本文關鍵詞：基于表面增強拉曼光譜法的新型化學傳感器研究　出處：《吉林大學》2017年博士論文　論文類型：學位論文

  更多相關文章： 表面增強拉曼光譜 快速檢測 納米粒子 食品 環(huán)境 化學傳感器

【摘要】：近年來,表面增強拉曼光譜法(SERS)已成為最具潛力的一種分析方法。由于它具有靈敏度高、光譜信息豐富、易操作、檢測速度快等優(yōu)勢,特別適合應用于食品和環(huán)境分析。到目前為止,如何提高檢測方法的靈敏度和選擇性、拓展可檢測的物質種類,成為SERS傳感器進行定量分析的最大瓶頸,它吸引了大量科研工作者的興趣�；赟ERS原理,利用便攜式的激光拉曼光譜儀器,我們成功的研究了幾種測定食品和水中有機小分子和無機離子的SERS傳感器。具體研究工作主要分為以下幾個部分:1.測定乳制品中三聚氰胺的SERS傳感器。我們在傳統(tǒng)銀鏡反應的基礎上,通過添加α-環(huán)糊精,阻礙銀鏡的形成,綠色地合成了一種環(huán)糊精修飾的銀納米粒子(CD-Ag NPs)。使用CD-Ag NPs作為SERS基底,構建了一種測定乳制品中三聚氰胺的SERS傳感器。相比傳統(tǒng)銀基底,該基底對于三聚氰胺更敏感,增強因子可達106。系統(tǒng)考察了CD-Ag NPs溶液、Na Cl溶液、Na OH溶液和三聚氰胺溶液的用量,以及反應的混合時間等條件對三聚氰胺檢測結果的影響。結果表明,SERS傳感器測定三聚氰胺的線性范圍為5.0~100μg L~(-1),線性相關系數(shù)為0.9995,檢出限為3.0μg L~(-1),通過分析牛奶和奶粉樣品,其回收率在89~104%,相對標準偏差小于10%。2.測定環(huán)境水中Hg~(2+)的超靈敏SERS傳感器。我們研究了一種利用甲巰咪唑功能化的CD-Ag NPs作為基底。高靈敏度和選擇性檢測環(huán)境水中Hg~(2+)的SERS傳感器。在p H=10的含有Na Cl的溶液中,502 cm~(-1)處出現(xiàn)了甲巰咪唑的特征拉曼峰。當加入Hg~(2+)后,拉曼信號顯著減弱,這種減弱與Hg~(2+)的濃度在一定范圍內成比例。使用響應曲面分析法對SERS傳感器實驗條件進行了系統(tǒng)優(yōu)化。SERS傳感器測定Hg~(2+)的線性范圍為50~150μg L~(-1),檢出限為0.10μg L~(-1)。常見的金屬離子對測定Hg~(2+)的實驗結果影響不大,方法選擇性較好。該方法應用于分析實際環(huán)境水樣品,其加標回收率為98.5~105.2%,相對標準偏差小于3.5%。3.選擇性測定環(huán)境水中鄰苯二胺的SERS傳感器。我們研究出一種選擇性檢測水中鄰苯二胺(OPD)的SERS傳感器�；谠谒嵝詶l件下OPD與亞硝酸根發(fā)生環(huán)化反應,生成苯并三氮唑(BTAH),間接的實現(xiàn)了對OPD的選擇性檢測。對反應介質的酸度、亞硝酸鹽的濃度、反應時間以及與SERS基底和被分析物的混合時間進行了系統(tǒng)的優(yōu)化。傳感器測定OPD的線性范圍為0.10~1.0μmol L~(-1),檢出限為30 nmol L~(-1),定量限為100 nmol L~(-1)。通過相關結構類似物干擾實驗發(fā)現(xiàn)該傳感器對OPD具有較高的選擇性。實際水樣品加標實驗,回收率在97.8~104.5%,相對標準偏差小于4%。4.基于衍生化反應的超靈敏甲醛SERS傳感器。我們研究出一種選擇性和超靈敏的檢測食物和環(huán)境水中的痕量甲醛(HCHO)的SERS傳感器。根據(jù)HCHO與4-氨基-5-肼基-3-巰基~(-1),2,4-三唑(AHMT)發(fā)生衍生化反應,生成產(chǎn)物6-巰基-5-三唑并[4,3-b]-s-三嗪(MTT)在832 cm~(-1)處拉曼光譜的變化,進行定量分析。對于衍生化反應的孵化時間,反應溶液的體積和混合時間進行了優(yōu)化。傳感器測定HOMO的線性范圍為1~1000μg L~(-1),檢出限為0.15μg L~(-1),定量限為0.45μg L~(-1)。通過測定2種環(huán)境水樣和2種食物加標樣品,得到回收率范圍為64.0~111.1%,該方法的測定結果與國家標準方法相比,無顯著性差異。5.基于羅丹明鍵合氨基化SiO_2包覆Au-Ag核殼納米棒測定環(huán)境水中Hg~(2+)的SERS傳感器。我們設計了一種基于水解反應的新型Hg~(2+)SERS傳感器。使用羅丹明6G(R6G)衍生物通過形成Schiff堿的方式化學鍵合到氨基功能化的SiO_2包覆Au-Ag核殼納米棒作為SERS基底,該基底表現(xiàn)出了卓越的增強因子和穩(wěn)定性。基于化學鍵在納米結構表明的良好可調控能力,顯著的提高了SERS傳感器的選擇性和敏感性,對Hg~(2+)的檢出限為0.33 pmol L~(-1)。此外,基底還表現(xiàn)出了對p H的良好響應能力。該傳感器通過結合便攜式激光拉曼光譜儀有望實現(xiàn)對Hg~(2+)和p H進行現(xiàn)場快速測定。6.基于羅丹明衍生物的一種新型熒光和SERS雙信號p H傳感器。我們設計合成了一種新型的羅丹明衍生物RGP,用作p H傳感探針。該探針的傳感原理是基于RGP在不同p H值下,分子螺內酰胺結構發(fā)生開-關環(huán)變化,表現(xiàn)出不同的熒光和SERS信號改變。RGP的酸度值(p Ka)和熒光量子產(chǎn)率值分別為2.43(±0.14)和0.48。當p H在1.0~4.0時,RGP的熒光變化是可逆的。p H在3.29和6.09之間更換5次之后SERS信號的變化很小。常見的無機離子和有機物對于傳感系統(tǒng)幾乎沒有影響。該傳感系統(tǒng)有望應用于測定酸性生物樣品的p H值。
[Abstract]:In recent years, surface enhanced Raman spectroscopy (SERS) analysis has become one of the most promising method. Because it has abundant spectral information, high sensitivity, easy operation, fast detection speed and other advantages, especially suitable for food and environmental analysis. So far, how to improve the detection sensitivity and selectivity, expand can detect the material types, become the biggest bottleneck for the quantitative analysis of the SERS sensor, it attracted a lot of researchers interest. Based on the principle of SERS, using laser Raman spectroscopy instrument portable, we successfully developed SERS sensor for determination of food and water of small organic molecules and inorganic ions. Some specific research work is mainly divided into the following part 1.: Determination of several SERS sensors of melamine in dairy products. We are based on the traditional silver mirror reaction, by adding alpha cyclodextrin, hinder the formation of silver mirror, green Color synthesis of a cyclodextrin modified silver nanoparticles (CD-Ag NPs). Using CD-Ag NPs as a SERS substrate, constructed a determination of melamine in dairy products SERS sensor. Compared with the traditional silver substrate, the substrate is more sensitive to melamine, the enhancement factor of up to 106. lines through CD-Ag NPs test solution and Na Cl solution Na, OH solution and melamine solution dosage, reaction condition and influence of mixing time on the melamine test results. The results show that the SERS sensor for determination of melamine concentration range of 5.0~100 g L~ (-1), the linear correlation coefficient was 0.9995, the detection limit was 3 G L~ (-1), through the analysis of milk and the milk powder samples, the recovery rate was 89~104%, the relative standard deviation is less than 10%.2. in environmental water by Hg~ (2+) of the ultra sensitive SERS sensor. We study a use of methimazole functionalized CD-Ag NPs as substrate. The sensitivity and selectivity of detection of environmental water Hg~ (2+) SERS sensor. In the solution containing Na Cl P H=10, 502 cm~ (-1) appeared the characteristic Raman peak. When adding Hg~ methimazole (2+), Raman signal is reduced, and the reduced Hg~ (2+) ratio in a certain range the use of concentration. The response surface analysis on the experimental conditions of SERS sensor system optimization.SERS sensor for determination of Hg~ (2+) of the linear range of 50~150 g L~ (-1), the detection limit was 0.10 g L~ (-1). The common metal ions on the determination of Hg~ (2+) had little effect on the experimental results. The method has good selectivity. The method was applied to the analysis of the actual environmental water samples, the recovery rate was 98.5~105.2%, the relative standard deviation is less than 3.5%.3. SERS sensor selective determination of phthalate two amines. We developed a selective determination of phthalate two amine (OPD) SERS. . under acidic conditions OPD and nitrite cyclization reaction based on the synthesis of benzo triazole three (BTAH), indirect realized selective detection of OPD. The reaction medium acidity, nitrite concentration, reaction time and mixed with SERS substrate and the analyte at the system optimization. Sensor for determination of the linear range of the OPD 0.10~1.0 mol L~ (-1), the detection limit was 30 nmol L~ (-1), the limit of quantification was 100 nmol L~ (-1). Through analogue interference experiments showed that this sensor has high selectivity for OPD. The actual water sample experiments, recovery rate in 97.8~104.5%, the relative standard deviation is less than 4%.4. of the derivatization reaction of formaldehyde sensor based on ultra sensitive SERS. We developed a trace formaldehyde selectivity and ultrasensitive detection of food and water (HCHO) SERS sensor. According to the HCHO and 4- amino hydrazine -5- -3- 6 Based on ~ (-1), 2,4- three (AHMT) of derivatization reaction, product 6- -5- three mercapto triazole and [4,3-b]-s- were three (MTT) in 832 cm~ (-1) change of Raman spectra, were quantitatively analyzed. The derivatization reaction incubation time, reaction solution volume and mixing time were optimization of sensor. The linear range were HOMO 1~1000 g L~ (-1), the detection limit was 0.15 g L~ (-1), the quantitative limit was 0.45 g L~ (-1). Through the determination of 2 water samples and 2 kinds of food samples with standard, recovery rate in the range of 64.0~111.1%, the method of determination of the results compared with the national standard method, no significant difference in.5. based on the Luo Danming bond of amino SiO_2 coated Au-Ag nanorods in environmental water by Hg~ (2+) SERS sensor. We designed a new type of hydrolysis of Hg~ (2+) based on SERS sensor. Using the Luo Danming 6G (R6G) through the formation of Schiff base derivatives the party Type of chemical bonding to the amino functionalized SiO_2 coated Au-Ag nanorods as SERS substrate, the substrate showed remarkable enhancement factor and stability. The chemical bonds in the nano structure shows good control ability based on improve the selectivity and sensitivity of the SERS sensor, the Hg~ (2+) detection limit 0.33 pmol L~ (-1). In addition, the base also showed a good response ability of P H to Hg~. The sensor is expected to achieve by combining the portable laser Raman spectrometer (2+) and P H.6. field rapid determination of a novel fluorescent SERS derivative and Luo Danming double signal sensor based on H P we design. Synthesis of novel derivatives of RGP p H Luo Danming, is used as a sensing probe. The sensing principle of the probe is RGP P at different H values based on the molecular structure of spirolactams on-off ring changes showed different fluorescence and SER The S signal change of.RGP (P Ka) and the pH value of the fluorescence quantum yield values were 2.43 (+ 0.14) and 0.48. P H as in 1.0~4.0, the fluorescence change of RGP is reversible after.P H replaced 5 times in 3.29 and 6.09 between the variation of the SERS signal is very small. The common inorganic ions and organic compounds almost no impact on the sensor system. The sensing system is expected to be applied to the determination of acid biological samples P H value.

【學位授予單位】：吉林大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O657.37;TP212.2

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