【摘要】：本論文以熒光金屬納米團(tuán)簇和碳點(diǎn)為研究對(duì)象,利用生物礦化法、高溫?zé)峤夥ǖ炔呗灾苽淞硕喾N金屬納米團(tuán)簇、碳點(diǎn)及復(fù)合熒光納米傳感材料,考察其結(jié)構(gòu)、穩(wěn)定性、熒光傳感性能,發(fā)展了幾種光學(xué)探針用于有機(jī)小分子和重金屬離子的含量檢測(cè)方法,揭示探針與分析物的相互作用機(jī)理,實(shí)現(xiàn)多種痕量目標(biāo)分析物的特異性敏感檢測(cè),并探討其在實(shí)際環(huán)境中的應(yīng)用。本論文主要研究?jī)?nèi)容如下:(1)基于銅納米團(tuán)簇的曲酸生物傳感器:以蛋白包覆的銅納米團(tuán)簇為熒光探針,以曲酸為檢測(cè)對(duì)象,通過(guò)穩(wěn)瞬態(tài)熒光光譜和紫外可見(jiàn)吸收光譜研究二者相互作用機(jī)制。研究結(jié)果表明,曲酸對(duì)銅納米團(tuán)簇的熒光猝滅機(jī)制為靜態(tài)猝滅;銅納米團(tuán)簇中銅元素呈現(xiàn)多價(jià)態(tài),曲酸與其中二價(jià)銅離子發(fā)生特異性反應(yīng)生成曲酸銅沉淀,進(jìn)而使銅納米簇?zé)晒忖纭；谠撟饔脵C(jī)制,在最佳檢測(cè)條件下,建立曲酸的熒光分析法。(2)基于金納米團(tuán)簇的熒光和共振光散射雙模式檢測(cè)植酸:采用溶菌酶為模板制備的金納米團(tuán)簇作為熒光和共振光散射探針,以植酸為檢測(cè)對(duì)象,重點(diǎn)研究溶菌酶包覆金納米團(tuán)簇與植酸相互作用后共振光散射光譜和熒光光譜變化,分析植酸對(duì)溶菌酶包覆金納米團(tuán)簇粒徑分布和形貌的影響機(jī)制,剖析二者相互作用機(jī)理。結(jié)果表明,植酸可以誘導(dǎo)生成包含有多個(gè)單分散金納米簇的聚集體結(jié)構(gòu),從而引起了熒光的猝滅和共振光散射信號(hào)的顯著增強(qiáng)。(3)碳點(diǎn)熒光“關(guān)-開(kāi)”模式檢測(cè)植酸:以檸檬酸和賴氨酸為原料制備熒光碳點(diǎn),考察碳點(diǎn)、碳點(diǎn)/鐵離子和碳點(diǎn)/鐵離子/植酸體系的穩(wěn)瞬態(tài)熒光光譜性質(zhì)變化,構(gòu)建基于碳點(diǎn)熒光“關(guān)—開(kāi)”模式的植酸檢測(cè)方法,并考察方法的穩(wěn)定性、特異性、檢測(cè)范圍和檢測(cè)限。綜合Zeta電位、熒光衰減和共振光散射多種分析手段對(duì)熒光恢復(fù)機(jī)理進(jìn)行分析。研究結(jié)果表明,植酸與碳點(diǎn)競(jìng)爭(zhēng)結(jié)合鐵離子,通過(guò)抑制碳點(diǎn)與鐵離子之間的光誘導(dǎo)電子轉(zhuǎn)移過(guò)程,實(shí)現(xiàn)熒光恢復(fù)。(4)雙發(fā)射比率型熒光傳感體系:制備碳點(diǎn)摻雜的二氧化硅粒子與蛋白質(zhì)穩(wěn)定的金納米團(tuán)簇,通過(guò)化學(xué)交聯(lián)兩種熒光納米材料,形成單一激發(fā)波長(zhǎng)下可發(fā)射雙熒光的復(fù)合納米粒子,并將其發(fā)展為Hg~(2+)濃度測(cè)定的比率型熒光探針;進(jìn)一步,將雙發(fā)射比率型熒光探針與分子印跡技術(shù)相結(jié)合,在雙發(fā)射納米粒子表面生長(zhǎng)印跡層,構(gòu)建分子印跡比率型熒光探針,并將其應(yīng)用于環(huán)境污染物對(duì)硝基苯酚的選擇性測(cè)定。
[Abstract]:In this paper, a variety of metal nanoclusters, carbon points and composite fluorescent nanosensors were prepared by biomineralization and pyrolysis, and their structures and stability were investigated. Fluorescence sensing properties. Several optical probes have been developed for the detection of organic small molecules and heavy metal ions. The mechanism of interaction between the probes and the analytes has been revealed, and the specific sensitive detection of trace target analytes has been realized. Its application in practical environment is also discussed. The main contents of this thesis are as follows: (1) kojic acid biosensor based on copper nanoclusters: protein coated copper nanoclusters are used as fluorescent probes, and kojic acid is used as the detection object. The mechanism of interaction between the two was studied by steady transient fluorescence spectroscopy and UV-Vis absorption spectra. The results showed that the fluorescence quenching mechanism of kojic acid on copper nanoclusters was static quenching. Furthermore, the fluorescence quenching of copper nanoclusters was observed. Based on this mechanism, under the best detection conditions, Fluorescence analysis of kojic acid was established. (2) phytic acid was detected based on fluorescence and resonance light scattering (RLS) of gold nanoclusters: gold nanoclusters prepared by lysozyme were used as fluorescence and resonance light scattering probes, phytic acid was used as the detection object. The changes of resonance light scattering (RLS) spectra and fluorescence spectra after the interaction of lysozyme coated gold nanoclusters with phytic acid were studied. The mechanism of phytic acid affecting the particle size distribution and morphology of lysozyme coated gold nanoclusters was analyzed. The results show that phytic acid can induce the formation of aggregates containing a number of monodisperse gold nanoclusters. The quenching of fluorescence and the enhancement of resonance light scattering signal were induced. (3) carbon spot fluorescence "off on" mode was used to detect phytic acid: fluorescent carbon points were prepared from citric acid and lysine, and carbon points were investigated. The stable transient fluorescence spectra of carbon spot / iron ion and carbon point / iron ion / phytic acid system were changed. A method of phytic acid detection based on the "on-off" mode of carbon spot fluorescence was constructed, and the stability, specificity, detection range and detection limit of the method were investigated. The mechanism of fluorescence recovery was analyzed by Zeta potential, fluorescence attenuation and resonance light scattering. The results show that phytic acid competes with carbon point to bind iron ion, which inhibits the photoinduced electron transfer process between carbon point and iron ion. (4) double emission ratio fluorescence sensing system: carbon dot-doped silica particles and protein stable gold nanoclusters were prepared by chemical crosslinking of two kinds of fluorescent nanomaterials. The composite nanoparticles which can emit double fluorescence at a single excitation wavelength were formed and developed into a ratio fluorescent probe for the determination of Hg~ (2) concentration. Further, the double emission ratio fluorescence probe was combined with molecular imprinting technique. A molecularly imprinted ratio fluorescent probe was constructed on the surface of double emission nanoparticles and applied to the selective determination of p-nitrophenol, an environmental pollutant.
【學(xué)位授予單位】：天津大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類號(hào)】：O657.3;TB383.1
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本文編號(hào)：2232449