Enzymatic hydroxyapatite as a carrier for yttrium-90 and copper and ruthenium radionuclides

The use of hydroxyapatite obtained by enzymatic synthesis (HAP_E) as a carrier of radionuclides (yttrium-90, copper(II) as a prototype of ⁶⁴Cu and ⁶⁷Cu and ruthenium-103 as a prototype of ⁹⁷Ru) is considered. The processes of sorption and desorption of ions in different solutions are compared. The sorption of copper and yttrium on HAP_E is almost irreversible, in contrast to the sorption of ruthenium, for which the reverse process depends on the medium.     

Synthesis and characterization of nanocrystalline hydroxyapatite and its catalytic behavior towards synthesis of 3,4‐disubstituted isoxazole‐5(4H)‐ones in water

In the present work, the nanocrystalline particles of hydroxyapatite (HAp) using an easy alkoxide‐based sol–gel technique including triethyl phosphate [PO (OC₂H₅)₃] and Ca (NO₃)₂·4H₂O as P and Ca precursors have been synthesized. The sample characterization was performed by X‐ray diffraction, Fourier transform‐infrared analysis, scanning electron microscopy, thermal analysis (thermogravimetric analysis/differential thermal analysis), and elemental analysis of energy‐dispersive X‐ray analysis. It is interesting that single phase of HAp was obtained at a low firing temperature of 500 ° C. Modified Scherrer equation as the Williamson?Hall method was applied for the measurement of crystallite size distributions and micro‐strain of the sample. The determined crystallite size by complementary technique of transmission electron microscopy has good consistency with those obtained from the Scherrer formula. Moreover, we reported the one‐pot synthesis of 3,4‐disubstituted isoxazole‐5(4H)‐ones through the aqueous solution reaction of three components of ethyl acetoacetate, hydroxylamine hydrochloride and various aromatic aldehydes at room temperature. This protocol offers several advantages, including a simple work‐up procedure, very short reaction times (under 25 min), in accordance with the principles of green chemistry, recyclability, excellent yields (87–98%) and environmentally friendly.     

溶胶凝胶模板法制备羟基磷灰石纳米线

以氯化钙和五氧化二磷的醇溶液为前驱体溶液,多孔阳极氧化铝(AAO)膜为模板,通过溶胶凝胶-模板法成功制备出羟基磷灰石(Ca10(PO4)6(OH)2,HAP)纳米线;利用扫描电镜、能量色散谱仪、透射电镜、X射线衍射仪及傅立叶变换红外光谱仪等分析了产物的组成和微结构;并讨论了纳米线的生长机理.结果表明,所制备的羟基磷灰石纳米线直径约为50nm、长度达20μm,分别与模板的孔径和厚度一致.     

非化学计量羟基磷灰石骨水泥的制备及性能研究

采用磷酸四钙和磷酸氢钙混合粉末制备了nCa/nP比为1.58的非化学计量羟基磷灰石骨水泥(n-HAC)及其多孔支架材料。结果表明:与nCa/nP=1.67的化学计量羟基磷灰石骨水泥(HAC)相比,n-HAC的凝结时间和抗压强度没有明显的区别。XRD和IR显示:n-HAC与HAC都为羟基磷灰石结构,但n-HAC在Tris-HCl缓冲溶液的降解性明显大于HAC。细胞培养结果表明:成骨细胞在n-HAC和HAC两种材料上的粘附和细胞形态没有明显的区别,但细胞在n-HAC上的增殖率明显高于HAC。将多孔n-HAC支架材料植入兔股骨缺损处,观察其修复骨缺损情况,组织学分析结果表明:新生骨在多孔支架的表面形成,并长入其内部;n-HAC在体内的降解比HAC快,能明显地促进新骨生成。     

Argon laser induced changes to the carbonate content of enamel

Argon laser irradiation can be used to cure orthodontic brackets onto teeth in significantly less time than conventional curing lights. In addition, it has been shown that the argon laser seems to impart a demineralization resistance to the enamel. The purpose of this study was to use surface science techniques to ascertain if this demineralization resistance is possibly a result of a decrease in the carbonate content of enamel. Eleven mandibular third molars previously scheduled for extraction were collected and used in the present study. The teeth were sectioned in two and randomly assigned to either the argon laser (457-502 nm; 250 mW cm⁻²) or the control (no treatment) group. The sections assigned to the argon laser group were cured for 10 s and analyzed. To exaggerate any potential changes the experimental sections were then exposed to a further 110 s of argon laser irradiation. Surface analysis was performed using X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The results showed no statistically significant change in the carbonate content of enamel after argon laser irradiation (p > 0.05). Thus, it is suggested that any demineralization resistance imparted to the enamel surface by argon laser irradiation is not due to alterations in carbonate content.     

旋涂法制备聚乳酸基聚酯复合膜的生物学评价

以旋涂法制备的聚乳酸（PLA）、聚丙交酯己内酯（PLCL）、聚乳酸-羟基磷灰石（PLA-HA）、聚丙交酯己内酯-羟基磷灰石（PLCL-HA）膜为功能性骨组织工程支架材料引导组织再生膜,用小鼠颅骨前成骨细胞系作为组织工程种子细胞,进行了平面细胞培养,通过四唑类化合物（MTS）比色法细胞活性定量检测、二乙酸荧光素（FDA）膜染色等研究了基材对成骨细胞的黏附、增殖以及矿化的影响;通过光学显微镜和荧光显微镜进行了细胞形态的观察。结果表明：HA对细胞的黏附和增殖有积极的作用,旋涂膜上的细胞进入增殖晚期和矿化期后性质更为稳定。     

Microdeformation in Poly-L-lactide and Poly-L-lactide + Hydroxyapatite Nanocomposite Thin Films

In order to gain new insight into failure mechanisms in poly-L-lactide (PLLA) and PLLA + hydroxyapatite nanocomposites, transmission electron microscopy has been used to investigate room temperature microdeformation in electron transparent thin films of these materials subjected to various heat treatments and deformed in tension using the “copper grid” technique. In amorphous PLLA the dominant microdeformation mechanism was crazing. Localized fibrillar deformation zones (DZs) were also observed in semicrystalline films, tending to propagate in regions where the lamellar trajectories were at high angles to the tensile axis. Thus, in spherulitic films, in which the lamellae formed well-defined stacks with approximately straight trajectories at the scale of the spherulite radii, individual DZs were observed to propagate over relatively large distances, as in the amorphous films. On the other hand, films cold crystallized by heating from the glassy state showed more homogeneous lamellar textures. These were associated with a relatively high density of low aspect ratio DZs. Addition of well dispersed nanosized hydroxyapatite (nHA) to the amorphous PLLA films was also found to result in an increase in the craze density, attributed to stress concentrations associated with void formation at the PLLA-particle interfaces during deformation. However, interpretation was less straightforward in cold crystallized PLLA + nHA thin films, owing to a correlation between the lamellar texture and the nHA particles. In this case, both void formation and favorable lamellar orientations may have contributed to initiation of the DZs in the vicinity of the particles. The results are argued to be broadly consistent with previous observations of the behavior of bulk PLLA and PLLA + nHA films with a range of microstructures, in which there was evidence for an improvement in ductility in the presence of the nHA, again attributed to voiding at the PLLA-particle interfaces.     

Microwave assisted synthesis of hydroxyapatite nano strips

Synthesis of hydroxyapatite (HAP) nano strips was carried out by chemical precipitation method followed by microwave irradiation. The microwave assisted reactions proceed at fast rates. It is found that the presence of the complex reagent EDTA plays an important role in the morphological changes of nanostructure hydroxyapatite. EDTA acts as a hexadentate unit by wrapping itself around the Ca²⁺ metal ion with, four oxygen and two nitrogen atoms and forms several five member chelate rings. The relative specific surface energies associated with the facets of the crystal determines the shape of the crystal. Scanning electron microscopy revealed the presence of hydroxyapatite nano strips with the range 50‐100 nm in EDTA influenced HAP powders. Fourier transform‐infrared spectroscopy (FT‐IR) result combined with the X‐ray diffraction (XRD) indicates the presence of amorphous hydroxyapatite (HAP) in the as‐prepared material. X‐ray patterns collected on the powder after heat‐treatment at 1100 °C for 2 h in air exhibits single phase of HAP. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Bone‐nanohydroxyapatite spheres interface evaluation by synchrotron radiation X‐ray microfluorescence

Hydroxyapatite (HA) is largely used as bone graft; it seems to be the most promising synthetic implant material, mainly because of its excellent biocompatibility. The crystallinity, particle and pore size of HA are important characteristics and can be modified by decreasing basic structural form below 100 nm and have evoked a great amount of attention for improving prevention, diagnosis, and disease treatment, besides improving bone repair through the biodegradation of the material. The aim of this study was to investigate bone mineral content in bone samples with nanohydroxyapatite and HA spheres, specially its spatial distribution on bone microarchitecture. Circular bone defects were made in both tibiae of 12 White New Zeland adult rabbits (Oryctolagus cuniculus) and were divided randomly into five groups – blood clot (control group), sintered HA, non‐sintered HA, sintered nanoHA and non‐sintered nanoHA – all materials in spherical shape, to smooth handling and accommodation of the surgical bed, and to minimize inflammatory response. The rabbits were euthanatized according to the experimental period of 1 and 4 weeks after surgery. The samples were evaluated by polarized microscopy as well as X‐ray microfluorescence in order to account the bone mineral content bone‐implant interfaces, through synchrotron radiation. Our results revealed greater newly formed bone area in the non‐sintered materials and control groups, and the used technique showed that the amount of calcium of new bone was consistent with both mature bone and HA spheres. In conclusion, the present findings suggest that HA‐based biomaterials are biocompatible, promote osteoconduction and favored bone repair. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis and evaluation of new phosphonic acid‐functionalized acrylamides with potential biomedical applications

Phosphorus‐containing acidic monomers are able to interact with the inorganic phase of mineralized tissues such as enamel, dentin, and bone. From this perspective, three phosphonic acid‐containing acrylamide monomers with different lengths of alkyl chains were synthesized to be used for both self‐etching dental adhesives and mineralized hydrogel scaffolds. Monomers were synthesized by the reaction of α‐aminophosphonates (diethyl aminomethylphosphonate, diethyl 2‐aminobutan‐2‐ylphosphonate, and diethyl 2‐aminooctan‐2‐ylphosphonate) with acryloyl chloride followed by the hydrolysis of phosphonate groups by using trimethylsilyl bromide. The properties such as pH in the range of mild self‐etching adhesives, hydrolytic stability, high rate of copolymerizations with 2‐hydroxyethyl methacrylate (HEMA) and HEMA/glycerol dimethacrylate, giving high‐molecular‐weight polymers on thermal polymerization, and strong decalcification ability of hydroxyapatite make these monomers good candidates for self‐etching adhesives, although no appreciable effect of the number and size of the α‐substituents was observed. Hydrogel scaffolds containing phosphonic acid groups were fabricated, characterized, and mineralized. Altogether, the results suggest that these phosphonic acid‐containing monomers have suitable properties to be used in fabrication of biomaterials for both dental and bone tissue engineering applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2755–2767