基于碳納米復(fù)合材料手性識別電活性小分子電化學(xué)傳感器研究
發(fā)布時間：2018-08-22 07:55
【摘要】：手性是自然界的基本屬性,手性化合物是生物體的基本組成成分。不同構(gòu)型的手性化合物在醫(yī)藥科學(xué)、生命科學(xué)、食品科學(xué)、材料科學(xué)及環(huán)境等方面發(fā)揮著獨特的作用,從而手性化合物對映體純度和含量的測定成為當(dāng)前化學(xué)的研究熱點。因此發(fā)展低成本、檢測快速的手性識別技術(shù)成為新的研究發(fā)展要求。電化學(xué)傳感器因具有操作簡便、檢測快速、響應(yīng)靈敏以及低成本、污染小等優(yōu)點而作為一類新的測試手段應(yīng)用于手性識別研究。碳納米材料因具有大的比表面積、良好的化學(xué)穩(wěn)定性及優(yōu)良的電化學(xué)性質(zhì),被廣泛用于合成納米復(fù)合材料構(gòu)建電化學(xué)傳感界面,為電化學(xué)傳感器應(yīng)用于手性識別開拓了新的發(fā)展前景。本文主要通過合成新型碳納米復(fù)合材料,并將其應(yīng)用于構(gòu)建手性傳感表面,實現(xiàn)對電活性手性小分子實時在線、快速靈敏的手性識別檢測。主要研究內(nèi)容分為以下三部分：1.研究了新型多孔納米復(fù)合材料對色氨酸對映體的手性識別。通過循環(huán)伏安技術(shù)在多壁碳納米管(MWCNTs)修飾的玻碳電極上電聚合L-半胱氨酸(L-Cys),形成具有手性識別能力的多孔納米復(fù)合材料(PLC/MWCNTs),并采用掃描電子顯微鏡(SEM)、循環(huán)伏安技術(shù)(CV)和電化學(xué)交流阻抗技術(shù)(EIS)對該材料進行表征。利用循環(huán)伏安技術(shù)研究該多孔納米復(fù)合材料對色氨酸(Trp)對映體的手性識別作用。實驗結(jié)果表明：該納米復(fù)合材料與D-Trp的作用更強,從而實現(xiàn)了對色氨酸對映異構(gòu)體的手性識別。2.研究了巰基化-β-環(huán)糊精/納米金/石墨烯構(gòu)建的手性表面對多巴對映異構(gòu)體的手性識別作用。利用氨基化離子液體(IL-NH2)還原氧化石墨烯制備離子液體還原的氧化石墨烯(IL-rGO),并將其滴涂于玻碳電極表面,然后在其表面電沉積納米金(dpAu),最后通過金-硫鍵作用在納米金上自組裝巰基化-β-環(huán)糊精(β-CD-SH),從而構(gòu)建了具有手性識別能力的電化學(xué)傳感界面。采用差分脈沖伏安法(DPV)研究多巴(DOPA)對映異構(gòu)體在該手性表面上的電信號響應(yīng),發(fā)現(xiàn)D-DOPA的電流響應(yīng)信號明顯大于L-DOPA,由此說明：該手性表面與D-DOPA的作用強于L-DOPA。3.采用循環(huán)伏安技術(shù)和方波伏安技術(shù)對比研究了多壁碳納米管、傒四甲酸(PTCA)和L-半胱氨酸形成的復(fù)合材料對多巴對映體的手性識別。利用π-π堆積作用制備傒四甲酸功能化的多壁碳納米管,將其通過EDC/NHS與 L-半胱氨酸共價鍵合形成納米復(fù)合材料(MWCNTs-PTCA-Cys),并利用循環(huán)伏安技術(shù)和掃描電子顯微鏡對該材料進行表征。然后將該復(fù)合材料修飾于玻碳電極上,利用循環(huán)伏安法(CV)和方波伏安法(SWV)對比研究其對多巴對映體的手性識別。實驗結(jié)果表明：該復(fù)合材料與D-DOPA的作用時,電流響應(yīng)更大,采用方波伏安法比循環(huán)伏安法達到了更好的識別效果。
[Abstract]:Chirality is the basic attribute of nature and chiral compounds are the basic components of organism. Chiral compounds of different configurations play a unique role in medicine science, life science, food science, material science and environment, so the determination of enantiomeric purity and content of chiral compounds has become a hot spot in current chemistry. Therefore, the development of low-cost, rapid detection of chiral recognition technology has become a new research and development requirements. Electrochemical sensors have been used as a new testing method for chiral recognition due to their advantages of simple operation, rapid detection, sensitive response, low cost and low pollution. Because of its large specific surface area, good chemical stability and excellent electrochemical properties, carbon nanocomposites are widely used in the synthesis of nanocomposites to construct electrochemical sensing interfaces. It opens up a new prospect for the application of electrochemical sensors in chiral recognition. In this paper, a new type of carbon nanocomposites was synthesized and applied to construct chiral sensing surface to realize real-time on-line detection of electroactive chiral small molecules and rapid and sensitive chiral recognition detection. The main research content is divided into the following three parts: 1. Chiral recognition of tryptophan enantiomers by new porous nanocomposites was studied. A porous nanocomposite (PLC/MWCNTs) with chiral recognition was prepared by electropolymerization of L-cysteine (L-Cys) on a multiwalled carbon nanotube (MWCNTs) modified glassy carbon electrode by cyclic voltammetry. A scanning electron microscope (SEM),) cyclic voltammetry technique was used. The material was characterized by (CV) and electrochemical impedance spectroscopy (EIS). The chiral recognition of tryptophan (Trp) enantiomers by the porous nanocomposites was investigated by cyclic voltammetry. The experimental results show that the nanocomposite has stronger interaction with D-Trp, thus realizing chiral recognition of tryptophan enantiomers. The chiral recognition of dopa enantiomers on the chiral surface of mercapto- 尾 -cyclodextrin / nano-gold / graphene was studied. Aminated ionic liquids (IL-NH2) were used to deoxidize graphene oxide to prepare graphene oxide (IL-rGO) reduced by ionic liquids, which were dripped on the surface of glassy carbon electrode. Then electrodeposition of nano-gold (dpAu), on its surface was carried out. Finally, the self-assembly of 尾 -CD-SH on nano-gold was carried out by gold-sulfur bond, and the electrochemical sensing interface with chiral recognition ability was constructed. Differential pulse voltammetry (DPV) was used to study the electrical response of the enantiomers of dopa (DOPA) on the chiral surface. It was found that the current response signal of D-DOPA was obviously larger than that of L-DOPA, which indicated that the interaction between the chiral surface and D-DOPA was stronger than that on L-DOPA. 3. Cyclic voltammetry and square wave voltammetry were used to investigate the chiral recognition of Dopa enantiomers in composites composed of multiwalled carbon nanotubes (MWNTs), tetracarboxylic acid (PTCA) and L-cysteine (L-cysteine). The functionalized multiwalled carbon nanotubes of tetracarboxylic acid were prepared by 蟺-蟺 stacking, and covalently bonded by EDC/NHS and L-cysteine to form nanocomposites (MWCNTs-PTCA-Cys). The materials were characterized by cyclic voltammetry and scanning electron microscopy. Then the composite was modified on glassy carbon electrode and the chiral recognition of dopa enantiomers was studied by cyclic voltammetry (CV) and square wave voltammetry (SWV). The experimental results show that the current response of the composite is greater than that of D-DOPA, and the square wave voltammetry is more effective than cyclic voltammetry.
【學(xué)位授予單位】：西南大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TB33;O657.1
本文編號：2196479
[Abstract]:Chirality is the basic attribute of nature and chiral compounds are the basic components of organism. Chiral compounds of different configurations play a unique role in medicine science, life science, food science, material science and environment, so the determination of enantiomeric purity and content of chiral compounds has become a hot spot in current chemistry. Therefore, the development of low-cost, rapid detection of chiral recognition technology has become a new research and development requirements. Electrochemical sensors have been used as a new testing method for chiral recognition due to their advantages of simple operation, rapid detection, sensitive response, low cost and low pollution. Because of its large specific surface area, good chemical stability and excellent electrochemical properties, carbon nanocomposites are widely used in the synthesis of nanocomposites to construct electrochemical sensing interfaces. It opens up a new prospect for the application of electrochemical sensors in chiral recognition. In this paper, a new type of carbon nanocomposites was synthesized and applied to construct chiral sensing surface to realize real-time on-line detection of electroactive chiral small molecules and rapid and sensitive chiral recognition detection. The main research content is divided into the following three parts: 1. Chiral recognition of tryptophan enantiomers by new porous nanocomposites was studied. A porous nanocomposite (PLC/MWCNTs) with chiral recognition was prepared by electropolymerization of L-cysteine (L-Cys) on a multiwalled carbon nanotube (MWCNTs) modified glassy carbon electrode by cyclic voltammetry. A scanning electron microscope (SEM),) cyclic voltammetry technique was used. The material was characterized by (CV) and electrochemical impedance spectroscopy (EIS). The chiral recognition of tryptophan (Trp) enantiomers by the porous nanocomposites was investigated by cyclic voltammetry. The experimental results show that the nanocomposite has stronger interaction with D-Trp, thus realizing chiral recognition of tryptophan enantiomers. The chiral recognition of dopa enantiomers on the chiral surface of mercapto- 尾 -cyclodextrin / nano-gold / graphene was studied. Aminated ionic liquids (IL-NH2) were used to deoxidize graphene oxide to prepare graphene oxide (IL-rGO) reduced by ionic liquids, which were dripped on the surface of glassy carbon electrode. Then electrodeposition of nano-gold (dpAu), on its surface was carried out. Finally, the self-assembly of 尾 -CD-SH on nano-gold was carried out by gold-sulfur bond, and the electrochemical sensing interface with chiral recognition ability was constructed. Differential pulse voltammetry (DPV) was used to study the electrical response of the enantiomers of dopa (DOPA) on the chiral surface. It was found that the current response signal of D-DOPA was obviously larger than that of L-DOPA, which indicated that the interaction between the chiral surface and D-DOPA was stronger than that on L-DOPA. 3. Cyclic voltammetry and square wave voltammetry were used to investigate the chiral recognition of Dopa enantiomers in composites composed of multiwalled carbon nanotubes (MWNTs), tetracarboxylic acid (PTCA) and L-cysteine (L-cysteine). The functionalized multiwalled carbon nanotubes of tetracarboxylic acid were prepared by 蟺-蟺 stacking, and covalently bonded by EDC/NHS and L-cysteine to form nanocomposites (MWCNTs-PTCA-Cys). The materials were characterized by cyclic voltammetry and scanning electron microscopy. Then the composite was modified on glassy carbon electrode and the chiral recognition of dopa enantiomers was studied by cyclic voltammetry (CV) and square wave voltammetry (SWV). The experimental results show that the current response of the composite is greater than that of D-DOPA, and the square wave voltammetry is more effective than cyclic voltammetry.
【學(xué)位授予單位】：西南大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TB33;O657.1
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