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表面印跡ZnO熒光傳感器的制備及其選擇性檢測(cè)四環(huán)素類抗生素的研究

發(fā)布時(shí)間:2018-05-27 00:34

  本文選題:分子印跡聚合物 + 四環(huán)素; 參考:《江蘇大學(xué)》2017年碩士論文


【摘要】:四環(huán)素(TC)是一種具有高濃度滅菌的廣譜抑菌劑,由于價(jià)格低且抗菌效果明顯,已廣泛應(yīng)用于水產(chǎn)養(yǎng)殖和獸藥,以促進(jìn)動(dòng)物的快速生長和預(yù)防動(dòng)物疾病。但是TC的過量使用會(huì)導(dǎo)致其在一些肉類食物和水體中嚴(yán)重超標(biāo)。超標(biāo)的食物會(huì)直接危害人類健康,而進(jìn)入水體的TC不僅會(huì)危害生態(tài)環(huán)境,還會(huì)通過生態(tài)食物鏈系統(tǒng)進(jìn)入人體,同樣危害人類健康;跓晒鈧鞲衅鞯臒晒夥治鰴z測(cè)方法由于具有樣品處理簡單、檢出限低、靈敏度高、響應(yīng)時(shí)間短、抗干擾能力強(qiáng)、可直接觀察等優(yōu)點(diǎn),被用于檢測(cè)各類有毒有害的物質(zhì)。然而熒光傳感器一般并不具備選擇性識(shí)別能力,而與表面分子印跡技術(shù)(SMIT)的結(jié)合能賦予熒光傳感器專一識(shí)別目標(biāo)分子的能力,并且在不影響熒光傳感器光學(xué)性能的基礎(chǔ)上,提高其物化穩(wěn)定性。而制備分子印跡聚合物(MIPs)的方法有很多種,例如沉淀聚合、溶膠-凝膠(Sol-gel)聚合和原子轉(zhuǎn)移自由基聚合(ATRP)等。但對(duì)不同聚合方法制備的分子印跡熒光傳感器的形貌、結(jié)構(gòu)、熒光性能和分析檢測(cè)性能之間的相互關(guān)系,還未有報(bào)道。本論文以TC為目標(biāo)分子,以氧化鋅納米棒(ZnO NRs)為固體基質(zhì)和熒光傳感器,分別通過沉淀聚合、Sol-gel聚合和ATRP制備表面分子印跡ZnO熒光傳感器(MIPs-ZnO NRs);利用透射電子顯微鏡(TEM)、傅立葉變換紅外光譜儀(FT-IR)、紫外光譜儀(UV-vis)、X射線衍射儀(XRD)和分子熒光分光光度計(jì)等表征儀器研究了MIPs-ZnO NRs的形貌、結(jié)構(gòu)和光學(xué)性能;通過對(duì)MIPs-ZnO NRs的濃度、穩(wěn)定性和響應(yīng)時(shí)間等因素的研究,確定了最佳的檢測(cè)TC的條件。通過選擇性識(shí)別和定量檢測(cè)實(shí)驗(yàn),研究了這幾種不同聚合方法制備的MIPs-ZnO NRs對(duì)水相中TC的熒光識(shí)別和檢測(cè)能力。主要研究成果如下:(1)首先通過水熱法制備ZnO NRs,并通過KH570在其表面修飾上乙烯基,將其作為熒光材料和支撐材料;再通過沉淀聚合法制備MIPs-ZnO NRs;最后將其用于選擇性檢測(cè)水環(huán)境中TC。(2)將ZnO NRs作為熒光材料和支撐材料、十六烷基三甲基溴化銨(CTAB)作為致孔劑,通過Sol-gel法制備了介孔表面印跡ZnO熒光傳感器(PMIPs-ZnO NRs)。洗脫完TC和CTAB的PMIPs-ZnO NRs可以實(shí)現(xiàn)對(duì)TC的選擇性檢測(cè)。在本實(shí)驗(yàn)中,將特殊結(jié)構(gòu)(介孔)引入到MIPs-ZnO NRs,同時(shí)也制備了無介孔的MIPs-ZnO NRs(NPMIPs-ZnO NRs),通過對(duì)兩者選擇性檢測(cè)TC的研究,分析總結(jié)介孔在MIPs-ZnO NRs選擇性檢測(cè)TC中的作用。(3)首先,在ZnO NRs修飾上NH_2,在此基礎(chǔ)上修飾上溴代烷烴,將其作為熒光材料、支撐材料和引發(fā)劑。通過ATRP法制備一種印跡聚合層超薄的MIPs-ZnO NRs,并將其用于選擇性檢測(cè)TC。在本實(shí)驗(yàn)中,ATRP法是一種新型的活性自由基聚合法,可以實(shí)現(xiàn)聚合層厚度可控,有助于提高選擇性檢測(cè)TC性能。
[Abstract]:Tetracycline (TCC) is a broad-spectrum bacteriostatic agent with high concentration of sterilization. Because of its low cost and obvious antibacterial effect, it has been widely used in aquaculture and veterinary drugs to promote the rapid growth of animals and prevent animal diseases. But the overuse of TC can cause it to exceed the standard in some meat food and water body. Food in excess of the standard will directly harm human health, while TC entering the water body will not only harm the ecological environment, but also enter the human body through the ecological food chain system, which will also endanger human health. Due to the advantages of simple sample processing, low detection limit, high sensitivity, short response time, strong anti-interference ability and direct observation, the fluorescence detection method based on fluorescence sensor is used to detect various toxic and harmful substances. However, fluorescence sensors generally do not have selective recognition ability, and the combination with surface molecular imprinting technology can give fluorescence sensors the ability to specifically recognize target molecules, and on the basis of not affecting the optical properties of fluorescence sensors, The physicochemical stability is improved. There are many methods for preparing molecularly imprinted polymer (MIPs), such as precipitation polymerization, sol-gel polymerization and atom transfer radical polymerization (ATRP). However, the relationship between the morphology, structure, fluorescence properties and analytical properties of molecularly imprinted fluorescent sensors prepared by different polymerization methods has not been reported. In this thesis, TC was used as target molecule, ZnO NRs was used as solid matrix and fluorescence sensor was used. Surface molecularly imprinted ZnO fluorescence sensors MIPs-ZnO NRsO were prepared by precipitation polymerization of sol-gel and ATRP, respectively, using transmission electron microscopy (TEM), Fourier transform infrared spectrometer (FTIR), UV-VIS X-ray diffractometer (XRD) and molecular fluorescence spectroscopy (MFS). The morphology of MIPs-ZnO NRs was studied by means of meter and other characterization instruments. The optimum conditions of TC detection were determined by studying the concentration, stability and response time of MIPs-ZnO NRs. The fluorescence recognition and detection of TC in aqueous phase by MIPs-ZnO NRs prepared by different polymerization methods were studied by selective recognition and quantitative detection experiments. The main research results are as follows: firstly, ZnO NRs were prepared by hydrothermal method, and then modified with vinyl on the surface by KH570, which were used as fluorescent materials and support materials. MIPs-ZnO NRs were prepared by precipitation polymerization, and then used for selective detection of TC.Rs2 in water environment. ZnO NRs was used as fluorescent material and supporting material, and cetyltrimethylammonium bromide (CTAB) was used as pore-forming agent. A mesoporous surface imprinted ZnO fluorescence sensor, PMIPs-ZnO NRsO, was prepared by Sol-gel method. After eluting TC and CTAB PMIPs-ZnO NRs can realize the selective detection of TC. In this experiment, special mesoporous structure (mesoporous) was introduced into MIPs-ZnO NRs, and MIPs-ZnO NRs(NPMIPs-ZnO NRsS without mesoporous was also prepared. The role of mesoporous in MIPs-ZnO NRs selective detection of TC was analyzed and summarized. NH _ 2 was modified by ZnO NRs and then brominated alkanes were modified as fluorescent materials, supporting materials and initiators. A kind of ultra-thin MIPs-ZnO NRs with imprinted polymerization layer was prepared by ATRP method and used for selective detection of MIPs-ZnO. In this experiment, ATRP is a new active radical polymerization method, which can control the thickness of polymerization layer and improve the performance of selective detection of TC.
【學(xué)位授予單位】:江蘇大學(xué)
【學(xué)位級(jí)別】:碩士
【學(xué)位授予年份】:2017
【分類號(hào)】:O657.3;X832

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