本文選題：銀 + 原位化學(xué)還原　； 參考：《大連理工大學(xué)》2016年碩士論文

【摘要】：表面增強(qiáng)拉曼散射(SERS)光譜由于具有靈敏度高、抗干擾能力強(qiáng)、無(wú)損檢測(cè)等優(yōu)點(diǎn),成為了一種重要的分析手段,被廣泛應(yīng)用在生物、化學(xué)和環(huán)境檢測(cè)等方面。合適的基底是實(shí)現(xiàn)表面增強(qiáng)拉曼的重要前提。因此,對(duì)SERS基底的研究一直是一個(gè)重要的研究領(lǐng)域。目前,研究比較多的金銀電極和膠體分散液由于增強(qiáng)拉曼“熱點(diǎn)”分布無(wú)規(guī)律,重復(fù)性不好。因此,人們制備出貴金屬納米陣列作為拉曼活性基底,能夠得到穩(wěn)定的拉曼信號(hào)。但納米陣列的制備存在制備過(guò)程復(fù)雜以及成本高的缺點(diǎn),限制了它們的廣泛應(yīng)用。針對(duì)上述問(wèn)題,本文利用原位化學(xué)還原法制備出銀包苯乙烯-順丁烯二酸酐共聚微球(PSMA@Ag)核殼結(jié)構(gòu)納米微球,并進(jìn)行自組裝得到PSMA@Ag核殼結(jié)構(gòu)蛋白石光子晶體膜,以此作為SERS活性基底,表現(xiàn)出較強(qiáng)的SERS活性。本文通過(guò)原位化學(xué)還原法制備出了PSMA@Ag核殼結(jié)構(gòu)微球。首先,利用乳液聚合法合成出了單分散PSMA微球,以PSMA微球?yàn)楹?用聚乙烯亞胺(PEI)對(duì)其進(jìn)行表面修飾；然后加入AgNO3溶液,通過(guò)在PSMA微球表面原位還原生成銀核；進(jìn)一步加入乙二胺四乙酸四鈉(Na4EDTA)還原,促進(jìn)銀核生長(zhǎng),增加殼層的厚度。分別考察了反應(yīng)溫度、AgNO3溶液濃度以及Na4EDTA溶液濃度等實(shí)驗(yàn)條件對(duì)產(chǎn)物包覆層的影響,得到了最佳反應(yīng)條件,制備出了三種不同粒徑的分散性好、包覆均勻的核殼納米微球。制備出的PSMA@Ag微球表面電位值較高。利用垂直沉積法對(duì)其進(jìn)行組裝,得到三維有序PSMA@Ag微球蛋白石光子晶體膜。PSMA@Ag光子晶體膜在可見(jiàn)光區(qū)具有光子禁帶,能夠產(chǎn)生結(jié)構(gòu)色。PSMA@Ag光子晶體膜具有強(qiáng)的SERS效應(yīng),可以用作SERS基底。研究了基底的Ag納米顆粒負(fù)載量和禁帶位置對(duì)其SERS效應(yīng)的影響。隨基底Ag納米顆粒負(fù)載量增加,“熱點(diǎn)”的數(shù)量增加,SERS效應(yīng)增強(qiáng)。當(dāng)激發(fā)光波長(zhǎng)位于禁帶邊緣處時(shí),由于禁帶邊緣光子能態(tài)密度大,光與分子作用強(qiáng),起到增強(qiáng)拉曼散射光的作用。本文還研究了PSMA@Ag光子晶體膜對(duì)對(duì)氨基苯硫酚(PATP)的拉曼增強(qiáng)效果,發(fā)現(xiàn)其對(duì)對(duì)氨基苯硫酚(PATP)的檢測(cè)限可達(dá)到10-8M。測(cè)量5個(gè)隨機(jī)點(diǎn)的拉曼光譜,信號(hào)峰強(qiáng)度的最大相對(duì)偏差為15%。放置30天之后,拉曼光譜特征峰峰強(qiáng)度衰減幅度不大。說(shuō)明基底靈敏度高、均勻性好、穩(wěn)定性好。綜上所述,本文以簡(jiǎn)便的操作和低廉的成本制備出了性能優(yōu)越的SERS基底,在生物、化學(xué)和環(huán)境分析檢測(cè)上有重要的潛在應(yīng)用。
[Abstract]:Surface enhanced Raman scattering (SERS) spectroscopy has been widely used in biological, chemical and environmental detection because of its high sensitivity, strong anti-jamming and nondestructive testing. An appropriate substrate is an important prerequisite for surface enhanced Raman. Therefore, the study of SERS substrate has been an important research field. At present, more gold and silver electrodes and colloidal dispersions have been studied because of irregular distribution of Raman hot spots and poor reproducibility. Therefore, noble metal nanoarrays were prepared as Raman active substrates, and stable Raman signals were obtained. However, the preparation of nanoscale arrays has the disadvantages of complex preparation process and high cost, which limits their wide application. In order to solve the above problems, the Silver-encapsulated styrene-maleic anhydride copolymer nanospheres were prepared by in-situ chemical reduction, and the PSMAAg core-shell opal photonic crystal films were obtained by self-assembly. As a substrate for SERS activity, it shows strong SERS activity. In this paper, PSMA-R Ag core-shell microspheres were prepared by in situ chemical reduction method. Firstly, monodisperse PSMA microspheres were synthesized by emulsion polymerization, and then modified by polyethylene imine (PEI) with PSMA microspheres as core, then silver nuclei were formed by in-situ reduction of silver nuclei on PSMA microspheres by adding AgNO3 solution. Further addition of tetra-sodium ethylenediamine tetraacetate (Na _ 4EDTA) can promote the growth of silver nuclei and increase the thickness of shell. The effects of reaction temperature and concentration of AgNo3 solution and Na4EDTA solution on the coating layer were investigated respectively. The optimum reaction conditions were obtained and three core-shell nanoparticles with good dispersion and uniform coating were prepared. The surface potential of the prepared PSMA-O-Ag microspheres is high. By using vertical deposition method, we found that the photonic crystal film with ordered PSMA-AG opal has photonic band gap in the visible region, which can produce a strong SERS effect on PSMAAg photonic crystal film. Can be used as SERS substrate. The effects of the loading amount of Ag nanoparticles and the position of band gap on the SERS effect of Ag nanoparticles on the substrate were studied. With the increase of Ag nanoparticles loading, the number of "hot spots" increases and the SERS effect increases. When the excited wavelength is located at the edge of the band gap, because of the high energy density of photons at the edge of the band gap and the strong interaction between the light and the molecule, it plays the role of enhancing the Raman scattering light. The Raman enhancement effect of p-aminophenylthiophenol (PATP) on PSMA-@ Ag photonic crystal film is also studied. It is found that the detection limit of p-aminophenol (PATP) can reach 10-8M. The Raman spectra of five random points were measured and the maximum relative deviation of the peak intensity was 15. After 30 days of storage, the intensity attenuation of the characteristic peak of Raman spectrum is not large. It shows that the substrate has high sensitivity, good uniformity and good stability. In conclusion, SERS substrates with superior performance have been prepared with simple operation and low cost, and have important potential applications in biological, chemical and environmental analysis.
【學(xué)位授予單位】：大連理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類(lèi)號(hào)】：O657.37

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本文編號(hào)：2118491