phosphate in Langmuir-Blodgett films of stearic acid

The nucleation of calcium phosphate on the substrate of steatic acid Langmuir-blodgett film at the initial stage was investigated by atomic force microscopy. Nano-dots, nano-wires and nano-islands were observed in sequence for the first time, reflecting the nucleation of calcium phosphate and the molecular arrangement of carboxylic layer. The nucleation rates perpendicular and parallel to the carboxylic terminal group were estimated from the height and diameter of the calcium phosphate crystals, respectively. And this stage was distinct from the late explosive grown stage, in which the change of the morphology was not obvious. The approaches based on this discovery would lead to the development of new strategies in the controlled synthesis of inorganic nano-phases and the assembly of organized composite and ceramic materials.

Structure and catalytic properties of magnesia-supported copper salts of molybdovanadophosphoric acid

The structure and stability of magnesia-supported copper salts of molybdovanadophosphoric acid (Cu2PMo11VO40) were characterized by different techniques. The catalyst was prepared in ethanol by impregnation because this solvent does not hurt texture of the water-sensitive MgO and Cu2PMo11VO40. The Keggin-type structure compound may be degraded partially to form oligomerized polyoxometalate when supported on MgO. However, the oligomers can rebuild as the Keggin structure again after thermal treatment in air or during the reaction. Meanwhile, the V atoms migrate out of the Keggin structure to form a lacunary structure, as observed by Fourier transform IR spectroscopy. Moreover, the presence of Cu2+ as a countercation showed an affirmative influence on the migration of V atoms, and the active sites derived from the lacunary species generated after release of V from the Keggin anion. The electron paramagnetic resonance data imply that V5+ autoreduces to V4+ in the fresh catalyst, and during the catalytic reaction a large number of V4+ ions are produced, which enhance the formation of O2- vacancies around the metal atoms. These oxygen vacancies may also improve the reoxidation function of the catalyst. This behavior is correlated to higher catalytic properties of this catalyst. The oxidative dehydrogenation of hexanol to hexanal was studied over this catalyst.

Modification of electrode surface through electrospinning followed by self-assembly multilayer film of polyoxometalate and its photochromic

Electrospun poly (vinyl alcohol) (PVA) nanofibers mat was collected on indium tin oxide (ITO) substrate. Heat crosslinked nanofibers mat became water-insoluble and firmly fixed on ITO substrate even in water. Oppositely charged poly (allylamine hydrochloride) (PAH) and Dawson-type polyoxometalate (POM), Na6P2Mo18O62 (P2Mo18), were alternately assembled on PVA nanofibers-coated ITO substrate to construct multilayer film through an electrostatic layer-by-layer (LBL) technique. The scanning electron microscope (SEM) images showed that P2Mo18 multilayer film was selectively deposited on PVA nanofibers while the unoccupied space by nanofibers on bare ITO was acted as substrate at the same time because the electrospun nanofibers have larger surface area and surface energy than the flat substrate. The cyclic voltammograms current responses of the P2Mo18 multilayer film on PVA/ITO electrode showed three well-defined redox couples of P2Mo18, but very small because P2Mo18 multilayer film was selectively deposited on PVA nanofibers with poor conductivity. In addition, the photochromic behavior of P2Mo18 multilayer film on PVA/ITO was investigated through UV-vis spectra and electron spin resonance (ESR). Fourier-transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) proved that the charge-transfer complex was formed between PAH and P2Mo18 after UV irradiation.

Synthesis and surface morphology of tetraaniline-block-poly(L-lactate) diblock oligomers

Tetraaniline-block-poly(L-lactide) diblock oligomers are synthesized via ring-opening polymerization. The diblock oligomers cast from all L-lactide selective solvent (chloroform) show spherical aggregates for the leucoemeraldine state, and ring-like structures that are composed of much smaller spherical aggregates for the emeraldine state. The formation mechanisms of the two different surface morphologies are discussed in detail.

One-step synthesis of 3D dendritic gold/polypyrrole nanocomposites via a self-assembly method

Novel spherical three-dimensional (3D) dendritic gold-polypyrrole nanocomposites were successfully prepared in the presence of an amphiphilic p-toluene sulfonic acid (TSA) as dopant and surfactant via a self-assembly process which is based on the oxidation of pyrrole (Py) and the reduction of the chloroaurate ions, yielding PPy and Au(0) simultaneously. It was found that the probability of obtaining dendritic Au@PPy/TSA nanostructures depended on the concentration of TSA and the rate of addition of the oxidant (HAuCl4), It was also proposed that the supramolecular micelles formed by Py and TSA play the role of a 'soft template' to produce the dendritic Au@PPy/TSA nanocomposites.

An effective layer-by-layer adsorption and polymerization method to the fabrication of polyoxometalate-polypyrrole nanoparticle ultrathin films

A layer-by-layer (LbL) adsorption and polymerization method was developed for the controllable preparation of polypyrrole (PPy) nanoparticles within ultrathin films. By repetitive adsorption of pyrrole and subsequent polymerization with 12-molybdophosphoric acid, the polyelectrolyte multilayer films containing PPy nanoparticles were fabricated. UV-visible absorption spectrocopy, Fourier transform infrared (FTIR) spectroscopy, atomic force microscopy (AFM), transmission electron microscopy (TEM) and cyclic voltammograras (CVs) were used to characterize the PPy nanoparticles and their multilayer thin films. UV-visible spectra indicate that the growth of PPy nanoparticles was regular and occurred within the polyelectrolyte films. The size of prepared PPy nanoparticles was found by TEM to increase with the increasing of polymerization cycles. The electrochemistry behavior of the multilayer thin films was studied in detail on ITO. The results suggest that the LbL adsorption and polymerization method developed herein provides an effective way to prepare PPy nanoparticles in the polymer matrix.

Electropolyrnerization of polypyrrole on PFIL-PSS-modified electrodes without added support electrolytes

A novel polyelectrolyte-functionalized ionic liquid (PFIL)/poly(4-styrene sulfonate sodium) (PSS) modified electrode composed of the coaxial and coplanar working, reference and counter electrodes, was used to electropolymerize the polypyrrole. The PFIL/PSS was modified on the integrated electrode (IE) and connected by the working, reference and counter electrodes, resulting in an available charge transfer and lower Ohmic potential drop between the working and counter electrodes. Then polypyrrole (PPy) film was successfully prepared electrochemically without any participation of supporting electrolytes, only in a pyrrole monomer solution. The resulting PPy film in PFIL/PSS matrix exhibited a preferable electroactivity. Subsequently, influence of the modifications on the formation of PPy was further discussed. The results indicated that the synergetic cooperation of PFIL and PSS components accomplished such a successful electropolymerization of PPy.

Biodegradable electrospun poly(L-lactide) fibers containing antibacterial silver nanoparticles

Biodegradable poly(L-lactide) (PLA) ultrafine fibers containing nanosilver particles were prepared via electrospinning. Morphology of the Ag/PLA fibers and distribution of the silver nanoparticles were characterized. The release of silver ions from the Ag/PLA fibers and their antibacterial activities were investigated. These fibers showed antibacterial activities (microorganism reduction) of 98.5% and 94.2% against Staphylococcus aureus and Escherichia coli, respectively, because of the presence of the silver nanoparticles.

Crystal structure and morphology of phenyl-capped tetraaniline in the leucoemeraldine oxidation state

A series of crystals of phenyl-capped tetraaniline in the leucoemeraldine oxidation state were obtained at different isothermal temperatures and were observed directly under transmission electron microscope. The crystals obtained at higher temperatures exhibit more perfect structures than those obtained at lower temperatures. Both the lamella thickness and the crystal size increase with crystallization temperature. The tetraaniline is apt to form larger scale crystals under lower degree of supercooling. However, their crystal structures keep steady with the crystallization temperature. The tetramer was found to adopt a monoclinic lattice with unit cell parameter of a = 13.93 angstrom, b = 8.82 angstrom, c = 23.20 angstrom, and beta = 95.03 degrees, as determined using electron diffraction tilting method combined with wide-angle X-ray diffraction experiment.