氧化石墨烯/羟基磷灰石复合材料对酸蚀牛牙釉质体外再矿化的影响

考察不含氧化石墨烯(GO)的羟基磷灰石(HAP)和含GO质量分数为0.1;的氧化石墨烯/羟基磷灰石复合材料(GO/HAP)对酸蚀牛牙釉质体外再矿化的影响.通过场发射扫描电镜、EDX能谱、X射线衍射仪和维氏显微硬度测试仪,对再矿化前/后牛牙釉质表面和剖面形貌、表面元素、晶体结构和力学性能进行表征.结果 表明:GO/HAP复合材料在酸蚀牙釉质表面生成了结合力较弱的花状晶体,将这些晶体超声剥离后发现脱矿釉质表面和釉柱间隙均得到良好的修复.剖面形貌分析显示,GO/HAP复合材料使釉质深层脱矿得到良好修复,促进了牙釉质棱晶间大量微小晶粒的生成,以及脱矿釉柱间隙中有序排列晶体的生成.同时,经GO/HAP处理后,酸蚀牙釉质表面的Ca/P摩尔比和晶体成分均得到良好的恢复.     

壳聚糖分子对共沉淀法合成羟基磷灰石/壳聚糖粉体材料晶体形貌的影响

采用沸腾水浴共沉淀法,以尿素为pH调节剂制备羟基磷灰石/壳聚糖(HA/CS)复合粉体材料,通过XRD、FTIR和SEM对晶体组成、形貌进行表征,考察了壳聚糖平均分子量、添加量及反应物浓度对HA/CS晶体形貌的影响.结果表明,沸腾水浴共沉淀法可在较短时间内制备HA/CS复合粉体,改变反应物浓度可使晶体形貌由针状与球状同时存在转变为几乎全部是球状晶体,而CS平均分子量和添加量的影响较小.     

磁改性HAP/CS/SiO2骨组织工程支架的制备及性能研究

本文以氢氧化钙(Ca(OH)2)、磷酸(H3PO4)和CS为原料,湿法合成了CS改性的纳米羟基磷灰石(Nano HAP)复合粉体.以上述粉体为原料,采用模具成型法,以硅胶为粘接剂,通过添加硬脂酸微球作造孔剂制成多孔骨组织工程支架;通过添加纳米四氧化三铁(Nano Fe3O4)对复合材料进行磁改性制得了磁性多孔支架.通过X射线衍射仪(XRD),红外光谱分析(FT-IR),透射电镜(TEM)和扫描电镜(SEM)对材料的成分和结构进行了表征.采用力学试验机、体外降解实验和细胞毒性实验对材料的力学性能和生物学性能进行了检测.结果表明:制备的Nano HAP在成分和结构上类似于自然骨羟基磷灰石;多孔骨组织工程支架具有良好的成骨性能,并且其三维孔洞结构满足骨组织工程支架的要求;磁改性多孔支架具有良好的磁性能.以上材料均无细胞毒性.因此,该材料有望被用于临床的骨修复治疗.     

SiO2改性超长羟基磷灰石晶须的制备及研究

通过水热共沉淀反应法成功制备出超长羟基磷灰石晶须,并通过溶解正硅酸乙酯与羟基磷灰石晶须烧结得到二氧化硅表面改性羟基磷灰石.通过X射线衍射仪(XRD),红外分析(FT-IR)和扫描电镜(SEM)对样品的晶相组成、形貌、晶须长度进行了表征.结果表明:所得晶须的平均长度为230 μm,SiO2球形颗粒均匀的分布在晶须表面,其直径为600 nm,二氧化硅改性羟基磷灰石晶须可显著提高义齿基托树脂的抗拉强度.     

聚乳酸/羟基磷灰石晶须复合多孔支架的制备与性能研究

采用溶剂浇铸/真空挥发/粒子沥滤方法,采用氯化钠为造孔剂、氯仿为溶剂,最终制备出聚乳酸(PLA)/羟基磷灰石晶须(HAw)复合多孔支架.通过SEM表征了聚乳酸支架的表面形貌,用XRD、SEM、FT-IR等分析了加入不同量HAw的聚乳酸的成分、形貌以及结构特征,并研究羟基磷灰石晶须的添加量对支架的孔洞结构参数、力学性能及生物性能的影响,结果表明:可以通过控制氯化钠的粒度及用量来调节支架的孔径及孔隙率;聚乳酸(PLA)/羟基磷灰石晶须(HAw)复合多孔支架结构均匀,具有较高的孔隙率和良好的孔隙连通性;支架孔隙率在83.94;～91.08;范围内,可以满足骨组织工程对支架材料的要求;复合多孔支架的抗压强度达到5.72～ 12.73 MPa,在羟基磷灰石晶须质量比为10;时达到最大值,为12.73 MPa.     

二氧化硅@羟基磷灰石颗粒的制备及其药物装载与体外释放行为研究

以改性的St(o)ber方法制备二氧化硅核心颗粒,并用改性的Pechini方法在其表面沉积羟基磷灰石壳层,制备得到具有核壳结构的二氧化硅@羟基磷灰石颗粒.通过扫描电子显微镜、X射线衍射分析和红外光谱分析手段表征颗粒的物相和结构,确定颗粒的形成机制为羟基磷灰石壳层在聚乙二醇-柠檬酸作用下均匀地沉积在非晶态二氧化硅表面.含亚甲基蓝的二氧化硅@羟基磷灰石药物颗粒在磷缓冲液(pH =7.2 ～7.4)和lysosome-like缓冲液(pH=4.7)中的释放行为表明药物释放对颗粒结构和溶液的pH值非常敏感.     

氢键影响羟基磷灰石结晶形态的理论模型研究

在矿化环境下,羟基磷灰石晶体生长习性受矿化剂的影响.本文着重研究了氢键对羟基磷灰石结晶形态的影响,建立了矿化剂OH-晶面OH动态平衡吸附模型,引入动态平衡吸附参数k,用来描述这种影响的程度.根据Wulff定理,通过结晶学计算可知随着羟基磷灰石晶体的长大,{10 10}邻位面最终将消失;若不存在矿化剂(k=0)或者矿化剂对羟基磷灰石晶体的氢键作用很小(0≤k≤0.11865)时,{10 11}晶面也将逐渐消失;矿化剂对羟基磷灰石晶体的氢键作用较大(0.11865＜k＜1)时,{10 11}晶面将保留;作出长径比H～k曲线,可知H随k的增大而增大,k对H影响甚微.     

Ti3Al/HAP复合材料的制备与性能研究

采用化学沉淀法在模拟体液中制备了纳米羟基磷灰石(HAPs)粉体,用金属钛粉和铝粉经过机械合金法,制备了金属间化合物Ti3 Al;将制备的HAP粉体作为基体材料加入第二相Ti3Al粉体,经过球磨分散得到Ti3Al/HAP复合粉体,经过热压烧结,得到羟基磷灰石与金属间化合物Ti3Al的复合材料.通过XRD、SEM及TEM等测试方法,分析了用普通化学沉淀法制备的羟基磷灰石(HAPc)和在模拟体液中生成的羟基磷灰石(HAPs)的区别及Ti3Al对羟基磷灰石结构和性能的影响.测试结果显示:在模拟体液中生成的羟基磷灰石颗粒均匀细小,纯度较高,结晶度较低;羟基磷灰石掺入一定量的Ti3Al后,弯曲强度和断裂韧性有所降低,X射线衍射显示复合材料中只有Ti3 Al和HAP两种物质,没有新物质生成.     

超音速火焰喷涂HA/Ti复合涂层组织与性能研究

采用超音速火焰喷涂技术在304不锈钢基体上制备了纯HA涂层、30wt;HA/Ti及70wt;HA/Ti复合涂层,运用扫描电镜、X射线衍射和傅立叶变换红外光谱研究了涂层微观组织,物相和化学结构,并分析了涂层的结合强度和显微硬度及模拟体液下的生物性能.结果表明:HA/Ti复合涂层截面呈现典型的层状组织结构,表面存在大量球形/扁平化熔化颗粒及破碎粒子;大量Ti粒子在喷涂过程中被氧化且部分HA粒子产生分解,复合涂层主相为HA和TiO相,并含有少量TiO2、CaTiO3、CaO、Ti和α-TCP;Ti粒子添加有利于提高复合涂层力学性能,30wt; HA/Ti和70wt;HA/Ti涂层的结合强度分别为46.3 MPa和21.5 MPa,显微硬度分别为329 HV0.1和198 HV0.1;复合涂层经模拟体液浸泡7 d后,表面生成了磷灰石相,呈现出良好生物活性且随着HA含量增加而提高.     

TiAl金属间化合物/羟基磷灰石生物复合材料的制备及性能表征

首先采用机械合金化的方法制备出TiAl金属间化合物,用化学沉淀法制备出HA粉体,然后将二者球磨混合,经过真空热压烧结工艺制得TiAl/HA复合材料.力学性能检测结果表明,TiAl/HA复合材料的硬度比纯HA生物陶瓷要低,并且随TiAl质量分数的增加呈现降低趋势;复合材料的抗弯强度随着TiAl金属间化合物含量的增加呈上升趋势,含量为15;以下,其强度低于纯羟基磷灰石,含量处于15;到30;之间,其强度高于纯羟基磷灰石;断裂韧性高于纯HA生物陶瓷,最高可比纯羟基磷灰石提高78.7;,并且随着TiAl质量分数的增加呈上升趋势.X射线衍射结果表明复合材料中只含有TiAl金属间化合物和HA两种成分;断口扫描电镜照片显示,纯羟基磷灰石材料比较致密,而复合材料中存在一定量的气孔,其部分断裂区域显示出穿晶断裂的形态.     

水热均匀沉淀法制备Zn-Sr-HA微球

通过调整反应溶液中Zn/Sr摩尔比和水热反应时间,制备了锌锶替代羟基磷灰石(Zn-Sr-HA)微球.利用光学显微镜、X射线荧光光谱(XRF)、X射线衍射仪(XRD)和场发射扫描电子显微镜(SEM)研究了微球的组成、结构和形貌特征.结果表明,当初始溶液中Zn/Sr摩尔比为3:2或1:1、反应温度180℃、反应时间3～4h时,产物全部由HA微球组成.微球的平均直径约10～20 μm,大小均匀、分散性好.随着初始溶液中Zn/Sr摩尔比的增加,HA微球中Zn/Sr摩尔比逐渐增加,晶胞参数a值和c值逐渐减小.     

Influence of solution conditions on deposition of calcium phosphate on titanium by NaOH-treatment

The present paper demonstrated a biomimetic method to coat calcium phosphate (Ca-P) on the surface of titanium induced by NaOH-treatment from a simple supersaturated hydroxyapatite solution (SHS). The influence of pH value and calcium ions concentration on the precipitation process was investigated. It is necessary for the solution to be supersaturated than the critical concentration of octacalcium phosphate (OCP) to get Ca-P coatings on titanium surface. In the precipitating process, it seems that amorphous calcium phosphate (ACP) precipitated first, then OCP, and finally hydroxyapatite (HA). The system was in continuous evolution and the phase transitions occurred in sequence.     

Preparation of Conjugated Polymer Dots as a Fluorescence Turn-On Assay for Bovine Serum Albumin by Interaction with Graphene Oxide

Fluorescent conjugated polymers with various monomer compositions were synthesized via Suzuki coupling polymerization and spherically-shaped conjugated polymer dots (CPdot) with uniform size were prepared via conventional reprecipitation technique. Chemically modified graphene oxide (GO) was prepared to use as a component of sensor platform for protein detection. GO showed an excellent interaction with CPdot on its surface via hydrophobic interaction, which, in turn, induced the quenching of the fluorescence of CPdot. Upon exposure to bovine serum albumin (BSA), the quenched fluorescence was recovered, resulting from the release of CPdot from the complex with GO, as BSA adsorbed preferentially on the GO surface.     

热电池MnO2/石墨烯正极制备及电性能研究

采用水热法合成了MnO2/石墨烯复合材料,通过扫描电子显微镜( SEM)分析了材料的表面形貌,通过X射线衍射(XRD)和X射线光电子能谱(XPS)表征了材料的晶相结构和组成,采用恒流放电的方式对LiSi/LiCl-KCl/( MnO2/G)单体电池进行了电性能的测试。测试结果表明反应体系中加入GO后获得的材料由大量的纳米花球式和纳米棒式结构无规则的交织排列在一起,α-MnO2纳米簇结构依附在石墨烯纳米片上;产物在2θ为22°~27°时出现了较宽的无序堆叠的石墨烯的衍射峰;Mn元素氧化后离子状态为Mn4+;LiSi/LiCl-KCl/( MnO2/G)单体电池有两个放电平台,分别为2.58 V、1.96 V,放电电压截止到1.0 V时,对应的放电比容量达到1150.2 mAh/g。     

Borophosphate glass-ceramic scaffolds by a sodium silicate bonding process

A borophosphate glass with the mol% composition 25Na₂O-25CaO-5P₂O₃-45B₂O₅ was melted. The crystalline phase rheanite crystallized spontaneously during cooling the sample. Porous glass-ceramic scaffolds were prepared by bonding glass particles with size distributions in the range of approximately 100-500 μm by 0.1 M Na₂SiO₃ solutions. The scaffolds porosities were 40 ~ 60% and their compressive strengths were 0.1 ~ 0.4 MPa. The conversion of the binding scaffolds to hydroxyapatite (HA) was investigated by measuring the weight loss after soaking the sample in a solution of 0.25 M K₂HPO₄ with a pH value of 9.0 at 37 °C as a function of time. Hydroxyapatite (HA) was observed by XRD and SEM after soaking for 7 days. Cell attachment, spreading and proliferation on both unconverted scaffolds and on scaffolds coated with HA were determined by MTT [3-(4,5-Dimethylthiazol-2-yl)-2,5-Diphenyltetrazolium Bromide] assay method using Murine osteoblastic-like MC3T3-E1 cells. The scaffolds are biocompatible and their biocompatibility is enhanced after the formation of a HA layer.     

Precipitation of Stoichiometric Hydroxyapatite by a Continuous Method

In this paper we present the precipitation of hydroxyapatite (HA), Ca₅(OH)(PO₄)₃, from highly concentrated CaCl₂ and K₂HPO₄ solutions, carried out by a continuous method in a MSMPR reactor. The procedure consists of adding the reagents in a ratio Ca to P equal to 1.67, maintaining a temperature of 85 °C, inert N2 atmosphere inside the reactor, and monitoring and adjusting automatically the pH by means of a pH‐stat system (pH = 9.0 ∓ 0.1). Under these conditions HA with a Ca to P ratio equal or close to the stoichiometric composition (Ca/P=1.667), with a high yield (up to 99%) and a high production rate (up to 1.17 g/l.min) is obtained at steady state. The CSD, morphology, crystallinity of the precipitates and impurities present fit the requirement for its biomedical applications.     

Controlled growth and kinetics of porous hydroxyapatite spheres by a template-directed method

Porous hydroxyapatite (HA) spheres with high purity of phase and well-controlled pore size were grown by a template-directed method. We studied for the initial concentration of Ca–P how to control the chemical component of the products, and for the concentration of template how to control the aperture and the morphology of porous HA spheres. The experimental results indicated that the lower concentration of Ca–P was prone to pure HA phase and the aperture decreased gradually with the increase of the concentration of template. Correspondingly, the crystallization thermodynamics and template-directed growth kinetics were discussed in details. The solubility isotherms of HA and dicalcium phosphate (DCPD) were calculated based on classical crystallization theories of thermodynamics. The results suggested that there was a critical concentration of in the case of Ca:P=5:3 and thus DCPD could be avoided only when in this given reaction system. Kinetic analysis of HA crystal growth revealed that the template depressed the interfacial potential energy E, then enhanced the roughness on the surface of crystal nucleus and directed HA crystal to selectively grow along the [0 0 0 1] direction, and consequently governed the aperture of porous HA spheres. The experimental results were in agreement with the theoretical analysis.     

Synthesis of Poly(ϵ-caprolactone) Grafted Poly(2-hydroxyethyl methacrylate) Functionalized Hydroxyapatite by RAFT and ROP

Poly(?-caprolactone) grafted poly(2-hydroxyethyl methacrylate) functionalized hydroxyapatite (HAP@PHEMA-g-PCL) nanocomposites were synthesized by the combination of reversible addition fragmentation chain transfer (RAFT) polymerization and ring-opening polymerization (ROP). The RAFT agent was anchored on the surface of hydroxyapatite nanocrystals (HAPs) through the silane condensation process of 3-chloropropyltrimethoxysilane followed by reaction with potassium xanthogenate. Poly(2-hydroxyethyl methacrylate) (PHEMA) was covalently functionalized on the surface of HAPs by RAFT polymerization. Then, poly(?-caprolactone) (PCL) was grafted on HAPs by ROP based on the hydroxyl groups of PHEMA to afford HAP@PHEMA-g-PCL. The structure and composition of HAP@PHEMA-g-PCL nanocomposites were characterized by FT-IR, XRD, and TGA analyses. The morphology and formation of the polymer encapsulating HAPs were demonstrated from SEM and TEM images, while the ¹H MNR analysis of the cleaved PHEMA-g-PCL confirmed the grafting.