南京师范大学戴志晖团队通过定向超分子组装的化学机制主导和报告器可调表面增强拉曼散射。相关研究成果于2022年9月8日发表于国际一流学术期刊《美国化学会杂志》。

分子共振可以通过电荷转移增强，有利于化学机制（CM）相关的表面增强拉曼散射（SERS）。

该文中，通过将对磺酸基氯化铝[4]芳烃（pSC4）官能化到Au₃Cu纳米晶体（NCs）上，建立了超分子组装启用的SERS系统。由于Au和Cu的协同作用，pSC4通过范德瓦尔斯力定向组装在Au₃Cu NCs表面，实现光诱导和氢键诱导电荷转移，这显著增强了pSC4捕获亚甲基蓝（MB）的拉曼散射。特别是，对于MB的C-N和C-C拉伸，共振拉曼散射的贡献增加到80%。此外，SERS系统能够显示不同主客体相互作用的亲和力，并进一步用于评估药物治疗阿尔茨海默病的效果。

该项工作中，电荷转移是通过在等离子体纳米材料表面进行超分子组装来实现的，为设计CM相关的和报告可调SERS系统提供了途径。

附：英文原文

Title: Chemical Mechanism-Dominated and Reporter-Tunable Surface-Enhanced Raman Scattering via Directional Supramolecular Assembly

Author: Zhaoyin Wang, Lili Huang, Min Zhang, Zijun Li, Lei Wang, Haozhe Jin, Xijiao Mu, Zhihui Dai

Issue&Volume: September 8, 2022

Abstract: Molecular resonance can be strengthened by charge transfer, profiting chemical mechanism (CM)-related surface-enhanced Raman scattering (SERS). Herein a supramolecular assembly enabled SERS system is established by functionalizing para-sulfonatocalix[4]arene (pSC4) onto Au3Cu nanocrystals (NCs). Due to the cooperation of Au and Cu, pSC4 is directionally assembled on the surface of Au3Cu NCs via van der Waals force, enabling photoinduced and hydrogen bond-induced charge transfer, which remarkably enhances the Raman scattering of methylene blue (MB) captured by pSC4. In particular, for the C–N and C–C stretching of MB, the contributions of resonance Raman scattering increase up to 80%. In addition, the SERS system is able to display affinities of different host–guest interactions, and further employed to evaluate effects of drugs for Alzheimer’s disease. In this work, charge transfer is realized by performing supramolecular assembly on the surface of plasmonic nanomaterials, providing an avenue to design CM-related and reporter-tunable SERS systems.

DOI: 10.1021/jacs.2c06026

Source: https://pubs.acs.org/doi/10.1021/jacs.2c06026