Chiang Chia-Yen, Liu Ting-Yu, Su Yu-An, Wu Chien-Hsin, Cheng Yu-Wei, Cheng Ho-Wen, Jeng Ru-Jong
Institute of Polymer Science and Engineering, National Taiwan University, Taipei 10617, Taiwan.
Department of Materials Engineering, Ming Chi University of Technology, New Taipei City 24301, Taiwan.
Polymers (Basel). 2017 Mar 6;9(3):93. doi: 10.3390/polym9030093.
We have successfully developed novel surface-enhanced Raman scattering (SERS) substrates with three-dimensional (3D) porous structures for effectively improving the sensitivity and reproducibility of SERS, which can rapidly detect small molecules (rhodamine 6G as an example). Periodical arrays of the honeycomb-like substrates were fabricated by self-assembling polyurethane--azetidine-2,4-dione (PU-PAZ) polymers. PU-PAZ comprising amphiphilic dendrons could stabilize the phase separation between the water droplets and polymer solution, and then organize into regular porous structures during the breath figure method. Subsequently, SERS substrates were fabricated by immobilizing gold nanoparticles (AuNPs) onto the honeycomb-like films with various 3D porous structures, controlled by the different PU-PAZ concentrations and relative humidities. Results show that surface enhancement factors of honeycomb-like substrates were 20 times higher than that of flat-film substrates (control group) due to enormous hot-spots resonance effects by the 3D porous structure, verified through Raman mapping at various positions of the -axis. Furthermore, the particle size effects were evaluated by immobilized 12 and 67 nm of AuNPs on the honeycomb-like substrates, indicating larger AuNPs could induce more pronounced hot-spots effects. The generation of hot-spots resonance to enhance Raman intensity is strongly dependent on the diameter of AuNPs and the pore size of the honeycomb-like and 3D porous substrates for label-free and rapid SERS detection.
我们成功开发了具有三维(3D)多孔结构的新型表面增强拉曼散射(SERS)基底,以有效提高SERS的灵敏度和重现性,该基底能够快速检测小分子(以罗丹明6G为例)。通过自组装聚氨酯-氮杂环丁烷-2,4-二酮(PU-PAZ)聚合物制备了蜂窝状基底的周期性阵列。包含两亲性树枝状分子的PU-PAZ可以稳定水滴与聚合物溶液之间的相分离,然后在呼吸图案法过程中组织成规则的多孔结构。随后,通过将金纳米颗粒(AuNP)固定在具有各种3D多孔结构的蜂窝状薄膜上制备SERS基底,这些结构由不同的PU-PAZ浓度和相对湿度控制。结果表明,由于3D多孔结构产生的巨大热点共振效应,蜂窝状基底的表面增强因子比平膜基底(对照组)高20倍,这通过在x轴不同位置的拉曼映射得到验证。此外,通过将12和67 nm的AuNP固定在蜂窝状基底上来评估粒径效应,结果表明较大的AuNP可以诱导更明显的热点效应。产生热点共振以增强拉曼强度强烈依赖于AuNP的直径以及蜂窝状和3D多孔基底的孔径,用于无标记和快速SERS检测。