本文關(guān)鍵詞： 金屬納米結(jié)構(gòu)陣列 SERS襯底 修飾劑 表面修飾 有機(jī)膦毒劑分子 模擬劑 非貴金屬SERS襯底 痕量檢測(cè)　出處：《中國(guó)科學(xué)技術(shù)大學(xué)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：神經(jīng)毒劑(如沙林、梭曼等),屬于有機(jī)膦酰氟類化合物,毒性極強(qiáng),使人在幾分鐘之內(nèi)即可致命。因此,對(duì)此類神經(jīng)毒劑的快速、痕量檢測(cè),對(duì)于保障人們生命健康,維護(hù)國(guó)家公共安全等都具有重大的現(xiàn)實(shí)意義�；诒砻嬖鰪�(qiáng)拉曼散射(SERS)效應(yīng)的檢測(cè)方法,是實(shí)現(xiàn)快速、痕量檢測(cè)的有效途經(jīng)。然而,由于有機(jī)膦毒劑分子與金屬SERS襯底之間相互作用力很弱,不能被SERS襯底所有效捕捉和選擇性富集,而無(wú)法實(shí)現(xiàn)基于SERS效應(yīng)的有效檢測(cè)。針對(duì)這一問(wèn)題,本論文從高SERS活性襯底和非貴金屬襯底設(shè)計(jì)制備以及襯底的表面修飾著手,開(kāi)展了基于SERS效應(yīng)的有機(jī)膦毒劑分子檢測(cè)的研究,包括高密度納米針尖陣列SERS基底的構(gòu)筑,金屬納米結(jié)構(gòu)陣列的表面修飾及其SERS效應(yīng),以及非貴金屬SERS襯底的設(shè)計(jì)合成等,旨在改善SERS襯底與有機(jī)膦毒劑分子的相互作用,實(shí)現(xiàn)強(qiáng)選擇性吸附和高效富集,進(jìn)而實(shí)現(xiàn)基于SERS效應(yīng)的有機(jī)膦毒劑分子快速、痕量的檢測(cè)。取得了主要?jiǎng)?chuàng)新性結(jié)果如下。(1)發(fā)展了一種高密度納米針尖陣列SERS基底的構(gòu)筑策略。在玻璃襯底上,基于膠體模板刻蝕與沉積的方法,構(gòu)筑了高密度金納米針尖陣列的SERS襯底,該襯底表面潔凈,均一性好,實(shí)現(xiàn)了對(duì)三苯基膦分子的痕量檢測(cè),為構(gòu)筑高SERS活性襯底提供了一種簡(jiǎn)便方法。(2)提出了基于襯底表面修飾-化學(xué)反應(yīng)的SERS檢測(cè)策略。在金納米結(jié)構(gòu)陣列SERS襯底上修飾巰基乙胺,實(shí)現(xiàn)了對(duì)沙林模擬劑甲基膦酸的選擇性、高效捕捉以及酰胺反應(yīng),進(jìn)而實(shí)現(xiàn)了對(duì)甲基膦酸的拉曼痕量檢測(cè);發(fā)現(xiàn)了在大濃度范圍[1ppb～1OOOppm]具有很好的拉曼強(qiáng)度-濃度雙對(duì)數(shù)線性關(guān)系,揭示了其源自于Freudlisch吸附機(jī)制。這一策略為基于SERS效應(yīng)檢測(cè)與金屬襯底弱相互作用的分子提供了有效的途徑。(3)提出了利用氫氧化物表面活性基團(tuán)實(shí)現(xiàn)有機(jī)膦分子有效捕捉的設(shè)想。通過(guò)α-Co(OH)2表面豐富的官能團(tuán)與有機(jī)膦分子中的活性基團(tuán)形成氫鍵,進(jìn)而實(shí)現(xiàn)了對(duì)有機(jī)膦分子的高效捕捉;發(fā)現(xiàn)了 α-Co(OH)2有顯著的拉曼增強(qiáng)效應(yīng),增強(qiáng)因子高達(dá)～2000,拉曼特征峰強(qiáng)度與有機(jī)膦毒劑分子濃度滿足雙對(duì)數(shù)線性關(guān)系。這項(xiàng)工作,為設(shè)計(jì)、尋找非貴金屬SERS活性材料提供了新思路,也為下一步將此與高SERS活性金屬納米結(jié)構(gòu)陣列的結(jié)合、研究高性能復(fù)合SERS襯底奠定基礎(chǔ)。
[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.

【學(xué)位授予單位】：中國(guó)科學(xué)技術(shù)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：D919.4;O657.37
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本文編號(hào)：1498271