Effect of microgravity and a high magnetic field on hydroxyapatite deposition and implications for bone loss in space

The microgravity and high magnetic field simulated by a superconducting magnet were used to investigate the dynamics of deposition mechanisms of hydroxyapatite (HAp) on the surface of Ti-6Al-4V samples. The HAp coatings were derived by a self-assembly-induced biomineralization method in simulated body fluid. The experimental results showed that the amount and growth rate of HAp deposition in the simulated microgravity condition were far less than those in the gravity field, as were those in the high magnetic field compared with those outside the magnet. This may provide insight into the bone loss of astronauts in spaceflight from the viewpoint of the dynamic balance between HAp nucleation, deposition and decomposition on the surface of substrates.     

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.     

Effect of poly (ethylene glycol) coating on the magnetic and thermal properties of biocompatible magnetic liquids

The aim of this study was to investigate the influence of poly(ethylene glycol) surface-active coating on the magnetic and thermal properties of biocompatible magnetic liquids. The data were analyzed using the high-temperature approximation model taking into account polydispersity of a system. Heating ability of the PEG-stabilized magnetic fluids was determined by the calorimetric measurement of specific absorption rate (SAR) at a frequency of 750 kHz and a magnetic field of 0-2 kA/m. MF-Oleate/PEG heating properties were found to be comparable to the ones of MF-Oleate. The PEG shell thus does not seem to effect the thermal characteristics and SAR values and might make the magnetic fluid useful for application in hyperthermia treatment.     

Self-assembly of silanated poly(ethylene glycol) on silicon and glass surfaces for improved haemocompatibility

Surface immobilization of poly(ethylene glycol) (PEG) is an effective method to produce a material surface with protein repulsive property. This property could be made permanent by using covalent grafting of the PEG molecules onto material surfaces. In this study, self-assembled monolayers (SAMs) of PEG on silicon-containing materials (silicon chip and glassplate) were obtained through a one-step coating procedure of one kind of silanated PEG molecules made through the reaction between monomethoxy PEG and 3-isocyanatopropyltriethoxysilane. Atomic force microscopy (AFM) and water static contact angle measurement were employed to investigate the surface topography and wettability of the PEGylated material surfaces. The changes in the topography and the water contact angle of the surfaces with time of incubation in PBS solution were also measured. The results revealed that stable and uniform self-assembled monolayers of PEG could be formed on silicon or glass surfaces by simply soaking the substrates in the solution of silanated PEGs. The covalent coupling of PEGs to the substrates was also confirmed. In order to evaluate the stability of the SAMs, blood compatibility of the modified glassplate surface was evaluated by measuring full blood activated partial thromboplastin time (APTT), prothrombin time (PT), and thrombin time (TT), as well as by scanning electron microscopy (SEM) analysis of the appearance of adherence and denaturation of blood platelets onto the glassplate. The silanated PEGs were shown to have good effect on the protein-repulsion as well as haemocompatibility of the substrates.     

Effect of the shell on the transport properties of poly(glycerol) and Poly(ethylene imine) nanoparticles

Dendritic core–shell architectures containing poly (glycerol) and poly (ethylene imine) cores and poly(lactide) shell (PG-PLA and PEI-PLA respectively) were synthesized. Analogous of these core–shell architectures containing the same cores but poly (L-lactide) shell (PG-PLLA and PEI-PLLA, respectively) were also synthesized. In this work PG and PEI were used as macroinitiator for ring opening polymerization of the lactid and L-lactide monomers. Different molar ratios of monomer to end functional groups of PG ([LA]/[OH]) and PEI ([LA]/[NHn] (n = 1 or 2)) were used to prepare the core–shell architectures with different shell thickness. These core–shell architectures were able to encapsulate and transport the small guest molecules. Their transport capacity (TC) depended on the type and thickness of the shells. TC of core–shell architectures containing PLLA shell was higher than that for their analogs containing PLA shell. The diameter of core–shell architectures was between 20–80 nm. The rate of release of guest molecules from chloroform solution of nanocarriers to water phase was investigated and it depended on the type of the core, shell and solvent.     

Influence of laser irradiation on the optical and structural properties of poly(ethylene terephthalate) fibres

Laser irradiation has been previously investigated for achieving uniform heating of polyethylene terephthalate (PET) fibres in the hot-drawing stage of the production process, so as to obtain better fibre mechanical properties. The optical properties and dye uptake of PET fibres also depend on the polymer chain orientation and crystallinity within the fibre structure. This paper reports an investigation of a concept whereby laser irradiation and interferometry could be used to modify and trace a small change in the optical properties of a PET monofilament fibre, but the corresponding change in the dye uptake would not be detected visually. A copper vapour laser (550-580 nm wavelengths) was used to expose consecutive 4 mm lengths along a running length of monofilament to 39.8 W cm⁻², at a pulse rate of 9.89 kHz in order to modify, in a controlled way, the polymer crystallinity and orientation. A 3D finite element simulation, based on uncoupled heat-transfer analysis, indicated that rapid heating and cooling could be obtained with the laser to give the small changes required. Irradiated and untreated samples were analysed by interferometry and a 0.16% change was detected in the birefringence profiles, corresponding to a small reduction in the degree of orientation and crystallinity of the irradiated samples. Density measurements and wide-angle X-ray scattering (WAXS) analysis confirmed the change in crystallinity. Tests conducted for dye adsorption and tensile strength showed a small increase in the former and only a very small decrease in the latter. It was concluded that these changes in property provide the opportunity for a laser-irradiated PET monofilament fibre to be used as a subtle tracer element in brand labels for textile garments as an anti-counterfeit measure.     

Chemical modification of poly(ethylene terephthalate) and immobilization of the selected enzymes on the modified film

Poly(ethylene terephthalate) (PET) film was modified by reaction with hydrazine (HD), ethylenediamine (EDA), 1,2-diaminopropane (1,2-DAP) and 1,3-diaminopropane (1,3-DAP). The maximal amount of amine functionalities introduced in the chosen conditions on the surface was found as 0.07, 3.35, 0.76 and 1.99 nmol cm⁻² for HD, EDA, 1,2-DAP and 1,3-DAP respectively. During the modification process etching of the sample and an increase of stiffness takes place. FTIR-ATR spectra prove that the surface chemistry after modification in amine solution is very complex. The lack of clear correlation between the surface tension and surface concentration of amine functionalities seems to confirm that. For immobilization purpose invertase, laccase and tyrosinase were used. The amount of covalently attached proteins at first increases with the increase of surface concentration of amine groups but after reaching a certain level of amine groups, decrease of the immobilization level was observed. All enzymes tested showed highest activity for a moderate level of aminolysis and this activity had the highest values for EDA-modified PET.     

Effect of temperature on the intrinsic viscosity of poly(ethylene glycol) in water/dimethyl sulfoxide solutions

In this work, the intrinsic viscosities of poly(ethylene glycol) with molar mass of 20 kg mol^− 1 were measured in water/dimethyl sulfoxide solutions from (298.15 to 318.15) K. The expansion factors of the polymer chains were calculated from the intrinsic viscosity data. The expansion factor were decreased by increasing temperature; therefore the chain of PEG shrinks and the end-to-end distance become smaller by increasing temperature. Perhaps the interactions of segment-segment are favored toward segment-solvent by increasing temperature; therefore the hydrodynamic volumes of the polymer coils become smaller by increasing temperature. The thermodynamic parameters (entropy of dilution parameter, the heat of dilution parameter, theta temperature and polymer-solvent interaction parameter) were derived by the temperature dependence of the polymer chain expansion factor. The thermodynamic parameters indicate that the interactions of segment-segment were increased by increasing temperature.     

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.     

Enrichment of poly(methyl methacrylate) and its graft copolymer of polybutadiene on the surface of polypropylene blends

Poly(methyl methacrylate) (PMMA) and its graft copolymer of polybutadiene were used as the macromolecular surface modifiers of polypropylene. The enrichment and diffusion of the modifiers onto the surface of polypropylene blends were investigated using FTIR-ATR, CDA and SEM. It has been found that the selective aggregation of the modifier component on the surface of polypropylene was mainly affected by the content, molecular weight and size of the segregated domains. Lower content and higher surface energy die were in favor of the enrichment of the additive. PMMA with higher molecular weight showed larger domain phase and lower diffusion velocity which resulted in less enrichment on the surface of PP blends.     

A new approach to the immobilisation of poly(ethylene oxide) for the reduction of non-specific protein adsorption on conductive substrates

Biomedical and biotechnological devices often require surface modifications to improve their performance. In most cases, uniform coatings are desired which provide a specific property or lead to a specific biological response. In the present work, we have generated pinhole-free coatings providing amine functional groups achieved by electropolymerisation of tyramine on highly doped silicon substrates. Furthermore, amine groups were used for the subsequent grafting of poly(ethylene oxide) aldehyde via reductive amination. All surface modification steps were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The results indicate that the stability and the density of amine functional groups introduced at the surface via electropolymerisation compare favourably with alternative coatings frequently used in biomedical and biotechnological devices such as plasma polymer films. Furthermore, protein adsorption on amine and poly(ethylene oxide) coatings was studied by XPS and a colorimetric assay to test enzymatic activity. The grafting of poly(ethylene oxide) under cloud point conditions on electropolymerised tyramine layers resulted in surfaces with extremely low protein fouling character.     

Optical absorption and spectrophotometric studies on the optical constants and dielectric of poly (o-toluidine) (POT) films grown by spin coating deposition

In this work, a poly(o-toluidine) “POT” was synthesized by chemical oxidative polymerization method in aqueous media. High uniform and good adhesion thin films of POT have been successfully deposited by the spin coating technique. The films were characterized by X-ray diffraction (XRD) and Fourier transforms infrared (FTIR) spectroscopy. The XRD pattern of the POT shows the semi-crystalline nature of the films. FTIR studies show the information of functional groups in POT. The optical transmittance and reflectance of POT film was measured in the 200–2500 nm wavelength range. The absorption coefficient analysis shows that the optical band gaps of POT film are direct allowed transition band gaps with 1.2 and 2.6 eV. Other optical absorption parameters such as extinction molar coefficient, oscillator strength and electric dipole strength were also calculated. The dispersion parameters were determined and discussed based on the single oscillator model. According to the analysis of dispersion curves some important parameters such as dispersion energy (E_d), oscillator energy (E_o), high frequency dielectric constant ₍ε_∞) and lattice dielectric constant (ε_L) were also evaluated. Discussion of the obtained results and their comparison with the previous published data were also given. The obtained desirable results of POT thin film can be useful for the optoelectronic applications.     

Molecular dynamics simulation study on the structural properties of poly (ethylene terephthalate) under uniaxial extension and thermal shrinkage processes

In thermal shrinkage process for polyethylene terephthalate (PET) films, PET film is uniaxially stretched and then thermally relaxed. We investigate the effect of heat relaxation temperature on the thermal shrinkage of uniaxially stretched PET film using molecular dynamics simulation method. Through our investigation, we find that the thermal shrinkage ratio of the amorphous PET film is reduced as a function of heat relaxation temperature, whereas the skirt ratio is weakly correlated with the heat relaxation temperature, exhibiting the most negative skirt ratio in the case of the highest thermal shrinkage ratio. Our analysis on the PET film at molecular level further verifies that the trans-gauche transformation observed in ethylene glycol units during the simulated process is a driving force for the thermal shrinkage of uniaxially stretched PET systems.     

Kinetics of reversible surface crystallization and melting in poly(ethylene oxide): Effect of crystal thickness observed in the dynamic heat capacity

Poly(ethylene oxide) (PEO) in the semi-crystalline state shows a reversible surface crystallization and melting; a temperature decrease leads to a certain crystal thickening, a temperature increase reversely to an expansion of the amorphous intercrystallite layers. Dynamic calorimetry provides a means to investigate the kinetics of the process. The structural rearrangement in the region of the crystalline-amorphous interface can only be accomplished if the chains can slide through the crystallites. One therefore expects the associated time to change with the crystallite thickness. Variations of the crystal thickness of PEO can be achieved by choosing different crystallization temperatures. We studied the effect of the crystal thickness employing temperature-modulated differential scanning calorimetry and heat wave spectroscopy, and by carrying out small-angle X-ray scattering experiments for the structural characterization. The effect of the crystal thickness is clearly observed. Results indicate that the sliding diffusion through the crystallites takes place by helical jumps of whole stems. Data yield the activation energy per unit length of the stems. Received 20 April 2001 and Received in final form 13 August 2001     

Characteristic variations in the effect of diluents on polymer crystallization and melting observed for a sample of poly(ethylene-co-octene)

Melting points in mixtures of a crystallizable polymer with a low-molar-mass diluent depend on both, the diluent fraction and the crystal thickness. A differentiation of the two factors can be achieved by temperature-dependent SAXS experiments. A corresponding study, complemented by DSC, dilatometry, microscopy and AFM-imaging, was carried out for mixtures of a poly(ethylene-co-octene) with n-C₁₆H₃₄, c-C₁₆H₃₂ and methyl-anthracene, respectively. All diluents lead for a constant crystal thickness to melting point depressions in agreement with Raoult's law. On the other hand, the effect of the diluents on the thickness of the crystals formed at a fixed crystallization temperature varies. While in the presence of the two alkanes thicker crystals form, no effect arises for the methyl-anthracene—as was previously found for the octene-co-units. We consider these observations as a further support for our view that polymer crystallization follows a multi-stage route which includes a passage through an intermediate mesomorphic phase. Under such conditions crystal thicknesses would only be affected if the diluent is still present in the mesomorphic phase and stay invariant if the diluent molecules are already rejected when this intermediate phase forms.     

On the dissolution/reaction of small-grain Bioglass 45S5 and F-modified bioactive glasses in artificial saliva (AS)

The reaction of small-grain Bioglass^® 45S5 in artificial saliva (AS), to produce a layer of hydroxy-apatite (HA) and/or hydroxy-carbonate apatite (HCA), has been studied and compared to the results obtained in a simple buffered solution (TRIS). Some potentially bioactive glasses based on the composition of Bioglass^® and containing CaF₂ (HCaCaF₂ 5% and HNaCaF₂ 5%) have also been studied, in order to analyze the effects/changes produced when a F-containing glass surface is contacted with AS. The insertion of fluorine has been proposed to improve bioactive glass bone-bonding ability, and to parallel fluorine-containing glass-ceramics currently used in dentistry. ICP-OES analysis of the solution, and FTIR spectroscopy of the solid samples provided compositional information on the stages of reaction. These data were integrated with XRD and the textural and morphological data, obtained by specific surface areas determination and TEM-EDS measurements. In the case of Bioglass^® 45S5, a comparison at corresponding reaction times indicates that the precipitation of an amorphous Ca-phosphate phase is faster in AS, but the crystallization of HA/HCA is delayed in AS with respect to the TRIS solution. For fluoride-containing glasses, the sample HCaCaF₂ 5%, in which CaF₂ replaces part of CaO, possesses the fastest rate for HA/HCA crystallization (1 week) in AS. Some lines of interpretation for these results are proposed.     

Study on the mechanism of dark enhancement in phenanthrenequinone-doped poly(methyl methacrylate) photopolymer for holographic recording

The dark enhancements with various exposure energies are studied in thick PQ/PMMA photopolymer. Considered the weak molecules diffusion of PQ component and the grating detuning, a new mechanism of dark reaction is proposed to explain the dark enhancement. Moreover, the influences of dark reaction on Bragg angular selectivity and grating recording are analyzed. The results are beneficial to the practical holography application.     

Preparation and in vitro evaluation of poly(D,L-lactide-co-glycolide) air-filled nanocapsules as a contrast agent for ultrasound imaging

The aim of this study was to prepare air-filled nanocapsules intended ultrasound contrast agents (UCAs) with a biodegradable polymeric shell composed of poly(d,l-lactide-co-glycolide) (PLGA). Because of their size, current commercial UCAs are not capable of penetrating the irregular vasculature that feeds growing tumors. The new generation of UCAs should be designed on the nanoscale to enhance tumor detection, in addition, the polymeric shell in contrast with monomolecular stabilized UCAs improves the mechanical properties against ultrasound pressure and lack of stability. The preparation method of air-filled nanocapsules was based on a modification of the double-emulsion solvent evaporation technique. Air-filled nanocapsules with a mean diameter of 370 ± 96 nm were obtained. Electronic microscopies revealed spherical-shaped particles with smooth surfaces and a capsular morphology, with a shell thickness of ∼50 nm. Air-filled nanocapsules showed echogenic power in vitro, providing an enhancement of up to 15 dB at a concentration of 0.045 mg/mL at a frequency of 10 MHz. Loss of signal for air-filled nanocapsules was 2 dB after 30 min, suggesting high stability. The prepared contrast agent in this work has the potential to be used in ultrasound imaging.     

交叉极化时间对分子间交叉极化的影响的研究

以C₆₀和聚氧乙烯(PEO)复合物为研究对象,系统地研究了交叉极化时间对分子间交叉极化实验的影响. 结果表明,在使用分子间交叉极化方法研究复合体系相结构和界面结构时,必须考虑交叉极化时间的影响才能获得更可靠的结论. 同时,系统地改变交叉极化时间也能为分子间交叉极化实验的设计引入一个新的维度,从而可能得出一些在单个交叉极化时间下难以获得的结论. 例如,本实验发现C₆₀}的分布并不完全局限于PEO的非晶区,至少部分C₆₀和PEO的晶区在空间上比较接近.