本文選題：表面增強拉曼散射 + 復合納米粒子�。� 參考：《上海師范大學》2017年碩士論文

【摘要】：在最近的幾十年里,大量的研究團隊制備了各種表面增強拉曼散射(SERS)基底來增強目標分析物的拉曼信號。特別是在可見近紅外區(qū)有很高等離子活性的銀(Ag)和金(Au)納米結(jié)構(gòu)已經(jīng)被廣泛使用。但是普通的SERS基底由于團聚程度難以控制,導致增強效率不均勻。要克服這些缺點,發(fā)展均勻的、結(jié)構(gòu)可控的SERS基底是必需的。因此,本文引入了具有粘附性、反應性、吸附性、還原性、螯合作用、親水性等特性的聚多巴胺(PDA),以及具有多刺激響應性的聚(N-異丙基丙烯酰胺)(PNIPAAm),結(jié)合Ag、Au等貴金屬,采用簡單有效的方法制備了三種不同的功能性原位SERS基底,實現(xiàn)了對農(nóng)藥,有機染料,有機污染物的原位定性定量檢測。具體內(nèi)容如下:1、利用簡單快速的方法,制備了由聚多巴胺(PDA)殼覆蓋立方氯化銀(AgCl)核的復合材料,該復合材料表面鑲嵌銀納米粒子(AgNPs),命名為AgCl/PDA/AgNPs。由此產(chǎn)生的AgCl/PDA/AgNPs可用作原位檢測的SERS基底,由于該基底在激光照射下可以產(chǎn)生更多的AgNPs,因此,其SERS活性可以進一步大大改進。4-巰基吡啶(4-Mpy)作為探針分子,增強因子可以達到107。此外,這種SERS基底具有長期穩(wěn)定性(暗處保存100天之后,SERS活性強度依然可以保持在75%以上)和良好的重現(xiàn)性(相對標準偏差在7.32%)。激光照射AgCl/PDA/AgNPs,原位增強其SERS活性可能有利于其在實用性領域中的靈敏性分析。2、上述復合材料由于表面PDA層的存在而具有反應性,故該復合材料很容易用含巰基的溫敏性聚(N-異丙基丙烯酰胺)(PNIPAAm-SH)修飾成為多刺激響應的動態(tài)SERS基底。向修飾后的SERS基底(AgCl/PDA/AgNPs@PNIPAAm)體系中加入鹵化物鹽后不僅可誘導PNIPAAm在室溫下發(fā)生相轉(zhuǎn)變,還可以富集微量物質(zhì),導致待測物SERS信號的進一步增強,故該基底可以實現(xiàn)對有機染料亞甲基藍(MB)的pM級檢測,檢測限可以達到1pM。我們的發(fā)現(xiàn)可能有助于發(fā)展綠色、低成本的SERS基底,用作快速、定量檢測微量有機分子。3、利用金納米粒子(AuNPs)在聚多巴胺粒子(PDA)中的可控合成制備了PDA-Au復合材料,它在拉曼激光、紫外燈或者超聲等外界條件刺激下會發(fā)生破裂,并且釋放出AuNPs@PDA核殼納米粒子。由于PDA中心負載了大量的AuNPs,所以該復合材料在紫外燈或者拉曼光譜照射下顯示出了卓越的光熱轉(zhuǎn)換能力,導致PDA-Au可以“遙控爆炸”,快速釋放出大量AuNPs@PDA。而且這個釋放過程可以通過關(guān)閉或重啟拉曼激光/紫外燈來實現(xiàn)立即停止或再次啟動。此外,利用AuNPs@PDA表面的PDA與PAHs之間存在的π-π相互作用,完成了對水環(huán)境中PAHs的定性定量檢測。因此,我們已經(jīng)證明由于PDA-Au NPs具有原位生成新鮮吸附劑、催化劑的能力,所以在水中PAHs的檢測方面顯示出了優(yōu)異、持續(xù)的性能。
[Abstract]:In recent decades, a large number of research teams have prepared various surface-enhanced Raman scattering (SERS) substrates to enhance the Raman signal of target analytes. Especially silver (Ag) and gold (Au) nanostructures with high plasma activity in the near infrared region have been widely used. However, the common SERS substrate is difficult to control the degree of agglomeration, resulting in uneven enhancement efficiency. To overcome these shortcomings, it is necessary to develop uniformly and structurally controllable SERS substrate. In this paper, PDAs with adhesion, reactivity, adsorbability, reduction, chelation and hydrophilicity were introduced, as well as poly (N-isopropylacrylamide) (PNIPAAm) with multiple stimuli response, and noble metals such as Agna au, etc. Three kinds of functional in situ SERS substrates were prepared by a simple and effective method, and the in situ qualitative and quantitative detection of pesticides, organic dyes and organic pollutants was realized. The main contents are as follows: 1. By using a simple and rapid method, a composite material coated with cubic silver chloride (AgCl) nucleus was prepared. The composite was coated with silver nanoparticles (AgNPs) on the surface of the composite named AgCl / PDA / AgNPs. The resulting AgCl / PDA / AgNPs can be used as SERS substrates for in situ detection. Since the substrate can produce more AgNPs under laser irradiation, its SERS activity can be further improved by using 4-mercaptopyridine (4-Mpy) as a probe molecule, and the enhancement factor can reach 107. In addition, the SERS substrate has long-term stability (the intensity of SERS activity remains above 75% after 100 days of dark storage) and good reproducibility (relative standard deviation is 7.32%). Laser irradiation of AgCl / PDA / AgNPs and in situ enhancement of SERS activity may be beneficial to the sensitivity analysis of AgCl / PDA / AgNPs in the practical field. The above composite materials are reactive because of the existence of PDA layer on the surface. Therefore, it is easy to modify the composite into a dynamic SERS substrate with multiple stimuli response by thermo-sensitive poly (N-isopropylacrylamide) (PNIPAAm-SH) containing sulfhydryl group. Adding halides to the modified SERS substrate can not only induce the phase transition of PNIPAAm at room temperature, but also enrich trace substances, resulting in the further enhancement of SERS signal. Therefore, this substrate can be used to detect methylene blue (MB) with a detection limit of 1 pm. Our findings may contribute to the development of green, low-cost SERS substrates for rapid, quantitative detection of microamounts of organic molecules. PDA-Au composites are prepared by the controllable synthesis of gold nanoparticles (AuNPs) in polydopamine particles (PDA-Au), which are used in Raman lasers. External stimuli such as ultraviolet lamp or ultrasound will rupture and release AuNPs @ PDA core-shell nanoparticles. Because the PDA center is loaded with a large amount of AuNPs, the composite shows excellent photothermal conversion ability under ultraviolet lamp or Raman spectroscopy irradiation, resulting in PDA-Au "remote explosion", rapidly releasing a large number of AuNPs PDAs. And the release process can be stopped or restarted immediately by turning off or restarting the Raman laser / UV lamp. In addition, qualitative and quantitative detection of PAHs in water environment was carried out by the 蟺-蟺 interaction between PDA and PAHs on the surface of AuNPs @ PDA. Therefore, we have demonstrated that PDA-Au NPs have excellent and continuous performance in the detection of PAHs in water because of their ability to produce fresh adsorbents and catalysts in situ.
【學位授予單位】：上海師范大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TB383.1;O657.37

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