贵金属纳米锥有序阵列的表面双官能团分子修饰及对有机膦毒性分子的SERS效应研究

Aiming at problem of very weak interaction between the organophosphine toxic molecules (such as, sarin and VX) and noble metals, in this project, we propose the idea to realize the efficient capture of the organophosphine toxic molecules by surface modification of bifunctional group molecules on the noble metal substrates, and carry out the research on the noble metal nanostructured arrays’ surface modification and the surface enhanced Raman scattering (SERS) effect to the organophosphine toxic molecules, mainly including the preparation of the noble metal nanocone arrays and their structural parameter optimization; structural design and screening of bifunctional group molecules, and surface modification on the nanocone arrays; SERS effect of the nanocone arrays and influences from the surface modification, and the SERS-based detection method for the organophosphine toxic molecules, in order to develop the preparation methods for the organic template-based noble metal nanostructured arrays; obtain the efficient modifying agents for the specific organophosphine toxic molecules; reveal the structural dependence of noble metal nanostructured arrays’ SERS effect; establish the relations between the characteristic Raman peak intensities of the organophosphine toxic molecules and their concentration and realize the SERS-based trace detection of the organophosphine toxic molecules, etc. These could not only present new approaches to the SERS-based detection of the target molecules weakly interacted with noble metals, but also provide the theoretical and material bases for design and construction of the SERS–based devices for the organophosphine toxic molecules.

针对有机膦毒性分子(沙林、维埃克斯等)与贵金属相互作用非常弱的问题，本项目提出通过双官能团有机分子的表面修饰实现贵金属衬底对有机膦毒性分子有效捕捉的思路，开展贵金属纳米结构阵列表面修饰及对有机膦毒性分子的表面增强拉曼散射(SERS)效应研究，主要包括：贵金属纳米锥有序阵列的制备及其结构参数优化；双官能团修饰剂分子的结构设计、筛选及在阵列表面的修饰；纳米锥阵列的SERS效应与表面修饰的影响以及基于SERS效应的有机膦分子检测方法等。旨在发展基于有机模板的贵金属纳米结构阵列制备方法；筛选针对特定有机膦毒性分子的高效修饰剂；揭示贵金属纳米阵列SERS效应的结构相关性；建立有机磷毒性分子拉曼峰强度与浓度之间的对应关系，实现基于SERS效应的痕量检测等。这项研究不仅有望为与贵金属弱相互作用的目标分子SERS检测提供新途径，而且可为有机膦毒性分子SERS检测器件的研制提供理论依据与材料基础。

沙林等有机膦毒剂具有高毒性和快速致命的特点，传统的传感器及谱学技术难以实现快速、痕量和特异性现场检测。基于贵金属表面增强拉曼散射（SERS）效应的分子检测有望满足这一需求，但毒剂分子不含与贵金属强相互作用的官能团，无法吸附在敏感单元表面，通常仅局限于定性识别，且信号不稳定，更无法实现痕量检测。针对这一难题，项目负责人提出高活性贵金属纳米锥有序阵列的可控构筑策略，并通过设计、合成和表面修饰双官能团捕捉剂分子，对有机膦毒剂分子进行选择性富集，进而实现高效SERS检测。项目执行过程中，重点开展了以下研究：贵金属纳米锥有序阵列的灵敏性、信号均一性、重复性等性能指标及与微结构、组分的相关性；双官能团捕捉剂分子的结构设计、筛选及表面修饰参数优化；功能化的SERS衬底对沙林等毒性分子的检测性能及增强机制；等等。通过本项目的执行：发展了基于有机模板的贵金属纳米结构阵列制备方法；筛选出了针对特定有机膦毒剂的高效捕捉剂分子；揭示了贵金属纳米阵列SERS效应的结构相关性；建立有机磷毒性分子拉曼峰强度与浓度之间的对应关系，实现基于SERS效应的痕量检测等。更为关键的是，基于本项目双官能团特异性捕捉这一思路，项目团队进一步将目标分子拓展至汞离子、H2S等毒性分子，并研发出了一系列专用型SERS检测芯片。目前，高增强效果的SERS芯片已推向市场，沙林专用检测传感器已向军队某研究所供货，初步实现了科研成果的落地转化。本项目，不仅为与贵金属弱相互作用的目标分子SERS检测提供了全新途径，而且毒性分子专用型SERS检测器件的研制提供了理论依据与材料基础。