基于碳納米復(fù)合材料及β-環(huán)糊精對(duì)手性小分子識(shí)別研究
發(fā)布時(shí)間:2018-05-26 11:53
本文選題:手性識(shí)別 + 手性表面; 參考:《西南大學(xué)》2015年碩士論文
【摘要】:電化學(xué)手性傳感器是將電化學(xué)測(cè)試分析技術(shù)和手性識(shí)別結(jié)合起來的一類新型分析方法,具有準(zhǔn)確度高、靈敏度高、選擇性好、操作便捷、價(jià)格低廉、易于微型化和自動(dòng)化等優(yōu)點(diǎn)。碳納米材料作為常見的納米材料之一,因其具有良好的導(dǎo)電性能和大的比表面積,穩(wěn)定性優(yōu)良等特點(diǎn)廣泛用于化學(xué)修飾電極及電化學(xué)領(lǐng)域等。環(huán)糊精(cyclodextrins,CDs)是由D-型吡喃葡萄糖通過a-1,4-糖苷鍵連接而成的圓錐形筒狀化合物,外緣親水,內(nèi)部疏水結(jié)構(gòu),從而能與許多分子形成包合物,使其成為常見的手性選擇劑。本文結(jié)合納米材料的優(yōu)良電化學(xué)性能和環(huán)糊精的手性選擇作用,構(gòu)建電化學(xué)手性傳感器。主要工作如下:1.構(gòu)建了碳納米管-離子液體/β-環(huán)糊精修飾電極,采用循環(huán)伏安技術(shù)、交流阻抗技術(shù)和掃描隧道顯微鏡對(duì)修飾電極進(jìn)行表征,并以此作為手性界面,探討了擬構(gòu)建手性界面對(duì)多巴的選擇性作用。實(shí)驗(yàn)結(jié)果表明,該手性界面對(duì)D-多巴的選擇性作用更強(qiáng)。此外還探討了可能的機(jī)理,并和相關(guān)電化學(xué)識(shí)別方法做了對(duì)比研究,我們構(gòu)建的手性傳感器具備識(shí)別能力強(qiáng),線性寬,檢測(cè)限低等優(yōu)點(diǎn)。2.通過原位還原法制備了石墨烯-納米鉑復(fù)合材料,并通過它與L-色氨酸的π-π堆積作用形成了石墨烯-納米鉑-L-色氨酸復(fù)合物,一步修飾于玻碳電極用于對(duì)多巴的手性識(shí)別。實(shí)驗(yàn)結(jié)果表明該手性傳感界面與D-多巴的作用強(qiáng)于L-多巴的作用,此外,也做了最佳條件優(yōu)化,在最佳優(yōu)化條件下,能達(dá)到較低的檢測(cè)限和較寬的線性范圍。3.通過循環(huán)伏安技術(shù)在裸玻碳電極上聚合L-天門冬氨酸,并浸泡β-環(huán)糊精過夜,構(gòu)建了β-環(huán)糊精-聚-L-天門冬氨酸膜修飾電極(β-CD-P-L-Asp/GCE)手性界面,用于對(duì)電活性小分子抗壞血酸的手性識(shí)別研究。實(shí)驗(yàn)結(jié)果表面,該手性界面對(duì)D-抗壞血酸的作用更強(qiáng),從而實(shí)現(xiàn)了對(duì)抗壞血酸異構(gòu)體的手性區(qū)分。并且在有酪氨酸干擾的條件下,依舊有較大的選擇作用。利用環(huán)糊精與抗壞血酸的相互作用來構(gòu)建手性小分子識(shí)別,在電化學(xué)手性分析中提供了簡(jiǎn)單的方法和參考。
[Abstract]:Electrochemical chiral sensor is a new kind of analytical method which combines electrochemical testing and analysis technology with chiral recognition. It has high accuracy, high sensitivity, good selectivity, convenient operation and low price. It is easy to miniaturize and automate. Carbon nanomaterials, as one of the common nano-materials, are widely used in chemically modified electrodes and electrochemical fields because of their good conductivity, large specific surface area and good stability. Cyclodextrins (CDS) is a conical cylindrical compound which is connected by a-1O4-glucoside bond with D-glucopyranose. It is hydrophilic and hydrophobic, and can form inclusion complex with many molecules, making it a common chiral selector. In this paper, electrochemical chiral sensors were constructed by combining the excellent electrochemical properties of nanomaterials and the chiral selectivity of cyclodextrin. The main work is as follows: 1. Carbon nanotube ionic liquid / 尾 -cyclodextrin modified electrode was constructed. The modified electrode was characterized by cyclic voltammetry, AC impedance technique and scanning tunneling microscope. The selective effect of chiral interface on dopa was discussed. The experimental results show that the chiral interface has stronger selectivity to D-dopa. In addition, the possible mechanism is discussed and compared with the electrochemical recognition methods. The chiral sensor has the advantages of strong recognition ability, wide linearity, low detection limit and so on. Graphene nano-platinum composites were prepared by in-situ reduction method, and formed graphene nano-platinum-L-tryptophan complex by 蟺-蟺 accumulation of L-tryptophan, which was modified into glassy carbon electrode for chiral recognition of dopa. The experimental results show that the interaction between the chiral sensing interface and Ddopa is stronger than that of L- dopa. In addition, the optimal conditions are optimized. Under the optimal conditions, the detection limit is lower and the linear range is wide. The chiral interface of 尾 -cyclodextrin-poly (L-aspartate) modified electrode (尾 -CD-P-Asp-GCE-GCE) was constructed by cyclic voltammetry (CV) polymerization of L-aspartate on bare glassy carbon electrode and immersion of 尾 -cyclodextrin overnight. It is used to study the chiral recognition of ascorbic acid, a small electroactive molecule. On the surface of the experimental results, the chiral interface has a stronger effect on D-ascorbic acid, thus realizing the chiral differentiation of ascorbic acid isomers. And in the presence of tyrosine interference, there is still a greater role in the selection. Using the interaction of cyclodextrin and ascorbic acid to construct chiral small molecule recognition, this paper provides a simple method and reference for electrochemical chiral analysis.
【學(xué)位授予單位】:西南大學(xué)
【學(xué)位級(jí)別】:碩士
【學(xué)位授予年份】:2015
【分類號(hào)】:TB332;O636.12
【參考文獻(xiàn)】
中國(guó)期刊全文數(shù)據(jù)庫 前1條
1 LI MinMin;QING GuangYan;ZHANG MingXi;SUN TaoLei;;Chiral polymer-based biointerface materials[J];Science China(Chemistry);2014年04期
,本文編號(hào):1937144
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