超疏水微纳米阵列的制备及高灵敏表面增强拉曼散射分析研究

We proposed the preparation of superhydrophobic Surface-enhanced Raman Scattering (SERS) active substrates for high sensitive detection. The area irradiated by Raman laser is about 1-2 square micron in which the molecules could be detected. The superhydrophobic SERS substrates will restrict the spread of probe solution, so the probe molecules will be locked in a small area, which is very important for decreasing the detection limit. .We proposed to fabricate superhydrophobic SERS substrates by two kinds of strategies. First, superhydrophobic SERS substrates were fabricated by chemical synthesis and assembly; second, by nanolithography and manipulation using Scanning Probe Microscopy (SPM), a small hydrophilic spot was obtained on the surface of superhydrophobic surface.These substrates will be utilized as SERS substrates to investigate how the size, shape and arrangement of silver，gold nanoparticles in laser irradiated area influence on the SERS effect, and the enhancement mechanism will be explored furtherly. The effect of hydrophobic properties of substrates to SERS will be studied, and some effort will be made for finding the relationship of SERS band enhancement factor and the contact angle between the water drop and the substrate. Using these superhydrophobic SERS active substrates, the high sensitive detection for organic pollutants will be accomplished. Finally, we will explore the possibility to directly detect specific organic pollutant in food or water without purification.

申请者提出制备超疏水的表面增强拉曼散射（SERS）活性基底，为实现高灵敏的SERS检测提供基础。由于SERS实际检测到的探针分子仅分布在激光照射的微区约1-2平方微米内，超疏水基底能够限制探针分子溶液的铺展，将探针分子"锁定"在尽可能小的区域内，对降低检测限具有重要意义。申请者拟利用化学合成与组装方法制备超疏水微纳米结构；利用扫描探针显微镜纳米加工与纳米操纵技术，在超疏水表面构筑"纳米粒子亲水微区"；将以上两种微纳米结构用作SERS基底，研究拉曼激光照射微区内银、金等纳米粒子的尺寸、形状等对SERS的影响，探索SERS的增强机理；研究表面的疏水性质对SERS的影响，寻找水溶液液滴和超疏水表面间的接触角与SERS谱峰的增强因子之间的联系；实现有机污染物的高灵敏检测，探索利用拉曼光谱的指纹效应，不经分离直接从食品、水中检测特定有机污染物的可能性。

申请者提出制备超疏水的表面增强拉曼散射（SERS）活性基底，为实现高灵敏的SERS检测提供基础。由于SERS实际检测到的探针分子仅分布在激光照射的微区约1-2平方微米内，超疏水基底能够限制探针分子溶液的铺展，将探针分子“锁定”在尽可能小的区域内，对降低检测限具有重要意义。. 项目组成员利用光还原等多种化学方法构筑了几种 SERS 基底，包括：泡沫镍为模板的银纳米粒子薄膜、铜片为基底的粗糙的银基底、二氧化钛-银纳米粒子三维复合可自清洁基底，研究了银纳米粒子的尺寸、形状等信息对拉曼增强的影响；通过水热等方法制备了氧化锌为模板的银纳米超疏水基底；通过光刻、扫描探针显微技术、直接滴加等方法，在超疏水表面构建了“亲水微区”，间接实现了超疏水的浓缩作用。. 利用上述制备的基底，探索和证实了超疏水SERS增强的机理，实现了对罗丹明6G、对巯基苯胺、亚甲基蓝、结晶紫、三聚氰胺、农药福美双等的高灵敏检测，并且可以实现福美双在实际样品果汁和果皮中的低浓度检测。. 发表SCI收录的致谢论文29 篇，其中影响因子≥3的27 篇，影响因子<3的2篇。申请中国发明专利5项，均已获授权。

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