中国南方古人骨中羟磷灰石稳定同位素分析的可行性初探——以浙江省庄桥坟遗址为例

对人骨保存与污染情况的研究是利用骨骼进行测年和食谱分析的前提，而国际上热带/亚热带地区人骨骨胶原普遍流失的现状促使国际学界不断加强对人骨中无机质（羟磷灰石）的研究；然而我国对南方热带/亚热带地区人骨保存情况研究甚少，极大限制了对当地史前先民食谱分析研究的进展。本文以浙江庄桥坟遗址（3700-5000a B.P.）出土的50例人和动物骨骼为例，运用元素分析仪、X射线衍射（XRD）、红外光谱（FTIR）等现代分析手段从骨胶原和羟磷灰石两方面，探索当地骨骼保存及污染情况。结果表明这50例样品的骨胶原已经全部降解或被污染；骨胶原实验后尚余44例样品，对其进行XRD实验，结果表明14例样品中含有相当数量的石英、钠长石和钾长石，说明骨样受到了外来物质的污染。而另外30例骨骼样品的最主要成分是羟磷灰石，不含其他杂质。将这30例样品进行FTIR实验后发现，图谱中PO4^3-和CO3^2-主要振动带的特征峰明显；引入PCI、BPI、C/P等FTIR指数进行定量分析、并在指数间进行相关性分析后发现，样品中羟磷灰石的保存状况较好，可以进一步用于今后的稳定同位素研究。

纳米羟基磷灰石/聚酰胺复合人工椎板预防脊柱后路术后椎管内瘢痕粘连的实验研究

目的:探讨纳米羟基磷灰石/聚酰胺(nano-hydroxyapatite/polyamide-66,n-HA/PA66)复合人工椎板在防止脊柱后路术后椎管内瘢痕粘连,重建脊柱后部结构完整性的价值。方法:22只1岁龄雄性家犬行L5椎板切除,实验组13只行复合人工椎板植入,另9只作空白对照。术后4、8、16、24周各时相点摄X线片,行组织学、扫描电镜观察;术后24周行MRI检查。结果:实验组术后16～24周复合人工椎板界面观察到软骨细胞及板层骨,硬膜粘连程度比对照组明显减轻(P<0.01)。术后24周时MRI显示实验组椎管完整性恢复。结论:n-HA/PA66复合材料具有良好的生物相容性,能有效阻止硬膜外粘连。

Influence of anodization conditions on deposition of hydroxyapatite onα/βTi alloys for osseointegration:Atomic force microscopy analysis

Integrating titanium-based implants with the surrounding bone tissue remains challenging.This study aims to explore the impact of different anodization voltages(20−80 V)on the surface topography of two-phase(α/β)Ti alloys and to produce TiO_(2) films with enhanced bone formation abilities.Scanning electron microscopy coupled with energy dispersive spectroscopy(SEM−EDS)and atomic force microscopy(AFM)were applied to investigate the morphological,chemical,and surface topography of the prepared alloys and to confirm the growth of hydroxyapatite(HA)on their surfaces.Results disclosed that the surface roughness of TiO_(2) films formed on Ti−6Al−7Nb alloys was superior to that of Ti−6Al−4V alloys.Ti−6Al−7Nb alloy anodized at 80 V had the highest yields of HA after immersion in simulated body fluid with enhanced HA surface coverage.The developed HA layer had a mean thickness of(128.38±18.13)μm,suggesting its potential use as an orthopedic implantable material due to its promising bone integration and,hence,remarkable stability inside the human body.

比较不同来源钙剂对大鼠骨密度的影响

目的:研究纳米碳酸钙、微晶体羟磷灰钙、乳钙对大鼠骨密度和钙表观吸收率的影响。方法:SPF级4周龄雌性SD大鼠90只,随机分为9组,即纳米碳酸钙、微晶体羟磷灰钙、乳钙低、高剂量组和相应剂量碳酸钙对照组(低、高剂量组饲料钙含量分别为500mg/100g和1000mg/100g),以及低钙对照组(饲料钙含量为150mg/100g)。喂养13周,测钙表观吸收率、骨钙含量和骨密度。结果:不同钙剂组大鼠骨密度均明显高于低钙对照组(P<0.05);不同钙剂低剂量组大鼠钙表观吸收率介于52.96%～68.16%之间,高剂量组吸收率介于41.78%～61.30%,均明显低于低钙对照组(P<0.05)。结论:与低钙对照组相比,纳米碳酸钙、微晶体羟磷灰钙、乳钙均可明显改善大鼠的骨密度。

Surface modification of biomedical magnesium alloy wires by micro-arc oxidation

Magnesium alloy wires were processed by micro-arc oxidation （MAO） in a modified silicate-phosphate composite electrolyte containing hydroxyapatite （HA） nanopowders and NaOH. Effects of NaOH content in the composite electrolyte on the microstructure and properties of the MAO ceramic coatings on magnesium alloy wires were studied. It is found that the arc voltage of magnesium alloy wires in the micro-arc oxidation process is significantly reduced while the oxidation rate is accelerated. Addition of 2 g/L NaOH in the composite electrolyte is a better choice for improving corrosion resistance of magnesium alloy wires. During early simulated body fluids （SBF） immersion, the micro-arc oxidized magnesium alloy wires undergo a slow and stable degradation. After soaking for 28 d, the protective ceramic coating still shows no damage but significant degradation is observed for magnesium alloy wires after immersion for more than 60 d.

Arginine functionalized hydroxyapatite nanoparticles and its bioactivity for gene delivery

In order to further improve the transfection efficiency of hydroxyapatite nanoparticle （HAp）, arginine functionalized hydroxyapatite （HAp/Arg） was synthesized by hydrothermal synthesis. The morphology, crystallite size and zeta potential of the HAp/Arg were characterized by transmission electron microscopy （TEM）, atomic force microscopy （AFM） and zeta potential analyzer. The loading and protecting properties of HAp/Arg to DNA were tested by electrophoresis. Its cytotoxicity was also measured in Hela cells and HAEC cells by MTT and LDH, and its transfection efficiency was examined by fluorescence microscope and flow cytometry. The results reveal that HAp/Arg is short rod-like and nano single crystal, the mean diameter is 50-90 nm and zeta potential is 35.8 mV at pH 7.4. HAp/Arg to DNA can be condensed by electrostatic effect and protect DNA against degradation in DNase I, and shows high transfection efficiency without cytotoxicity. These results suggest that HAp/Arg can be a promising alternative as a novel gene delivery system.

Effect of cetyltrimethylammonium bromide on morphology and porous structure of mesoporous hydroxyapatite

The mesoporous hydroxyapatite （HA） was synthesized by hydrothermal method utilizing cationic surfactant cetyltrimethylammonium bromide （CTAB） as template. The crystalline phase, morphology and porous structure were characterized respectively by different detecting techniques. The results reveal that the particles are highly crystalline hydroxyapatite phase. The surfactant has little influence on the morphology of the crystals, but affects the porous structure obviously. The sample without CTAB has a low surface area not exceeding 33 m^2/g, and no distinct pores can be observed by TEM. While the samples obtained with the surfactant get better parameters. Numerous open-ended pores centered at 2-7 nm spread unequally on the surface of the hydroxyapatite nanorods. The N2 adsorption-desorption experiments show type IV isotherms with distinct hysteresis loops, illustrating the presence of mesoporous structure. When the mole ratio of CTAB to HA is 1：2, the sample has the largest surface area of 97.1 m^2/g and pore volume of 0.466 cm^3/g.

Synthesis of Crystalline Hydroxyapatite from CaCO_3 and CaHPO_4·2H_2O by Mechanochemical Method

The mixture of CaHPO 4·2H 2O and CaCO 3 was ground in an aqueous system under appropriate conditions to investigate the mechanochemical reaction for the synthesis of crystalline hydroxyapatite (HA) powder. Hydroxyapatite of high crystallinity powder including trace Ca 10 (PO 4) 6CO 3(OH) and Ca 9HPO 4(PO 4) 6OH can be synthesized by mechanical activation without further thermal treatment at a high temperature. The synthesis reaction during the grinding process was almost completed within 1h. The as-ground powder exhibits a particle distribution of 20-100nm in size with a spherical or rodlike morphology. The composition and degree of crystallinity of the mechanochemical synthesized hydroxyapatite powders were coincident with the cement-type hydroxyapatite.

Synthesis and characterization of arginine-modified and europium-doped hydroxyapatite nanoparticle and its cell viability

The arginine-modified and europium-doped hydroxyapatite nanoparticles（HAP-Eu） were synthesized by hydrothermal synthesis.The prepared nanoparticles were characterized by transmission electron microscopy（TEM）,X-ray diffractometry（XRD）,Fourier transform infrared（FTIR） and zeta potential analyzer.The cell viability of HAP-Eu was tested by image flow cytometry.The results indicated that HAP-Eu is short column shapes and its size is approximately 100 nm,its zeta potential is about 30.10 mV at pH of 7.5,and shows no cytotoxicity in human epithelial cells and endothelial cells.

Effects of Nanometer Hydroxyapatite on Proliferation of Periodontal Ligament Fibroblasts

Objective:To investigate possible effects of nanophase powder of hydroxyapatite on proliferation of periodontal ligament cells. Methods: With sol-gel method, the nanophase hydroxyapatite powders were fabricated. These powders were proved nanopaticles by transmission electron microscope. The effects on proliferation of periodontal ligament cell(PDLC) were observed in vitro with MTT [3-(4,5dimethylthiazo;-2-yl)-2,5-diphenytetralium bromide] method. Results: On the 2nd,3rd,4th day after treated with nanoparticles of hydroxyapatite, the proliferate activity of the PDLC increases significantly, compared with those with dense hydroxyaoatite and control but no significant difference could be found between the dense hydroxyapatite and the control. Conclusion: Nanophase hydroxyapatite can promote the regeneration of periodontal tissue.

Effect of hydroxyapatite nanoparticles on the growth and p53/c-Myc protein expression of implanted hepatic VX_2 tumor in rabbits by intravenous injection

AIM： To evaluate the effect of hydroxyapatite nano- particles （Nano HAP） by intravenous injection on the inhibition of implanted hepatic VX2 tumor growth in rabbits and cell p53/c-Myc protein expression. METHODS： 60 hepatic VX2 tumor-bearing rabbits was randomly divided into five groups. Nano HAP collosol 20 mglkg, 40 mg/kg, 5-FU solutions 20 mg/mL, mixed liquor of 5-FU solution 20 mg/mL and Nano HAP collosol 20 mg/kg were infused by vein, normal saline conducted as the control. The general state, weight, liver function and gross tumor volume were detected dynamically. The expression of p53 and c-Myc gene protein in tumor tissue was detected by immunohistochemistry methods. RESULTS： The growth of implanted hepatic VX2 tumors was significantly inhibited in all therapy groups, 3 wk after the injection, the tumor control rates in Nano HAP collosol groups were 25.5% and 32.5% respectively, and the gross tumor volumes were obviously less than that of control group. （24.81 ± 5.17 and 22.73 ± 4.23 vs 33.32 ± 5.26, P 〈 0.05）. The tumor control rate of 5-FU group was 43.7% （18.74 4± 4.40 vs 33.32 ± 5.26, P 〈 0.05）, but the general state of the animals after injection aggravated; and the adverse reaction in the drug combination group obviously decreased. Due to the effect of Nano HAP, the positive expression of tumor associated the mutated p53 and c-Myc in tumor tissue was decreased obviously compared with the control group. CONCLUSION： Nano HAP has evident inhibitory action on rabbit implanted hepatic VX2 tumor in vivo, which may be the result of decreasing the expression of the mutated p53 and c-myc, and drug combination can obviously decrease the adverse reaction of 5-FU.

In-vitro degradation behavior of Mg alloy coated by fluorine doped hydroxyapatite and calcium deficient hydroxyapatite

Fluorine-doped hydroxyapatite(FHA) and calcium deficient hydroxyapatite(CDHA) were coated on the surface biodegradable magnesium alloy using electrochemical deposition(ED) technique. Coating characterization was investigated X-ray diffraction(XRD), Fourier-transformed infrared spectroscopy(FTIR), transmission electron microscopy(TEM), scanni electron microscopy(SEM) and energy dispersive X-ray spectroscopy(EDS). The result shows that nano-FHA coated samp presents nano needle-like structure, which is oriented perpendicular to the surface of the substrate with denser and more unifo layers compared to the nano-CDHA coated sample. The nano-FHA coating shows smaller crystallite size(65 nm) compared to t nano-CDHA coating(95 nm); however, CDHA presents thicker layer(19 μm in thickness) compared to the nano-FHA(15 μm thickness). The corrosion behaviour determined by polarization, immersion and hydrogen evolution tests indicates that the nano-FH and nano-CDHA coatings significantly decrease corrosion rate and induce passivation. The nano-FHA and nano-CDHA coatings c accelerate the formation of bone-like apatite layer and significantly decrease the dissolution rate as compared to the uncoated M alloy. The nano-FHA coating provides effective protection to Mg alloy and presents the highest corrosion resistance. Therefore, t nano-FHA coating on Mg alloy is suggested as a great candidate for orthopaedic applications.

Effects of electrolytic concentration on properties of micro-arc film on Ti6Al4V alloy

To study the effect of electrolytic concentration,bioactive ceramic films containing Ca and P on the surface of the Ti6Al4V alloy were prepared by micro-arc oxidation(MAO) in aqueous solutions of different concentrations.Composition,micro-morphology,wettability of the films and their corrosion behavior in a Hank's SBF were studied.Our experimental results show that the film is mainly composed of anatase,rutile and amorphous phases.With an increase in electrolytic concentration,the ratio of rutile in films enlarge and small amounts of calcium phosphate(Ca3(PO4)2) and hydroxyapatite(HA) appear.The number of micropores in films increases but their dimensions decrease and their porosities increase slightly.As the surface roughness of MAO film increases with concentration,the wettablility of the oxide film improves continually,while micro-hardness increases at first and then decreases.MAO treatment clearly improves the corrosion resistance of substrates in a Hank's SBF.

Mechanical properties of hydroxyapatite-zirconia coatings prepared by magnetron sputtering

Hydroxyapatite （HA）-zirconium （ZrO2） composite coating was produced by magnetic sputtering on Ti6Al4V titanium alloy substrate, the coatings of 50HA-50ZrO2 and 75HA-25ZrO2 （mass fraction, %） were characterized by scanning electron microscopy, energy disperse spectroscopy, X-ray diffraction and scratch test, respectively, and the effects of HA contents in the coating on residual stress were analyzed. The experimental results show that the phases of HA-ZrO2 composite coatings are HA, ZrO2 and Y2O3, and the HA has a certain decomposition in the combination process, producing TCP and CaO impurity phases. The porous surface of coating is conducive to the growth of bone tissue, and the surface roughness values of 50HA-50ZrO2 and 75HA-25ZrO2 are 1.61 μm and 2.92 μm, respectively. The coating interface is of mechanical integration, the bonding strength values of 50HA-50ZrO2 and 75HA-25ZrO2 are 30 N and 17.5 N, respectively, showing a downward trend with the HA contents increasing. The residual stress values in the coating of 50HA-50ZrO2 and 75HA-25ZrO2 are （-399.1±3.0） MPa, （-343.2±20.3） MPa, respectively, as a result, the appropriate increase of HA contents in the coating will reduce its residual stress.

Oxidative esterification of acetol with methanol to methyl pyruvate over hydroxyapatite supported gold catalyst: Essential roles of acid-base properties

Acetol is a major light oxygenate and readily produced from staged or fast pyrolysis of lignocellulose biomass. Herein we report that acetol can be selectively converted to methyl pyruvate, an important fine chemical, through oxidative esterification over Au-based catalysts. Detailed experimental studies showed that Au on amphoteric supports with appropriate strength and balanced ratio of acid and base sites can facilitate the desired oxidative-esterification pathway without accelerating undesired aldol-condensation or Cannizzaro reactions. In particular, hydroxyapatite (with a Ca/P ratio of 1.62) supported Au achieved 87% selectivity to methyl pyruvate at an acetol conversion of 62%.

Biotribological behavior of ultra high molecular weight polyethylene composites containing bovine bone hydroxyapatite

Wear particles of ultrahigh molecular weight polyethylene （UHMWPE） are the main cause of long-term failure of total joint replacements. Therefore, increasing its wear resistance or bioactivity will be very useful in order to obtain high quality artificial joints. In our study, UHMWPE composites filled with the bovine bone hydroxyapatite （BHA） were prepared by the method of compression moulding. A ball-on-disc wear test was carried out with a Universal Micro-Tribometer to investigate the friction and wear behavior of a Si3N4 ceramic ball, cross-sliding against the UHMWPE/BHA composites with human plasma lubrication. At the same time, the profiles of the worn grooves on the UHMWPE/BHA surface were scanned. The experimental results indicate that the addition of BHA to UHMWPE had a significant effect on the biotribological behavior of UHMWPE cross-sliding against the Si3N4 ceramic ball. The addition of BHA powder enhanced the hardness and modulus of elasticity of these composites and decreased the friction coefficients and wear rates under conditions of human plasma lubrication. When the added amount of BHA powders was up to 20%-30%, UHMWPE/BHA composites demonstrated the designed performance of the mechanical properties and biotribological behavior.

Rubidium-modified bioactive glass-ceramics with hydroxyapatite crystals for bone regeneration

In order to study the influence of rubidium(Rb)addition on the phase composition,microstructure,mechanical properties and cell response of bioactive glass-ceramics,CaO−SiO2−Na2O−B2O3−MgO−ZnO−P2O5 glass system was designed with and without addition of Rb.The results show that hydroxyapatite(HA)and Mg−whitelockite(Ca18Mg2H2(PO4)14)crystalline phases are formed in the glass matrix without Rb.After the addition of Rb,only HA phase is detected.The grain size of the crystals in the glass-ceramics is larger with the addition of Rb than that of samples without Rb.Rb addition can improve the bending strength of glass-ceramics.The cultivation of human bone marrow mesenchymal stem cells(hBMSCs)on Rb-containing glass-ceramics demonstrates enhanced cell adhesion,proliferation and ALP activity.In conclusion,Rb-modified glass-ceramics exhibit good mechanical property,excellent bioactivity and biocompatibility,which have potential for bone regeneration application.

Influence of Zirconia on Hydroxyapatite Coating on Ti-Alloy by Laser Cladding

Coating titanium alloy with the bioceramic material hydroxyapatite(HAP) has been used to improve the poor osteoinductive properties of pure titanium alloy. But in clinical applications, the mechanical failure of HAP-coated titanium alloy implant suffered at the interface of the HAP coatings and titanium alloy substrate will be a potential weakness in prosthesis. Yttria-stablized zirconia (YSZ) is expected to enhance the mechanical properties of the HAP coating and reduce the coefficient of thermal expansion difference between the coated layer and the substrate. These may reinforce the bonding strength between the coatings and the substrate. In this paper, HAP/YSZ composite coatings were cladded by laser. The effects of zirconia on the microstructure, mechanical properties and formation of tricalcium phosphate (TCP, Ca 3(PO 4) 2) of the HAP/YSZ composite coatings were evaluated. XRD, SEM and TEM were used to investigate the phase composition, microstructure and morphology of the coatings. The experimental results showed that adding YSZ in coatings was favorable to the composition and stability of HAP, and to the improvement of the adhesion strength, microhardness and microtoughness. A well uniform, crack-free coating of HAP/YSZ composites was formed on Ti-alloy substrate by laser cladding.

Hydroxyapatite Coatings on Titanium Prepared by Electrodeposition in a Modified Simulated Body Fluid

Hydroxyapatite coatings were directly prepared on anodized titanium by electro-deposition method in a modified simulated body fluid.The configuration,structure and bioactivity of the coating were investigated with scanning electron microscopy(SEM),X-ray diffraction analyzer(XRD)and Fourier transform infrared spectros-copy(FTIR)techniques.The results demonstrated that pure and homogeneous hydroxyapatite coating can be obtained without any post-treatment.The prepared coating showed good bioactivity in simulated body fluid(SBF).The time required for a fully covered dense hydroxyapatite coatings was 4 days immersion in SBF.

Thermal decomposition and mechanical properties of hydroxyapatite ceramic

Pure hydroxyapatite（HAP）ceramic and HAP composite ceramic with B2O3 were prepared by isostatic press forming and pressureless sintering.The relationships between thermal decomposition ratio and mechanical properties for pure HAP ceramic and the composite ceramic were investigated by means of FTIR,X-ray diffraction and three-point bending method.The results indicate that the decomposition ratio of pure HAP ceramic increases with ascending the sintering temperature and nearly reaches 80%at 1 350？殆or the HAP composite ceramic,the thermal decomposition is inhibited obviously due to the addition of B2O3.The added B atoms incorporate into the crystal lattice of HAP to form solid solution,resulting in an enlargement in the crystal spacing and an improvement in the binding strength of HAP crystal cell.Thermal decomposition ratio of HAP decreases but bending strength and fracture toughness are enhanced for HAP composite ceramics.However,when the added B2O3 is more than 5%（mass fraction）,HAP decomposition is promoted and a steady？-TCP is formed due to the fact that when B atoms with higher negative electricity are combined with O,sp2 and a full-air p are formed,and those voids have a strong trend to intake of the outer electrons.So,it is very possible to occupy the place where HAP loses OH - or PO4 3- .