磷酸三钙的制备与应用研究

磷酸三钙具有良好的生物相容性、生物活性以及生物降解性,是理想的人体硬组织修复和替代材料,在生物医学工程学领域一直受到人们的密切关注。本文综述了磷酸三钙制备研究的最新进展,并对其在生物医用材料方面的应用进行了阐述。     

可降解β-磷酸三钙的制备及应用

磷酸三钙、羟基磷灰石以及它们的混合物等磷酸钙陶瓷，其成分与骨矿物组成类似，生物学相容性好。它们在生理环境下能发生不同程度的降解，被组织吸收，称为生物降解或生物吸收。本文对可降解β-磷酸三钙进行了综述，介绍了可降解β-磷酸三钙的制备、应用及以后研究的发展趋势。     

β相磷酸三钙骨水泥性能研究

为了利用β-磷酸三钙优良的性能,通过实验确定适当的调和液,使不具备水化特性的β-磷酸三钙拥有骨水泥性能,在人体环境下凝同硬化并具有一定的强度,继而对该骨水泥及其碳纳米管(CNTs)复合材料与相应的α-磷酸三钙骨水泥材料进行了对比研究.方法:配制稀磷酸、柠檬酸、柠檬酸钠等调和液,与β-磷酸三钙细粉混合,测定浆体pH值、初凝、终凝时间等.对获得的β-磷酸三钙骨水泥及其碳纳米管(CNTs)复合材料,分别制备φ6mm×12mm圆柱形、4mm×4mm×25mm条形试样,测试样品的耐压强度、抗弯强度、气孔率等机械性能,用SEM对材料的断口进行观察,与相应的α磷酸三钙骨水泥材料进行对比.结果:以柠檬酸作为调和液,β-磷酸三钙骨水泥表现出与α-磷酸三钙骨水泥类似的自行固化硬化性能;但CNTs对β-磷酸三钙骨水泥复合材料力学性能的影响与对α磷酸三钙骨水泥材料不同,并在其断口处观察到一"笼形"结构.     

磷酸钙骨水泥制备方法的改进及其性能研究

采用2种方法探索了磷酸钙骨水泥(CPC)固体粉末的制备,即沉淀法和固相反应法,并合成了CPC;对CPC的固化时间、抗压强度、产物物相组成等进行了分析。沉淀法生成的固相粉末为磷酸三钙、焦磷酸钙,通过实验确定适当的调和液为柠檬酸,使固相粉末拥有骨水泥特性,并探讨了温度、缓冲液、模拟体液浸泡等对其性能的影响。固相反应法制备的固相粉末应为磷酸四钙(TTCP),但在空气中,1 500℃下煅烧6h制得的TTCP结晶度不好且含有杂质CaO。综合2种方法,结果表明以焦磷酸钙、磷酸三钙为主要成分的骨水泥的性能优于以磷酸四钙为主要成分的骨水泥。     

最新磷酸钙、亚磷酸盐专利文摘

可在体内降解成孔的磷酸钙骨水泥的制备方法;等离子喷涂羟基磷灰石涂层后处理方法;生物活性硅酸三钙自固化材料、制备方法及用途；纳米结构化可降解生物医用复合材料及其制备方法；药物载体磷酸钙纳米线及其制备方法；抗菌过磷酸钙及其制作方法。[第一段]     

硅磷酸钙骨水泥固化性质及生物降解性

共沉淀反应法制备硅酸三钙(C3S),研究了含硅酸三钙(C3S)的磷酸钙系(磷酸四钙+磷酸氢钙)骨水泥(CPC)材料的固化性质和在模拟体液(SBF)中浸泡后材料降解性。与CPC骨水泥相比,复合C3S骨水泥的固化时间延长,一定量的C3S可提高CPC的抗压强度。在模拟体液浸泡设定时间后,含C3S骨水泥降解率明显增加。含C3S的骨水泥水化反应产物有缺钙型羟基磷灰石(CDHA)相生成,因此有良好的生物相容性,有可能作为一种可降解的骨组织再生材料使用。     

材料的的过程仿仿生制备技技术研究究进展

“材料的过程仿生制备技术”是一种从自然物质精妙的结构形成过程中得到启示、找到灵感,发展材料的合成与制备新技术。本文结合近年来“材料的过程仿生制备技术”的发展现状,围绕自然制造过程及自然制造过程-生物结构的关系,从生物矿化启示的合成与制备、光合作用启示的合成、光合作用和生物矿化相结合的合成与制备等方面综述了该方向现有的研究工作。最后,对“材料的过程仿生制备技术”的研究目标进行了总结,并对其发展趋势进行展望。     

羟基磷灰石生物陶瓷材料的研究趋势及展望

本文综述羟基磷灰石(hydroxyapatite,HA)生物陶瓷材料的研究进展,通过调控HA形貌以优化其使用性能。用不同方法制备多孔HA,旨在强化骨传导性和诱导性,同时能实现骨的增强与增韧。设计HA复合材料以弥补单一HA力学性能的不足。从仿生学角度提出HA的研究趋势:合成具有类似于自然骨精细结构的仿生学骨组织材料,实现HA生物陶瓷材料与有机体力学相容性和生物相容性尽可能理想地匹配。     

专利技术

生产高浓度过氧化氢的结晶方法；具有高硫酸钠含量的沉淀二氧化硅；一种烟气中二氧化硫的脱除方法；磷酸八钙前驱体制备β-磷酸三钙新工艺；高纯碳酸锶制备方法。     

利福平/磷酸八钙骨水泥载药体系的制备及体外释放特性

为了研究磷酸八钙骨水泥(cotacalcium phosphate,OCP)作为药物载体的体外释药行为,以利福平(rifampicin,RFP)作为模型药物,制备利福平/酸八钙骨水泥药物缓释体系.通过X射线衍射、红外光谱、场发射扫描电镜分析、万能电子试验机及紫外-可见分光光度计等测试方法,研究RFP对OCP的相组成、抗...     

The ionic substituted octacalcium phosphate for biomedical applications: A new pathway to follow?

Numerous studies have found that octacalcium phosphate possesses promising biological properties applicable to bone tissue regeneration. To further improve the osteogenic and regenerative properties of octacalcium phosphate, substitutions with Sr²⁺, Zn²⁺, Mg²⁺, Fe³⁺, Na⁺, F^? and CO₃^2? ions have been investigated in recent years. Despite that, hydroxyapatite is still considered the most promising calcium phosphate for bioactive bone grafts due to its biocompatibility, physicochemical similarity to biological apatite, osteoconductivity and strong bonding with the surrounding tissue. However, better biological properties of octacalcium phosphate in vivo as well as a larger volume of regenerated bone tissue, compared to hydroxyapatite, were confirmed by many studies. This review summarizes recent and relevant studies on cationic and anionic substitutions in the crystal lattice of octacalcium phosphate and its in vitro biological performance. It also discusses future challenges and prospects for the use of substituted octacalacium phosphate.     

Effects of strontium doping on the degradation and Sr ion release behaviors of α‐tricalcium phosphate bone cement

Strontium plays important physicochemical and biological roles in the applications of bone repair materials. The available methods of Sr doping in bone cements were believed to make a key effect on the biodegradation and Sr ion release behaviors of cements. In this work, Sr‐doped octacalcium phosphate (Sr‐OCP), Sr‐doped α‐tricalcium phosphate (Sr‐α‐TCP), SrCO₃, and SrCl₂ with different actual availability of Sr²⁺ were imported into α‐TCP bone cements, and their effects on the biodegradation and ions release of cements were comparatively investigated. Incorporation of different Sr carriers had led to distinct hydration morphologies, crystal evolutions, degradation rates, and microenvironments of bone cements during their in vitro biodegradation. Compared with other Sr carriers, Sr‐OCP facilitated the hydration reaction of α‐TCP, which induced the enhanced degradation and Sr ion release behaviors. In conclusion, Sr‐OCP was supposed to be a more potential Sr carrier applied in the synthesis of biodegradable Sr‐doped calcium phosphate bone cements.     

溶胶-凝胶法二氧化钛薄膜诱导沉积磷酸钙层

碳／碳复合材料作为骨植入材料具有良好的生物力学相容性，但没有生物活性。以玻璃片为基板进行预试，发现溶胶凝胶法制备的锐钛矿型二氧化钛薄膜呵在快速钙化溶液中诱导沉积出由磷酸八钙和羟基磷灰石组成的磷酸钙层，二氧化钛薄膜的微观形貌对快速钙化溶液中磷酸钙沉积物的沉积速度和组成影响不大。在以上预试的基础上，通过溶胶凝胶法制备的二氧化钛薄膜在碳/碳复合材料上复合了生物活性磷酸钙涂层。     

Investigation of Magnesium Incorporation within Gelatin/Calcium Phosphate Nanocomposite Scaffold for Bone Tissue Engineering

In this study, diffusional method was used to prepare a calcium phosphate/gelatin nanocomposite as a scaffold for bone tissue repair. Incorporation of magnesium (Mg) into mineral phase of the scaffold was also investigated. Addition of Mg ions to the synthesis process caused formation of magnesium phosphate (MgP) and hydroxyapatite (HAp). However, analyses data for the sample lacking Mg showed that the mineral formed within GEL had a low crystalline nature, consisting of HAp and octacalcium phosphate (OCP). With addition of Mg within the structure of precipitated minerals, morphology of minerals was dramatically changed toward being irregular and less ordered.     

Regulating the multifactor during wet chemical synthesis to obtain calcium phosphate powders with controllable phase purity for bone repair

Calcium phosphate ceramics are widely used as bone repair materials owing to their excellent biocompatibility, bone conductivity, bone induction, and degradability. Although there are many methods for synthesizing calcium phosphate and controlling its phase composition, it is necessary to explore effective preparation methods by understanding the formation of calcium phosphate and its influencing factors. In this study, calcium phosphate powders with controllable phase compositions were synthesized using a wet chemical precipitation method by adjusting the process parameters (aging time, bipolar solution, initial Ca-P molar ratio, capping agent concentration, and system concentration). Subsequently, a certain biphasic proportion of (biphasic calcium phosphate, BCP) products was prepared, and pure (β-tricalcium phosphate, β-TCP) can be obtained according to the customer's requirements. BCP ceramics with desired phase compositions were obtained by pressing and sintering different calcium-deficient powders. Specifically, β-TCP powder with a purity of 99.83 wt% was obtained when the aging time, bipolar solution, initial Ca-P molar ratio, capping agent concentration, and system concentration were 0 h, 50% ethanol, 1, 0.27 M, and 0.0135 M, respectively. The BCP synthesized in this study shows great application potential in the field of bone tissue repair materials.     

Targeted synthesis of octacalcium phosphate and a study of its properties

The optimal conditions of synthesis of one of the most promising precursors of biological apatites— octacalcium phosphate (OCP)—have been determined. The OCP synthesis was carried out by two main methods: hydrolysis of brushite and precipitation from an aqueous solution. The samples’ phase composition, morphology, and thermal stability, as well as their bioresorbability in electrolytes of different acidity, have been investigated.     

The threonine effect on calcium phosphate preparation from a solution containing Ca/P = 1.33 molar ratio

In this study, calcium phosphate materials were prepared by a modified precipitation method using high-speed dispersing equipment. A solution with a Ca/P molar ratio of 1.33 (octacalcium phosphate stoichiometry) was transferred into the reactor vessel with different concentrations of threonine at temperature 97 °C. A white precipitant was collected after the addition of condensed ammonium solution and the samples were subsequently calcined at 900 °C. From the XRD patterns and FT-IR spectra of the uncalcined samples, three phases of octacalcium phosphate (OCP), monetite (DCP) and hydroxyapatite (HA) were obtained. Calcined samples showed two phases of β-tricalcium phosphate (β-TCP) and calcium pyrophosphate (CPP). SEM micrographs showed the different morphology of samples. The specific surface areas (ssa) were 45–53 m²/g for and 5–6 m²/g for calcined samples. From the obtained results, we found that threonine added in various amounts in the initial solution inhibits the formation of HA and consequently creates OCP and DCP.     

Electrocrystallization of Calcium Phosphates

The interest in electrocrystallization of calcium phosphates (CaP) in general, and of hydroxyapatite (HAp) specifically, results from the promising industrial benefits, unique microstructures, and properties of the deposits produced by this process, and the possible similarity to bone mineralization in vivo. In this paper, our work on electrocrystallization of HAp and octacalcium phosphate (OCP) on CP-Ti and Ti-6A1-4V alloy, in solution containing calcium nitrate and ammonium dihydrogen phosphate, is briefly reviewed. The early stages of nucleation and growth are characterized in real time by means such as electrochemical quartz crystal microbalance (EQCM) and electrochemical atomic force microscope (EC-AFM). The change in growth mode and the role of precursors to HAp are explained. The role of charge transfer and local increase in pH is discussed.     

含锌磷酸钙生物材料的研究进展

在钙磷酸盐基础上设计生物活性材料有望发展出高性能临床应用的硬组织修复材料。含锌钙磷酸盐材料能刺激骨组织生长,成为研究的热点。综述了含锌的钙磷酸盐材料研究状况,着重讨论钙磷酸盐材料中锌离子的存在状态以及掺锌后的物理化学性能,包括:含锌钙磷酸盐材料的合成和性能,锌的生物学性能以及含锌钙磷酸盐材料在体内和体外的研究状况。这些对于含锌钙磷酸盐材料植入后促进骨形成具有重要的影响。     

磷酸钙生物降解陶瓷的研究现状与发展

磷酸钙类陶瓷其成分与骨矿物组成类似,生物相容性好,被视为典型的生物陶瓷。它们在生理环境下能发生不同程度的降解,被组织吸收。这种特性与材料的化学成分、结晶相、结构形态等材料学因素有关,同时也与宿主个体差异、植入部位、与骨接触方式等生物学因素有关。目前主要的研究方法有体外模拟实验及体内埋植实验,通过观测材料结构、性能及成分的变化,与骨界面结合状态、细胞学、组织学等,探讨陶瓷的生物降解机理及控制降解的途径,以寻找新型骨修复材料。