新型熒光銅納米顆粒的制備及其在環(huán)境分析中的應(yīng)用
發(fā)布時(shí)間：2018-10-09 07:26
【摘要】：隨著經(jīng)濟(jì)社會的不斷進(jìn)步,環(huán)境中出現(xiàn)了大量有毒有害的污染物,如重金屬、持久性有機(jī)污染物等。因此分析和檢測環(huán)境中污染物質(zhì)的種類、成分、含量以及化學(xué)形態(tài)等已成為環(huán)境分析化學(xué)的重要研究內(nèi)容。傳統(tǒng)的檢測手段主要有色譜法、原子吸收光譜法、電感耦合等離子體質(zhì)譜法、生物芯片技術(shù)、電化學(xué)方法以及免疫學(xué)方法等。但是這些傳統(tǒng)的方法存在檢測過程繁瑣、耗時(shí)長、花費(fèi)高等缺點(diǎn),很難實(shí)現(xiàn)有效、快速的分析檢測,且環(huán)境中的分析檢測對象往往是微量、痕量的離子和分子,還具有空間性和時(shí)間性,因此對分析方法的要求越來越高。而熒光分析法以其靈敏度高、選擇性好、操作簡便等優(yōu)勢近年來在環(huán)境分析領(lǐng)域得以迅速發(fā)展。本文構(gòu)建了不同類型的銅納米顆粒(CuNPs)熒光傳感器,并以用于對環(huán)境和人類健康有重大影響的Hg~(2+)、Fe~(3+)和苦味酸(PA)的靈敏檢測為目標(biāo)做了初步的研究與探索。主要包括以下三方面的內(nèi)容:(1)以D-青霉胺(DPA)為模板,抗壞血酸為還原劑合成的DPA-CuNPs作為熒光探針靈敏地檢測Hg~(2+)。CuNPs的制備實(shí)驗(yàn)是在避光條件下進(jìn)行的,且可能由于金屬銅和DPA上的巰基配體之間的電荷轉(zhuǎn)移,合成的DPA-CuNPs是聚集態(tài)的,發(fā)射紅色的熒光。Hg~(2+)加入到DPA-CuNPs溶液中時(shí),嗜金屬性的Hg~(2+)與DPA-CuNPs上的Cu易發(fā)生結(jié)合生成復(fù)合物,從而破壞DPA上的巰基與Cu的結(jié)合力,導(dǎo)致聚集態(tài)的DPA-CuNPs發(fā)生分散,從而致使熒光猝滅,基于此現(xiàn)象,實(shí)現(xiàn)對Hg~(2+)的檢測。同時(shí)也對實(shí)驗(yàn)體系的合成比例、反應(yīng)時(shí)間和pH值等實(shí)驗(yàn)參數(shù)進(jìn)行了優(yōu)化,在最優(yōu)條件下,考察DPA-CuNPs對Hg~(2+)濃度的線性響應(yīng)以及方法的選擇性,該方法對Hg~(2+)濃度的檢測限為32 nM。據(jù)此,構(gòu)建了測定Hg~(2+)的新方法并用于實(shí)際水樣品中Hg~(2+)含量的檢測,并獲得令人滿意的結(jié)果。(2)利用簡單的一鍋法,以L-組氨酸(L-His)為模板,抗壞血酸為還原劑合成的L-His-CuNPs為熒光探針實(shí)現(xiàn)高效、靈敏地檢測Fe~(3+)。作為一個(gè)帶有空d軌道的順磁性過渡金屬離子,Fe~(3+)能夠通過能量或電子轉(zhuǎn)移淬滅鄰近熒光團(tuán)的熒光。而且,Fe~(3+)具有較高的熱力學(xué)親和力,能快速螯合胺基上的氮原子,拉近了鄰近的L-His-CuNPs的距離,從而分散性較好的L-His-CuNPs會發(fā)生團(tuán)聚,造成熒光猝滅,由此構(gòu)建了檢測Fe~(3+)的新方法,并實(shí)現(xiàn)對自然水樣中Fe~(3+)的分析測定。此外,將具有強(qiáng)螯合性的EDTA溶液加入到L-His-CuNPs與Fe~(3+)的混合溶液中后,發(fā)生了熒光恢復(fù)現(xiàn)象。由此推斷,Fe~(3+)和L-His-CuNPs之間的相互作用比較弱,EDTA通過與Fe~(3+)競爭打破了Fe~(3+)與L-His分子中氨基上的氮原子的結(jié)合力,從而熒光得以恢復(fù)。同時(shí)也對實(shí)驗(yàn)體系的合成比例、反應(yīng)時(shí)間和pH值等相關(guān)參數(shù)進(jìn)行了優(yōu)化,在最優(yōu)條件下,考察L-His-CuNPs對Fe~(3+)濃度的線性響應(yīng)以及方法的選擇性,該方法對Fe~(3+)濃度的檢測限為82 nM。據(jù)此,建立了測定Fe~(3+)的新體系并用于實(shí)際水樣品中Fe~(3+)含量的檢測,得到了較好的結(jié)果。(3)通過刻蝕法制備熒光CuNPs實(shí)現(xiàn)PA的創(chuàng)新檢測。首先以檸檬酸三鈉作為模板,硼氫化鈉作為還原劑,合成無熒光的尺寸較大的銅納米晶。然后利用谷胱甘肽(GSH)將銅納米晶刻蝕后制得發(fā)射藍(lán)色熒光的尺寸較小的水溶性CuNPs。制得的CuNPs在水介質(zhì)中具有良好的穩(wěn)定性,且展現(xiàn)出較廣的pH范圍的響應(yīng)能力,其熒光強(qiáng)度會隨著pH的升高而明顯增強(qiáng)。此外,可能是由于PA和CuNPs之間的內(nèi)濾效應(yīng),合成的CuNPs的熒光能被PA有效猝滅,而其它結(jié)構(gòu)類似的化合物和硝基爆炸物幾乎不能猝滅CuNPs的熒光。因此,所制備的CuNPs熒光探針能在水溶液中實(shí)現(xiàn)PA的特異性和靈敏檢測,該方法對PA濃度的檢測限為65 nM。據(jù)此,發(fā)展了測定PA的新方法并用于實(shí)際水樣品中PA含量的檢測,得到了滿意的結(jié)果。
[Abstract]:With the progress of economy and society, a lot of toxic and harmful pollutants, such as heavy metals, persistent organic pollutants and so on occur in the environment. Therefore, the analysis and detection of the species, composition, content and chemical form of pollutants in the environment have become the important research contents of environmental analytical chemistry. Traditional detection methods include chromatography, atomic absorption spectrometry, inductively coupled plasma mass spectrometry, biochip technology, electrochemical methods, and immunological methods. but the traditional method has the disadvantages of complicated detection process, long time consumption, high cost and the like, is difficult to realize effective and rapid analysis detection, and therefore the requirements for the analysis method are higher and higher. The fluorescence analysis method has the advantages of high sensitivity, good selectivity, simple operation and the like, and has been rapidly developed in the field of environmental analysis. Different types of Cu nanoparticles (CuNPs) fluorescence sensors have been constructed, and the sensitive detection of Hg ~ (2 +), Fe ~ (3 +) and picric acid (PA) which have a great influence on the environment and human health have been studied and explored. The method mainly comprises the following three aspects: (1) the DPA-CuNPs synthesized with D-Penicillamine (DPA) as a template and ascorbic acid as a reducing agent are used as a fluorescent probe to sensitively detect Hg ~ (2 +). The preparation experiment of CuNPs is carried out under light protection conditions, and the resultant DPA-CuNPs are aggregated and emit red fluorescence due to charge transfer between the metal copper and the disulfide ligands on DPA. When Hg ~ (2 +) is added to the DPA-CuNPs solution, the metallic Hg ~ (2 +) binds to the Cu on DPA-CuNPs to form the complex, thus destroying the binding force between the Cd and Cu on DPA, leading to the dispersion of DPA-CuNPs on DPA, which leads to the inactivation of the fluorescence. Based on this phenomenon, the detection of Hg ~ (2 +) is realized. At the same time, the experimental parameters such as the synthesis ratio, reaction time and pH value of the experimental system were optimized. Under the optimum conditions, the linear response of DPA-CuNPs to Hg ~ (2 +) concentration and the selectivity of the method were investigated. The detection limit of Hg ~ (2 +) concentration was 32 nM. Accordingly, a new method for determination of Hg ~ (2 +) was constructed and used in the detection of Hg ~ (2 +) content in actual water samples, and satisfactory results were obtained. (2) Using a simple pot method, L-His-CuNPs synthesized by L-histidine (L-His) as a template and ascorbic acid as a reducing agent are used as a fluorescent probe to realize high-efficiency and sensitive detection of Fe ~ (3 +). As a paramagnetic transition metal ion with an empty d-orbit, Fe ~ (3 +) can quench the fluorescence of adjacent fluorophores by energy or electron transfer. Moreover, Fe ~ (3 +) has a higher thermodynamic affinity, can rapidly change the nitrogen atom on the amino group, shortens the distance of the adjacent L-His-CuNPs, so that the L-His-CuNPs with good dispersivity can be agglomerated, so that the fluorescence quenching is destroyed, thus a new method for detecting Fe ~ (3 +) is constructed. The analysis and determination of Fe ~ (3 +) in natural water samples were carried out. In addition, a fluorescence recovery phenomenon occurred after the EDTA solution with strong affinity was added to the mixed solution of L-His-CuNPs and Fe ~ (3 +). It is concluded that the interaction between Fe ~ (3 +) and L-His-CuNPs is weak. EDTA has broken the binding force between Fe ~ (3 +) and N atom in L-His molecule by competition with Fe ~ (3 +), so that fluorescence can be recovered. At the same time, the synthesis ratio, reaction time and pH value of the experimental system were optimized. Under the optimum conditions, the linear response of L-His-CuNPs to the concentration of Fe ~ (3 +) and the selectivity of the method were investigated. The detection limit of the method on the concentration of Fe ~ (3 +) was 82 nM. Therefore, a new system for determination of Fe ~ (3 +) was established and used in the detection of Fe ~ (3 +) in actual water samples. (3) preparing the fluorescent CuNPs through an etching method to realize the innovative detection of the PA. firstly, sodium citrate is used as a template, sodium borohydride is used as a reducing agent, and copper nanocrystals without fluorescence are synthesized. and then the copper nanocrystalline is etched by using glutathione (GSH) to produce water-soluble CuNPs which emit blue fluorescence. The prepared CuNPs have good stability in aqueous medium, and exhibit a broader pH range response capability, whose fluorescence intensity will be significantly enhanced as the pH increases. In addition, the fluorescence energy of the synthesized CuNPs can be effectively extinguished by the PA due to the internal filtration effect between the PA and the CuNPs, while other structurally similar compounds and nitro explosives can hardly destroy the fluorescence of the CuNPs. Therefore, the prepared CuNPs fluorescent probe can achieve the specificity and sensitive detection of PA in aqueous solution, which limits the detection limit of PA concentration to 65 nM. Based on this, a new method for measuring PA was developed and used in the detection of PA in actual water samples, and satisfactory results were obtained.
【學(xué)位授予單位】：西南大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O657.3;TP212;X830
本文編號：2258475
[Abstract]:With the progress of economy and society, a lot of toxic and harmful pollutants, such as heavy metals, persistent organic pollutants and so on occur in the environment. Therefore, the analysis and detection of the species, composition, content and chemical form of pollutants in the environment have become the important research contents of environmental analytical chemistry. Traditional detection methods include chromatography, atomic absorption spectrometry, inductively coupled plasma mass spectrometry, biochip technology, electrochemical methods, and immunological methods. but the traditional method has the disadvantages of complicated detection process, long time consumption, high cost and the like, is difficult to realize effective and rapid analysis detection, and therefore the requirements for the analysis method are higher and higher. The fluorescence analysis method has the advantages of high sensitivity, good selectivity, simple operation and the like, and has been rapidly developed in the field of environmental analysis. Different types of Cu nanoparticles (CuNPs) fluorescence sensors have been constructed, and the sensitive detection of Hg ~ (2 +), Fe ~ (3 +) and picric acid (PA) which have a great influence on the environment and human health have been studied and explored. The method mainly comprises the following three aspects: (1) the DPA-CuNPs synthesized with D-Penicillamine (DPA) as a template and ascorbic acid as a reducing agent are used as a fluorescent probe to sensitively detect Hg ~ (2 +). The preparation experiment of CuNPs is carried out under light protection conditions, and the resultant DPA-CuNPs are aggregated and emit red fluorescence due to charge transfer between the metal copper and the disulfide ligands on DPA. When Hg ~ (2 +) is added to the DPA-CuNPs solution, the metallic Hg ~ (2 +) binds to the Cu on DPA-CuNPs to form the complex, thus destroying the binding force between the Cd and Cu on DPA, leading to the dispersion of DPA-CuNPs on DPA, which leads to the inactivation of the fluorescence. Based on this phenomenon, the detection of Hg ~ (2 +) is realized. At the same time, the experimental parameters such as the synthesis ratio, reaction time and pH value of the experimental system were optimized. Under the optimum conditions, the linear response of DPA-CuNPs to Hg ~ (2 +) concentration and the selectivity of the method were investigated. The detection limit of Hg ~ (2 +) concentration was 32 nM. Accordingly, a new method for determination of Hg ~ (2 +) was constructed and used in the detection of Hg ~ (2 +) content in actual water samples, and satisfactory results were obtained. (2) Using a simple pot method, L-His-CuNPs synthesized by L-histidine (L-His) as a template and ascorbic acid as a reducing agent are used as a fluorescent probe to realize high-efficiency and sensitive detection of Fe ~ (3 +). As a paramagnetic transition metal ion with an empty d-orbit, Fe ~ (3 +) can quench the fluorescence of adjacent fluorophores by energy or electron transfer. Moreover, Fe ~ (3 +) has a higher thermodynamic affinity, can rapidly change the nitrogen atom on the amino group, shortens the distance of the adjacent L-His-CuNPs, so that the L-His-CuNPs with good dispersivity can be agglomerated, so that the fluorescence quenching is destroyed, thus a new method for detecting Fe ~ (3 +) is constructed. The analysis and determination of Fe ~ (3 +) in natural water samples were carried out. In addition, a fluorescence recovery phenomenon occurred after the EDTA solution with strong affinity was added to the mixed solution of L-His-CuNPs and Fe ~ (3 +). It is concluded that the interaction between Fe ~ (3 +) and L-His-CuNPs is weak. EDTA has broken the binding force between Fe ~ (3 +) and N atom in L-His molecule by competition with Fe ~ (3 +), so that fluorescence can be recovered. At the same time, the synthesis ratio, reaction time and pH value of the experimental system were optimized. Under the optimum conditions, the linear response of L-His-CuNPs to the concentration of Fe ~ (3 +) and the selectivity of the method were investigated. The detection limit of the method on the concentration of Fe ~ (3 +) was 82 nM. Therefore, a new system for determination of Fe ~ (3 +) was established and used in the detection of Fe ~ (3 +) in actual water samples. (3) preparing the fluorescent CuNPs through an etching method to realize the innovative detection of the PA. firstly, sodium citrate is used as a template, sodium borohydride is used as a reducing agent, and copper nanocrystals without fluorescence are synthesized. and then the copper nanocrystalline is etched by using glutathione (GSH) to produce water-soluble CuNPs which emit blue fluorescence. The prepared CuNPs have good stability in aqueous medium, and exhibit a broader pH range response capability, whose fluorescence intensity will be significantly enhanced as the pH increases. In addition, the fluorescence energy of the synthesized CuNPs can be effectively extinguished by the PA due to the internal filtration effect between the PA and the CuNPs, while other structurally similar compounds and nitro explosives can hardly destroy the fluorescence of the CuNPs. Therefore, the prepared CuNPs fluorescent probe can achieve the specificity and sensitive detection of PA in aqueous solution, which limits the detection limit of PA concentration to 65 nM. Based on this, a new method for measuring PA was developed and used in the detection of PA in actual water samples, and satisfactory results were obtained.
【學(xué)位授予單位】：西南大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O657.3;TP212;X830
【參考文獻(xiàn)】
相關(guān)期刊論文 前1條
1 劉清明;周德璧;山本雄也;市野良一;興戶正純;;NaBH_4的水性還原法制備納米銅顆粒(英文)[J];Transactions of Nonferrous Metals Society of China;2012年01期
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