Etude de la Reactivite Entre L'orthophosphate Tricalcique Apatitique et L'oxalate de Calcium

Several difficulties arise when studying the mineral component of calcified tissues: This material is complex due to the large number of atomic components, its heterogeneous composition, and varying factors. It is linked strongly to the organic component, and today no available technique allows a complete separation of these two components without alteration of one of them. In the present work the interaction of apatitic calcium phosphate with calcium oxalate has been studied. By heating stoechiometric amounts of these two solids, it was found that the presence of CO 3 2 m and CaO produced by calcium oxalate induces a decrease in P 2 O 7 4 m arising from HPO 4 2 m content of apatitic calcium phosphate. L'étude physico-chimique de la partie minérale des tissus calcifiés est extrêmement étendue et complexe. Fortement liée à des composés organiques, des difficultés de séparation, d'identification et d'étude du comportement de ces matériaux ont été signalées par de nombreux auteurs. En vue d'identifier l'effet des ions carbonate CO 3 2 m et du CaO sur la détermination de la teneur des ions (HPO 4 2 m ) des apatites synthétiques, les interactions entre le phosphate tricalcique apatitique et l'oxalate de calcium ont été étudiées. Il a été constaté que les ions CO 3 2 m produits par le carbonate de calcium issu de l'oxalate de calcium, conduisent à une diminution relative de la teneur des ions P 2 O 7 4 m (provenant des ions HPO 4 2 m ) dans le mélange équimolaire de phosphate apatitique et d'oxalate de calcium, dans le domaine de températures 400-520°;C. Au-delà de 520°;C la seconde diminution de la teneur des ions P 2 O 7 4 m est attribuée aux interactions des ions P 2 O 7 4 m et du CaO.     

皮肤组织工程支架材料的研究进展

皮肤组织工程支架为种子细胞提供粘附、生长、增殖和代谢的环境,并起支撑和模板作用,引导组织再生和控制组织结构,是人工皮肤的重要组成部分。探索理想的支架材料是当前皮肤组织工程领域的热点,本文综述了近年来皮肤组织工程支架材料的国内外研究进展,包括天然支架材料、合成支架材料和复合支架材料三大类,全面探讨了皮肤组织工程支架材料的制备方法及应用情况,本文还分析了皮肤组织工程支架材料存在的一些问题,并对其未来的发展进行了展望。     

改性高粱秸秆对磷酸根的吸附性能研究

将改性高粱秸秆用于磷酸根的吸附,研究了时间、酸度、温度以及改性高粱秸秆用量等因素对其吸附性能的影响。结果表明,在常温下,改性高粱秸秆对磷酸根具有良好的吸附性能,吸附时间快。改性高粱秸秆对磷酸根的吸附符合Langmuir和Freundli-ch吸附等温方程及准二级动力学方程,吸附过程以单分子层物理吸附为主。     

Carbohydrate-Based Scaffolds for the Generation of Sortiments of Bioactive Compounds

Summary.  The polyfunctionality and conformational rigidity of carbohydrates make this class of compounds ideal scaffolds for the production of sortiments¹ of bioactive compounds. Examples of carbohydrate-derived peptidomimetics of biological interest, such as somatostatin agonists and integrin antagonists, are presented. In order to have access to solid phase supported sortiments of compounds, orthogonally protected or unprotected carbohydrates were linked to polymers and reacted in the solid phase employing different regioselective strategies. Original bicyclic and tricyclic glycidic scaffolds were easily obtained starting from natural sugars such as D-arabinose and D-fructose. Manipulation of these conformationally blocked compounds afforded different carbohydrate-based derivatives, among which azidoacids are useful precursors of β-turn peptidomimetics. Received September 10, 2001. Accepted November 2, 2001     

含磷C_(60)衍生物的电化学性能研究

利用循环伏安法测试了 3种新合成的C60 膦酸酯衍生物的电化学性能 .通过比较不同取代基的C60 衍生物的电化学性能 ,研究引入基团的结构特性与其得电子能力之间的关系     

胆盐与磷酸钙的相互作用

胆汁的pH条件下(pH=6～8)，应该生成无定形磷酸钙(ACP)，而在胆结石中磷酸钙通常以羟基磷灰石的形式出现.利用谱学方法研究了ACP与胆盐的作用.结果表明，胆盐以胶团的形式与ACP作用，在溶液中形成复合胶团，使其溶解度增加.不同类型胆盐与ACP的作用能力不同：脱氧胆酸钠(NaDC) > 牛磺胆酸钠(NaTC) > 胆酸钠(NaC).胆盐与ACP中结合钙的亲和能力大于结合钙的亲和能力，使ACP在胆汁的环境下容易转化为羟基磷灰石.     

新银盐光度法测定磷酸氢钙中的微量砷

以硝酸银－乙酸－聚忆烯醇－乙醇作为砷化氢吸收液,Ｚｎ－ＫＩ－ＳｎＣｌ２为还原体系的新银盐光度法测定了磷酸氢钼中的微量砷。Ａｓ＾２－含量在０－７．５μｇ／５ｍＬ范围内服从比耳定律。应用于磷酸氢钙样品中Ａｓ呈测定,回收率９６－１０３％,方法检出限为２．８８×１０＾－６ｇ／Ｌ,ＲＳＤ为０．９４－５．５０％,测定结果与标准方法基本一致。     

Evaluation of Chitosan/Biphasic Calcium Phosphate Scaffolds for Maxillofacial Bone Tissue Engineering

Porous, 3D chitosan/biphasic calcium phosphate (BCP) scaffolds were used to prepare tissue engineering constructs for maxillofacial bone tissue reconstruction. Mesenchymal stem cells (MSC's) were seeded and cultured on clinically relevant sized scaffolds. In vitro engineered constructs facilitated the healing of mandibular defects in pigs if accompanied with delivery of basic fibroblast growth factor (bFGF).     

离子色谱法测定磷酸锂中微量的杂质元素

对离子色谱法测定磷酸锂中钾、钙、镁杂质离子的方法进行研究。采用DX-80型离子色谱仪,分离柱为Ion Pac CS12A-5μm阳离子分离柱,用2×10-2mol.L-1甲基磺酸溶液为淋洗液,流速为2 mL.min-1,测定了磷酸锂中各钾、钙、镁杂质离子的含量,相关系数分别为0.9996,0.9993,0.9994,相对标准偏差小于3%,样品回收率为98.1%~100.3%。     

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.     

PLGA-磷酸钙复合载药纳米粒的制备

利用聚氧乙烯硬脂酸酯(Brij78)和帕米膦酸二钠制备新型表面活性剂Pa-Brij78,以此为表面活性剂,聚乳酸-羟基乙酸共聚物(poly(lactic-co-glycolic acid),PLGA)为油相,采用水包油包水的微乳液法制备载卵清蛋白(ovalbumin,OVA)的表面带有磷酸根的PLGA纳米粒,再用共沉淀法在其表面修饰一层磷酸钙,并装载寡核苷酸Cp G,形成一种核-壳结构的复合载药纳米粒Cp G/Ca P/PLGA(OVA).通过动态光散射粒度仪、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)对纳米粒进行表征,并测定OVA、Cp G的载药量、包封率.结果表明以Pa-Brij78为表面活性剂制备的PLGA(OVA)纳米粒确实能被磷酸钙修饰,粒径增大40~60 nm,表面变粗糙,XRD测得该磷酸钙层的主要存在形式为Ca3(PO4)2.OVA平均载药量为5%,包封率大于80%;Cp G平均载药量为0.47%,平均包封率为89.9%.     

协同催化合成磷酸酯的研究

由磷酸和醇直接酯化合成了磷酸酯，探讨了无机盐及其复合体系的催化特性，发现Ｎａ＿２ＳＯ＿４－ＴｉＯ＿２－Ｈ＿２ＳＯ＿４和Ｎａ＿２ＳＯ＿４－Ａｌ＿２Ｏ＿３－Ｈ＿２ＳＯ＿４两种复合体系具有协同催化作用和较高的活性。     

Crystal Structure and Properties of Strontium Phosphate Apatite with Oxocuprate Ions in Hexagonal Channels

Strontium phosphate apatites containing different amounts of copper were prepared by a solid state reaction at 1100 °C or by arc melting above 1600 °C in air. The samples were characterized by X‐ray diffraction, ICP analysis, scanning electron microscopy, IR spectroscopy, MAS—¹H—NMR, diffuse reflectance spectroscopy, and SQUID magnetometry. X‐ray crystal structure determination was carried out for a single crystal obtained from the melt. The compound is formulated as Sr₅(PO₄)₃(CuO₂)_1/3 and has an apatite structure (space group P6₃/m, a = 9.7815(4)Å, c = 7.3018(4)Å, Z = 2) with linear CuO₂^3— ions occupying hexagonal channels. For solid state synthesized samples, Rietveld refinement of powder XRD patterns was performed. The samples obtained at 1100 °C acquire the composition Sr₅(PO₄)₃Cu_xOH_y, with x changing from 0.01 to 0.62 and y < 1—x. The copper content can be increased to x = 0.85 by annealing in argon at 950 °C. The compounds represent a hydroxyapatite in which part of the protons is substituted by Cu⁺ and Cu²⁺ ions. The ions form linear O—Cu—O units which are progressively condensed creating the Cu—O—Cu bridges on increasing copper content. IR and NMR data testify existence of OH groups, non‐disturbed and disturbed by neighboring Cu atoms. In the electron spectra, the samples exhibit absorption bands at 7800‐7900, 14200‐14500 and 17500‐17550 cm^—1, which were assigned to Cu²⁺ d‐electron transitions. By annealing the sample with x = 0.1 in oxygen at 800 °C copper is fully oxidized while retaining in channels in unusual for Cu²⁺ linear coordination.     

磷酸钙骨水泥/聚肽共聚物生物复合材料力学性能及微观结构

磷酸钙骨水(Calcium Phosphate Cement,CPC)是一种新型的人工骨材料,可用于人体骨缺损的修复,具有良好的生物相容性、骨传导性和骨替代性．然而,磷酸钙骨水泥的抗压强度较低,脆性较大,限制了其应用,因而提高抗压强度和减小其脆性成为CPC研究领域的一个重要课题．目前,普遍采用添加纤维的方法来提高CPC材料的抗压强度和韧性．然而大多数的纤维是非降解性的．     

多巴胺对磷酸钙骨水泥性能影响的研究

本论文研究含儿茶酚的多巴胺对磷酸钙骨水泥(calcium phosphate cement,CPC)的理化性能和体外降解的影响。将多巴胺溶于Tris-HCl缓冲液于空气中氧化2 d,作为液相与固相粉末混合成型。选取多巴胺浓度、液固比、pH值三因素,通过正交试验选取最优组合。采用万能力学试验机、吉尔摩(Gilmore)针、X射线衍射仪(XRD)、傅立叶红外光谱仪(FTIR)表征含多巴胺CPC的理化性能,用扫描电镜(SEM)观察微观形貌、用紫外可见光分光光度计研究含多巴胺CPC的体外降解。抗压强度结果表明最优组为多巴胺浓度40 mg.mL-1、液固比0.3 mL.g-1、pH值8.5,最优组CPC抗压强度最高,与空白CPC相比具有极显著性差异(p<0.01);最优组CPC凝结时间与空白组比较无显著性差异且符合临床要求;XRD和FTIR结果表明多巴胺的加入促进了二水磷酸氢钙(DCPD)的转化;SEM观察发现多巴胺的加入使CPC内部形成了片状结构及较多紧密结合的块状晶体且与空白CPC相比孔隙明显减少;最优组CPC体外降解过程中,多巴胺的累积释放量为加入总量的29.7%,且浸泡过程中浸泡液的pH变化处于人体安全范围内。     

Phosphate imbalance conducting by BPs-based cancer-targeting phosphate anions carrier induces necrosis

As a vital nutrient closely related to the cancer-cells proliferation, phosphate anions have been paid great attention as a promising anticancer agent. Generally, the transport of phosphate anions depends on a protein transport system which is regulated by ion homeostasis regulations. Herein, we designed a reactive anionic nanocarrier based on black phosphorus nanosheets (BPs) and artesunate (ART), which could enter cells through endocytosis to generate phosphate anions, avoiding the regulation of cell homeostasis. The ionic nanocarrier was coated by polydopamine to defend BPs and ART and functionalized by folate (FA) and hyaluronic acid (HA) for targeting factor. With the anchoring groups FA/HA targeted the carrier into cells, polydopamine coating decomposed to expose ART for further generating reactive oxygen species (ROS) in cancer cell microenvironment, providing oxidation conditions. Next, ROS generated by ART makes BPs decompose to phosphate anions with effectively speed, giving rise to the destruction of ion homeostasis to induce necrosis and inhibit the proliferation for cancer cells. In consequence, this research provides novel idea and direction for the ionic carriers and tumor therapeutics.     

The Relationship between Pendant Phosphate Groups and Mechanical Properties of Polyisoprene Rubber

It is still a great challenge to mimic the structure and function of natural rubber by introducing polar components into synthetic polyisoprene. In order to explore the function of phosphate groups on the mechanical properties of polyisoprene rubber, a terminally functionalized compound(PIP-P) containing phosphate groups was synthesized and further vulcanized to prepare the model compound V-PIP-P.Through analyzing the test results, it was found that these phosphate groups formed polar aggregates in non-polar polyisoprene rubber matrix,serving as an additional dynamic cross-linking sites, which increases the cross-linking density and improves mechanical properties. The influence of the phosphate groups on the strain-induced crystallization(SIC) was further investigated via synchrotron wide-angle X-ray diffraction(WAXD)experiment. These phosphate group aggregates not only reduced the onset strain of SIC, but also slowed down the molecular chain mobility,which hinder the crystal lateral growth. The above results help us to gain a deeper understanding for the function of phosphate groups in the formation of "naturally occurring network" and guide the molecular design of next generation polyisoprene rubber.     

Properties of Ruthenium Complex-Doped Calcium Phosphate/Porous Silicon Nanostructures

In this work, we focus on the optical properties of the ruthenium complexes [Ru(phen)₃]Cl₂ and [Ru(bpy)₃]Cl₂ incorporated into biocompatible calcium phosphate films on porous Si substrates to both characterize the distribution of such species in the film as well as analyze their diffusion from the porous matrix upon aqueous exposure. For the latter measurements, photoluminescence spectroscopy is employed to monitor the changes in emission intensity for the both the calcium phosphate surface and surrounding aqueous environment as a consequence of diffusion from the film. In selected cases, visible absorption spectroscopy was also utilized to measure the appearance of a given complex in the surrounding solution. The effects of heating and anodic bias on the calcium phosphate/porous Si/Si substrate on the kinetics and available equilibrium concentrations of a given Ru complex have also been evaluated.