通过利用具有高度规整孔道结构、一致孔径分布、高比表面积、高孔隙率等优点的介孔材料为模板，采用纳米铸造的办法制备出具有周期性阵列排布的贵金属纳米材料，其在表面增强拉曼散射光谱(SERS)、催化、生物等领域有自身特有的优势，引起了人们的广泛关注。“纳米铸造法”成为构建尺寸、形状、组成二致且具有新颖构型的一种成本低廉、环境友好、适用于大规模生产纳米结构的制备方法。 1.采用“纳米铸造”的方法以有序超大孔介孔材料EP-FDU-12为填充模板，硝酸银为无机前驱体，在真空干燥箱中真空吸附，合成出沉积银离子的EP-FDU-12模板材料，在真空干燥箱中向上述复合材料加入不同还原剂(如硼氢化钠、抗坏血酸、柠檬酸钠及乙二醇)。其中，硼氢化钠、抗坏血酸及柠檬酸钠作为还原剂未合成出复制EP-FDU-12模板材料的有序模板银纳米结构，获得在模板外成核、生长形成的无序的银纳米结构。在乙二醇的作用下成功合成出复制EP-FDU-12模板形貌的银纳米结构。对乙二醇的反应温度及二氧化硅模板的去除剂分别进行优化，研究表明合成模板银纳米结构的还原温度确定为160℃，连续多次使用热的氢氧化钠溶液是快速去除二氧化硅模板的有效解决途径。三维银纳米结构对结晶紫、对氨基苯硫酚两种探测分子均表现出高的检测灵敏度、低的检测限及高的信号一致性。以稀硝酸为化学腐蚀剂，在三维银纳米结构上成功构建出不同尺寸的纳米孔、纳米间隙。对原位及非原位腐蚀后的三维银纳米结构进行表面增强拉曼散射光谱性能测试。通过有限时域差分法分别模拟了三维银纳米结构及三维银纳米结构上纳米孔、纳米间隙的电磁场场强分布。研究表明，相比原位腐蚀后的三维银纳米结构的表面增强拉曼散射光谱图，非原位腐蚀后的三维银纳米结构的表面增强拉曼散射光谱与其遵循相同的腐蚀规律。不同尺寸的纳米孔、纳米间隙调控三维银纳米结构的电磁场场强分布结果与吸附结晶紫探测分子的原位及非原位腐蚀后的三维银纳米结构的表面增强拉曼散射光谱的结论一致。 2.以氯金酸提供金物种，采用在表面修饰氨基或未修饰氨基的介孔材料KIT-6为模板，无论采用高温煅烧还是不同还原强度的还原剂，均未合成出有序的介孔金纳米结构。上述研究结果说明，金物种的还原环境对有序金纳米结构的合成至关重要。采用正己烷提供非极性环境，1，1，3，3-四甲基二硅氧烷为还原剂及表面未修饰氨基的介孔材料KIT-6为模板，成功合成出三维有序介孔金纳米结构。同时研究了三维有序介孔金纳米颗粒的生长机理。论文分别用十二硫醇、甲氧基聚乙二醇、硫辛酸聚乙二醇在二氧化硅模板的去除过程中修饰三维有序介孔金纳米颗粒，成功合成出3DOM-Au@SH、3DOM-Au@SH-mPEG及3DOM-Au@LA-PEG纳米化合物。通过比较经甲氧基聚乙二醇及硫辛酸聚乙二醇表面修饰的三维有序介孔金纳米颗粒的稳定性、近红外吸收、光热转换能力及阿霉素抗癌药物载药能力相关方面的研究，确定以在二氧化硅模板的去除过程中表面修饰硫辛酸聚乙二醇制备的3DOM-Au@LA-PEG作为阿霉素的药物装载体。在细胞水平上对3DOM-Au@LA-PEG、3DOM-Au@LA-PEG／DOX分别进行细胞毒性研究，可以看出3DOM-Au@LA-PEG无明显的细胞毒性，具有良好的生物相容性。3DOM-Au@LA-PEG／DOX在近红外激光的照射下，加速了阿霉素抗癌药物的释放，同时将近红外光迅速转换为热能，显著提高了癌变细胞的死亡率。三维有序介孔金纳米颗粒在单分子表面增强拉曼散射光谱方面的研究表明，三维有序介孔金纳米颗粒对结晶紫分子、对氨基苯硫酚探测分子均表现出高检测灵敏度，拉曼信号具有高的稳定性和重复性。 3.以Ag@MSN为牺牲模板材料，通过在抗坏血酸还原剂的协助下发生连续的共还原及空间限域生长，在聚乙烯比咯烷酮(PVP)、抗坏血酸(AA)、氢氧化钠(NaOH)、亚硫酸钠(Na₂SO₃)及Na₃Au(SO₃)₂的共同作用下，成功合成出中空金／银、海胆状中空金／银纳米结构。与中空金／银的表面增强拉曼散射光谱图比较，海胆状中空金／银纳米结构上出现的金尖端二级结构有利于提高其表面增强拉曼散射光谱的信号。海胆状中空金／银纳米结构纸基对吸附的结晶紫(CV)、孔雀石绿(MG)两种探测分子的表面增强拉曼散射光谱均体现出高的灵敏性、重复性、一致性。采用水热法合成出四氧化三铁微球，然后将氯金酸溶液与四氧化三铁微球直接反应合成出四氧化三铁／金纳米复合材料。以结晶紫为探测分子，比较四氧化三铁微球、四氧化三铁／金纳米复合材料的表面增强拉曼散射光谱性能。四氧化三铁微球表面上出现的金纳米结构引起四氧化三铁／金纳米复合材料上吸附的结晶紫探测分子表面增强拉曼散射光谱信号的显著增强。 关键词：纳米铸造法；介孔材料；贵金属；表面增强拉曼散射光谱；光热联合治疗 论文类型：应用基础 本研究获得高校基本业务科研经费资助(编号：xkjc2014004)

 Mesoporous materials are used as the templates for preparing highly ordered noble metal nanostructures by nano-replication routes, because it can steadily provide highly ordered pore structures, uniform pore size distributions, high pore volume and large surface area. The highly ordered noble metal nanostructures have been firstly used in the fields, such as Surface Enhanced Raman Scattering Spectrum and catalysts, which have attracted broad attention. Nano-replication routes are the method to prepare the size-, shape- and formconsistent metal nanostructures, which are low-cost, friendly environment, and suitable for mass production. 1.We prepare the template Ag nanostructures by the nano-replication routes. Here, we take the highly ordered mesoporous silicas with very large pores EP-FDU-12 as the template, silver nitrate as the inorganic precursor. The silver ions are deposited along the channel of the mesoporous material EP-FDU-12 under the vacuum drying oven. When the above nanocomposites are dry, we add different reductant, such as sodium borohydride, ascorbic acid, sodium citrate and ethylene glycol. Among them, the sodium borohydride, ascorbic acid and sodium citrate make the silver ions nucleate and grow outside the template. They are are not successfully to duplicate the ordered template of the mesoporous material EP-FDU-12 and are the unordered silver nanostructures. Under the action of ethylene glycol, the prepared silver nanostructures have successfully duplicate the template morphology of the mesoporous material EP-FDU-12. Furthermore, we have optimized the reduction temperature of the ethylene glycol, and the methods to remove the mesoporous silica template. We can conclude that the reduction temperature of the ethylene glycol is 160 ℃ to obtain the ordered template Ag nanostructures. It is an effective way to quickly remove silica template by continuously hot sodium hydroxide solution. The three-dimensional silver superlattice nanostructures exhibit the high detection sensitivity, low detection limit and high signal consistency to the probe molecules, crystal violet and 4-Aminothiopheno. We have fabricated different sizes of nanopores and nanogaps on the 3D Ag NP supercrystals through dilute nitric acid as chemical etchant. We test the in-situ and ex-situ Surface Enhanced Raman Scattering spectrum for the corrosive 3D Ag NP supercrystals. We compute the intensity distribution of the electromagnetic fields on the surface for the 3D Ag NP supercrystals, the nanopores and nanogaps from the 3D Ag NP supercrystals through finite difference time domain (FDTD) simulations. We can conclude that the ex-situ Surface Enhanced Raman Scattering Spectrum of the 3D Ag NP supercrystals have the same law of corrosion in comparision with the in-situ Surface Enhanced Raman Scattering Spectrum of the 3D Ag NP supercrystals. The finite difference time domain (FDTD) simulations further illustrate that the enhanced electric fields can be attributed to the occurrence of different sizes of nanopores, which agrees well with the in-situ and ex-situ Surface Enhanced Raman Scattering Spectrum of the 3D Ag NP supercrystals. 2.We take HAuCl₄·4H₂O as the Au species, mesoporous materials KIT-6 with or without surface modification as the template, respectively. Neither the calcination nor the different strength reductant make the ordered Au nanostructures.The above research results indicate that the reduction environment of Au species is essential to the preparation of the orderd Au nanostructures. Therefore, we take n-hexane as the nonpolar environment, 1,1,3,3-tetramethyldisiloxane as the reducing agent, mesoporous materials KIT-6 without surface modification as the template, to successfully prepare the three-dimensionally ordered mesoporous Au nanoparticles. Meanwhile, we have studied the growth mechanism of the the three-dimensionally ordered mesoporous Au nanoparticles. To acquire stable nanocomposites, we modify the 1-Dodecanethiol, methoxy polyethylene glycol thiol and lipoic acid polyethylene glycol on the surface of the three-dimensionally ordered mesoporous Au nanoparticles. In the process of above surface modification, the mesoporous silica templates are removed, and the 3DOM-Au@SH 、 3DOM-Au@SH-mPEG and 3DOM-Au@LA-PEG are prepared respectively. We compare the stability, NIR absorption, NIR heat conversion and the load capacity of the DOX between the 3DOM-Au@SH and the 3DOM-Au@SH-mPEG nanocomposites. We take 3DOM-Au@LA-PEG as the drug delivery system, which are prepared in the removing process of the mesoporous silica templates. To evaluate the cytotoxicity of the 3DOM-Au@LA-PEG and 3DOM-Au@LA-PEG/DOX nanocomposites, they are conducted in cancer cells. There are no apparent cytotoxicity of the cells incubated with 3DOM-Au@LA-PEG nanocomposites, which indicates 3DOM-Au@LA-PEG nanocomposites have the good biocompatibility. Thus, the 3DOM-Au@LA-PEG/DOX nanocomposites under laser irradiation accelerate the anticancer drug release, have the high photothermal heating conversion and show the higher inhibition cells rate. 3.The hollow Au/Ag and the hollow Au/Ag nanourchins are synthesized via the co-reduction and the spatially confined growth methods. Where, the Ag@MSN as sacrifical templates, are dissolved into the aqueous solution containing H₂O, PVP, AA, NaOH, Na₂SO₃, and Au precursor of Na₃Au(SO₃)₂. In comparison with hollow Au/Ag, the growth of the tipped Au on the surface of the hollow Au/Ag are benefical to boost the SERS signals. Hollow Au/Ag nanourchins exhibit high sensitivity, reproducipility and high uniformity for trace detecting of the crystal violet (CV) and amalachite green (MG) molecules. We first synthesize Fe₃O₄ microspheres by hydrothermal method. Then, the Fe₃O₄ microspheres react with the HAuCl₄·4H₂O solution, leading to the formation of the Fe₃O₄/Au nanocomoposites. To explore the SERS performance of the Fe₃O₄/Au nanocomposites and the Fe₃O₄ microspheres, crystal violet (CV) molecules are used as the probe molecules. The appearance of the Au nanostructures on the surface of the Fe₃O₄ microspheres are benefical to boost the SERS signals. KEYWORDS: Nano-replication routes; Noble metal; SERS;Photothermal-chemotherapy therapy TYPE OF DISSERTATION: Application Fundamentals