丝素纤维/硫酸钙抗感染骨材料的制备及性能

通过控制丝素蛋白自组装过程制备了溶液状态下的丝素纳米纤维（silk fibroin nanofibers,SFFs）,与硫酸钙、万古霉素（vancomycin,VCM）复合,制备了VCM/CS/SFFs抗菌骨材料。通过SEM、XRD、紫外分光光度计、万能力学试验机、抑菌圈、MTT等手段分别研究了复合材料的微观形貌与结构、药物释放、力学、抑菌及细胞相容性等性能。结果显示,与水作为固化液相比,随着SFFs溶液（0.017 5~2.1 mg·mL^-1）的加入,复合材料凝固时间可控,降解率逐渐降低,抗水性增强,韧性提高;同时随丝素纳米纤维含量的增加骨材料抗压强度表现为先增加后减小的趋势,一周内药物释放速率降低;材料同时具有抑菌作用;MTT实验结果显示,加入丝素纳米纤维后与纯的硫酸钙相比MC3T3细胞增殖明显。     

甲醇-水混合溶剂后处理制备丝素蛋白膜及其药物释放研究

采用溶液浇注法制备丝素蛋白薄膜, 应用傅里叶红外光谱(FTIR)和X 射线衍射(XRD)研究了浓度不同的甲醇-水混合溶剂处理后丝素蛋白薄膜的结构变化, 并以罗丹明B 为模型药物与丝素蛋白构建药物缓释体系, 考察了丝素蛋白膜的结晶结构对药物释放动力学的影响. 结果显示, 在甲醇体积比浓度Φ_MeOH＝50%～90%的范围内, 丝素蛋白材料中以β-折叠为主的silk Ⅱ 结晶含量随着混合溶剂中甲醇浓度的增加而先增加后下降, 在Φ_MeOH＝80%附近出现最大值. 罗丹明B 从丝素蛋白膜的释放属于Fickian 扩散机理, 其扩散指数n 随着丝素蛋白膜中β-折叠含量的增加而增加, silk Ⅱ结晶是丝素蛋白材料药物释放的天然调节器.     

静电纺制备丝素蛋白纳米纤维及其复合纳米纤维的研究进展

将生物材料通过静电纺丝制备成的纳米纤维,具有比表面积大、空隙率高、生物相容性好等优点,因此得到广泛研究。本文主要综述了近年来国内外静电纺丝制备丝素蛋白纳米纤维的研究现状,重点介绍了采用不同溶剂制备的纯丝素蛋白纳米纤维和丝素蛋白与其它材料复合制备的丝素蛋白复合纳米纤维,并展望丝素蛋白纳米纤维潜在的应用前景。     

具有抗菌性能的载药复合微纳米纤维的制备及其结构和性能表征

利用静电纺丝技术制备了一种具有抗菌性能的氧化锌(ZnO)/聚乳酸(PLA)/聚己内酯(PCL)载药微纳米纤维膜,并通过扫描电子显微镜(SEM)、X射线衍射(XRD)和傅里叶变换红外光谱(FTIR)分别对复合膜的表面形态、元素组成和化学结构进行表征。通过抗菌实验评价了复合膜的抗菌性能,用紫外分光光度计测试复合膜在体外的药物释放行为。结果显示,以物理共混的方式将ZnO和氢溴酸高乌甲素(LAH)成功载入复合微纳米纤维;与PLA/PCL复合微纳米纤维膜相比,ZnO/PLA/PCL复合微纳米纤维膜表现出更好的抗菌效率。当ZnO含量为10%(wt)时,复合微纳米纤维膜具有最佳的抗菌性能;药物释放性能结果表明,ZnO/PLA/PCL复合微纳米纤维膜具有良好的药物缓释性能。     

乳液聚合法制备剥离型PS/MMT纳米复合材料

以阳离子表面活性剂十八烷基三甲基氯化铵(OTAC)和烯丙基十八烷基二甲基氯化铵(ATAC)为插层处理剂改性蒙脱土(MMT),原位乳液聚合分别制备了PS/C18MMT和PS/AC18MMT两种纳米复合材料.XRD和TEM分析表明,MMT均被剥离成单个或几个片层无规的分散在PS基体中,TGA分析表明,MMT的加入提高了材料的耐热性能,当PS基体与有机化处理的MMT片层发生一定的化学连接后,PS/AC18MMT纳米复合材料表现出更好的耐热性能.动态力学分析表明,MMT的加入提高了PS的玻璃态储能模量,降低了材料的动态损耗;PS/AC18MMT纳米复合材料的玻璃化温度较PS有所提高,而PS/C18MMT的玻璃化温度与PS相比略有降低.     

聚丙烯腈/纳米掺锑SnO_2复合导电材料的制备及性能研究

采用超声波辅助溶液共混的方式制备了聚丙烯腈(PAN)/纳米掺锑SnO_2(ATO)复合材料,采用扫描电镜(SEM)、广角X衍射(WXRD)、动态力学分析仪(DMA)及热失重分析仪(TGA)研究了复合材料的微观相态结构、动态力学性能及热性能,对复合材料的导电性能进行了测试.结果表明:经过钛酸酯偶联剂处理的纳米ATO在PAN基体中分散良好;纳米ATO的加入可以有效地提高PAN的导电性能,当其质量分数为8%时,复合材料电导率可达10~(-4)S/cm;添加纳米ATO后PAN的储存模量及玻璃化转变温度提高;PAN/ATO复合材料的热稳定性与纯PAN相比明显提高.     

纳米羟基磷灰石/丝素蛋白复合支架材料的降解特性及生物相容性研究

应用共混法制备了纳米羟基磷灰石/丝素蛋白复合支架材料, 通过体外降解和细胞培养实验研究了复合支架材料的降解特性和生物相容性. 体外降解实验结果显示, 复合支架材料具有稳定的降解能力; 在降解过程中, 羟基磷灰石由于与降解液发生钙、磷等离子的交换, 使其结晶得到了进一步生长和完善. 利用细胞计数法、四甲基偶氮唑盐(MTT)比色法和碱性磷酸酶(ALP)活性测定等分析了复合支架材料的生物相容性, 结果表明, MG63细胞在复合支架材料上具有良好的粘附、增殖能力, 并可引起早期的骨分化. 因此, 纳米羟基磷灰石/丝素蛋白复合支架作为骨组织工程的支架材料具有良好的应用前景.     

多孔载药纳米羟基磷灰石/聚酰胺/壳聚糖复合材料的制备与性能

以纳米羟基磷灰石(n-HA)、聚酰胺(PA)、壳聚糖(CS)为原料,以聚乙烯吡咯烷酮(PVP)与氯化钠(Na Cl)为致孔剂采用溶液共混法和粒子致孔法,载入抗生素红霉素(EM),研制一种新型多孔载药纳米羟基磷灰石/聚酰胺/壳聚糖/红霉素复合骨组织修复材料。研究了其孔隙率、抗压强度、X射线衍射谱图、红外光谱图、SEM和药物释放曲线,探讨了CS含量及红霉素释放量对材料性能的影响。结果表明,当PVA/Na Cl为1:6时,材料总孔隙率为72%和抗压强度为0.71MPa,扫描电镜显示多孔n-HA/PA/CS复合材料孔的直径在100~500μm之间,适合血管、骨组织的长入以及营养物质的运输。当CS的含量从0增到30%时复合材料药物的释放量从41.6%增到82.4%,表明可降解材料CS的加入有利于药物溶出。     

冷冻干燥法制备天然高分子复合聚电解质纳米纤维

将壳聚糖(CS)溶液和透明质酸钠(SH)溶液共混,制备成CS-SH复合聚电解质溶液,并对溶液中所形成的胶粒进行了粒径分布和ZETA电位表征。用冷冻干燥法除去溶剂,制备了CS-SH复合聚电解质纳米纤维膜。用FT-IR对其结构进行分析,并用SEM对其形貌进行了表征。并将复合聚电解质纳米纤维膜作为疏水性药物紫杉醇(PTX)的载药体系,研究了其药物释放行为。结果表明,PTX在该载体中的释放较为平缓,这可以延长药物的有效时间,降低给药次数,增强治疗效果,降低药物的毒副作用。     

石墨烯/二氯化镁负载钛系齐格勒-纳塔催化剂制备及其乙烯聚合性能

石墨烯自2004年发现以来,由于其独一无二的优异性迅速成为科学家们的研究热点.由于石墨烯具有极其优异的电学、力学和热学等性能,因此被广泛应用于高性能聚合物基复合材料的制备.众所周知,纳米填料在聚合物中的分散状态以及与基体间的界面作用是构筑高性能聚合物纳米复合材料的关键因素.由于石墨烯极易团聚,难以通过传统的熔融共混法制备均匀分散的石墨烯增强-聚烯烃纳米复合材料.另一方面,聚烯烃通常需要在较高温度下才能溶于部分有毒溶剂(如:三氯苯和二甲苯等),因此溶液共混法也不适用于聚烯烃-石墨烯纳米复合材料的制备.有鉴于此,本文开发了一种共沉积法制备石墨烯/二氯化镁负载钛系齐格勒-纳塔催化剂的路线.通过原位聚合直接制备出石墨烯均匀分散的聚烯烃/石墨烯纳米复合材料.考察了石墨烯的加入量对催化剂形态及其催化乙烯聚合行为的影响.当石墨烯加入量较低时,多个石墨烯片被包裹于较大的催化剂粒子中.随着石墨烯加入量的增加,催化剂趋向于在石墨烯表面聚集.继续增加石墨烯量将导致石墨烯包裹催化剂粒子,降低过渡金属钛的负载效率.通过三乙基铝活化后,所制备的催化剂具有非常高的乙烯催化活性,所生成的聚乙烯/石墨烯纳米复合材料复制了催化剂的片状结构.同时,通过对所制备的聚乙烯/石墨烯纳米复合材料进行电子显微镜和X射线衍射分析可知,石墨烯均匀分散于聚乙烯基体中,并且没有任何团聚现象发生.该复合材料的热重分析表明,仅加入非常少量的石墨烯就可以使其具有比纯聚乙烯更高的热稳定性,当石墨烯加入量为0.66 wt%时,其5 wt%热分解温度较纯聚乙烯升高了54°C.同时,所制备聚乙烯/石墨烯纳米复合材料具有更优异的机械性能.因此,本研究提供了一个简单高效的高性能聚烯烃/石墨烯纳米复合材料的制备方法.     

Preparation and thermal analysis kinetics of the core–nanoshell composite materials doped with Sm

The core–nanoshell composite materials with magnetic fly-ash hollow cenosphere as core and nano SmFeO₃ as shell were synthesized by high-energy ball milling method. The magnetic fly-ash hollow cenosphere, samarium nitrate, and iron nitrate were used as raw materials. The synthesis and growth kinetics of the composite materials were investigated using the thermogravimetry and differential thermal analysis (TG–DTA) at different heating rates. The results show that the precursor of the composite materials decomposes in three steps. The apparent activation energy of each stage was calculated using the Doyle–Ozawa and Kissinger methods. The reaction order, frequency factor, and rate equations were also determined. The activation energy of the nano crystallite growth is calculated to be 16.12 kJ mol^?1 according to kinetics theory of nano crystallite growth. It can be inferred that the crystallite grows primarily by means of an interfacial reaction during the thermal treatment. The magnetic properties and microwave absorbing properties of samples were analyzed by the vibrating sample magnetometer analysis and vector network analyzer. The results indicated that the exchange coupling interaction happens between ferrite of magnetic fly-ash hollow cenosphere and nanosized ferrite coating, which cause outstanding magnetic properties. In the frequency between 1 MHz and 1 GHz, the absorbing effectiveness of the composite absorbers can achieve ?32 dB. The magnetic properties of the composite material are better than those of single phase. So it is consistent with requirements of the microwave absorbing material at the low-frequency absorption.     

二维六方p6mm有序介孔WO_3-TiO_2复合材料的制备及其可见光光催化性能

以非离子型表面活性剂为模板剂,采用蒸发诱导自组装法制备了一系列不同WO3含量的有序介孔WO3-TiO2复合材料,并表征了其孔结构、形貌、孔隙率、光谱性质及组成.结果表明,该材料呈二维六方p6mm对称和锐钛矿晶相结构;与无序WO3-TiO2复合材料相比,其比表面积(152～154m2/g)更大,孔径更均一(5.3nm),且比纯TiO2的帯隙宽度(3.0eV)更窄.将该WO3-TiO2样品用于可见光光催化降解水相中罗丹明B和2,4-二氯苯氧乙酸的反应中,发现WO3含量适当的有序介孔WO3-TiO2样品的光催化活性比无序的样品和纯TiO2的更高.     

锂离子电池复合正极材料xLiFePO4·yLi3V2(PO4)3的复合机制

以FePO4·xH2O、V2O5、NH4H2PO4和Li2CO3为原料, 以乙二酸为还原剂, 通过湿化学还原-低温热处理方法制备出锂离子复合正极材料xLiFePO4·yLi3V2(PO4)3. X射线衍射(XRD)结果表明, 合成的材料中橄榄石结构的LiFePO4和单斜晶系的Li3V2(PO4)3两相共存; 从复合材料中LiFePO4、Li3V2(PO4)3相对于相同条件下制备的纯相LiFePO4和Li3V2(PO4)3的晶格常数变化以及结合高分辨透射电子显微镜(HRTEM)、能量散射X射线(EDAX)的结果可以看出, 在复合材料xLiFePO4·yLi3V2(PO4)3中存在部分V和Fe, 分别掺杂在LiFePO4和Li3V2(PO4)3中, 并形成固溶体; X射线光电子能谱(XPS)结果表明, Fe/V在复合材料中的价态与各自在LiFePO4和Li3V2(PO4)3中的价态保持一致, 分别为+2 和+3价. 充放电测试表明, 制备出的复合正极材料电化学性能明显优于单一的LiFePO4和Li3V2(PO4)3; 循环伏安测试表明, 复合正极材料具有优良的脱/嵌锂性能.     

Calcification mechanism and bony bonding studies of calcium carbonate and composite aluminosilicate/calcium phosphate applied as biomaterials by using radioactivation methods

Bony grafts are used as a filling biomaterial for defective bone. The introduction of new range of synthetic materials offers to surgeons additional possibilities to avoid virus transmission risks by using natural grafts in bony surgery. In this work, two materials, synthetic calcium carbonate and composite aluminosilicate/calcium phosphate were synthesized by an original method and experimented “in vivo” as biomaterials for bony filling. Extracted biopsies were studied by several physico chemical and biological methods. The aim was to evaluate the kinetic resorption and bioconsolidation of these materials. We focused on the bioconsolidation between implant and bone by realising cartographies from the implant to the bone and on the calcification mechanism by determination of the origin of Ca and Sr responsible of the neo-formed bone. Neutron activation analysis (NAA), radiotracers ⁴⁵Ca* and ⁸⁵Sr* and proton-induced X-ray emission (PIXE) were used. Concerning the synthetic calcium carbonate, results show that twelve months after implantation, the mineral composition of implant becomes similar to that of the mature bone. The neoformed bone is composed with Ca and Sr coming from the organism when the Ca and Sr of the implant were progressively eliminated. Concerning the composite geopolymer/calcium phosphate, PIXE and histological studies reveal the intimate links between the bone and the implant starting with the first month after implantation.     

High rate capability of Fe/FeO/Fe3O4 composite as anode material for lithium-ion batteries

Fe/FeO/Fe₃O₄ composite was synthesized by a simple solid method using ferric citrate and phenolic resin as raw materials. The reaction processes of raw materials mixture were characterized by thermogravimetric analysis (TGA) under nitrogen. X-Ray diffraction (XRD) and scanning electron microscopy (SEM) were used to investigate the structure and morphology of the products. The results showed that the obtained material was octahedral Fe/FeO/Fe₃O₄ composite with a size of 2-4 μm. The electrochemical performances of Fe/FeO/Fe₃O₄ composite as anode material were also evaluated, which exhibited a stable specific capacity of 260.3 mAh g^-1 and an ideal initial coulombic efficiency of 90.8% in the range of 0.05~3 V at the 5C rate. A good rate capacity of Fe/FeO/Fe₃O₄ composite electrode was also shown by the charge-discharge testing even at the rate of 60C. The better rate capability of Fe/FeO/Fe₃O₄ electrode could be measured in higher temperature.     

Bioactive Properties of Chitin/Chitosan—Calcium Phosphate Composite Materials

Calcium phosphate coating over phosphorylated derivatives of chitin/chitosan material was produced by a process based on phosphorylation, Ca(OH)₂ treatment and SBF (simulated body fluid solution) immersion. Chitin/chitosan phosphorylated using urea and H₃PO₄ and then soaked in saturated Ca(OH)₂ solution at ambient temperature, which lead to the formation of thin coatings formed by partial hydrolysis of the PO₄ functionalities, were found to stimulate the growth of a calcium phosphate coating on their surfaces after soaking in 1.5 × SBF solution for as little as one day. The Ca(OH)₂ treatment facilitates the formation of a calcium phosphate precursor over the phosphorylated chitin/chitosan, which in turn encourages the growth of a calcium deficient apatite coating over the surface upon immersion in SBF solution. The bio-compatibility of calcium phosphate compound—chitin/chitosan composite materials was evaluated by cell culture test using L-929 cells. The initial anchoring ratio and the adhesive strength of L-929 cells for composites was higher than that for the polystyrene disk (LUX, control). The results of in-vitro evaluation suggested that the calcium phosphate—chitin/chitosan composite materials were suitable for cell carrier materials.     

新型超分子复合发光材料四足配体铕配合物-蒙脱土的插层组装及发光性质

通过离子交换反应将四足配体铕配合物[EuL(NO3)]2+[L=1,1,1’,1’-四(吡啶-2-羧酸酯基)联三甲基丙烷]插层组装到蒙脱土(MT)层板间, 制备出一种新型的超分子复合发光材料[EuL(NO3)]2+-MT. 用元素分析、XRD、FTIR、UV-Vis和热分析对材料进行了表征, 并对其荧光性质进行了研究. 结果表明, 复合材料保持了蒙脱土良好的层柱结构特征, 其层间距d(001)值与插层配离子的直径吻合得较好, 配离子以单层形式分布于蒙脱土层板间. 在紫外光激发下, 复合材料发出较强的Eu3+特征荧光, 其相对荧光强度、荧光单色性和荧光寿命大大优于相应配合物的乙醇溶液. 复合材料中配合物的发光性能、光稳定性和热稳定性较纯配合物有明显提高.     

Preparation of Chitinous Compound/Gelatin Composite and Their Biological Application

Chitin, a natural abundant polysaccharide, have been investigated as prospected biochemical material due to its several biological advantages. It is insoluble in the most of the organic solvents due to its rigid crystalline structure. However, chitin regenerated hydrogel (RG) has been prepared by using the saturated calcium solvent system under mild conditions. And also, swelling hydrogel (SG) was prepared by using water. In this study, we prepared the suspension of chitinous hydrogel, and applied to fabricated the chitinous compound/gelatin composite sheets. Additionally, N-acetyl D-(+)-glucosamine was added into some composite sheets. We investigated the mechanical properties and growth of NIH/3T3 fibroblast cell for the prepared composite sheet.     

Co(OH)2/Ni(OH)2复合电极材料制备及其超级电容性质

以Co(NO_3)_2·6H_2O和Ni(NO_3)_2·6H_2O为钴源和镍源,采用溶剂热法一步合成了Co(OH)_2/Ni(OH)_2复合材料,通过煅烧该复合材料可得到NiCo_2O_4。采用XRD、SEM、BET等对材料进行了表征,结果表明,Co(OH)_2/Ni(OH)_2复合材料是薄片组成的花状形貌,比表面积为37. 48m~2/g。电化学性能测试表明,Co(OH)_2/Ni(OH)_2复合材料比NiCo_2O_4具有更高的比电容值和容量保持率。在0. 5A/g的电流密度下,复合材料比电容值可达到1097. 8F/g,而NiCo_2O_4比电容值仅为86. 1F/g。因此,与煅烧后的NiCo_2O_4材料相比,Co(OH)_2/Ni(OH)_2复合材料具有更加优良的电化学性能,这为高性能超级电容器材料的制备提供了一个新思路。