Vancomycin release from bioresorbable calcium phosphate–polymer composites with high ceramic volume fractions

Bioresorbable calcium phosphate–polymer composite implants are a desirable alternative to the traditional metal bone-healing devices. Incorporation of antimicrobial drugs into the composite material and their sustained delivery may dramatically reduce the risk of implant infections. The paper reports the fabrication of drug-incorporated bioresorbable CaP–polymer nanocomposites that can be used for fracture fixation devices and at the same time function as local delivery systems. Vancomycin was incorporated into β-tricalcium phosphate (β-TCP)- and biphasic CaP (BCP)-based composites containing ≤30 vol.% polycaprolactone (PCL) or polylactic acid (PLA), during their high pressure consolidation at 2.5 GPa and room temperature. The antibiotic release was studied in Tris buffer solution at 37 °C. Up to 5 wt% vancomycin could be included without compromising material’s integrity upon immersion into Tris solution. Vancomycin release profile was found to depend on the specific surface area of the test specimens and on the composite porosity. β-TCP–30 vol.% PLA composites were found to have the best combination of compression strength and drug release pattern. Complete drug release was accompanied by only negligible material dissolution suggesting a diffusion mechanism of release. In the context of bone-healing applications, such a release-dissolution pattern will allow local prophylaxis against implant-related infection at the early stages after implantation followed by a much more slow dissolution of the load-carrying device.     

In situ growth kinetics of ZnO nanobelts

For the first time, the growth of ZnO nanobelts was monitored in?situ using x-ray diffraction. The growth was carried out by heating metallic zinc powder in air at temperatures ranging from 368 to 568?°C. The morphology depends on both the growth temperature and the rate of heating to that temperature. A morphology diagram for the synthesized products was generated after systematic study of the experimental parameters. Higher temperatures and faster heating rates favor one-dimensional growth. Faster growth was observed for samples with higher growth temperatures, lower heating rates, and one-dimensional growth. These results give insight into the mechanism for the growth of ZnO nanobelts by metal oxidation.     

Two- and three-dimensional micro/nanostructure patterning of CdS-polymer nanocomposites with a laser interference technique and in situ synthesis

Two-?and three-dimensional (2D and 3D) micro/nanostructures of CdS-polymer nanocomposites have been successfully patterned, combining photopolymerization via a laser four-beam interference technique with in situ synthesis of CdS nanoparticles in the patterned polymer matrix. The morphology and optical properties of CdS nanoparticles in polymer matrices have been confirmed using TEM, XRD, FTIR, UV-vis absorption and fluorescence spectroscopy. Laser irradiation time and film thickness are certified to be the key factors for the control of the micro/nanostructures. With thickening film, the fabricated microstructures of CdS-polymer nanocomposites were dramatically changed from 2D rods to 3D networks which were composed of nanofibres, nanometre-scale walls and micrometre-scale rods. These kinds of 2D and 3D micro/nanostructures could be expected as potential applications in the development of nanotechnology, such as nanomedical systems, micro-fluidic chips, nanoreactors and micro/nanopurification or separation systems.     

In situ synthesis of gold–polyaniline composite in nanopores of polycarbonate membrane

In situ one-step chemical synthesis route for the preparation of a gold–polyaniline composite in nanopores of polycarbonate (PC) membrane is reported. PC membrane, which was placed in a specially designed two-compartment cell, separated the aqueous solution of aniline from HAuCl₄ solution. Concentration gradient across the membrane caused movement of AuCl₄ ⁻ and anilinium ions in the pores of polycarbonate membrane. Nanopores in PC membrane acted as reaction vessels where aniline and HAuCl₄ were allowed to mix together, and the redox reaction between aniline and HAuCl₄ led to the formation of gold–polyaniline composite. The gold–polyaniline composite in PC membrane was characterised by EDXRF, XRD, UV–Vis spectroscopy, FTIR and TEM. Peak broadening in XRD suggests that Au particles formed in the membrane are nanocrystallites and average crystallite size is (24 ± 4) nm. TEM studies show that gold nanoparticles are randomly dispersed in polyaniline clusters formed in the nanopores of PC membrane. Characterisation results show that the surfaces of the PC membrane exposed to HAuCl₄ and aniline have significantly higher concentrations of Au nanoparticles and polyaniline, respectively.     

In situ synthesis of transparent fluorescent ZnS–polymer nanocomposite hybrids through catalytic chain transfer polymerization technique

We report the controllable synthesis of zinc sulfide (ZnS) nanocrystals (NCs)/polymer transparent nanocomposite hybrids in situ based on the catalytic chain transfer polymerization (CCTP) technique. Firstly, a polymeric ligand PMAA [PMAA = poly(acrylic acid)] with controllable low-molecular-weight and a terminal double bond was synthesized through CCTP. Secondly, with the use of this versatile polymeric ligand containing a large number of anchors as the stabilizer, the ZnS NCs were fabricated. Finally, the surface polymeric ligands containing terminal double bonds were copolymerized with methyl methacrylate monomer to form NCs–polymer hybrids through free radical polymerization. The properties of as-prepared ZnS NCs and their nanocomposite hybrids were thoroughly investigated by Fourier transform Raman spectra, Fourier transform infrared spectrum, transmission electron microscope, ultraviolet–visible, photoluminescence, and thermogravimetric analyses measurements. The spectroscopic studies reveal that ZnS–polymer nanocomposite hybrids have good optical properties.     

In situ investigation of surfactants’ effect onto electrochemical synthesis and properties of polyfurans

Polyfuran (PFu) films were electrochemically deposited onto gold electro-quartz crystal microbalance (EQCM) electrodes using acetonitrile (ACN)/LiClO₄ solvent-electrolyte in presence of dodecylbenzenesulfonic acid (anionic, DBSA) and polyethylene glycol sorbitan monolaurate (non-ionic, Tween 20) surfactants. The effect of surfactants on structural and conductivity properties of the polymer films was investigated using Fourier transform-infrared spectroscopy (FT-IR) and four-probe conductivity measurements. The doping effects of surfactants onto the properties of PFu were correlated with mass gain using in situ EQCM. The conductivity of PFu polymer was measured for PFu with no surfactant and for PFu in presence of two surfactants (Tween 20 and DBSA). Our data indicate that although a fast polymerization, a sharp shift in the frequency and mass changes of the polymer films as well as the highest recorded conductivity of 0.048 S cm^?1 were all obtained for the PFu/Tween 20-2 sample, significantly more PFu films formed with PFu/DBSA than with PFu/Tween 20 samples. We concluded that more PFu films can be obtained when an oxidant and an anionic surfactant (DBSA) are used than when an oxidant is used alone, or when an oxidant is used with a non-ionic surfactant (Tween 20). A part of an anionic surfactant can be incorporated into a PFu structure like an oxidant anion and can act as co-dopant.     

In situ fabricated metal-carbide with core–shell structure for high impact-toughness iron-matrix composite

A series of metal-carbide (Ta–TaC, Nb–NbC and W–WC) with core–shell structure for iron-matrix composites are fabricated by in situ solid-phase diffusion. Results show that the formation of metal-carbide with a rod-shaped core–shell structure, in which the metal-rod surface was covered with a carbide shell layer, in the iron- matrix after in situ solid-phase diffusion. The TaC, NbC, and WC shell layers are in situ synthesised by the diffusion of carbon atoms from the iron-matrix onto the surface of the Ta, Nb, and W rods, respectively. Metallurgical integration occurs between metal-carbide and iron-matrix. The metal-carbide-reinforced iron-matrix composites show excellent impact resistance, and the shell-layer hardness is extremely high.     

Laser synthesis of magnetic iron–carbon nanocomposites with size dependent properties

Iron–carbon nanocomposites have gained interest due to their new engineering and biomedical applications. Carbon coated iron nanoparticles (Fe@C) were obtained continuously and in a single step using the laser pyrolysis method. The continuous wave CO₂ laser beam was used to continuously heat a sensitized (with ethylene) precursor gas mixture, in which iron pentacarbonyl (vapor) and acetylene were the iron and carbon donors, respectively. The effect of varying the residence time in the reaction zone through the variation of the internal nozzle diameter was explored in order to improve the particle size and the phase distributions. At increased nozzle diameter, (i) the particle mean diameter increases (from about 3.5 to 10.5 nm), (ii) higher ordering of the crystallographic network seems to occur, (iii) the dominance of the α-Fe and iron carbide phases is revealed. Onion-like graphenic layers often cover the buried iron cores. Magnetic measurements and temperature dependent Mössbauer spectroscopy were used in order to find correlations concerning the magnetic behavior and the Fe phase composition of samples. Preliminary experiments for obtaining stable water-based magnetic nanofluids are discussed.     

In situ prepared polypyrrole–Ag nanocomposites: optical properties and morphology

Polypyrrole–silver (PPy–Ag) nanocomposites with various silver contents have been synthesized via a kinetically favorable one-step chemical oxidative polymerization process. The oxidant, ammonium persulfate, was used to oxidize pyrrole monomer for growing chains of PPy. And AgNO₃ was used as a precursor for metallic silver nanoparticles. The detailed characterization techniques, UV–Vis–NIR, fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction spectroscopy, field-emission scanning electron microscopy, and transmission electron microscopy (TEM), have been used to reveal electronic environment, structure, and morphology of composites as well as as-synthesized PPy. The synthesis environment prior to polymerization has also been investigated by absorption spectroscopy. The TEM images of PPy–Ag nanocomposites reveal that silver nanoparticles are deeply embedded into the polymer matrix in addition to surface adsorption. It is observed that the size distribution of inorganic nanoparticles (ca. 4–10 nm, depending on the metal ion concentrations) as well as structural morphology is altered by the initial concentrations of silver ions.     

In vivo behaviour of two different biphasic ceramic implanted in mandibular bone of dogs

Alloplastic calcium phosphate bone substitutes such as hydroxyapatite (HA) and tricalcium phosphate (TCP) have been studied extensively due to their composition closely resembling the inorganic phase of bone tissue. On the same way, by manipulating the HA/TCP ratio it may be possible to change the substitution rate and the bioactivity of these materials, an advantage which has brought them to clinical use in oral and orthopaedic surgery. In this work, we evaluated the histological response in bone of two biphasic calcium phosphate ceramics by varying the proportion of their components. All premolars of 6 beagle dogs were removed from both sides of the mandible. Three months later, four cylinders composed of 85% HA and 15% β-TCP (BCP 1) were implanted in the right side of mandible and other four cylinders composed of 15% HA and 85% β-TCP (BCP 2) were implanted in the left side of mandible of dogs for 4, 12 ad 26 weeks, respectively. Two dogs were used in each time point. The histological study indicated that both biphasic ceramic were biocompatible. The earlier and more quantity of bone formed in BCP 2 than in BCP 1 suggested that the first one had a higher osteoinductive potential than the second one in mandibular bone. The resorption of the phosphate phase and the subsequent migration of bone into the resorbed portions were detected in both biphasic ceramics although two processes appeared faster in BCP 2 than in BCP 1. These dates conclude that varying the components of our biphasic ceramic we improve its osteoinductive potential.     

In situ controllable synthesis of Ag@AgCl core–shell nanoparticles on graphene oxide sheets

Graphene oxide-supported uniform Ag@AgCl core–shell nanoparticle composites have been successfully prepared by a facile two-step synthetic process. First, graphene oxide sheets were used as carriers to anchor and disperse Ag nanoparticles on their surface. Then these fixed Ag nanoparticles on carbon sheets are utilized as precursors, around which AgCl nanocrystals form in situ using FeCl₃ as oxidant, forming graphene oxide-supported Ag@AgCl core–shell nanoparticle composites. The composition of these attached Ag@AgCl core–shell nanoparticles can be easily controlled by adjusting the usage of FeCl₃, resulting in the formation of controllable core–shell nanostructures. Furthermore, these as-prepared graphene oxide–Ag@AgCl nanoparticle composites display effective photodegradation of methylene orange dye under visible light irradiation, which indicates their potential applications in environmental areas.     

In situ intercalative polymerization of poly(methyl methacrylate)/clay nanocomposites by γ-ray irradiation

Poly(methyl methacrylate) (PMMA)/clay nanocomposites was prepared by in situ intercalative polymerization initiated by γ-ray irradiation. The degree of dispersion and the intercalation spacing of these nanocomposites were investigated with the X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM), respectively. The thermal stabilities of the samples were studied by the thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC).     

In situ monitoring of NiO–Al2O3 nanoparticles synthesis by thermo-Raman spectroscopy

Simultaneous thermogravimetric analysis and thermo-Raman spectroscopy (TRS) measurements for in situ monitoring of wet chemical reaction of Ni(OH)₂·4H₂O and Al(OH)₃ forming NiO–Al₂O₃ nanoparticles is studied and compared with the solid-state reaction. Herein, a different approach of synthesis and monitoring of NiO–Al₂O₃ by TRS is presented, in which, in situ thermo-Raman spectra are recorded at every degree interval from 25 to 800 °C to understand the structural and compositional changes in NiO–Al₂O₃ as a function of temperature. Slow controlled heating of the sample as in TRS, enables better control over morphology and particle size distribution (～10–20 nm diameter). The X-ray diffraction (XRD) shows that smaller particle size is obtained using wet chemical reaction than the solid-state reaction (～25 nm diameter). TRS studies also reveal that, the bulk NiAl₂O₄ forms at temperatures above 800 °C, although, the onset of formation is around 600 °C. Condensation of Al(OH)₃ forming Al₂O₃ is also monitored, wherein, presence of hydrocarbon is found to contribute to the observed fluorescence background. Based on the TRS and complementary characterizations using XRD, scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray analysis, the formation of supported NiO–Al₂O₃ is discussed.     

Simulation of rafting type and stress distribution in nickel-based superalloys with different volume fractions of γ′ phase

A representative volume element is introduced to represent the microstructure of γ/γ′ morphology with periodic boundary conditions to formulate the full mode of the micromechanical analysis. [0 0 1]-oriented alloys with γ′ volume fractions from 60 to 70% are simulated under tensile loading. A raft criterion is implemented into the user subroutine to predict the rafting type. The misfit stress is considered by different thermal expansion coefficients of the two phases. It is very high in γ phase and slightly decreases with the increasing of γ′ volume fraction. The stress distributions in the two phases change during creep deformation. The creep crack initiation time slightly increases with the increase of γ′ volume fraction. The stress components decrease with the increasing of γ′ volume fraction at the beginning and change due to the stress redistribution during creep loading.     

In vitro study on the influence of strontium-doped calcium polyphosphate on the angiogenesis-related behaviors of HUVECs

Angiogenesis is of great importance in bone tissue engineering, and has gained large attention in the past decade. Strontium-doped calcium polyphosphate (SCPP) is a novel biodegradable material which has been proved to be able to promote in vivo angiogenesis during bone regeneration. An in vitro culture system was developed in the present work to examine its influence on angiogenesis-related behaviors of human umbilical vein endothelial cells (HUVECs), including cell adhesion, spreading, proliferation and migration. The effects of microtopography, chemical property and the ingredients in the degradation fluid (DF) on cell behaviors were discussed. The results showed that cells attached and spread better on SCPP scaffold than on calcium polyphosphate (CPP), which might partially result from the less rough surface of SCPP scaffold and the less hydrogel formed on the surface. In addition, cell proliferation was significantly improved when treated with SCPP DF compared with the treatment with CPP DF. Statistical analysis indicated that Sr(2+) in SCPP DF might be the main reason for the improved cell proliferation. Moreover, cell migration, another important step during angiogenesis, was evidently stimulated by SCPP DF. The improved in vivo angiogenesis by SCPP might be assigned to its better surface properties and strontium in the DF. This work also provides a new method for in vitro evaluation of biodegradable materials' potential effects on angiogenesis.     

In situ assembly of ZSM-5 nanocrystals into micro-sized single-crystal-like aggregates via acid-catalyzed hydrolysis of tetraethylorthosilicate

ZSM-5 aggregates were synthesized with the silica source tetraethylorthosilicate (TEOS) being hydrolyzed at acidic conditions to produce siliceous precursors, followed by the addition of aluminum sulfate and tetrapropyl ammonium bromide (TPABr), and with the resulting gel mixture being hydrothermally crystallized at basic conditions. The obtained products were characterized by XRD, SEM, and N₂ adsorption. Well crystallized ZSM-5 can be successfully synthesized through the sulfuric acid-catalyzed hydrolysis of TEOS within a short crystallization time 35 h. The thus produced micro-sized single-crystal-like zeolite ZSM-5 aggregates (10 μm) are made of uniformly distributed nanocrystals with sizes of about 200 nm. Moreover, by adjusting the hydrothermal reaction parameters, such as increasing the crystallization temperature, the TPABr/SiO₂ ratio and the pH value of reaction solution, the crystallization is accelerated substantially. Also, the moderate H₂O/SiO₂ molar ratio of 20–60 in the synthesis mixture can lead to pure ZSM-5, and yet the optimal ratio is 40. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Fabrication and biological characteristics of β-tricalcium phosphate porous ceramic scaffolds reinforced with calcium phosphate glass

The fabrication process, compressive strength and biocompatibility of porous β-tricalcium phosphate (β-TCP) ceramic scaffolds reinforced with 45P₂O₅–22CaO–25Na₂O–8MgO bioglass (β-TCP/BG) were investigated for their suitability as bone engineering materials. Porous β-TCP/BG scaffolds with macropore sizes of 200–500 μm were prepared by coating porous polyurethane template with β-TCP/BG slurry. The β-TCP/BG scaffolds showed interconnected porous structures and exhibited enhanced mechanical properties to those pure β-TCP scaffolds. In order to assess the effects of chemical composition of this bioglass on the behavior of osteoblasts cultured in vitro, porous scaffolds were immersed in simulated body fluid (SBF) for 2 weeks, and original specimens (without soaked in SBF) seeded with MC3T3-E1 were cultured for the same period. The ability of inducing apatite crystals in simulated body fluid and the attachment of osteoblasts were examined. Results suggest that apatite agglomerates are formed on the surface of the β-TCP/BG scaffolds and its Ca/P molar ratio is ~1.42. Controlling the crystallization from the β-TCP/BG matrix could influence the releasing speed of inorganic ions and further adjust the microenvironment of the solution around the β-TCP/BG, which could improve the interaction between osteoblasts and the scaffolds.     

Mechanochemical preparation of BaTiO3–Ni nanocomposites with high dielectric constant

A mechanochemical procedure is proposed for an easy preparation of a BaTiO₃–Ni composite in a single step. BaTiO₃ and Ni powders available in the market are mixed by dry ball milling producing a decrease of particle size and an evenly distribution of both phases. In the sintered pellets the nickel particles are homogeneously distributed into the BaTiO₃ matrix and isolated from others Ni particles. The dielectric constant of the composite is considerably higher than that of the barium titanate. Moreover, the temperature of the ferroelectric ↔ paraelectric transition of the BaTiO₃–Ni composite here prepared is much lower than the one of the pure BaTiO₃ single phase.