Degradation and biocompatibility of porous nano-hydroxyapatite/polyurethane composite scaffold for bone tissue engineering

Porous scaffold containing 30 wt% nano-hydroxyapatite (n-HA) and 70 wt% polyurethane (PU) from castor oil was prepared by a foaming method and investigated by X-ray diffraction (XRD), Fourier transform infrared absorption (FTIR), scanning electron microscopy (SEM) techniques. The results show that n-HA particles disperse homogeneously in the PU matrix. The porous scaffold has not only macropores of 100-800 μm in size but also a lot of micropores on the walls of macropores. The porosity and compressive strength of scaffold are 80% and 271 kPa, respectively. After soaking in simulated body fluid (SBF), hydrolysis and deposition partly occur on the scaffold. The biological evaluation in vitro and in vivo shows that the n-HA/PU scaffold is non-cytotoxic and degradable. The porous structure provides a good microenvironment for cell adherence, growth and proliferation. The n-HA/PU composite scaffold can be satisfied with the basic requirement for tissue engineering, and has the potential to be applied in repair and substitute of human menisci of the knee-joint and articular cartilage.     

Synthesis and properties of the nanocomposite of zink oxide and poly(amic acid)

The composite comprised of zinc oxide quantum dots and poly(amic acid) (PAAc) was prepared and studied by X-rays diffraction, X-ray photoelectron spectroscopy, light scattering, UV absorbance and UV fluorescence. The UV absorbance of the ZnO/PAAc composite was found to be much larger than that of its components taken separately. The fluorescence of the ZnO/PAAc composite was found to be shifted to longer wavelengthes in comparison with pure ZnO. The presence of the dopant dodecylbenzenesulfonic acid was found to affect the observed fluorescence.     

In vitro bioactivity and biocompatibility of calcium phosphate cements using Hydroxy-propyl-methyl-Cellulose (HPMC)

In this study, the bioactivity and biocompatibility of new calcium phosphate bone cements (CPC) using Hydroxy-propyl-methyl-Cellulose (HPMC) was evaluated to understand the effect of HPMC on bone-bonding apatite formation and biocompatibility. In vitro bioactivity was investigated by incubating the CPC samples containing different ratios of HPMC (0%, 2% and 4% HPMC) in simulated body fluid (SBF) for 2, 7, 14 and 28 days. The formation of bone like apatite was confirmed on CPC surfaces by SEM and XRD analysis. Higher HPMC content of CPC showed faster apatite deposition in SBF. A high Ca ion dissolution profile was also reported with an increase of pH in all samples in SBF. The apatite formation ability of these CPC samples was found to be dependent on both surface chemistry and immersion time in SBF. The In vitro cytotoxicity test showed that the CPC samples with 4% HPMC were fairly cytocompatible for fibroblast L-929 cells. SEM images showed that MG-63 cells were successfully attached to the CPC samples and well proliferated.     

Measurement of speed of sound in poly(lactic acid)-clay composite

We measured longitudinal speed of sound for matrix[poly(lactic acid)]-additive(clay particles) composite rectangular-solid specimen prepared by injection molding. It was found that the speed of sound measured in the direction along the longer side of the specimen was the highest at the middle of the specimen. This trend corresponded with that for crystallinity determined through differential scanning calorimetry (DSC). A cross section view of the specimen parallel to its longer side showed that there was a transverse flow trace of resin in the vicinity of the injection gate while the flow trace along the direction of the longer side spread wider as getting far from the gate toward the middle of the specimen. The high crystallinity appeared in the middle of the specimen was inferred to come from the promotion of crystallization by molecular orientation induced with the above flow trace parallel to the direction along the longer side of the specimen.     

Adsorption and desorption of Ca and PO4 species from SBFs on RF-sputtered calcium phosphate thin films

RF magnetron sputtering of calcium phosphate (CaP) coatings is a promising technique to apply thin bioactive films on bulk implant materials. In this paper the properties of the interface between RF sputtered coatings and simulated body fluids (SBFs) are related to the ability to form CaP crystals on the coating surface. Two types of coatings were compared: coatings with a low Ca over P ratio (∼0.8; CaP_low), which remain inert when immersed in SBF₂ (i.e. SBF with twice the Ca and PO₄ concentrations), and coatings with a high Ca over P ratio (1.6; CaP_high), which show the formation of CaP crystals on their surface within 2 h. Low energy ion scattering (LEIS) and radioactive labeling of the SBFs combined with liquid scintillation counting (LSC) allowed us to study very accurately the composition of the adsorbates of both coating groups after 10 min of immersion in SBF₂. For the adsorbate on CaP_high and CaP_low coatings coverages were found consistent with ionic adsorption and Ca/P ratios of 1.24 ± 0.02 and 2.17 ± 0.10, respectively. Adsorption was found to be reversible over the studied immersion period. After an induction period of 40 min a CaP precipitate started to form on the CaP_high coatings with a Ca/P ratio of 1.30 ± 0.02. Further, no significant desorption of coating species was observed during this induction period.     

Electrical properties of expanded graphite/poly(styrene-co-acrylonitrile) composites

A four probe method was used to measure the electrical conductivities of poly(styrene-co-acrylonitrile)/expanded graphite composites. The composites showed excellent electrical conductivities in both a- and c-axes. The different effects of temperature and the applied current on the conductivities in a-axis and in c-axis were observed. It was found that the conductive behaviors of the composite were different from those of semiconductor and carbon black loaded polymer composites. All these differences and excellent conductivity were considered to be related to the structure of the composites.     

Development of poly(butylene succinate)/calcium phosphate composites for bone engineering

Bone tissue engineering offers the prospect of alternative therapies for clinically relevant skeletal defects. Poly(butylene succinate) (PBSu) is a biodegradable and biocompatible polyester which possesses some unfavorable biomaterial properties. In order to improve this limitation, we developed PBSu/hydroxyapatite (HA) and PBSu/β-tricalcium phosphate (TCP) composites to support the growth and osteogenic differentiation of human mesenchymal stem cells (hMSCs). The results showed that phase separation morphology of the composites were detected in both PBSu/HA and PBSu/TCP films where calcium phosphate (HA and TCP) dispersed thoroughly into PBSu. The addition of either HA or TCP increased the hydrophilicity of the resulting composites. All the materials appeared to be biocompatible and supported in vitro growth and osteoblast differentiation of hMSCs. In conclusion, the currently developed composite materials possess good biocompatibility and allow the growth and osteogenic differentiation of hMSCs in vitro, suggesting their potential application in stem cell-based bone engineering.     

Thermal transitions and degradative processes in Fe(III)-tetracarboxyphthalocyanine-grafted poly(N-vinylcarbazole)

The introduction of 2,9,16,23-tetracarboxy-Fe(III)phthalocyanine [Fe(III)tcPc] units onto fractions of poly(N-vinylcarbazole) (PVK) by Friedel-Crafts reaction leads to amorphous PVK-based grafted compounds that show major interchain distances by the wide-angle x-ray scattering (WAXS) technique. Glass transition temperatures of the products are lower than the main glass transition temperature of PVK and are attributed to local movements of the voluminous added groups. Dynamic thermogravimetric experiments show decarboxylation processes within the 250°C-500°C range and little weight loss. The large remaining residue, up to 70% of the sample at 800°C, is suggested to be the consequence of successive cross-linking reactions. The Fourier transform infrared (FTIR) spectrum of the residue is similar to that of the grafted sample before degradation.     

Influence of ultrasonic processing on the macromolecular properties of poly (d,l-lactide-co-glycolide) alone and in its biocomposite with hydroxyapatite

In this work poly(d,l-lactide-co-glycolide) (PLGA) and a poly(d,l-lactide-co-glycolide)/hydroxyapatite (PLGA/HAp) composite processed in an ultrasonic field at higher (25 °C) and lower (8 °C) temperatures were studied with respect to the molecular properties of the obtained materials. The processing of the PLGA and the PLGA/HAp composite in an ultrasonic field resulted in a change of molar mass averages of the polymer/polymeric part of these materials, while an amorphous structure and a 50:50 lactide-to-glycolide co-monomer ratio were preserved without the formation of crystalline oligomers. However, mobility of polymeric chains obtained after ultrasonic processing was lower indicating ordering the structure of polymeric chains as a result of processing. Additionally, it was observed that the mobility of the PLGA macromolecules was lower within the composite in comparison with the mobility of the chains within the PLGA alone in the case when both were obtained after ultrasonic processing. This was a consequence of the structure formation through the interactions between the PLGA and the HAp. Based on these results different degradation rate of PLGA in composite can be expected, which is important in the application of this material for the controlled drug delivery of medicaments.     

The characterization of mechanical and surface properties of poly (glycerol-sebacate-lactic acid) during degradation in phosphate buffered saline

The present study synthesized a poly (glycerol-sebacate-lactic acid) (PGSL) with 1:1:0.5 mole ratio of glycerol, sebacate and lactic acid and investigated the degradation characteristics of the polymer in phosphate buffered saline (PBS) at 37 °C in vitro by means of mass loss tests, geometry, differential scanning calorimeter (DSC) measurements, tensile analysis and scanning electron microscopy (SEM). The maintained geometry, linear mass loss, and minor crack formation on the surface during degradation characterized both the bulk degradation and surface erosion of the polymer. By day 30 of degradation, the mass lost reached 16%. The elastic modulus, tensile strength and elongation at breakage of PGSL were correlative to the period of degradation.     

Dielectric relaxation and ac conductivity behavior of carboxyl functionalized multiwalled carbon nanotubes/poly (vinyl alcohol) composites

We study the dielectric relaxation and ac conductivity behavior of MWCNT-COOH/Polyvinyl alcohol nanocomposite films in the temperature (T) range 303–423 K and in the frequency (f) range 0.1 Hz–1 MHz. The dielectric constant increases with an increase in temperature and also with an increase in MWCNT-COOH loading into the polymer matrix, as a result of interfacial polarization. The permittivity data were found to fit well with the modified Cole-Cole equation. Temperature dependent values of the relaxation times, free charge carrier conductivity and space charge carrier conductivity were extracted from the equation. An observed increment in the ac conductivity for the nanocomposites was analysed by a Jonscher power law which suggests that the correlated barrier hopping is the dominant charge transport mechanism for the nanocomposite films. The electric modulus study revealed deviations from ideal Debye-type behavior which are explained by considering a generalized susceptibility function. XRD and DSC results show an increase in the degree of crystallinity.     

Kinetics and product distribution of p‐nitrophenyl phosphate dianion solvolysis in ternary DMSO/alcohol/water mixtures are compatible with metaphosphate formation

The rate of solvolysis of p‐nitrophenyl phosphate (PNPP) dianion in DMSO/water strongly decreases by increasing water concentration. Addition of linear alcohols (methanol, propanol, butanol, pentanol, and hexanol) at constant DMSO/water molar ratio produced an even sharper rate decrease. Alkyl phosphate formation, resulting from PNPP solvolysis in ternary DMSO/water/alcohol mixtures, increased with alcohol concentration and was essentially temperature independent. Methanol and hexanol were the poorest nucleophiles under all conditions. Activation energies and enthalpies for solvolysis in ternary mixtures were similar and entropies varied with alcohol concentration. Taken together these results can be best interpreted in terms of a dissociative mechanism with the intervention of metaphosphate. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis and properties of a new copper(II)-hafnium phosphate Cu0.5Hf2(PO4)3

Phosphates of general formula M_0.5Hf₂(PO₄)₃ with M=Cd²⁺, Ca²⁺, Sr²⁺ and Cu²⁺ were prepared by coprecipitation and characterized by several physical techniques. The compounds containing Cd²⁺, Ca²⁺, Sr²⁺ belong to the Nasicon-type structure, whereas Cu_0.5Hf₂(PO₄)₃ exhibited substantially different DRX patterns. Combined temperature programmed reduction (TPR) and temperature-programmed oxidation (TPO) showed that the copper in Cu_0.5Hf₂(PO₄)₃ was distributed between two energetically different sites in proportions respectively equal to 40 and 60%. Electron Paramagnetic Resonance (EPR) investigations confirmed the TPR/TPO results and revealed that the two sites hosting the Cu²⁺ ions are of orthorhombic symmetry. Moreover, the Cu²⁺ ions might be reduced by hydrogen to Cu⁺. These results were also supported by the UV–visible studies that showed the disappearance, under reducing conditions, of the band corresponding to crystal field transitions of Cu²⁺ ions and the emergence of a new peak attributed to the transitions between (3d)¹⁰ and (3d)⁹(4s)¹ Cu⁺ levels. At the same time, IR spectroscopy confirmed that protons entered the open lattice framework of the material and gave rise to a new protonated phase containing monovalent copper Cu_0.5^IH_0.5Hf₂(PO₄)₃. This redox process was proven to be reversible without any subsequent change in the network of the phosphate.     

用软刻蚀方法制备PbS纳米晶复合聚丙烯酸微图形

利用软刻蚀方法制备了包裹有硫化铅纳米颗粒的聚丙烯酸微图形 .首先通过毛细微模塑法制备了丙烯酸铅的微条纹 ,并使之在γ射线引发下固态聚合 ,最后用硫化钠溶液处理聚合物微条纹 ,将铅离子转化为包埋在聚合物体系中的硫化铅颗粒 ,得到了包裹有硫化铅纳米颗粒的高清晰度的聚丙烯酸微图形 .利用X射线衍射(XRD)、X射线光电子能谱仪 (XPS)、透射电镜 (TEM)对其结构和性质进行了表征 .结果表明包埋在聚合物体系中的PbS颗粒直径小于 2 0nm .     

Preparation of nano-hydroxyapatite/poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide) biocomposite microspheres

Nano-hydroxyapatite (HA)/poly(l-lactide) (PLLA) composite microspheres with relatively uniform size distribution were prepared by a solid-in-oil-in-water (s/o/w) emusion solvent evaporation method. The encapsulation of the HA nanopaticles in microshperes was significantly improved by grafting PLLA on the surface of the HA nanoparticles (p-HA) during emulsion process. This procedure gave a possibility to obtain p-HA/PLLA composite microspheres with uniform morphology and the encapsulated p-HA nanoparticle loading reached up to 40 wt% (33 wt% of pure HA) in the p-HA/PLLA composite microspheres. The microstructure of composite microspheres from core-shell to single phase changed with the variation of p-HA to PLLA ratios. p-HA/PLLA composite microspheres with the diameter range of 2–3 μm were obtained. The entrapment efficiency of p-HA in microspheres could high up to 90 wt% and that of HA was only 13 wt%. Surface and bulk characterizations of the composite microspheres were performed by measurements such as wide angle X-ray diffraction (WAXD), thermal gravimetric analysis (TGA), environmental scanning electron microscope (ESEM) and transmission electron microscopy (TEM).     

Effects of poly(ethylene glycol) on electrical conductivity of poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonic acid) film

A series of poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonic acid) composite thin films with prescribed concentrations of poly(ethylene glycol) were prepared. The PEDOT–PSS pristine film and PEDOT–PSS/PEG films were studied using four-probe method, photoelectron spectroscopy and atomic force microscopy. The electrical conductivity of PEDOT–PSS/PEG hybrid films was found to be enhanced compared to the PEDOT–PSS pristine film, depending on the PEG concentration and molecular weight. XPS analysis and AFM results showed that PEG induces the phase separation between the PEDOT–PSS conducting particles and the excessive PSSNa shell. Simultaneously PEG may form hydrogen bond with sulfonic groups of PSSH, and hence weaken the electrostatic interactions between PEDOT cationic chains and PSS anionic chains. These resulted in the creation of a better conduction pathway among PEDOT–PSS particles, attributed to the improvement of conductivity.     

Preparation and characterization of poly(lactic acid)-grafted TiO2 nanoparticles with improved dispersions

Poly(lactic acid) (PLA)-grafted TiO₂ particles were prepared by in situ melt polycondensation of lactic acid onto the surface of TiO₂ nanoparticles. The resulting products were characterized by FTIR, XPS, TG-FTIR, XRD analysis and electron microscopy observation so as to have a better understanding of bonding between the graft polymer and nanoparticles. New characteristic peaks of Ti-carboxylic coordination bond, the changes in the relative intensities of the infrared absorption bands of graft polymer and the two decomposition stage of PLA-grafted TiO₂ confirmed that PLA was grafted on the surface of TiO₂ nanoparticles. By attachment of PLA, the PLA-grafted TiO₂ samples exhibited much better dispersion and a slightly larger particle size than bare TiO₂ particles. PLA-grafted TiO₂ nanoparticles will find wide applications in biomedical and eco-friendly materials, especially as fillers in PLA matrix.     

Vitamin C functionalized multi-walled carbon nanotubes and its reinforcement on poly(ester-imide) nanocomposites containing L-isoleucine amino acid moiety

The aim of this research was to prepare poly(ester–imide) (PEI)-based nanocomposites (NCs) through the functionalization of carboxylated-multiwalled carbon nanotubes (MWCNT)s with ascorbic acid, in order to ensure better filler dispersion and good interfacial adhesion between filler and matrix. Chiral and biodegradable PEI was synthesized from amino acid-based diacid with 4,4′-thiobis(2-tert-butyl-5-methylphenol) by a direct polycondensation method. Using the solution mixing technique, the NCs containing modified MWCNTs with different loading levels of 5,10, 15 wt% were produced and examined in terms of chemical structure, morphology, and thermal stability by FT-IR spectroscopy, thermogravimetric analysis (TGA), X-ray diffraction, transmission electron microscopy (TEM), and field emission scanning electron microscopy (FE-SEM). TEM and FE-SEM photographs of the obtained NCs indicated well-dispersed morphologies and strong interaction between the functionalized MWCNTs and the polymer matrix. TGA results revealed that the addition of MWCNT resulted in a significant increase of the thermal stability and char yields of the NCs compared to those of the neat PEI.     

N-(茄呢基哌嗪烷基)蒽甲胺的合成及其与DNA作用的研究

以茄呢醇为原料合成了两个新的N-(茄呢基哌嗪烷基)蒽甲胺类三胺化合物,其结构均经1H NMR,IR,MS,元素分析等方法确证,初步的体外生理活性测试表明两个化合物对L1210(淋巴性白血病细胞)的IC₅₀(抑制浓度)分别为4.3和3.1 μmol。用紫外光谱、荧光光谱研究了N-(茄呢基哌嗪丁基)-9-蒽甲胺(4b)与DNA的相互作用方式,并与N1-(4-丁胺基)-N4-(9-蒽甲基)-1,4-丁二胺(5)与DNA相互作用的光谱进行了对比。实验结果表明,化合物4b对DNA-EB体系产生荧光增色作用而5对DNA-EB体系则产生荧光猝灭作用,但DNA对两种化合物作用的荧光光谱均表现出荧光猝灭现象。推测结构中含有茄呢基长链及两个叔氮原子的化合物4b与DNA可能仅是静电结合或分子部分嵌入DNA,而化合物5与DNA的作用表现为典型的嵌入式作用。     

Moisture barrier of AlxOy coating on poly(ethylene terephthalate), poly(ethylene naphthalate) and poly(carbonate) substrates

The moisture barrier property of Al_xO_y coated poly(ethylene terephthalate) (PET), poly(ethylene naphthalate) (PEN) and poly(carbonate) (PC), have been investigated. The differences in the morphology of the Al_xO_y sputtered grown on these substrate were investigated using atomic force microscopy (AFM). The initial growth of the Al_xO_y followed closely the topology of the substrate and an amplified roughness was observed. In the fully grown Al_xO_y, the comparative roughness followed that of the substrates. It has been found that a single layer Al_xO_y improved the moisture barrier of PET by an order of magnitude, PC by two orders of magnitude while no improvement was observed for PEN. UV-ozone treatment on PC further improved the moisture barrier, while no improvement was observed for PET and PEN. The comparative effects of the substrate surface roughness and surface energy on the moisture barrier are discussed.