Synthesis and characterization of a nano‐hydroxyapatite/chitosan/polyethylene glycol nanocomposite for bone tissue engineering

A novel nanocomposite involving nano‐hydroxyapatite/chitosan/polyethylene glycol (n‐HAP/CS/PEG) has been successfully synthesized via co‐precipitation approach at room temperature. The purpose to synthesize such nanocomposite is to search for an ideal analogue which may mimick the composition of natural bone for bone tissue engineering with respect to suitable biocompatibility, cytotoxicity and mechanical properties. The FTIR spectra of n‐HAP/CS and n‐HAP/CS/PEG scaffolds indicated significant intermolecular interaction between the various components of both the nanocomposites. The results of XRD, TEM and TGA/DTA suggested that the crystallinity and thermal stability of the n‐HAP/CS/PEG scaffold have decreased and increased respectively, relative to n‐HAP/CS scaffold. The comparison of SEM images of both the scaffolds indicated that the incorporation of PEG influenced the surface morphology while a better in‐vitro bioactivity has been observed in n‐HAP/CS/PEG than in n‐HAP/CS based on SBF study, referring a greater possibility for making direct bond to living bone if implanted. Furthermore, MTT assay revealed superior non‐toxic nature of n‐HAP/CS/PEG to murine fibroblast L929 cells as compared to n‐HAP/CS. The comparative swelling studies of n‐HAP/CS/PEG and n‐HAP/CS scaffolds revealed a better swelling rate for n‐HAP/CS/PEG. Also n‐HAP/CS/PEG showed higher mechanical strength relative to n‐HAP/CS supportive of bone tissue ingrowths. Copyright © 2014 John Wiley & Sons, Ltd.     

羟基磷灰石/丝素蛋白复合纤维的制备及其矿化研究

在以静电纺丝法制备羟基磷灰石(HAP)/丝素蛋白(SF)复合纤维的前提下, 采用同轴共纺法获得了以HAP为“芯”、SF为“皮”的双组分电纺纤维(电纺膜), 并通过扫描和透射电镜、红外光谱以及X射线衍射等手段对电纺纤维进行了表征. 结果表明, HAP均存在于上述两种方法制备的纳米纤维中, 但同轴共纺法不仅可以避免HAP/SF共混电纺时pH值对丝素蛋白结构的影响, 并且能大大提高电纺膜中HAP的含量. 同时, 我们还分别以SF纤维、HAP/SF复合纤维和HAP/SF“皮-芯”纤维作为有机基质, 对羟基磷灰石在其上的矿化过程进行了探索, 结果表明含较多羟基磷灰石的HAP/SF“皮-芯”纤维更有利于矿化的进行.     

Roles of amorphous calcium phosphate and biological additives in the assembly of hydroxyapatite nanoparticles

Potential mechanisms for formation of highly organized biomineralized structures include oriented crystal growth on templates, the aggregation of nanocrystals by oriented attachment, and the assembly of inorganic nanoparticles mediated by organic molecules into aggregated structures. In the present study, the potential role of amorphous calcium phosphate (ACP) in facilitating the assembly of hydroxyapatite (HAP) nanoparticles into highly ordered structures was evaluated. The physical characteristics of HAP nanoparticles prepared by three different methods were analyzed after extended exposure to additives in solution. Higher order HAP architecture was detected only when the starting particles were aggregates of nanospheres with HAP cores and ACP shells. Enamel-like HAP architecture was produced when the biologic additive was 10 mM glycine or 1.25 microM amelogenin. Large platelike crystals of the type present in bone were induced when the additive was 10 mM glutamic acid. Surface ACP initially links the HAP nanoparticles in a way that allows parallel orientation of the HAP nanoparticles and then is incorporated into HAP by phase transformation to produce a more highly ordered architecture with features that are characteristic for HAP in biologic structures. These studies provide evidence for a new mechanism for assembly of biominerals in which ACP functions by linking HAP nanocrystals while they assume parallel orientations and then is incorporated by phase transformation into HAP molecules that rigidly link HAP nanocrystals in larger fused crystallites. Biologic molecules present during this process of biomineral assembly specifically regulate the assembly kinetics and determine the structural characteristics of the final HAP architecture.     

Self-assembled histidine acid phosphatase nanocapsules in ionic liquid [BMIM][BF4] as functional templates for hollow metal nanoparticles

We report the biomacromolecular self-assembly of histidine acid phosphatase (HAP), an enzyme of significant biomedical and industrial importance, in the ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF(4)]). The spontaneous self-assembly of HAP enzyme in [BMIM][BF(4)] results in the formation of HAP nanocapsules. The HAP enzyme molecules were found to retain their enzymatic activity after the self-assembly process, which enabled us to utilize self-assembled HAP capsules as self-catalyzing templates for the synthesis of a range of hollow metal nanoparticles (Au, Ag, Pd, and Ni) without employing any additional reducing agent. The hollow metal nanospheres with HAP encapsulated within their cavity were found to retain enzymatic activity for at least up to four cycles, as demonstrated in the case of Au-coated HAP capsules as the model system.     

羟基磷灰石表面改性的研究进展

羟基磷灰石（HAP）由于其良好的生物相容性及骨诱导作用而被广泛应用于生物复合材料中。但是,其本身容易聚集,与聚合物之间相容性差,会导致复合材料的力学性能和生物学性能下降。在HAP表面改性既可以有效防止颗粒间的聚集,增强其与基体间的相互作用,同时,还可以通过接上具有特殊功能的聚合物,赋予HAP新的用途。本文综述了羟基磷灰...     

Solvothermal Transformation of a Calcium Oleate Precursor into Large‐Sized Highly Ordered Arrays of Ultralong Hydroxyapatite Microtubes

Hydroxyapatite (HAP), a well‐known member of the calcium phosphate family, is the major inorganic component of bones and teeth in vertebrates. The highly ordered arrays of HAP structures are of great significance for hard tissue repair and for understanding the formation mechanisms of bones and teeth. However, the synthesis of highly ordered HAP structure arrays remains a great challenge. In this work, inspired by the ordered structure of tooth enamel, we have successfully synthesized three‐dimensional bulk materials with large sizes (millimeter scale) that are made of highly ordered arrays of ultralong HAP microtubes (HOAUHMs) by solvothermal transformation of calcium oleate precursor. The core–shell‐structured oblate sphere consists of a core that is composed of HAP nanorods and a shell that consists of highly ordered HAP microtube arrays. The prepared HOAUHMs are large: 6.0 mm in diameter and up to 1.4 mm in thickness. With increasing solvothermal reaction time, the HOAUHMs grow larger; the microtubes become more uniform and more ordered. This work provides a new synthetic method for synthesizing highly ordered arrays of uniform HAP ultralong microtubes that are promising for biomedical applications.     

Comparative study of particle size analysis of hydroxyapatite-based nanomaterials

The purpose of this work was to compare hydroxyapatite (HAP) and composites of HAP, HAP with chitosan (CS), and HAP with poly(vinyl pyrrolidone) (PVP), in terms of their particle size and morphology, using different methods, such as Coulter counter analysis, X-ray diffraction (XRD), and transmission electron microscopy (TEM). Although many researchers have studied HAP and CS/HAP and PVP/HAP composites extensively, there is no evidence of a comparative study of their particle sizes. For this reason, different complementary methods have been used so as to provide a more complete image of final product properties — particle size — from the perspective of possible applications. The syntheses of HAP and HAP with polymer nanoparticles were carried out employing a precipitation method. Variation in particle size with synthesis time and influence of the reactants’ concentration on the materials’ preparation were systematically explored. Crystallite size calculated from XRD data revealed nanosized particles of HAP, CS/HAP, and PVP/HAP materials in the range of 2.5–9.2 nm. Coulter counter analysis revealed mean particle sizes of one thousand orders of magnitude larger, confirming that this technique measures agglomerates, not individual particles. In addition, the particles’ morphology and an assessment of their binding mode were completed by TEM measurements.     

Highly Flexible and Nonflammable Inorganic Hydroxyapatite Paper

A highly flexible and nonflammable inorganic hydroxyapatite (HAP) paper made from HAP ultralong nanowires is reported. The paper can be used for printing and writing and is promising for the permanent and safe storage of information, such as archives and important documents. The HAP paper is also an excellent and recyclable adsorbent for organic pollutants.     

分子动力学研究亚铁血红素激活蛋白转录激活机理

以3种亚铁血红素激活蛋白(Heme activator protein, HAP)-DNA 复合物(野生型HAP1-wt, Ser63/Arg63突变HAP1-18 和 Ser63/Gly63突变HAP1-PC7)为对象对亚铁血红素激活蛋白的转录激活机理进行了分子动力学研究. 对3个复合物分子动力学轨迹的比较性分析显示, 涉及到上游活化序列(Upstream activation sequences, UAS)识别的蛋白质-DNA 相互作用分布与实验观测到的3种蛋白转录活性一致. 进一步对3个复合物进行柔性分析显示, 3个DNA分子具有相似的柔性, 而又有所不同, 特别在涉及UAS识别的N-端和Zn2Cys6结构域前部有明显的柔性差异. 蛋白质柔性的差别导致不同的蛋白质-DNA相互作用. 因此亚铁血红素激活蛋白的N-端和Zn2Cys6结构域前部的柔性大小能够调节亚铁血红素激活蛋白转录激活功能.     

Preparation of poly(methyl methacrylate) grafted hydroxyapatite nanoparticles via reverse ATRP

Surface-initiated reverse atom transfer radical polymerization (reverse ATRP) technical was successfully employed to modify hydroxyapatite (HAP) nanoparticles with poly(methyl methacrylate) (PMMA). The peroxide initiator moiety for reverse ATRP was covalently attached to the HAP surface through the surface hydroxyl groups. Reverse ATRP of methyl methacrylate (MMA) from the initiator-functionalized HAP was carried out, and the end bromide groups of grafted PMMA initiated ATRP of MMA subsequently. Fourier transformation infrared (FTIR) spectroscopy, thermal gravimetric analysis (TGA) and transmission electron microscopy (TEM) were employed to confirm the grafting and to characterize the nanoparticle structure. The grafted PMMA gave HAP nanoparticles excellent dispersibility in MMA monomer. As the amount of grafted PMMA increased, the dispersibility of surface-grafted HAP and the compressive strength of HAP/PMMA composites were improved.     

Chicken Bone as a Bioresource for the Bioceramic (Hydroxyapatite)

Natural hydroxyapatite (HAP) is isolated from waste chicken bone by thermal calcinations at different temperatures in the range of 200 °C to 1000 °C. The isolated HAP has been characterized using thermo gravimetric analysis (TG) and differential thermal analysis (DTA), Fourier Transformed Infrared spectroscopy (FTIR), X-ray diffraction (XRD), field emission electron microscope (FE-SEM), and energy dispersive X-ray (EDX). The XRD results showed that the enhanced crystallinity of HAP phase by thermal calcination above 600 °C and the crystal size has been found to increase with increasing temperature of thermal calcinations due to agglomeration. Value addition for the waste chicken bone is given by the isolation of useful bioceramics (HAP) and the optimum temperature for the thermal calcination is found to be 600 °C. The isolated HAP has been characterized as carbonated HAP of B type with the hexagonal structure. These results will not only make the chicken bone as an important bioresource for the HAP but will also reduce the environmental pollution caused by dumping of the waste chicken bone.     

Zinc-Containing Polymers and Their Latexes: Structure and Properties

This work deals with the polymer latexes synthesized using zinc-containing monomers. The effect of the ligand environment of the zinc-containing monomers on the colloidal and rheological properties of the latexes, as well as on mechanical properties of their films is studied. Mixed zinc salts containing the residues of saturated and unsaturated carboxylic acids are shown to be more efficient cross-linking agents than the symmetric salts of this metal.     

预处理对丝素蛋白膜调控羟基磷灰石晶体生长的影响

以丝素蛋白膜为基质, 在模拟体液中诱导羟基磷灰石晶体在其表面沉积和生长. 利用XRD, SEM, HRTEM, AFM和FTIR等表征手段研究了不同预处理方法对羟基磷灰石晶体的形成及其微观形貌的影响. 结果表明, 丝素膜可有效地诱导羟基磷灰石晶体在其表面沉积和生长; 较长的矿化时间有利于形成较多结晶度良好的HAP晶体; 而不同预处理方法对丝素膜的表面结构产生了不同影响, 进而调制在其表面沉积的羟基磷灰石的形貌和生长方向. 同时对丝素蛋白膜调控羟基磷灰石晶体生长的机制进行了必要的探讨.     

Mechanism and kinetics of uric acid adsorption on nanosized hydroxyapatite coating

Uric acid (UA) produced from purine metabolism is rather harmful to human health when its concentration is high. To better understand the application of hydroxyapatite (HAP) as an adsorbent for UA removal, quartz crystal microbalance (QCM) technique was employed to in situ investigate the adsorption behavior of UA on nanosized HAP coatings. This work was mainly focused on the mechanism and kinetics of UA adsorption. The obtained results showed that nanosized HAP coatings produced physical adsorption for UA, and the driving force of UA adsorption on HAP coatings was electrostatic interaction. The adsorption kinetic parameter estimated from the in situ frequency measurement was about 3.08?×?10⁶?L/mol. The obtained information suggests that QCM measurement provides a useful method for monitoring the interaction between HAP and UA.     

Interaction between low molecular weight organic acids and hydroxyapatite with different degrees of crystallinity

In this study, two types of hydroxyapatite (HAP) with different degrees of crystallinity were prepared by a sol-gel method and a chemical precipitation method. Influences of crystallinity on the adsorption and dissolution properties of HAP, and the release of phosphorus (total phosphorus) during the adsorption of organic acid were investigated. Results showed that crystallinity had a great effect on the adsorption capacity and dissolution properties of HAP, as well as the adsorption mechanisms of organic acids on HAP surfaces. The poorly crystallized (the degree of crystallinity X_c = 0.23) HAP adsorbed greater amounts of oxalic, citric, or malic acid than the well crystallized (X_c = 0.86) HAP, and the former could release more phosphorus in the presence of organic acids. The adsorption capacity of oxalic acid was much higher than citric and malic acids on both the well and the poorly crystallized HAP, which was due to the strong coordination of oxalic acid with calcium on HAP surface, and that physical adsorption was more inclined to dominate the adsorption of malic or citric acid on the well crystallized HAP. These findings might be of importance in understanding the effects of crystallinity and organic acid binding on the dissolution of calcium phosphates and the adsorption characteristics of HAP.     

电化学沉积制备羟基磷灰石涂层及机理研究

控制电沉积溶液中钙 /磷离子的浓度 ,在钛合金表面直接沉积羟基磷灰石 (HAP)陶瓷涂层 .XRD、SEM实验证实 ,制备的HAP晶粒完整 ,粒度均匀 .热力学计算表明HAP比TCP更易于生成 .文中讨论了羟基磷灰石 (HAP)涂层电沉积的机理 ,指出电沉积是一个二步过程 ,HAP的形成是从溶液中离子到固体的直接过程 ,没有前驱体的生成     

Microemulsion synthesis of hydroxyapatite nanomaterials and their adsorption behaviors for Cr<Superscript>3+</Superscript> ions

Hydroxyapatite (HAP) nanoparticles with different morphologies, such as nanorods, nanospheres, and their mixtures were successfully synthesized by microemulsion method with soluble additive. Their adsorption capacity for Cr³⁺ ion was investigated. Most of the Cr³⁺ were absorbed by HAP within 60 min. The adsorption capacity of the HAP nanospheres was the best, and the maximum Cr³⁺ removal ratio was 96.4%, revealing that the metal ions adsorption by HAP is dependent on the morphology of its particles.     

Microwave-Assisted Hydrothermal Rapid Synthesis of Ultralong Hydroxyapatite Nanowires Using Adenosine 5′-Triphosphate

Ultralong hydroxyapatite (HAP) nanowires are promising for various biomedical applications owing to their chemical similarity to the inorganic constituent of bone, high biocompatibility, good flexibility, excellent mechanical properties, etc. However, it is still challenging to control the formation of ultralong HAP nanowires because of the presence of free PO₄³⁻ ions in the reaction system containing the inorganic phosphate source. In addition, it takes a long period of time (usually tens of hours) for the synthetic process of ultralong HAP nanowires. Herein, for the first time, we have developed an eco-friendly calcium oleate precursor microwave hydrothermal method using biocompatible adenosine 5′-triphosphate (ATP) as a bio-phosphorus source and water as the only solvent for the rapid synthesis of ultralong HAP nanowires. The controllable hydrolysis of ATP can avoid the premature formation of calcium phosphate nuclei and uncontrollable crystal growth. Microwave heating can significantly shorten the synthetic time from tens of hours required by the traditional heating to 1 h, thus achieving high efficiency, energy saving and low cost. The as-prepared ultralong HAP nanowires with high flexibility have lengths of several hundred micrometers and diameters of 10~20 nm, and they usually self-assemble into nanowire bundles along their longitudinal direction. The as-prepared ultralong HAP nanowire/chitosan porous scaffold has excellent bioactivity, good biodegradation and cytocompatibility owing to the bioactive adenosine adsorbed on the surface of ultralong HAP nanowires. It is expected that ultralong HAP nanowires will be promising for various applications in the biomedical fields, such as bone defect repair, skin wound healing, and as a drug nanocarrier.     

Investigations of gold nanoparticles-mediated carbon nanotube reinforced hydroxyapatite composite for bone regenerations

An excellent combination of biomaterials permits prompt features and high-throughput investigations in various fields, particularly in the biomedical applications. This article investigates the bone regeneration ability and compatibility of the Gold (Au) Nanoparticles (NPs) medicated carbon nanotube reinforced hydroxyapatite (HAP) composite. The morphologies of the synthesized Au NPs, HAP and HAP/CNT, and HAP/CNT-Au composites vary suggestively with modifying the components and the final composite showing as bone mimic extracellular matrix morphology. The structure, phase, and composition of the as-synthesized HAP were studied by FTIR, XRD, EDAX, and TEM techniques. The materials' biocompatibility was investigated in the Stimulated Body Fluid (SBF) solution, which resulted in the composite having good biocompatibility, bioactivity nature and hydroxyapatite layer formed on the composite surface. The composite shows good viability with Adipose Tissue-derived Stem Cells (ADSC) to cell growth and cell proliferation in the biological evaluation. It represented the composites having a good ability for cell formation development. Since the HAP/CNT-Au composite are useful in medicinal applications such as orthopedic and orthodontic repair/regenerations after the evaluations of animal and clinical investigations.