新型熒光量子點的制備及生物傳感器的構建
發(fā)布時間:2018-08-28 15:19
【摘要】:熒光量子點,是一種被稱之為準零維的納米材料,量子限域效應和邊緣效應賦予其獨特的光學性質。熒光量子點擁有良好的光穩(wěn)定性,激發(fā)光譜寬且連續(xù)分布,與其相對的發(fā)射光譜窄而對稱,熒光壽命長。近年來,熒光量子點已經(jīng)在化學傳感、成像等研究領域得到了廣泛應用。其中,類石墨烯量子點,如:二硫化鎢、黑磷及有機聚合物量子點,如:聚多巴胺量子點由于其優(yōu)異的光學性能,在生物或化學傳感等方面具有重要的研究價值。本碩士論文聚焦于新型二硫化鎢、黑磷及聚多巴胺量子點的制備并基于其熒光性能構建了多種新型傳感體系,成功實現(xiàn)了對硫辛酸、金屬銅離子及乙酰膽堿酯酶活性的檢測,具體內(nèi)容如下:第一章緒論主要介紹了類石墨烯量子點及聚合物點的特點,研究現(xiàn)狀以及應用;重點討論了基于新型量子點構建熒光探針及其應用于化學、生命領域中重要分子檢測。最后,對本碩士論文工作進行概述并闡述了研究工作的意義。第二章水溶性二硫化鎢量子點的制備及硫辛酸熒光傳感體系的構建我們通過超聲剝離與水熱法結合,利用表面活性劑CTAB成功創(chuàng)建了一種簡單、環(huán)保合成水溶性二硫化鎢量子點(WS2QDs)的新方法。所得量子點顯示出優(yōu)良的特性,包括尺寸分布窄、水溶性好、熒光穩(wěn)定等。實驗表明,此WS2QDs的熒光強度會被Fe3+通過光電子轉移作用所猝滅,并且對于Fe3+的檢測線性范圍較寬,這表明WS2QDs可以用于Fe3+的檢測。在硫辛酸(LA)的存在下,由于Fe3+與LA上的羧基的絡合作用強于Fe3+與WS2 QDs的作用,因此熒光強度會回升。基于該原理,我們成功構建了檢測LA的新方法,其檢測線性范圍為1~10 μmol/L,檢測下限為0.59 μmol/L。第三章 黑磷量子點的制備及免標記乙酰膽堿酶活性評估平臺構建我們基于黑磷量子點(BPQDs)和2-硝基-5-硫代苯甲酸(TNB)之間產(chǎn)生的熒光內(nèi)濾效應,建立了一種快速、靈敏、無標記的熒光檢測平臺,用于巰基化合物的檢測;我們基于巰基檢測平臺,進一步實現(xiàn)乙酰膽堿酯酶(AChE)活性的評估,并考察了酶抑制劑溴化新斯的明和敵百蟲對乙酰膽堿酯酶活性的抑制作用。實驗結果表明:測得敵百蟲的IC50值為1.95 μmol/L,新斯的明的IC50為18.1 nmol/L。第四章聚多巴胺點的制備及金屬銅離子熒光檢測體系構建神經(jīng)傳導物質多巴胺在堿性條件下會快速被氧化并自聚,生成聚多巴胺;诖颂匦,我們發(fā)展了一種在溫和條件下,利用Cu~(2+)的氧化性及Cu~(2+)/H2O2反應產(chǎn)生活性氧,協(xié)同氧化多巴胺自聚生成熒光聚多巴胺點的新方法。我們探索了不同金屬離子對聚多巴胺點合成速率及其熒光強度影響,研究發(fā)現(xiàn)Cu~(2+)對聚多巴胺納米點的合成有著極高的選擇性與靈敏度;谠撛,利用生成聚多巴胺納米點的自身熒光,我們構建了檢測Cu~(2+)的新方法,其線性范圍為0.05-3 μmol/L,檢測限為4.8 nM。
[Abstract]:Fluorescent quantum dots (QDs) are called quasi-zero dimensional nanomaterials, which are endowed with unique optical properties by quantum limiting effect and edge effect. The fluorescence quantum dots have good optical stability, wide excitation spectrum and continuous distribution. The emission spectrum is narrow and symmetrical, and the fluorescence lifetime is long. In recent years, fluorescent quantum dots have been widely used in chemical sensing, imaging and other fields. Among them, graphene like quantum dots, such as tungsten disulfide, black phosphorus and organic polymer quantum dots, such as polydopamine quantum dots, have important research value in biological or chemical sensing due to their excellent optical properties. This master thesis focused on the preparation of novel tungsten disulfide, black phosphorus and polydopamine quantum dots. Based on their fluorescence properties, a variety of novel sensing systems were constructed, and the activities of lipoic acid, metal copper ions and acetylcholinesterase were successfully detected. The main contents are as follows: in the first chapter, the characteristics, research status and applications of graphene like quantum dots and polymer dots are introduced, and the fluorescent probes based on new quantum dots and their applications in chemistry are discussed. Important molecular detection in the field of life. Finally, the thesis summarizes the work of this thesis and expounds the significance of the research work. In chapter 2, the preparation of water-soluble tungsten disulfide quantum dots and the construction of fluorescence sensing system for lipoic acid we have successfully created a simple one by ultrasonic stripping and hydrothermal method, using surfactant CTAB. A new method for the synthesis of water soluble tungsten disulfide quantum dots (WS2QDs) by environmental protection. The obtained QDs show excellent properties, including narrow size distribution, good water solubility and fluorescence stability. The experimental results show that the fluorescence intensity of the WS2QDs is quenched by Fe3 through photoelectron transfer, and the linear range of Fe3 detection is wide, which indicates that WS2QDs can be used for the detection of Fe3. In the presence of lipoic acid (LA), the fluorescence intensity will pick up due to the stronger complexation between Fe3 and the carboxyl groups on LA than between Fe3 and WS2 QDs. Based on this principle, we have successfully constructed a new method for detecting LA. The detection linear range is 1 ~ 10 渭 mol/L, and the detection limit is 0.59 渭 mol/L.. Chapter 3 preparation of Black phosphorus Quantum Dots and Evaluation platform of Non-labeled acetylcholinase activity We have established a rapid and sensitive method based on the fluorescence internal filtration effect between black phosphorus quantum dots (BPQDs) and 2-nitro-5-thiobenzoic acid (TNB). An unlabeled fluorescent detection platform for the detection of sulfhydryl compounds. We further evaluate the activity of acetylcholinesterase (AChE) based on the sulfhydryl detection platform. The inhibitory effects of enzyme inhibitors neostigmine bromide and trichlorfon on the activity of acetylcholinesterase were investigated. The results showed that the IC50 of trichlorfon was 1.95 渭 mol/L, and the IC50 of neostigmine was 18.1 nmol/L.. In chapter 4, the preparation of polydopamine spots and the construction of copper ion fluorescence detection system. Dopamine, a neuroconductive substance, is rapidly oxidized and self-polymerized under alkaline conditions to produce polydopamine. Based on this property, we developed a new method to produce reactive oxygen species (Ros) from Cu~ (2) and Cu~ (2) / H _ 2O _ 2 reaction under mild conditions, and to co-oxidize dopamine to produce fluorescent polydopamine point. We investigated the effects of different metal ions on the synthesis rate and fluorescence intensity of poly (dopamine). It was found that Cu~ (2) had a high selectivity and sensitivity to the synthesis of polydopamine nanoparticles. Based on this principle, a new method for the detection of Cu~ (2) was constructed by using the self-fluorescence of polydopamine nanoparticles. The linear range of the method was 0.05-3 渭 mol/L, and the detection limit was 4.8 nM..
【學位授予單位】:華東師范大學
【學位級別】:碩士
【學位授予年份】:2017
【分類號】:O657.3
[Abstract]:Fluorescent quantum dots (QDs) are called quasi-zero dimensional nanomaterials, which are endowed with unique optical properties by quantum limiting effect and edge effect. The fluorescence quantum dots have good optical stability, wide excitation spectrum and continuous distribution. The emission spectrum is narrow and symmetrical, and the fluorescence lifetime is long. In recent years, fluorescent quantum dots have been widely used in chemical sensing, imaging and other fields. Among them, graphene like quantum dots, such as tungsten disulfide, black phosphorus and organic polymer quantum dots, such as polydopamine quantum dots, have important research value in biological or chemical sensing due to their excellent optical properties. This master thesis focused on the preparation of novel tungsten disulfide, black phosphorus and polydopamine quantum dots. Based on their fluorescence properties, a variety of novel sensing systems were constructed, and the activities of lipoic acid, metal copper ions and acetylcholinesterase were successfully detected. The main contents are as follows: in the first chapter, the characteristics, research status and applications of graphene like quantum dots and polymer dots are introduced, and the fluorescent probes based on new quantum dots and their applications in chemistry are discussed. Important molecular detection in the field of life. Finally, the thesis summarizes the work of this thesis and expounds the significance of the research work. In chapter 2, the preparation of water-soluble tungsten disulfide quantum dots and the construction of fluorescence sensing system for lipoic acid we have successfully created a simple one by ultrasonic stripping and hydrothermal method, using surfactant CTAB. A new method for the synthesis of water soluble tungsten disulfide quantum dots (WS2QDs) by environmental protection. The obtained QDs show excellent properties, including narrow size distribution, good water solubility and fluorescence stability. The experimental results show that the fluorescence intensity of the WS2QDs is quenched by Fe3 through photoelectron transfer, and the linear range of Fe3 detection is wide, which indicates that WS2QDs can be used for the detection of Fe3. In the presence of lipoic acid (LA), the fluorescence intensity will pick up due to the stronger complexation between Fe3 and the carboxyl groups on LA than between Fe3 and WS2 QDs. Based on this principle, we have successfully constructed a new method for detecting LA. The detection linear range is 1 ~ 10 渭 mol/L, and the detection limit is 0.59 渭 mol/L.. Chapter 3 preparation of Black phosphorus Quantum Dots and Evaluation platform of Non-labeled acetylcholinase activity We have established a rapid and sensitive method based on the fluorescence internal filtration effect between black phosphorus quantum dots (BPQDs) and 2-nitro-5-thiobenzoic acid (TNB). An unlabeled fluorescent detection platform for the detection of sulfhydryl compounds. We further evaluate the activity of acetylcholinesterase (AChE) based on the sulfhydryl detection platform. The inhibitory effects of enzyme inhibitors neostigmine bromide and trichlorfon on the activity of acetylcholinesterase were investigated. The results showed that the IC50 of trichlorfon was 1.95 渭 mol/L, and the IC50 of neostigmine was 18.1 nmol/L.. In chapter 4, the preparation of polydopamine spots and the construction of copper ion fluorescence detection system. Dopamine, a neuroconductive substance, is rapidly oxidized and self-polymerized under alkaline conditions to produce polydopamine. Based on this property, we developed a new method to produce reactive oxygen species (Ros) from Cu~ (2) and Cu~ (2) / H _ 2O _ 2 reaction under mild conditions, and to co-oxidize dopamine to produce fluorescent polydopamine point. We investigated the effects of different metal ions on the synthesis rate and fluorescence intensity of poly (dopamine). It was found that Cu~ (2) had a high selectivity and sensitivity to the synthesis of polydopamine nanoparticles. Based on this principle, a new method for the detection of Cu~ (2) was constructed by using the self-fluorescence of polydopamine nanoparticles. The linear range of the method was 0.05-3 渭 mol/L, and the detection limit was 4.8 nM..
【學位授予單位】:華東師范大學
【學位級別】:碩士
【學位授予年份】:2017
【分類號】:O657.3
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