基于等离激元增强拉曼光谱的有机磷毒剂现场减毒检测新技术研究

The rapid detection of organophosphorous toxins is closely related with human health and ecological environment. It is significant to deal with sudden public safety and chemical terrorist attacks, ensure the national security, safeguard the human life, food safety and clinical medicine. It is in urgent need to develop methods for rapid qualitative and quantitative detection of organophosphorus agents, the goal of this study is to develop a rapid, sensitive, and reliable organophosphorus agents field rapid screening new strategy. Current research based on the specific reaction between the organophosphorous toxins and oxime compounds, synthesize a series of oxime. Firstly, a series of oximes were synthesized according to traditional methods.The high reactive raman probe molecule suitable for detection by plasmon enhanced raman scattering are obtained via optimization of the structrue of oxime compounds and reaction conditions. Secondly, the novel rapid qualitative and quantitative detection method for organophosphorous toxins integrate the advantage of plasmon enhanced raman scattering with the specific reaction between the the organophosphorous toxins and oxime compounds. The method was developed by the indirect measurement of probe molecule raman characteristic peak based on the excellent surface enhanced raman scattering of AuNPs. Meanwhile, the highly poisonous organophosphorous toxins were translated into low poisonous compounds. In addition, the method was used to enantiomeric discrimination of chiral organophosphorous toxins by coated AuNPs with oximes containing chiral center. Lastly, the novle dectection method was evaluated by its lowest detection limit, reproducibility and reliability. The method was applied to the determination of organophosphorous toxins in real aqueous solution samples. The realization of this research is of great significance to ensure the national security, safeguard the human life and property, and prevent terrorist attacks.

有机磷毒剂的快速检测，与人类的健康和生态环境密切相关，其对于应对突发公共安全和化学恐怖袭击事件、保障国家和人民安全及临床医学等方面具有十分重要的意义。针对目前缺乏快速定性定量检测有机磷毒剂的现状，本研究旨在建立一种快速、灵敏、可靠的有机磷毒剂现场快速甄别新策略。拟基于有机磷毒剂与肟类化合物的特异性反应，设计并合成不同类型的肟类化合物，系统考察并优化肟类化合物结构和反应条件，筛选适用于等离激元增强拉曼光谱检测的高活性拉曼探针分子；基于AuNPs优良的表面增强拉曼散射效应，将等离激元增强拉曼光谱的检测优势与特异性反应有机结合，通过化学转换技术间接测定探针分子的特征拉曼信号,不仅实现了对有机磷毒剂的快速定性、定量检测，同时还将高毒的有机磷化合物降解为低毒化合物。还将建立的方法尝试用于手性有机磷毒剂光学异构体的识别。本研究的实施在应对公共突发事件和化武恐怖袭击及卫生安全等方面具有广泛应用前景。

有机磷毒剂的快速检测，与人类的健康和生态环境密切相关，其对于应对突发公共安全和化学恐怖袭击事件、保障国家和人民安全及临床医学等方面具有十分重要的意义。本课题针对目前缺乏快速定性定量检测有机磷毒剂的现状，利用某些高反应活性的有机磷毒剂能与邻羰基肟类化合物发生快速特异性反应，生成拉曼探针分子氰根这一特性，通过制备系列肟类化合物和优化检测条件，结合有孔壳层隔绝纳米粒子能有效抑制氰化物溶金效应的优势，首次建立了一种基于表面增强拉曼光谱技术（SERS）的快速、灵敏、可靠的有机磷毒剂现场检测方法。相比于目前现有的现场检测方法具有如下优势：（1）检测速度快（每个样品检测仅需2-3min）；灵敏度高，最低检测限可达20 ng/mL；（2）具有谱学识别特性，能实现G-类和V-类神经性毒剂（属于有机磷毒剂）的区分检测；（3）在实现高灵敏检测的同时，剧毒神经性毒剂自发降解为低毒的有机磷酸，探针分子氰根被吸附于纳米金表面，通过简单离心即可被回收去除，整个检测流程有明显的减毒效果。可以说，我们构建的快检体系有效提升了剧毒有机磷化合物现场检测能力，为有机磷化合物中毒采取有效的医学救援措施提供了技术保障。在此基础上，还建立了系列剧毒有机磷涉恐化学品的谱学数据库，进一步为现场快速确证检测结果提供了坚实基础。.百草枯属于剧毒灭生性除草剂，数十毫升即可致人于死地。因误食百草枯而造成的中毒，目前依然没有特效药，因此百草枯中毒患者死亡率高达70%以上。但如发现及时，结合洗胃、肺部冲洗和血液透析等方法，患者依然有希望得到救治。因此，建立快速、准确和可靠的现场检测方法显得尤为重要，尤其是生物基质样品中百草枯的快速检测。我们通过巧妙设计和比较各类传感体系，最终构建并优选了一种“Au@I-@Paraquat”三明治传感体系。该体系具有两个突出优势：一是可有效抑制复杂基质干扰，即使是血液、尿液样品，几乎不需经过预处理即可直接实现其中百草枯的高灵敏检测，血液和尿样中的最低检测限均可达0.1 ng mL-1；二是该体系还可区分检测百草枯及其类似物，如百草枯与其合成原料联二吡啶等。因此，该体系大幅提升了复杂基质样品中百草枯的快速检测能力，为百草枯中毒患者得到有效及时的救治赢得了宝贵救援时间，曾被审稿人评价为百草枯快检方面的一个重要突破。