多孔纳米羟基磷灰石/聚乙烯醇复合水凝胶的表征

本文通过采用溶盐致孔法,制备了多孔纳米羟基磷灰石／聚乙烯醇复合水凝胶材料。用透射电子显微镜、红外光谱、扫描电子显微镜和图像分析对材料进行了表征。结果表明纳米羟基磷灰石与聚乙烯醇之间有一定键合,并且多孔纳米羟基磷灰石／聚乙烯醇复合水凝胶中大孔呈均匀分布且相互贯通,复合水凝胶的含水率在80％左右。该种多孔复合水凝胶是可用于人工角膜支架,是一种很有开发前景的生物医用材料。     

模拟体液法制备纳米级羟基磷灰石

用模拟体液法制备纳米羟基磷灰石(hydroxyapatite,HAP or HA)粉体。研究了反应温度、反应浓度和反应时间对合成的影响。结果发现,制备纳米级羟基磷灰石的最佳工艺条件为:反应温度60℃,浓度为15倍的模拟体液(simulate body fluid,SBF),反应时间为10h。在此工艺条件下制备的羟基磷灰石粉体的微观形貌为球形颗粒,平均颗粒直径为30 nm。     

磷酸氢钙水解法合成羟基磷灰石纳米晶

采用磷酸氢钙水解法和水热处理技术在模拟体液(SBF)介质中合成HA纳米晶,利用XRD研究了pH值、水热处理温度等制备工艺对合成HA纳米晶的影响。TEM、EDS和FTIR表征结果表明磷酸钙产物为长100 nm、直径10 nm的棒状含碳酸根羟基磷灰石纳米晶,其Ca/P比为1.69,这表明本工作获得的HA在组成与形态上与骨骼中的HA十分相似。     

纳米羟基磷灰石/聚乙烯醇/明胶复合材料的结构和力学性能

采用机械共混法、原位化学合成法、原位水热法制备了一系列纳米羟基磷灰石/聚乙烯醇/明胶(n-HA/PVA/GEL)复合材料;利用X射线衍射仪、透射电镜及傅立叶变换红外光谱仪等分析了复合材料的结构;利用材料试验机测定了复合材料的力学性能.结果表明,利用原位水热法可使n-HA有效地在PVA高分子中均匀分散,并提高n-HA颗粒...     

羟基磷灰石界面水行为的分子模拟

本文采用分子动力学模拟(MD)方法研究了羟基磷灰石(HAP)(001)和(100)晶面上的水分子行为，发现HAP晶面间的水是处在高电场和高内压的环境下，并可在晶面处形成2～3层高度结构化的水层，这些水具有有序结构和类冰固化特征。其中在HAP晶体的[001]方向具有较强的极性，相对于[100]方向能诱导产生更多的有序结构化水层。研究发现HAP-水界面处钙和磷酸根位点分布和水分子的吸附位点相关，并且水在HAP界面上的吸附形式具有多样性。该工作揭示了HAP界面结构化水层的形成及其结构细节特征。HAP晶面附近的结构化水层可阻止溶液离子自由出入晶面，对HAP颗粒在水溶液中的动力学稳定性具有重要的影响。     

聚乙烯醇/纳米羟基磷灰石/丝素蛋白复合水凝胶的制备及其性能研究

本文以聚乙烯醇(PVA)、纳米羟基磷灰石(n-HA)和丝素蛋白(SF)为原料,采用物理共混法、反复冷冻解冻法和NaCl粒子制孔法制得了具有三维结构的PVA/n-HA/SF多孔复合水凝胶,以作为人工角膜支架材料。测试了这种多孔复合材料的含水率、拉伸强度和断裂伸长率,并对其进行了红外谱图、X射线衍射光谱、热重及电子扫描显微镜分析。结果表明,丝素蛋白的添加量增加时,多孔复合水凝胶的含水率相应提高,含水率稳定在75～82%之间;其拉伸强度在0.43～1.00MPa之间,断裂伸长率在183.76～237.53%之间,可以达到人体正常状态下眼压要求,其中复合水凝胶的最佳配比为:PVA:SF:n-HA=10:5:1。;IR和XRD分析表明复合水凝胶在物理交联过程中,各种成分均匀复合,无化学键变化;扫描电镜显示该水凝胶材料具有均匀的三维多孔结构。     

化学-物理法制备聚乙烯醇/壳聚糖/纳米羟基磷灰石复合水凝胶及其性能

采用化学-物理交联法制备了聚乙烯醇/壳聚糖/纳米羟基磷灰石(PVA/CS/n-HA)复合水凝胶材料。通过对比其含水率、拉伸强度、红外光谱和TG谱图,探讨了PVA含量及戊二醛加入量对材料性能的影响。结果表明,m(PVA)∶m(CS+n-HA)=5∶1,戊二醛质量分数为2%时,复合水凝胶材料具有较好的综合性能:含水率为82.0%、拉伸强度为2.14 MPa、断裂伸长率为343.26%;同步热分析表明,25~140℃,仅存在水分的蒸发,直至360℃材料才发生分解,说明材料的热稳定性良好;红外分析表明,CS与戊二醛发生了交联反应。     

化学-物理法制备聚乙烯醇/壳聚糖/纳米羟基磷灰石复合水凝胶及其性能

采用化学 物理交联法制备了聚乙烯醇/壳聚糖/纳米羟基磷灰石（PVA/CS/n-HA）复合水凝胶材料。 通过对比其含水率、拉伸强度、红外光谱和TG谱图,探讨了PVA含量及戊二醛加入量对材料性能的影响。 结果表明,m(PVA)∶m（CS+n-HA）=5∶1,戊二醛质量分数为2%时,复合水凝胶材料具有较好的综合性能：含水率为82.0%、拉伸强度为2.14 MPa、断裂伸长率为343.26%;同步热分析表明,25~140 ℃,仅存在水分的蒸发,直至360 ℃材料才发生分解,说明材料的热稳定性良好;红外分析表明,CS与戊二醛发生了交联反应。     

聚富马酸丙二醇酯/羟基磷灰石复合多孔水凝胶的制备及其矿化性能研究

采用二步法合成了可降解的聚富马酸丙二醇酯(poly(propylene fumarate),PPF),并和N-乙烯基吡咯烷酮(N-vinyl pyrrolidone,NVP)共聚,以1,4-二氧六环为溶剂,通过改变溶剂的量制备了溶胀性能不同的PPF水凝胶.采用万能力学测试仪和扫描电子显微镜分别表征了水凝胶的压缩模量和形貌结构.选择20％ PPF和10％ NVP的聚合体系,预掺3％的纳米羟基磷灰石(hydroxyapatite,HA),以氯化钠粒子为致孔剂,制备了孔径在280～450 μm的纳米复合多孔水凝胶,使其压缩模量提高了61％.模拟体液矿化10天的结果显示,磷灰石成核位点的存在和良好的与外界液体环境物质交换的能力,促进了多孔水凝胶表面磷灰石的沉积,说明HA的复合可以有效提高PPF多孔水凝胶的成骨活性.     

碳纳米管对羟基磷灰石基复合材料力学性能的影响

将力学性能优良的碳纳米管(CNTs)与羟基磷灰石(HA)生物陶瓷相复合,发展CNTs/HA复合材料来应用于骨组织修复领域,有望解决HA生物陶瓷力学性能的不足。通过3种不同的制备方法,即通过表面活性剂将CNTs分散在HA基体中、通过酸碱中和反应将CNTs与HA共沉淀以及通过体外浸泡在CNTs上矿化生长HA等方法来获得CNTs/HA复合材料。深入研究CNTs的表面结构和分散状态对CNTs/HA复合材料力学性能的影响。结果表明,CNTs的添加改变了HA的脆性,导致复合材料抗压力学性能得到提高。但是,由于复合材料制备方法的不同,导致CNTs在HA基体中的分散状态、表面结构的完整性以及与HA的界面结合情况不同,导致其抗压力学性能不同。其中,通过表面活性剂将CNTs分散在HA基体中而获得复合材料的抗压力学性能表现最好,而CNTs与HA通过共沉淀法所获得复合材料的抗压力学性能表现最差。     

A study on the bioactivity of chitosan/nano-hydroxyapatite composite scaffolds for bone tissue engineering

In order to increase the biocompatibility and bioactivity of chitosan, hydroxyapatite had been in situ combined into chitosan scaffolds. The bioactivity of the composite scaffolds was studied by examining the apatite formed on the scaffolds by incubating in simulated body fluid and the activity of preosteoblasts cultured on them. The apatite layer was assessed using scanning electronic microscope (SEM), X-ray diffraction (XRD), Fourier-Transformed Infrared spectroscopy (FTIR) and weight measurement. Composite analysis showed that after incubation in simulated body fluid on both of the scaffolds carbonate hydroxyapatite was formed. With increasing nano-hydroxyapatite content in the composite, the quantity of the apatite formed on the scaffolds increased. Compared with pure chitosan, the composite with nano-hydroxyapatite could form apatite more readily during the biomimetic process, which suggests that the composite possessed better mineralization activity. Furthermore, preosteoblast cells cultured on the apatite-coated scaffolds showed different behavior. On the apatite-coated composite scaffolds cells presented better proliferation than on apatite-coated chitosan scaffolds. In addition, alkaline phosphatase activities of cells cultured on the scaffolds in conditioned medium were assessed. The cells on composite scaffolds showed a higher alkaline phosphatase activity which suggested a higher differentiation level. The results indicated that the addition of nano-hydroxyapatite improved the bioactivity of chitosan/nano-hydroxyapatite composite scaffolds. On the other hand, that is to say composition of substrates could affect the apatite formation on them, and pre-loaded hydroxyapatite can enhance the apatite-coating. It will also be significant in preparation of apatite-coating polymer scaffolds for bone tissue engineering.     

玩具材料在四种人体模拟液中特定元素迁移方法探讨

选择塑料、纺织品和油漆涂层三类常见玩具材料,采用模拟胃液、酸性汗液、碱性汗液和唾液浸泡提取样品,使用ICP-AES法测试提取液中17种欧盟玩具新指令限制元素(铝、锑、砷、钡、硼、镉、铬、钴、铜、铅、锰、汞、镍、硒、锶、锡、锌)迁移量,试验了前处理过程中不同振荡频率对金属元素迁移量的影响。试验结果表明：胃液对金属元素溶出能力最大,汗液溶出能力最弱,样品提取过程中,恒温水浴振荡器振荡频率在80-160U/min范围内时,特定元素溶出量基本不受振荡频率的影响。     

HPLC determination of tobramycin in a simulated body fluid

To evaluate the release kinetics, in a simulated body fluid, of tobramycin (TOB) from carbonated apatite (CHA) in the form of granulate, a sensitive and reliable liquid chromatographic method was developed. Chromatographic separation was performed on a Metrosep Carb 1 anionic column by using 0.1 M NaOH as mobile phase at a flow rate of 1.0 ml min^− 1. TOB was quantified by pulsed amperometric detection using a 3-potential waveform on Au electrode. A linear relationship for TOB was found in the range 0.17-2.50 mg l^− 1 with a LOD of 0.05 mg l^− 1. The method exhibited good retention time and peak area reproducibility.     

阳离子Gemini表面活性剂12-3-12与DNA在模拟体液中的相互作用研究

采用紫外透射光谱、透射电镜、原子力显微镜、圆二色谱(CD)等方法探讨了阳离子Gemini表面活性剂C12H25N+(CH3)2-(CH2)3-(CH3)2N+C12H25·2Br-(12-3-12)与DNA在模拟体液(SBF)中的相互作用。结果表明,SBF中较高反离子浓度不但屏蔽了DNA和12-3-12之间的静电吸引作用,而且促进了12-3-12聚集体的产生和生长,导致低盐条件下体系中出现的沉淀溶解现象的消失。SBF中DNA与12-3-12之间存在强烈的相互作用;随着12-3-12的加入,表面活性剂分子在DNA链周围聚集,类网络结构的DNA逐渐变为类似于串珠的复合物,随后出现尺寸较大的类球形复合物以及较大复合物与较小表面活性剂聚集体共存的现象。CD谱结果显示,SBF中12-3-12可以诱导DNA的构象发生改变,由自然的B构型变成高度致密的ψ相。分子动力学模拟的离子液体中表面活性剂与带相反电荷聚电解质的相互作用过程及模式与实验结果吻合良好。模拟结果也表明,SBF中较高的反离子浓度提高了聚电解质的可压缩程度,导致相同条件下SBF中聚电解质的均方回旋半径远小于稀盐水溶液(10mmol/L Na Br)体系中的聚电解质均方回旋半径。较强的离子强度不但导致体系中聚电解质和带相反电荷表面活性剂之间的相互作用存在"假饱和"现象,而且也造成体系中表面活性剂在聚电解质周围聚集数显著提高。     

多孔β-磷酸三钙/壳聚糖/聚乙烯醇复合水凝胶的制备与性能

以NaCl为致孔剂,采用溶盐致孔法制备了多孔β-磷酸三钙/壳聚糖/聚乙烯醇（β-TCP/CS/PVA）复合水凝胶材料。 通过对比其含水率、溶胀比、拉伸强度、X射线衍射谱图、SEM和热重分析曲线,探讨了在相同环境下壳聚糖与β-磷酸三钙（β-TCP）的不同用量对聚乙烯醇(PVA)的结晶度以及对材料性能的影响。 此复合材料含水率为70%~76%。 当壳聚糖与β-TCP的质量比为2∶8时,复合材料的拉伸强度为0.56 MPa,断裂伸长率达到370%,其较好的力学性能,足以承受正常人眼压,可用作人工角膜周边支架材料。     

Biomimetic polymer/apatite composite scaffolds for mineralized tissue engineering

The material surface must be considered in the design of scaffolds for bone tissue engineering so that it supports bone cells adhesion, proliferation and differentiation. A biomimetic approach has been developed as a 3D surface modification technique to grow partially carbonated hydroxyapatite (the bonelike mineral) in prefabricated, porous, polymer scaffolds using a simulated body fluid in our lab. For the rational design of scaffolding materials and optimization of the biomimetic process, this work focused on various materials and processing parameters in relation to apatite formation on 3D polymer scaffolds. The apatite nucleation and growth in the internal pores of poly(L-lactide) and poly(D,L-lactide) scaffolds were significantly faster than in those of poly(lactide-co-glycolide) scaffolds in simulated body fluids. The apatite distribution was significantly more uniform in the poly(L-lactide) scaffolds than in the poly(lactide-co-glycolide) scaffolds. After incubation in a simulated body fluid for 30 d, the mass of poly(L-lactide) scaffolds increased approximately 40%, whereas the mass of the poly(lactide-co-glycolide) scaffolds increased by about 15% (see Figure). A higher ionic concentration and higher pH value of the simulated body fluid enhanced apatite formation. The effects of surface functional groups on apatite nucleation and growth were found to be more complex in 3D scaffolds than on 2D films. Surprisingly enough, it was found that carboxyl groups significantly reduced the apatite formation, especially on the internal pore surfaces of 3D scaffolds. These findings are critically important in the rational selection of materials and surface design of 3D scaffolds for mineralized tissue engineering and may contribute to the understanding of biomineralization as well.SEM micrograph of a poly(L-lactide) scaffold.     

Stabilization of proteases by entrapment in a new composite hydrogel

A new one-step procedure for entrapping proteases into a polymeric composite calcium alginate-poly(N-vinyl caproladam) hydrogel was developed that provided 75–90% retention of the activity of entrapped enzymes compared to soluble ones. Properties of entrapped carboxypeptidase B, trypsin, and thrombin were investigated. The immobilized enzymes were active within a wide pH range. The temperature optima of entrapped trypsin and carboxypeptidase B were approx 25°C higher than that of the soluble enzymes, and the resistance to heating was also increased. The effects of various polar and nonpolar organic solvents on the entrapped proteases were investigated. The immobilized enzymes retained their activity within a wide concentration range (up to 90%) of organic solvents. Gel-entrapped trypsin and carboxypeptidase (CPB) were successfully used for obtaining human insulin from recombinant proinsulin. The developed stabilization method can be used to catalyze various reactions proceeding within wide pH and temperature ranges.     

Effect of Ni on the corrosion behavior of Fe–Al intermetallics in simulated human body fluid

The corrosion behavior of FeAl-type intermetallic alloy in the Hank’s solution has been investigated after additions of 1, 3, and 5 at.% Ni with or without thermal annealing at 400 °C for 144 h. Techniques included potentiodynamic polarization curves, linear polarization resistance, and change of the free corrosion potential with time and electrochemical noise in current. Regardless of the heat treatment, additions of Ni increased both the free corrosion potential and the pitting potential values. Additionally, both the corrosion current and the passive current densities were reduced with this element. The alloys which did not suffer from pitting type of corrosion were the heat-treated FeAL base alloy and the one containing 5Ni. Both additions of Ni and thermal annealing improved the adhesion of external protective layer either by avoiding the formation of voids or by lowering the number of precipitates and making them more homogenously distributed.     

Changes in the acid-base properties of hydrogels of metal oxide hydroxides induced by aging in solutions of electrolytes

Changes in the acid-base properties of titanium(IV), zirconium(IV), iron(III), chromium(III), and indium(III) hydrogels of oxide hydroxides induced by aging in sodium chloride and sulfate solutions were studied by the point of zero charge method. On aging in a solution of the sulfate electrolyte the hydrogels loose their basic properties much more rapidly than in the chloride solution. The most changes were observed in the region of high pH of the point of zero charge of the hydrogels. The changes in the acid-base properties can be explained by a decrease in the content of surface OH groups with are displaced by the supporting electrolyte ions, and due to the oxolation of the hydrogels. Published inIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1329–1332, August, 2000.