基于表面增强拉曼散射效应的有机膦毒剂分子检测研究

发布时间：2018-02-09 15:40

  本文关键词： 金属纳米结构阵列 SERS衬底 修饰剂 表面修饰 有机膦毒剂分子 模拟剂 非贵金属SERS衬底 痕量检测　出处：《中国科学技术大学》2017年博士论文　论文类型：学位论文

【摘要】：神经毒剂(如沙林、梭曼等),属于有机膦酰氟类化合物,毒性极强,使人在几分钟之内即可致命。因此,对此类神经毒剂的快速、痕量检测,对于保障人们生命健康,维护国家公共安全等都具有重大的现实意义。基于表面增强拉曼散射(SERS)效应的检测方法,是实现快速、痕量检测的有效途经。然而,由于有机膦毒剂分子与金属SERS衬底之间相互作用力很弱,不能被SERS衬底所有效捕捉和选择性富集,而无法实现基于SERS效应的有效检测。针对这一问题,本论文从高SERS活性衬底和非贵金属衬底设计制备以及衬底的表面修饰着手,开展了基于SERS效应的有机膦毒剂分子检测的研究,包括高密度纳米针尖阵列SERS基底的构筑,金属纳米结构阵列的表面修饰及其SERS效应,以及非贵金属SERS衬底的设计合成等,旨在改善SERS衬底与有机膦毒剂分子的相互作用,实现强选择性吸附和高效富集,进而实现基于SERS效应的有机膦毒剂分子快速、痕量的检测。取得了主要创新性结果如下。(1)发展了一种高密度纳米针尖阵列SERS基底的构筑策略。在玻璃衬底上,基于胶体模板刻蚀与沉积的方法,构筑了高密度金纳米针尖阵列的SERS衬底,该衬底表面洁净,均一性好,实现了对三苯基膦分子的痕量检测,为构筑高SERS活性衬底提供了一种简便方法。(2)提出了基于衬底表面修饰-化学反应的SERS检测策略。在金纳米结构阵列SERS衬底上修饰巯基乙胺,实现了对沙林模拟剂甲基膦酸的选择性、高效捕捉以及酰胺反应,进而实现了对甲基膦酸的拉曼痕量检测;发现了在大浓度范围[1ppb～1OOOppm]具有很好的拉曼强度-浓度双对数线性关系,揭示了其源自于Freudlisch吸附机制。这一策略为基于SERS效应检测与金属衬底弱相互作用的分子提供了有效的途径。(3)提出了利用氢氧化物表面活性基团实现有机膦分子有效捕捉的设想。通过α-Co(OH)2表面丰富的官能团与有机膦分子中的活性基团形成氢键,进而实现了对有机膦分子的高效捕捉;发现了 α-Co(OH)2有显著的拉曼增强效应,增强因子高达～2000,拉曼特征峰强度与有机膦毒剂分子浓度满足双对数线性关系。这项工作,为设计、寻找非贵金属SERS活性材料提供了新思路,也为下一步将此与高SERS活性金属纳米结构阵列的结合、研究高性能复合SERS衬底奠定基础。
[Abstract]:Nerve agents (such as sarin, soman, etc.) belongs to the organic phosphonic acid fluorine compounds, highly toxic, so that people in a few minutes to kill. Therefore, fast trace of such nerve agent detection, for the protection of people's lives and health, maintain public safety and has great practical significance. The surface enhanced based on Raman scattering (SERS) detection method of effect, is to achieve rapid, effective way to trace detection. However, because organic phosphine poison molecules and metal SERS substrate interaction is very weak, not by SERS substrate capture and selective enrichment, and can not achieve effective detection based on SERS effect. To solve this problem, the preparation and surface modification of the substrate from the high SERS active substrate and non noble metal substrate was designed to carry out the research on detection of organophosphorus toxicants molecules based on SERS effects, including high density nano needle Build a SERS tip array substrate, surface modification and SERS effect of metal nano structure array, and the non noble metal substrate SERS synthesis, interaction to improve SERS substrate and organic phosphine poison molecules, strong selective adsorption and enrichment, so as to realize based on molecular organic phosphine poison SERS effect fast, trace the detection. The main innovative results are as follows. (1) the development strategies of constructing a high density substrate. SERS nanotip arrays on a glass substrate, method of etching and deposition of colloidal template based on the constructed SERS substrate of high density gold nanotip arrays, the substrate surface is clean, good uniformity. Realize the trace detection of three phenyl phosphine molecules, provides a convenient method for constructing high SERS active substrate. (2) proposed SERS detection strategy is modified based on substrate surface chemical reaction in gold. M structure array SERS substrate modified Mercaptoethylamine, simulate agent methyl phosphonic acid selectivity for sarin, efficiently capture and amide reaction, so as to realize the Raman trace detection of methyl phosphonic acid; found in the concentration range of [1ppb ~ 1OOOppm] has very good Raman intensity concentration double logarithmic linear relationship was revealed it comes from the Freudlisch adsorption mechanism. This strategy provides an effective way for the detection of molecular interactions with metal substrate based on weak SERS effect. (3) proposed to realize the effective utilization of organic phosphine molecule capture hydroxide surface active groups. The alpha -Co (OH) activity group 2 abundant surface functional groups and organic phosphine in the molecule of hydrogen bond formation, so as to realize the efficient capture of organic phosphine molecules; found alpha -Co (OH) 2 significantly enhanced Raman effect, enhancement factor of up to 2000, Raman characteristic peaks Meet the double logarithmic linear relationship between intensity and concentration of organic phosphine poison molecules. This work, for the design, looking for non noble metal SERS active material provides a new idea for the next step will be to combine this with high SERS activity of metal nanostructure arrays on SERS substrate, high performance composite foundation.

【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：D919.4;O657.37
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本文编号：1498271