纳米结构羟基磷灰石的微波固相合成新方法

本文报道了一种简单的室温下微波辅助合成羟基磷灰石(HAP)的新方法。与常规方法相比，该方法具有反应条件温和、反应时间极短的优点。合成中，以Ca(NO₃)₂·4H₂O和Na₃PO₄·12H₂O为原料，经过研磨和微波加热得到了HAP纳米粒子和纳米棒。用XRD、FTIR，BET和SEM等对产物进行了表征。在反应过程中，微波辐射作为一种加热处理手段对HAP的形成起到非常重要作用。同时     

骨及生物材料中的纳米磷酸钙

纳米磷酸钙在自然界骨组织的形成过程中起到了关键作用。尽管骨的类型有所不同,但在其初级结构中的无机成分都是纳米磷酸钙。纳米磷酸钙结构能够给予骨良好的机械性能和生物学活性。在生物体中,无机纳米磷酸钙在有机基质的调控下能定向自组装成特定的生物矿物。体外细胞实验显示小尺寸纳米羟基磷灰石更能促进骨髓基质干细胞的增殖,而同尺寸的结晶型纳米磷酸钙则比无定形磷酸钙更能利于干细胞分化。鉴于纳米磷酸钙具有很好的生物相容性和骨诱导性,可以发展成为理想的生物材料常用于骨组织工程和生物医学。     

骨及生物材料中的纳米磷酸钙

纳米磷酸钙在自然界骨组织的形成过程中起到了关键作用。尽管骨的类型有所不同,但在其初级结构中的无机成分都是纳米磷酸钙。纳米磷酸钙结构能够给予骨良好的机械性能和生物学活性。在生物体中,无机纳米磷酸钙在有机基质的调控下能定向自组装成特定的生物矿物。体外细胞实验显示小尺寸纳米羟基磷灰石更能促进骨髓基质干细胞的增殖,而同尺寸的结晶型纳米磷酸钙则比无定形磷酸钙更能利于干细胞分化。鉴于纳米磷酸钙具有很好的生物相容性和骨诱导性,可以发展成为理想的生物材料常用于骨组织工程和生物医学。     

级次纳米结构材料及其液相合成

级次纳米结构材料因其新颖的结构,独特的化学、物理性质,以及形貌和尺寸对这些性质极大地影响,使得它在光、电、磁等方面的性质更加丰富, 为实现由下到上构建纳米器件提供了坚实的基础。由此级次纳米结构材料引起化学家和材料学家的极大兴趣, 成为纳米材料化学领域中引人注目的研究方向之一。本文综述了近年来国内外级次纳米结构材料的最新研究进展,重点介绍了介孔材料、具有级次结构的空心球、气凝胶和其他典型的级次纳米结构,归纳了级次纳米结构制备中的各种液相合成方法及其特点,讨论了级次纳米结构的合成机制及各种影响因素,并在此基础上对级次纳米结构材料在一些领域的应用前景进行了展望。     

微波辅助离子液体法在液相合成中的应用

作为一种新型的绿色化学合成方法,微波辅助离子液体法融合了离子液体与微波加热法的优点,具有合成快速、操作简便、产率高,绿色环保等特点,在液相合成方面体现出明显的优势。本文综述了离子液体作为微波吸收剂在液相有机合成、无机纳米材料合成方面的研究进展,对比分析了微波辅助离子液体法同多种传统方法的应用效果,阐明了该方法的优势,并展望该领域今后的发展方向。     

微波固相合成氧化锌纳米棒

通过前驱体的微波固相热分解法快速合成了氧化锌纳米棒, 其直径在60～385 nm之间, 长可达数微米. 前驱体则通过一步室温固相反应制备. 用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、能量色散X射线分析(EDX)和透射电子显微镜(TEM)对产物的结构和形貌进行了表征. 同时, 对氧化锌纳米棒的光致发光(PL)性能作了测试, 结果表明在355 nm处有一个明显的近带隙发射峰. 另外, 对比实验表明, 微波辐射在氧化锌纳米棒的形成过程中起了关键性作用, 并对其形成机理进行了初步探讨.     

微波辅助RGD环肽的固相合成

以2-氯代三苯甲基氯树脂为载体，采用Fmoc/t-Bu/Dmab正交保护策略，在微波辅助下合成了环肽c(fKRGD)，收率22.5%，纯度94.5%，其结构经MS(ESI), MS(MALDI-TOF)和HPLC确证。     

磷酸钙陶瓷颗粒微纳米结构对蛋白吸附的影响

用微波烧结和常规烧结方法分别制备了4种具有纳米和微米结构的磷酸钙陶瓷, 对陶瓷的相组成、 微观结构、 粒度分布、 比表面积、 孔径分布和表面Zeta电位进行了对比分析, 并进一步采用凝胶电泳法考察了陶瓷对牛血清白蛋白/溶菌酶双蛋白的吸附行为. 结果显示, 纳米陶瓷和常规陶瓷具有相似的相组成、 颗粒分布和表面Zeta电位, 但微孔结构、 比表面积和蛋白吸附差异明显. 纳米陶瓷具有较小的晶粒尺寸和更丰富的介孔结构, 使其能吸附更多的牛血清白蛋白和溶菌酶, 表明其具有更强的生物活性.     

微波辅助固相合成胸腺五肽的研究

在胸腺五肽的固相合成中, 引入微波辅助技术, 深入研究了微波作用下缩合试剂、溶剂、反应物浓度、反应时间和温度对产率的影响. 与传统方法相比, 微波将缩合反应速率提高了15倍以上, 氨基酸过量倍数也从传统的三倍降低到过量一倍, 减少胸腺五肽的合成成本约40%; 最终得到以吡啶/DMF为溶剂, 苯并三氮唑-N,N,N',N'-四甲基脲六氟磷酸酯为缩合试剂, 反应物浓度为0.113 mmol/L, 反应时间为4 min, 反应温度为20 ℃为最佳反应条件, 此时胸腺五肽的产率最高, 为88.7%.     

微波辐射下纳米水滑石的合成

在微波辐射下用变速滴加共沉淀法合成了粒径为10 nm~40 nm的Mg-A l纳米水滑石(nano-HT),其结构经XRD,TEM,TG和元素分析表征。以nano-HT为载体,制备了Cu/nano-HT和CuN i/nano-HT催化剂,通过苯酚羟基化反应考察了它们的催化活性,实验结果表明,双氧水有效利用率和产物的选择性均比以常规水滑石为载体的催化剂高。     

空心纳米磷酸钙载药体系的制备与表征

非离子表面活性剂Tween 80和PEG 6000在水溶液中以一定的比例混合可形成稳定的类磷脂囊泡结构,这些囊泡可以作为模板来合成磷酸钙纳米空球颗粒。所制备的磷酸钙材料的结构和形貌通过TEM,SEM,FTIR,XRD进行了表征,是尺寸为100～150 nm左右的无定形磷酸钙空心颗粒。磷酸钙具有良好的生物相容性,因此这些具有空心结构特征的磷酸钙可发展为理想的载药体系。我们以牛血清蛋白(BSA)为模型体系研究了材料的载药和释放性能,发现所获得的空心纳米磷酸钙不仅具有良好的蛋白质负载量而且还具有优异的可释放性,明显优于传统的羟基磷灰石体系。     

Highly Stable Amorphous Calcium Phosphate Porous Nanospheres: Microwave‐Assisted Rapid Synthesis Using ATP as Phosphorus Source and Stabilizer,and Their Application in Anticancer Drug Delivery

Highly stable amorphous calcium phosphate (ACP) porous nanospheres with a relatively uniform size and an average pore diameter of about 10 nm have been synthesized by using a microwave‐assisted hydrothermal method with adenosine 5′‐triphosphate disodium salt (ATP) as the phosphorus source and stabilizer. The as‐prepared ACP porous nanospheres have a high stability in the phosphate buffer saline (PBS) solution for more than 150 h without phase transformation to hydroxyapatite, and the morphology and size were essentially not changed. The important role of ATP and effects of experimental conditions on the formation of ACP porous nanospheres were also investigated. The ACP porous nanospheres were characterized by X‐ray powder diffraction (XRD), Fourier‐transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). This method is facile, rapid, surfactant‐free and environmentally friendly. The as‐prepared ACP porous nanospheres are efficient for anticancer drug (docetaxel) loading and release. The ACP porous nanosphere drug‐delivery system with docetaxel shows a high ability to damage tumor cells, thus, is promising for the application in anticancer treatment.     

Biological and Medical Applications of Calcium Phosphate Nanoparticles

Calcium phosphate nanoparticles have a high biocompatibility and biodegradability due to their chemical similarity to human hard tissue, for example, bone and teeth. They can be used as efficient carriers for different kinds of biomolecules such as nucleic acids, proteins, peptides, antibodies, or drugs, which alone are not able to enter cells where their biological effect is required. They can be loaded with cargo molecules by incorporating them, unlike solid nanoparticles, and also by surface functionalization. This offers protection, for example, against nucleases, and the possibility for cell targeting. If such nanoparticles are functionalized with fluorescing dyes, they can be applied for imaging in vitro and in vivo. Synthesis, functionalization and cell uptake mechanisms of calcium phosphate nanoparticles are discussed together with applications in transfection, gene silencing, imaging, immunization, and bone substitution. Biodistribution data of calcium phosphate nanoparticles in vivo are reviewed.     

电流密度对钙磷沉积层组成和结构的影响(英文)

用X射线衍射、激光拉曼光谱以及等离子体原子发射光谱等技术研究了电化学沉积钙磷陶瓷过程中 ,电流密度对电沉积层组成和结构的影响 .实验表明阴极表面得到的沉积物是几种钙磷盐组成的混合物 ,且其成份随电流密度的改变而发生较大的变化 .在电解液温度为 75℃条件下 ,当控制电流密度较低时 ,沉积层主要由CaHPO4· 2H2 O (DCPD)和Ca8H2 (PO4) 6· 5H2 O (OCP)组成 ;随着电流密度的增加 ,阴极表面逐渐生成Ca3 (PO4) 2 ·nH2 O (TCP)和Ca10 (PO4) 6(OH) 2 (HAP) .当电流密度大于 5mA/cm2 时 ,电沉积层的主要成份为羟基磷灰石 (HAP) .     

Calcium Phosphate Nanocarriers Dual‐Loaded with Bovine Serum Albumin and Ibuprofen: Facile Synthesis,Sequential Drug Loading and Sustained Drug Release

A simple and green strategy is reported for the preparation, drug loading, and release properties of a drug delivery system consisting of calcium phosphate (CP) nanocarriers dual‐loaded with bovine serum albumin (BSA) and hydrophobic drug ibuprofen (IBU). The sequential loading of BSA and IBU in calcium phosphate nanocarriers and in vitro simultaneous release of BSA and IBU are realized and investigated. In this method, BSA, which is used as a model protein drug, is encapsulated in situ in calcium phosphate nanocarriers. Subsequently, the typical hydrophobic drug IBU is loaded in the BSA/CP drug delivery system, forming the IBU/BSA/CP dual drug delivery system. The experiments reveal that the preloaded BSA not only reduces the cytotoxicity of calcium phosphate nanocarriers but also significantly improves the IBU drug loading capacity in calcium phosphate nanocarriers and greatly extends the duration of drug release. Thus, the as‐prepared IBU/BSA/CP dual drug delivery system is promising for drug delivery applications.     

Inorganic–Organic Hybrid Nanoparticles with Biocompatible Calcium Phosphate Thin Shells for Fluorescence Enhancement

Polymeric micelles consisting of asymmetric triblock copolymers were successfully used for fabrication of robust hybrid nanoparticles with highly biocompatible calcium phosphate shells. The hydrophobic polystyrene core encapsulates hydrophobic fluorescent dyes such as Nile red. The anionic polyacrylic acid provides the site for the mineralization reaction of calcium phosphate. The polyethylene glycol corona stabilizes the hybrid nanoparticles. Fluorescent dyes can be used as imaging agents for determining the location of the nanoparticles and to give an observable indication of drug delivery, while the calcium phosphate shell can enhance the fluorescence of the encapsulated dye.     

Synthesis of Calcium Phosphate Nanoparticles in Collagen Medium

Summary: Mineralization of the proteic matrix composed mostly of collagen type I is controlled by specific interactions of ions Ca²⁺ and PO, present in the biological fluid, with the matrix, and by the diffusion of these ions. The specific interactions and the diffusion of ions combined; result in the nucleation and formation of calcium phosphate particles. Moreover, they control the morphology, size, crystallinity and composition of the particles. In this work, precipitation of calcium phosphate particles in a collagen matrix type I was carried out through impregnation of the matrix with a Ca²⁺ and PO solution, with Ca/P ratio 1.67 and pH 2.5. Precipitation of particles associated with matrix structuring was carried out by adsorption of gaseous ammonia.     

Microwave‐Assisted Hydrothermal Rapid Synthesis of Amorphous Calcium Phosphate Mesoporous Microspheres Using Adenosine 5′‐Diphosphate and Application in pH‐Responsive Drug Delivery

Herein we report a rapid and green strategy for the preparation of amorphous calcium phosphate mesoporous microspheres (ACP‐MSs) using adenosine 5′‐diphosphate disodium salt (ADP) as an organic phosphorus source by a microwave‐assisted hydrothermal method. The effects of the pH value, the reaction time, and temperature on the crystal phase and morphology of the product are investigated. The ADP biomolecules used in this strategy play an important role in the formation of ACP‐MSs. The as‐prepared ACP‐MSs are efficient for anticancer drug delivery by using doxorubicin (Dox) as a model drug, and the Dox‐loaded ACP‐MSs show a high ability to damage cancer cells. Moreover, the ACP‐MSs drug delivery system exhibits a pH‐responsive drug‐release behavior due to the degradation of ACP‐MSs at a low pH value, thus, it is promising for applications in pH‐responsive drug delivery.