源自石榴籽的高發(fā)光熒光碳量子點(diǎn)的合成及應(yīng)用研究
發(fā)布時(shí)間：2019-06-09 20:16
【摘要】：熒光碳量子點(diǎn)自從2004年被首次發(fā)現(xiàn)以來(lái),就以細(xì)胞毒性低、耐光漂白、發(fā)射可調(diào)諧、生物相容性好以及穩(wěn)定性高等優(yōu)點(diǎn)受到了人們的廣泛關(guān)注。目前,已經(jīng)報(bào)道有各種各樣的合成方法和碳源用于碳量子點(diǎn)的制備,并且碳量子點(diǎn)已經(jīng)應(yīng)用于生物成像、生物傳感、光催化、光電設(shè)備等領(lǐng)域。但是合成高發(fā)光性能和具有表面功能化的碳量子點(diǎn),并將其作為熒光探針用于生物和環(huán)境分析仍然是科研工作者面對(duì)的挑戰(zhàn)。本論文以天然產(chǎn)物石榴籽為碳源,分別以乙二胺、氨基酸和核黃素為鈍化劑,制備出了4種發(fā)光性能各異的碳量子點(diǎn),并將其作為熒光探針?lè)謩e應(yīng)用于多巴胺、谷胱甘肽、對(duì)硫磷和汞離子含量的高靈敏檢測(cè)。主要研究工作概括如下:以石榴籽為碳源,乙二胺為鈍化劑,通過(guò)微波法一步合成了熒光碳量子點(diǎn)。在紫外燈照射下碳量子點(diǎn)發(fā)出藍(lán)色熒光,并且對(duì)溶液的酸堿性具有良好的感應(yīng)。所合成的碳量子點(diǎn)主要通過(guò)靜電作用與多巴胺發(fā)生相互作用使碳量子點(diǎn)的熒光猝滅。據(jù)此建立了一種以碳量子點(diǎn)作為熒光探針高靈敏、高選擇性檢測(cè)多巴胺含量的新方法,多巴胺的線性檢測(cè)范圍為0.1-8μg/mL,檢出限為31 ng/mL。該方法已經(jīng)應(yīng)用于血清和尿樣中多巴胺含量的檢測(cè),樣品的回收率在98.0~103.5%之間,相對(duì)標(biāo)準(zhǔn)偏差均在3.1%以內(nèi)。除此之外,所合成的碳量子點(diǎn)還可以用于斑馬魚(yú)成像,顯示出良好的生物相容性。利用石榴籽為碳源,乙二胺作為表面鈍化劑,采用水熱法合成熒光碳量子點(diǎn)。所合成的碳量子點(diǎn)具有藍(lán)色熒光,量子產(chǎn)率為23.80%。此外,汞離子能夠與碳量子點(diǎn)表面的-OH和-COOH配位鍵合,激發(fā)態(tài)的碳量子點(diǎn)將電子轉(zhuǎn)移給了汞離子空的d軌道,造成碳量子點(diǎn)熒光猝滅,而谷胱甘肽能通過(guò)形成Hg-S鍵和汞離子選擇性地鍵合,使得復(fù)合物解離,體系的熒光在一定程度上得到恢復(fù)。據(jù)此提出了一種熒光“關(guān)-開(kāi)”型高靈敏檢測(cè)谷胱甘肽的方法。當(dāng)谷胱甘肽的濃度在0.1-6μM的范圍內(nèi)時(shí),與體系的熒光增強(qiáng)值之間呈現(xiàn)良好的線性關(guān)系,檢出限為32 nM。該方法可以應(yīng)用于生物樣品中谷胱甘肽的檢測(cè)。以石榴籽、色氨酸和天冬氨酸為原料,利用水熱法制備了熒光碳量子點(diǎn)。該碳量子點(diǎn)在紫外光下發(fā)出藍(lán)色熒光,量子產(chǎn)率達(dá)到35.78%。有機(jī)磷農(nóng)藥對(duì)硫磷與碳量子點(diǎn)發(fā)生相互作用,減少了碳量子點(diǎn)表面的缺陷,不利于碳量子點(diǎn)導(dǎo)帶中的激發(fā)態(tài)電子(e-)和價(jià)帶中的空穴(h+)的非輻射復(fù)合,導(dǎo)致碳量子點(diǎn)熒光增強(qiáng)。從而建立了一種熒光增強(qiáng)型檢測(cè)對(duì)硫磷的新方法。對(duì)硫磷的線性范圍為0.01-1.1μM,檢出限為3.7 nM。將該方法應(yīng)用到環(huán)境水樣中對(duì)硫磷含量的檢測(cè),樣品的回收率在98.0-102.7%之間,相對(duì)標(biāo)準(zhǔn)偏差均在3.2%之內(nèi)。將石榴籽和核黃素通過(guò)水熱法得到了氮摻雜的熒光碳量子點(diǎn)。此碳量子點(diǎn)的量子產(chǎn)率高達(dá)38.83%,在紫外燈下發(fā)出黃綠色熒光。此外,汞離子能夠有效地猝滅碳量子點(diǎn)的熒光,據(jù)此建立了熒光探針?lè)ǜ哽`敏檢測(cè)汞離子的方法。該方法檢測(cè)汞離子的線性范圍是0.05-7μM,檢出限29 nM,并且可以應(yīng)用到河水、湖水和自來(lái)水中汞離子含量的檢測(cè)。熒光猝滅機(jī)理研究表明,汞離子對(duì)碳量子點(diǎn)的熒光猝滅為靜態(tài)和動(dòng)態(tài)的聯(lián)合猝滅。
[Abstract]:Since the first discovery in 2004, the fluorescent carbon quantum dot has been widely concerned by the advantages of low cytotoxicity, light bleaching, tunable emission, good biocompatibility and high stability. At present, various synthesis methods and carbon sources have been reported for the preparation of carbon quantum dots, and the carbon quantum dots have been applied in the fields of biological imaging, biological sensing, photocatalysis, photoelectric equipment and the like. However, that synthesis of high light-emitting performance and surface-functionalized carbon quantum dots and the use of them as a fluorescent probe for biological and environmental analysis are still a challenge for researchers. The carbon quantum dots with different luminescent properties were prepared by using the natural product of the pomegranate seeds as the carbon source, ethylenediamine, amino acid and riboflavin, respectively, and the carbon quantum dots with different light-emitting properties were prepared and used as the fluorescent probes respectively in the dopamine and the glutathione. And the high-sensitivity detection of the content of the parathion and the mercury ions. The main research work is as follows: the pomegranate seed is used as a carbon source, and the ethylenediamine is a passivating agent, and the fluorescent carbon quantum dot is synthesized in one step by the microwave method. The blue fluorescence is emitted at the carbon quantum point under the irradiation of the ultraviolet lamp, and the acid alkali of the solution is well induced. The synthesized carbon quantum dots are mainly excited by the interaction of the electrostatic action with the dopamine to cause the fluorescence of the carbon quantum dots to be quenched. A new method for high-sensitivity and high-selectivity detection of dopamine content with carbon quantum dots as a fluorescent probe was established. The linear detection range of dopamine was 0.1-8 & mu; g/ mL, and the detection limit was 31 ng/ mL. The method has been applied to the detection of the content of dopamine in the serum and urine sample, the recovery of the sample is between 98.0 and 103.5%, and the relative standard deviation is within 3.1%. In addition, the synthesized carbon quantum dots can also be used for zebra fish imaging to show good biocompatibility. By using the pomegranate seeds as the carbon source and the ethylenediamine as the surface deactivator, the fluorescent carbon quantum dots are synthesized by a hydrothermal method. The synthesized carbon quantum dot has blue fluorescence and the quantum yield is 23.80%. in addition, that mercury ion can be combine with the-OH and-COOH on the surface of the carbon quantum dot, the carbon quantum point of the excited state is transferred to the d-orbit of the mercury ion air to cause the fluorescence of the carbon quantum dot to be quenched, and the glutathione can be selectively bonded through the formation of the Hg-S bond and the mercury ion, So that the complex is dissociated and the fluorescence of the system is recovered to a certain extent. The invention provides a method for high-sensitivity detection of glutathione in a fluorescent "Off-On" type. When the concentration of glutathione is in the range of 0.1 to 6. m u.M, a good linear relationship is exhibited between the fluorescence enhancement values of the system, and the detection limit is 32 nM. The method can be applied to the detection of glutathione in biological samples. The fluorescent carbon quantum dots were prepared by hydrothermal method using pomegranate seeds, tryptophan and aspartic acid as raw materials. The carbon quantum dots emit blue fluorescence under the ultraviolet light, and the quantum yield reaches 35.78%. The interaction between the phoxim and the carbon quantum dot by the organophosphorus pesticide reduces the defects of the surface of the carbon quantum dots, and is not beneficial to the non-radiative recombination of the excited state electrons (e-) in the conduction band of the carbon quantum dots and the holes (h +) in the valence band, leading to the fluorescence enhancement of the carbon quantum dots. And a new method for detecting the parathion by fluorescence enhanced detection is established. The linear range of parathion was 0.01-1.1. m u.M and the detection limit was 3.7 nM. The method is applied to the detection of the content of parathion in the environment water sample, the recovery rate of the sample is between 98.0 and 102.7%, and the relative standard deviation is within 3.2%. And a nitrogen-doped fluorescent carbon quantum dot is obtained by a hydrothermal method by using the pomegranate seeds and the riboflavin. The quantum yield of the carbon quantum dot is as high as 38.83%, and the yellow-green fluorescence is emitted under the ultraviolet lamp. In addition, the fluorescence of the carbon quantum dots can be effectively quenched by the mercury ions, and a method for high-sensitivity detection of the mercury ions by the fluorescence probe method is established. The method detects that the linear range of the mercury ions is 0.05-7. m u.M, the detection limit is 29 nM, and can be applied to the detection of the mercury ion content in the river water, the lake water and the tap water. The study of the fluorescence quenching mechanism shows that the fluorescence quenching of the carbon quantum dots by the mercury ions is a static and dynamic joint quenching.
【學(xué)位授予單位】：河南師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O657.3
本文編號(hào)：2495868
[Abstract]:Since the first discovery in 2004, the fluorescent carbon quantum dot has been widely concerned by the advantages of low cytotoxicity, light bleaching, tunable emission, good biocompatibility and high stability. At present, various synthesis methods and carbon sources have been reported for the preparation of carbon quantum dots, and the carbon quantum dots have been applied in the fields of biological imaging, biological sensing, photocatalysis, photoelectric equipment and the like. However, that synthesis of high light-emitting performance and surface-functionalized carbon quantum dots and the use of them as a fluorescent probe for biological and environmental analysis are still a challenge for researchers. The carbon quantum dots with different luminescent properties were prepared by using the natural product of the pomegranate seeds as the carbon source, ethylenediamine, amino acid and riboflavin, respectively, and the carbon quantum dots with different light-emitting properties were prepared and used as the fluorescent probes respectively in the dopamine and the glutathione. And the high-sensitivity detection of the content of the parathion and the mercury ions. The main research work is as follows: the pomegranate seed is used as a carbon source, and the ethylenediamine is a passivating agent, and the fluorescent carbon quantum dot is synthesized in one step by the microwave method. The blue fluorescence is emitted at the carbon quantum point under the irradiation of the ultraviolet lamp, and the acid alkali of the solution is well induced. The synthesized carbon quantum dots are mainly excited by the interaction of the electrostatic action with the dopamine to cause the fluorescence of the carbon quantum dots to be quenched. A new method for high-sensitivity and high-selectivity detection of dopamine content with carbon quantum dots as a fluorescent probe was established. The linear detection range of dopamine was 0.1-8 & mu; g/ mL, and the detection limit was 31 ng/ mL. The method has been applied to the detection of the content of dopamine in the serum and urine sample, the recovery of the sample is between 98.0 and 103.5%, and the relative standard deviation is within 3.1%. In addition, the synthesized carbon quantum dots can also be used for zebra fish imaging to show good biocompatibility. By using the pomegranate seeds as the carbon source and the ethylenediamine as the surface deactivator, the fluorescent carbon quantum dots are synthesized by a hydrothermal method. The synthesized carbon quantum dot has blue fluorescence and the quantum yield is 23.80%. in addition, that mercury ion can be combine with the-OH and-COOH on the surface of the carbon quantum dot, the carbon quantum point of the excited state is transferred to the d-orbit of the mercury ion air to cause the fluorescence of the carbon quantum dot to be quenched, and the glutathione can be selectively bonded through the formation of the Hg-S bond and the mercury ion, So that the complex is dissociated and the fluorescence of the system is recovered to a certain extent. The invention provides a method for high-sensitivity detection of glutathione in a fluorescent "Off-On" type. When the concentration of glutathione is in the range of 0.1 to 6. m u.M, a good linear relationship is exhibited between the fluorescence enhancement values of the system, and the detection limit is 32 nM. The method can be applied to the detection of glutathione in biological samples. The fluorescent carbon quantum dots were prepared by hydrothermal method using pomegranate seeds, tryptophan and aspartic acid as raw materials. The carbon quantum dots emit blue fluorescence under the ultraviolet light, and the quantum yield reaches 35.78%. The interaction between the phoxim and the carbon quantum dot by the organophosphorus pesticide reduces the defects of the surface of the carbon quantum dots, and is not beneficial to the non-radiative recombination of the excited state electrons (e-) in the conduction band of the carbon quantum dots and the holes (h +) in the valence band, leading to the fluorescence enhancement of the carbon quantum dots. And a new method for detecting the parathion by fluorescence enhanced detection is established. The linear range of parathion was 0.01-1.1. m u.M and the detection limit was 3.7 nM. The method is applied to the detection of the content of parathion in the environment water sample, the recovery rate of the sample is between 98.0 and 102.7%, and the relative standard deviation is within 3.2%. And a nitrogen-doped fluorescent carbon quantum dot is obtained by a hydrothermal method by using the pomegranate seeds and the riboflavin. The quantum yield of the carbon quantum dot is as high as 38.83%, and the yellow-green fluorescence is emitted under the ultraviolet lamp. In addition, the fluorescence of the carbon quantum dots can be effectively quenched by the mercury ions, and a method for high-sensitivity detection of the mercury ions by the fluorescence probe method is established. The method detects that the linear range of the mercury ions is 0.05-7. m u.M, the detection limit is 29 nM, and can be applied to the detection of the mercury ion content in the river water, the lake water and the tap water. The study of the fluorescence quenching mechanism shows that the fluorescence quenching of the carbon quantum dots by the mercury ions is a static and dynamic joint quenching.
【學(xué)位授予單位】：河南師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O657.3
【參考文獻(xiàn)】
相關(guān)期刊論文 前1條
1 Wei Du;Xiaoqian Xu;Han Hao;Rongmei Liu;Di Zhang;Feng Gao;Qingyi Lu;;Green synthesis of fluorescent carbon quantum dots and carbon spheres from pericarp[J];Science China(Chemistry);2015年05期
，本文編號(hào)：2495868
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