【摘要】：金屬（如Au、Ag、Cu）納米團(tuán)簇是由幾個(gè)至幾十個(gè)原子組成的具有熒光性、水溶性的分子級(jí)聚集體。它因特有的量子尺寸效應(yīng)、生物相容性好、光穩(wěn)定性強(qiáng)、反聚合能力強(qiáng)、斯托克斯位移較大等特點(diǎn)，使其在生化傳感器、新型催化劑、生物標(biāo)記、環(huán)境檢測(cè)等領(lǐng)域有著廣泛的應(yīng)用前景。但是目前對(duì)于金屬納米團(tuán)簇的研究還存在一定的缺陷和不足�；诮饘偌{米團(tuán)簇的高靈敏度和高選擇性的分析方法有待提高，以及金屬納米團(tuán)簇的高化學(xué)性能和在水溶液中不穩(wěn)定等問題。因此，本論文主要以銀納米團(tuán)簇為研究對(duì)象，建立了基于聚甲基丙烯酸（PMAA）模板的熒光銀納米團(tuán)簇（AgNCs）在合成方法以及檢測(cè)分析中存在的問題，并進(jìn)行了相關(guān)性能的研究。主要研究內(nèi)容如下： 首先，成功合理地設(shè)計(jì)了以聚甲基丙烯酸（PMAA）為模板，采用日光照射法，一步合成了穩(wěn)定性好、高發(fā)光性能的AgNCs。該方法快速、簡單、易操作、對(duì)環(huán)境友好。同時(shí)，實(shí)驗(yàn)發(fā)現(xiàn)銀納米團(tuán)簇作為一種熒光探針可以高選擇性地和含巰基官能團(tuán)的生物化合物（半胱氨酸）通過Ag-S共價(jià)鍵發(fā)生相互作用，導(dǎo)致銀納米團(tuán)簇的聚集，形成沒有熒光的銀納米顆粒，從而使PMAA-AgNCs的熒光被猝滅。PMAA-AgNCs的熒光強(qiáng)度隨著生物巰基化合物（半胱氨酸）濃度的增大而降低，而其他常見氨基酸由于不含巰基官能團(tuán)，并不能使銀納米團(tuán)簇的熒光猝滅。銀納米團(tuán)簇對(duì)半胱氨酸檢測(cè)的線性范圍為1~200nM,檢出限為0.57nM�；谶@一原理，建立了快速、簡單、高靈敏和高選擇性的檢測(cè)生物巰基化合物的新方法。同時(shí)，研究了PMAA-AgNCs對(duì)革蘭氏陰性細(xì)菌（大腸桿菌）的抑菌性能。結(jié)果表明所制備的PMAA-AgNCs對(duì)大腸桿菌的生長有明顯的抑制作用。 其次，基于此新方法合成的穩(wěn)定性良好的銀納米團(tuán)簇，提出一種新型的熒光“關(guān)-開”式信號(hào)增強(qiáng)傳感策略,用于高選擇性地定量檢測(cè)藥物美洛西林鈉和L-抗壞血酸。在此，利用Hg2+作為熒光猝滅劑，當(dāng)其與PMAA-AgNCs接觸時(shí)會(huì)導(dǎo)致銀納米團(tuán)簇的熒光發(fā)生猝滅，，而Hg2+又可以同藥物與L-抗壞血酸進(jìn)行特異性識(shí)別，通過配位作用和銀納米團(tuán)簇表面負(fù)載的Hg2+發(fā)生絡(luò)合反應(yīng)生成一種絡(luò)合產(chǎn)物，從而使PMAA-AgNCs的熒光信號(hào)得到“恢復(fù)”。PMAA-AgNCs的熒光“關(guān) 開”現(xiàn)象，降低了方法的背景信號(hào)，提高了檢測(cè)方法的靈敏性，也實(shí)現(xiàn)了高特異性識(shí)別。本方法快速、簡單、靈敏度高、具有良好的檢測(cè)線性關(guān)系，而且該研究為選擇高靈敏度、高識(shí)別度的貴金屬納米團(tuán)簇作為一種熒光探針用于生化檢測(cè)開拓了新的思路。
[Abstract]:Metal (such as Au,Ag,Cu) nanoclusters are molecular aggregates with fluorescence and water solubility composed of several to dozens of atoms. Due to its unique quantum size effect, good biocompatibility, strong photostability, strong ability to reverse polymerization, and large Stokes shift, it is widely used in biochemical sensors, novel catalysts, biomarkers, and so on. Environmental detection and other fields have a wide range of application prospects. However, there are still some defects and shortcomings in the research of metal nanoclusters. Based on the high sensitivity and selectivity of metal nanoclusters, the high chemical properties and instability in aqueous solution of metal nanoclusters need to be improved. Therefore, in this thesis, silver nanoclusters were studied, and the problems in synthesis, detection and analysis of fluorescent silver nanoclusters based on polymethacrylate (PMAA) template were established, and the related properties were studied. The main research contents are as follows: firstly, AgNCs. with good stability and high luminescence performance was synthesized successfully and reasonably using polymethacrylate (PMAA) as template and sunlight irradiation method. The method is fast, simple, easy to operate and environmentally friendly. At the same time, it was found that silver nanoclusters, as a fluorescent probe, could interact with thiol functional compounds (cysteine) via Ag-S covalent bonds, which led to the aggregation of silver nanoclusters. The fluorescence intensity of PMAA-AgNCs decreases with the increase of the concentration of biological thiol compounds (cysteine), while other common amino acids are free of sulfhydryl functional groups. It can not quench the fluorescence of silver nanoclusters. The linear range for detection of cysteine in silver nanoclusters was 1 ~ 200 nm and the detection limit was 0.57 nm. Based on this principle, a rapid, simple, highly sensitive and highly selective method for the detection of biological thiol compounds has been established. At the same time, the inhibitory effect of PMAA-AgNCs on gram-negative bacteria (E. coli) was studied. The results showed that the PMAA-AgNCs could inhibit the growth of Escherichia coli. Secondly, based on the stable silver nanoclusters synthesized by the new method, a novel fluorescence "turn-on" signal enhancement sensing strategy is proposed for the quantitative detection of meloxicillin sodium and L-ascorbic acid. When Hg2 was used as a fluorescence quenching agent, the fluorescence of silver nanoclusters was quenched when it was in contact with PMAA-AgNCs, and Hg2 could be specifically identified with drugs and L-ascorbic acid. A complexation product is formed by the coordination reaction with Hg2 loaded on the surface of silver nanoclusters, which makes the fluorescence signal of PMAA-AgNCs "recover". The fluorescence of PMAA-AgNCs is "off" and the background signal of the method is reduced. The sensitivity of the detection method is improved, and the high specificity recognition is realized. The method is rapid, simple, sensitive, and has good linear relationship. Moreover, it opens up a new idea for the selection of noble metal nanoclusters with high sensitivity and recognition as a fluorescent probe for biochemical detection.
【學(xué)位授予單位】：淮北師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：O614.122;TB383.1

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