Surface modification of nanophase hydroxyapatite with chitosan

Nanophase hydroxyapatite (HAp) particles were aged in 0–2.5 wt.% chitosan acetate solutions for 30 days to evaluate the influence of chitosan on HAp surface chemistry. The HAp characterization results from Fourier transform infra-red spectroscopy (FTIR), thermal gravimetric analysis (TGA), Carbon–Hydrogen–Nitrogen (CHN) analysis, and BET N₂ adsorption revealed measurable changes in the HAp surface chemistry after aging in the chitosan acetate solutions. The TGA mass loss exhibited by HAp increased from 3.3–6.5 mass% as the chitosan acetate gel concentration increased from 0–2.5 mass%. The CHN analysis revealed an increase in C and H contents with increasing chitosan acetate concentration while the N concentration remained relatively constant (0.30–0.32 mass%). Chitosan interactions with HAp caused an increase in specific surface area from 85 m²/g up to 160 m²/g for HAp aged in 1.5 mass% chitosan acetate solution (HAp[1.5]). Chitosan exhibits strong adsorption interactions with HAp and enhances colloid stability for processing of chitosan/hydroxyapatite nanocomposites.     

Molecular flow transmission probabilities of any regular polygon tubes

Research on the molecular flow transmission probabilities of tubes is important in vacuum science and technology, as well as in some special applications in space technology. This study examines an algorithm based on Monte Carlo method to calculate the molecular flow transmission probabilities of any regular polygon tubes. This method fully utilizes the symmetries of regular polygons to simplify calculation. The results show that when the cross-sectional areas and lengths L of tubes remain constant, the molecular flow transmission probabilities of regular polygon tubes increase and approach those of cylindrical tubes with an increase in the number of sides. Moreover, any regular polygonal or cylindrical cross-section tube has nearly the same transmission probability within 2.8% of the maximum difference in the range of L ≤ 100 (the cross-sectional area of each tube is π).     

Regeneration of peripheral nerves by bioabsorbable polymer tubes with fibrin gel

We developed two types of nerve conduits, straight tubes, and bellows tubes, for peripheral nerve regeneration with bioabsorbable polymer membranes. Mechanical properties of these straight and bellows tubes were analyzed. 30 straight tubes and 30 bellows tubes were implanted to a nerve defect made in a rat sciatic nerve and the nerve regeneration in the tube was investigated. A half of these tubes were utilized alone and the others were filled with fibrin gel made from coagulated plasma and implanted. Bellows tubes were superior in mechanical characteristics to straight tubes and the inner cavities of the bellows tubes were suitably maintained after implantation. At 4 weeks after operations, remyelinations were observed in the regenerated tissue at the location of the middle parts of the tubes filled with fibrin gel whereas no remyelinations in the tubes without fibrin gel. The use of fibrin gel as filling materials within the tubes significantly enhanced the nerve regeneration. The fibrin gel might be soft nanomaterials significantly enhance the regeneration of the peripheral nerves. We concluded that the developed bioabsorbable bellows tubes filled with fibrin gel were effective for peripheral nerve regeneration.     

Synthesis and characterization of hydroxyapatite–bacterial cellulose nanocomposites

Biocomposites consisting of hydroxyapatite (HAp) and natural polymers such as collagen, chitosan, chitin, and gelatin have been extensively investigated. However, studies on the combination of HAp with bacterial cellulose (BC) have not been conducted yet. In this work, our latest results concerning the biomimetic synthesis and characterization of HAp-BC nanocomposites with a 3-dimensional (3-D) network are reported. The present research focuses on characterizing the structure of this novel class of nanocomposites. Scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), and Fourier-transformed infrared spectroscopy (FTIR) were employed to characterize the HAp-BC nanocomposites. It is found that HAp crystals are formed when the phosphorylated and CaCl₂-treated BC fibers are soaked in a 1.5 simulated body fluid (SBF). XRD reveals that the crystallite sizes of the HAp crystals are nano-sized and their crystallinities are low. The FTIR results show that the HAp crystals are partially substituted with carbonate, resembling natural bones. The nanocomposites containing HAp with structural features close to those of biological apatites are attractive for applications as artificial bones and scaffolds for tissue engineering.     

Experimental Study of Heat Transfer Enhancement in Solar Tower Receiver Using Internal Fins

The receiver is an important element in solar energy plants. The principal receiver’s tubes in power plants are devised to work under extremely severe conditions, including excessive heat fluxes. Half of the tube’s circumference is heated whilst the other half is insulated. This study aims to improve the heat transfer process and reinforce the tubes’ structure by designing a new receiver; by including longitudinal fins of triangular, circular and square shapes. The research is conducted experimentally using Reynolds numbers ranging from 28,000 to 78,000. Triangular fins have demonstrated the best improvement for heat transfer. For Reynolds number value near 43,000 Nusselt number (Nu) is higher by 3.5% and 7.5%, sequentially, compared to circular and square tube fins, but varies up to 6.5% near Re = 61000. The lowest friction factor is seen in a triangular fin receiver; where it deviates from circular fins by 4.6%, and square fin tubes by 3.2%. Adding fins makes the temperature decrease gradually, and in the case of no fins, the temperature gradient between the hot tube and water drops sharply in the planed tube by 7%.     

Synthetic collagen fibers coated with a synthetic peptide containing the YIGSR sequence of laminin to promote peripheral nerve regeneration in vivo

The usefulness of collagen fibers and the YIGSR sequence (Tyr-lle-Gly-Ser-Arg) of laminin for nerve regeneration were examined in vivo. Type I collagen gel (G-group), Type I collagen fibers (F-group), Type I collagen fibers coated with laminin (L-group) or the YIGSR sequence (Y-group) were packed into silicone tubes, 15 mm long, and transplanted to the sciatic nerves of Wistar rats. Empty silicone tubes were used as the control. The animals were sacrificed 8 weeks after transplantation. Bridging of the nerve was confirmed in the F-(7/12), Y-(7/10) and L-group (6/10), but no bridging was observed in any of the animals of the G- and control group. Nerve regeneration among the space of collagen fibers was observed, and it was suggested that fibroblasts infiltrated the gap in the substance of the degenerated collagen fibers were followed by Schwann cells on the basis of immunocytochemistry. The number of myelinated axons per regenerated tissue in the tube (density), and total area of myelinated axons per measured regenerated tissue in the tube (% axon area) in each the L- and Y-group were significantly higher than that in the F-group (P < 0.05). These results suggest the possibility of obtaining adequate nerve regeneration with new artificial materials only. © 1999 Kluwer Academic Publishers     

Influence of fluorine substitution on the morphology and structure of hydroxyapatite nanocrystals prepared by hydrothermal method

Hydroxyapatite (HAp) nanocrystals with different levels of fluorine substitution (P/F = 0, 6, 4 and 2) on the OH sites were produced via hydrothermal method. The fluorine substitution was found to alter the morphology of crystals appreciably. The aspect ratio and the crystallinity of HAp crystals increased with increasing fluorine substitution. The presence of broad ring and hallow ring patterns in electron diffraction suggests the low-crystalline nature of HAp crystals. With increasing fluorine substitution, the diffraction patterns exhibited discrete rings and numerous diffraction spots, implying the increased crystallinity. Raman spectra from the HAp nanoparticles also support the less-crystalline nature of the pristine HAp and the enhanced crystallization by fluorine substitution. In HAp crystals processed with no fluorine substitution, surface energy and planar Ca²⁺ density are less sensitive to the crystallographic orientation because of its low-crystalline nature, favoring equi-axed or slightly elongated particles. The addition of fluorine apparently increased the crystallinity, enhancing the orientation dependent growth and accordingly the aspect ratio. Osteoblast proliferation was observed to be enhanced by fluorine substitution in HAp. In vitro biological data support that the excellent osteoblastic cell viability and functional activity of the fluoridated apatite.     

Characterisation, corrosion resistance and in vitro bioactivity of manganese-doped hydroxyapatite films electrodeposited on titanium

This work elucidated the corrosion resistance and in vitro bioactivity of electroplated manganese-doped hydroxyapatite (MnHAp) film on NaOH-treated titanium (Ti). The NaOH treatment process was performed on Ti surface to enhance the adhesion of the MnHAp coating on Ti. Scanning electron microscopy images showed that the MnHAp coating had needle-like apatite crystals, and the approximately 10 μm thick layer was denser than HAp. Energy-dispersive X-ray spectroscopy analysis revealed that the MnHAp crystals were Ca-deficient and the Mn/P molar ratio was 0.048. X-ray diffraction confirmed the presence of single-phase MnHAp, which was aligned vertically to the substrate. Fourier transform infrared spectroscopy indicated the presence of phosphate bands ranging from 500 to 650 and 900 to 1,100 cm^?1, and a hydroxyl band at 3,571 cm^?1, which was characteristic of HAp. Bond strength test revealed that adhesion for the MnHAp coating was more enhanced than that of the HAp coating. Potentiodynamic polarisation test showed that the MnHAp-coated surface exhibited superior corrosion resistance over the HAp single-coated surface. Bioactivity test conducted by immersing the coatings in simulated body fluid showed that MnHAp coating can rapidly induce bone-like apatite nucleation and growth. Osteoblast cellular tests revealed that the MnHAp coating was better at improving the in vitro biocompatibility of Ti than the HAp coating.     

圆管纵向弧形试样横截面积的计算

针对GB/T 228.1-2010给出的3个计算圆管纵向弧形试样横截面积的公式,在计算上且存在着不便或限制的问题,笔者采用数学推导的方法建立了一个统一式,即S0=0.017 44 a(D-a).arcsinb、D-a。应用举例结果表明:采用该公式计算圆管纵向弧形试样的横截面积不仅计算简单,而且结果准确。     

Bridging defects in nerve continuity: influence of variations in synthetic fiber composition

Synthetic filaments introduced into a silicone tube may help to enhance axonal growth over extended defects in nerve continuity [1]. Here we test the influence of number (0, 3, 7 or 15), size (diameter 150 or 250 m) and material of filaments (polyamide or catgut) enclosed in such tubes (inner diameter 1.98 mm) on axonal growth across a 10 mm defect in rat sciatic nerve. The morphology of the tube content was analyzed four weeks post-surgery. The area of the formed tissue matrix inside the tube showed no difference between the groups. Myelinated axons were observed in the formed tissue matrix inbetween and peripheral to the filaments, however, separated from the filaments by concentric cell layers. The number of myelinated axons was less in the tubes with 15 filaments, most pronounced when catgut filaments were used. In most cases, except in tubes with 15 catgut filaments, fibers had grown into the distal nerve segment (pinch reflex test/light microscopy). We conclude that an intrinsic framework consisting of a limited number of synthetic filaments inside an extrinsic framework (silicone tube) does not disturb nerve regeneration. The formed tissue matrix was neither influenced by the presence or the numbers (if less than or equal to seven filaments), type of filaments nor the size of the filaments indicating the importance of the inserted nerve segments. © 1999 Kluwer Academic Publishers     

Biomimetic synthesis of enamel-like hydroxyapatite on self-assembled monolayers

Hydroxyapatite (HAp) crystals mimicking tooth enamel in chemical composition and morphology were formed on sulfonic-terminated self-assembled monolayer (SAM) in 1.5SBF with F⁻ at 50 °C for 7 days. F⁻ ions showed a marked effect on the composition and morphology of deposited HAp crystals. In the absence of F⁻ ions, HAp containing CO₃²⁻ were formed on SAM, and worm-like crystals of 200–300 nm in length aggregated to form a spherical morphology. When F⁻ was added, HAp crystals containing both CO₃²⁻ and F⁻ were formed on SAM. Needle-shaped crystals of high aspect ratio and 1–2 μm in length grew elongated along the c-axial direction. In addition, these needle-shaped crystals grew in bundles, mimicking HAp crystals in tooth enamel. After the process of ripening, the needles in bundle grew to large size of up to 10 μm in length, and still kept no crystal–crystal fusion like enamel HAp crystals. The formation of enamel-like HAp can be attributed to the substitute of F⁻ for OH⁻ by disturbing the normal progress of HAp formation on SAM. The results suggest potential applications in preparing a novel dental material by a simple method.     

A study of the process and kinetics of electrochemical deposition and the hydrothermal synthesis of hydroxyapatite coatings

Hydroxyapatite (HAp) coatings were prepared using electrochemical deposition and post-hydrothermal synthesis. The composition and morphology of coatings at each processing step was studied through the application of scanning electron microscopy (SEM), X-ray diffraction (XRD) and infra-red spectroscopy (IR). The mechanism and kinetics of hydrothermal synthesis were considered in particular, and the influnce of the temperature and time on the HAp formation rate was also investigated. The results show that the electrochemical deposition coatings are composed of CaHPO₄2H₂O crystals which are converted into needle-like HAp crystals after post-hydrothermal treatment. The HAp content of the coatings increases with the treatment temperature and time. The synthesis rate also increases with the pH value of the water. The formation of HAp coatings is considered to be a combination of several reactions. An Arrhenius relationship was found between the HAp formation rate and the temperature, and an apparent activation energy of 94.4 KJ/mol was obtained by calculation. © 2000 Kluwer Academic Publishers     

Synthesis and ultrastructure of plate-like apatite single crystals as a model for tooth enamel

Hydroxyapatite (HAp) is an inorganic constituent compound of human bones and teeth, with superior biocompatibility and bioactivity characteristics. Its crystal structure is hexagonal, characterized by a(b)- and c-planes. In vertebrate long bones, HAp crystals have a c-axis orientation, while in tooth enamel, they have an a(b)-axis orientation. Many methods can be used to synthesize c-axis oriented HAp single crystals; however, to the best of our knowledge, there have been no reports on a synthesis method for a(b)-axis oriented HAp single crystals. In this study, we successfully synthesized plate-like HAp crystals at the air–liquid interface of a starting solution via an enzyme reaction of urea with urease. Crystal phase analysis and ultrastructure observations were carried out, and the results indicated that the particles were single crystals, with almost the same a(b)-axis orientation as tooth enamel. It is hoped that by utilizing their unique surface charge and atomic arrangement, the resulting particles can be used as a high-performance biomaterial, capable of adsorbing bio-related substances and a model for tooth enamel.     

医用聚乳酸的合成及其管型材料性能的测定

本文以无毒的辛酸亚锡作催化剂,将丙交酯聚合成聚乳酸(PLA)。研究了在760～0.05mmHg范围内压力改变对PLA分子量的影响,并将PL制成内径为2mm的管型材料,经热稳定性、机械强度和降解性能等试验,结果都表明此管材可用作引导神经再生导管材料。     

In vitro study of the SBF and osteoblast-like cells on hydroxyapatite/chitosan–silica nanocomposite

Hydroxyapatite/chitosan–silica (HApCSi) nanocomposites were synthesized by co-precipitated method and their potential application as filler materials for bone regeneration were investigated in simulated body fluid (SBF). To study their biocompatibility, they were cultured with rat osteoblast-like UMR-106 cells for 3, 7, 14, and 21 days. Studies of the silica contents in chitosan matrix showed the presence of silinol (Si–OH) groups in CSi hybrid and their decrease after being composited with calcium phosphate (CaP) which is desirable for the formation of the apatite. XRD and TEM studies showed that the HAp formed in the CSi matrix were nanometer (20–40 nm) in size. Nanocomposites of HApCSi20 processed with 20%v/v silica whisker showed a micro hardness of 84.7 ± 3.3 MPa. Mineralization study in SBF showed the formation of apatite crystals on the HApCSi surface after being incubated for 7 days. In vitro biocompatibility, cell morphology, proliferation, and cell adhesion tests confirmed the osteoblast attachment and growth on the HApCSi20 surface. The density of cells and the production of calcium nodules on the substrate were seen to increase with increasing cultured time. The mechanical evaluation and in vitro experiment suggested that the use of HApCSi composite will lead to the formation of new apatite particles and thus be a potential implant material.     

Transmission electron microscopic observation of a metastable phase on the thermal decomposition process of Ca-deficient hydroxyapatite

Calcium-deficient hydroxyapatite (Ca-def HAp) decomposes to stoichiometric hydroxyapatite (HAp) and β-tricalcium phosphate (β-TCP) at high temperature. In a previous study, we reported that a metastable phase with a high Ca/P molar ratio appeared in the temperature range from 700 to 800°C. In the present study, the formation process of a metastable phase and the crystallographic relationship between the Ca-rich metastable phase and HAp matrix were investigated by high-resolution transmission electron microscopy (HRTEM). Ca-def HAp was annealed at 600–850°C for 2 or 6 h in air. TEM observations were performed before and after annealing Ca-def HAp. Based on analysis of image of Ca-def HAp before annealing, several HAp crystals with different aspect ratios agglomerated. The metastable phases grew thicker by long-term annealing. HRTEM image suggested that the Ca-rich metastable phase was formed by migration to the interface and continuous accumulation of calcium ions from HAp crystals with a small aspect ratio. From HRTEM images and results of the analysis of selected area electron diffraction patterns along the [010], [110] and [001] zone axes, lattice constants of the metastable phases were determined to be a = 2.86 nm, b = 0.94 nm, and c = 0.69 nm with orthorhombic crystals system.     

Poly(lactide-co-glycolide)/hydroxyapatite nanofibrous scaffolds fabricated by electrospinning for bone tissue engineering

Poly(lactide-co-glycolide) (PLGA) nanofibrous composite scaffolds having nano-hydroxyapatite particles (HAp) in the fibers were prepared by electrospinning of PLGA and HAp with an average diameter of 266.6 ± 7.3 nm. Microscopy and spectroscopy characterizations confirmed integration of the crystalline HAp in the scaffolds. Agglomerates gradually appeared and increased on the fiber surface along with increase of the HAp concentration. In vitro mineralization in a 5 × simulated body fluid (SBF) revealed that the PLGA/HAp nanofibrous scaffolds had a stronger biomineralization ability than the control PLGA scaffolds. Biological performance of the nanofibrous scaffolds of the control PLGA and PLGA with 5 wt% HAp (PLGA/5HAp) was assessed by in vitro culture of neonatal mouse calvaria-derived MC3T3-E1 osteoblasts. Both types of the scaffolds could support cell proliferation and showed sharp increase of viability until 7 days, but the cells cultured on the PLGA/5HAp nanofibers showed a more spreading morphology. Despite the similar level of the cell viability and cell number at each time interval, the alkaline phosphatase secretion was significantly enhanced on the PLGA/5HAp scaffolds, indicating the higher bioactivity of the as-prepared nano-HAp and the success of the present method for preparing biomimetic scaffold for bone regeneration.     

In-tube cooling heat transfer of supercritical carbon dioxide. Part 2. Comparison of numerical calculation with different turbulence models

Heat transfer of supercritical carbon dioxide cooled in circular tubes was investigated experimentally. The effect of mass flux, pressure, and heat flux on the heat transfer coefficient and pressure drop was measured for four horizontal cooling tubes with different inner diameters ranging from 1 to 6 mm. The radial distribution of the thermophysical properties (i.e. specific heat, density, thermal conductivity and viscosity) in the tube cross-section was critical for interpreting the experimental results. A modified Gnielinski equation by selecting the reference temperature properly was then developed to predict the heat transfer coefficient of supercritical carbon dioxide under cooling conditions. This proposed correlation was accurate to within 20% of the experimental data.     

Multifunctional hydroxyapatite and poly(d,l-lactide-co-glycolide) nanoparticles for the local delivery of cholecalciferol

Cholecalciferol, vitamin D₃, plays an important role in bone metabolism by regulating extracellular levels of calcium. Presented here is a study on the effects of the local delivery of cholecalciferol (D₃) using nanoparticulate carriers composed of hydroxyapatite (HAp) and poly(d,l-lactide-co-glycolide) (PLGA). Multifunctional nanoparticulate HAp-based powders were prepared for the purpose of: (a) either fast or sustained, local delivery of cholecalciferol, and (b) the secondary, osteoconductive and defect-filling effect of the carrier itself. Two types of HAp-based powders with particles of narrowly dispersed sizes in the nano range were prepared and tested in this study: HAp nanoparticles as direct cholecalciferol delivery agents and HAp nanoparticles coated with cholecalciferol-loaded poly(d,l)-lactide-co-glycolide (HAp/D₃/PLGA).Satisfying biocompatibility of particulate systems, when incubated in contact with MC3T3-E1 osteoblastic cells in vitro, was observed for HAp/D₃/PLGA and pure HAp. In contrast, an extensively fast release of cholecalciferol from the system comprising HAp nanoparticles coated with cholecalciferol (HAp/D3) triggered necrosis of the osteoblastic cells in vitro. Artificial defects induced in the osteoporotic bone of the rat mandible were successfully reconstructed following implantation of cholecalciferol-coated HAp nanoparticles as well as those comprising HAp nanoparticles coated with cholecalciferol-loaded PLGA (HAp/D₃/PLGA). The greatest levels of enhanced angiogenesis, vascularization, osteogenesis and bone structure differentiation were achieved upon the implementation of HAp/D₃/PLGA systems.     

Chemical vapour deposition of corrosion-resistant TiN film to the inner walls of long steel tubes

A uniform TiN film was coated on to the inner walls of long steel tubes by moving a chemical vapour deposition furnace along the tubes. The moving direction of the furnace from outlet side to inlet side gave a more homogeneous coating than the reverse moving direction. The TiN-coated steel tube (inside diameter 10 mm) was obtained under the following conditions; peak deposition temperature 1050° C, total flow rate of reactant gas (TiCl₄ + N₂ + H₂) 6.0 ml sec^–1, moving velocity of the furnace 2.8 mm min^–1. The inner wall of the coated tube showed high corrosion resistance for dipping in 6N HCI aqueous solution for 17 h.