三種電活性小分子對(duì)映體的電流識(shí)別研究
發(fā)布時(shí)間：2018-09-05 14:02
【摘要】：手性又稱為不對(duì)稱性,是廣泛應(yīng)用于化學(xué)和醫(yī)學(xué)領(lǐng)域中的專業(yè)術(shù)語(yǔ),屬于三維空間物體的基本屬性。當(dāng)一個(gè)物質(zhì)與其鏡像不能重合,就稱其為手性物質(zhì)。手性也是生物系統(tǒng)的基本特征,構(gòu)成生物系統(tǒng)的許多分子都是有手性的,常見的包括:人體所需基本營(yíng)養(yǎng)素如糖類和蛋白質(zhì),遺傳信息載體DNA,氨基酸對(duì)映體分子,酶,激素及結(jié)構(gòu)復(fù)雜的天然有機(jī)大分子等。手性對(duì)映體分子通常表現(xiàn)出不同的生理活性,尤其是手性藥物。對(duì)生命體而言,手性識(shí)別是一種重要的生命現(xiàn)象。因此對(duì)手性分子的分析、識(shí)別與檢測(cè)在現(xiàn)代藥學(xué)、醫(yī)學(xué)、生命科學(xué)、食品營(yíng)養(yǎng)學(xué)、農(nóng)藥學(xué)以及其他領(lǐng)域意義重大。電化學(xué)手性識(shí)別是利用電化學(xué)測(cè)試方法對(duì)手性對(duì)映體分子進(jìn)行識(shí)別的一種分析方法,與色譜法、熒光法、毛細(xì)管電泳法和紫外吸收光譜法等相比,電化學(xué)方法具有靈敏度高、響應(yīng)迅速、選擇性好、制備簡(jiǎn)易、可重復(fù)等優(yōu)點(diǎn)。在電化學(xué)分析方法中,常常借助納米材料構(gòu)建手性表面,這些納米材料導(dǎo)電性好、比表面大有利于提高手性分析的靈敏度。本文利用電化學(xué)聚合膜、碳納米管、金屬納米粒子、DNA等材料構(gòu)建了三種手性傳感界面,并研究了傳感界面與電活性小分子對(duì)映體的相互作用。主要研究?jī)?nèi)容包括以下三部分:1.研究了氧化型谷胱甘肽(GSSG)與L-賴氨酸多層電化學(xué)聚合膜形成的手性表面,對(duì)抗壞血酸(AA)和異抗壞血酸(IAA)的相互作用。實(shí)驗(yàn)采用循環(huán)伏安法將GSSG和L-賴氨酸分步聚合在玻碳電極表面,用掃描電子顯微鏡(SEM)觀察了聚合膜的表面形貌,用電化學(xué)循環(huán)伏安技術(shù)(CV)與交流阻抗技術(shù)(EIS)探究不同修飾電極的電化學(xué)行為,利用差分脈沖伏安法(DPV)探討了聚合膜與AA和IAA相互作用后的電流變化。實(shí)驗(yàn)結(jié)果表明:該手性表面與AA和IAA均能產(chǎn)生作用,但與AA的作用更強(qiáng),產(chǎn)生的電流信大于IAA,具有選擇性識(shí)別作用。2.實(shí)驗(yàn)首先在玻碳電極表面修飾碳納米管(MWCNT),再用循環(huán)伏安法電聚合L-精氨酸(p-L-Arg),然后利用恒電位法沉積金納米粒子(Au NPs),最后通過Au-S鍵結(jié)合手性選擇劑N-異丁�；�-L-半胱氨酸(NILC),得到NILC修飾的傳感界面。用掃描電子顯微鏡(SEM)觀察修飾材料的形貌特征,用方波伏安法(SWV)探究了所得手性界面與酪氨酸(Tyr)對(duì)映體之間的選擇性作用,實(shí)驗(yàn)結(jié)果表明:NILC修飾的手性界面對(duì)D-Tyr的作用比L-Tyr更強(qiáng),D-Tyr與L-Tyr電流差異明顯,由此實(shí)現(xiàn)了對(duì)酪氨酸對(duì)映體的安培識(shí)別。3.用碳納米管與鉑鈀納米合金復(fù)合材料(MWCNT/Pt-Pd NPs)修飾玻碳電極,再修飾上手性選擇劑分子小牛胸腺DNA,得到手性傳感器并研究該傳感器與色氨酸對(duì)映體(Trp)的選擇性作用。采用SEM和X射線能譜儀(EDX)觀測(cè)材料的的表面形貌及組成元素,采用CV等方法探究了修飾材料的電化學(xué)性質(zhì),同時(shí)利用DPV探討修飾界面與色氨酸對(duì)映體之間的選擇性作用。實(shí)驗(yàn)結(jié)果表明,該傳感界面對(duì)L-Trp的電流響應(yīng)強(qiáng)于D-Trp。
[Abstract]:Chirality, also known as asymmetry, is a specialized term widely used in chemistry and medicine. It belongs to the basic properties of three-dimensional space objects. When a substance does not coincide with its mirror image, it is called a chiral substance. Chirality is also the basic characteristic of biological system. Many molecules that make up biological system are chiral. The common ones include basic nutrients such as carbohydrate and protein, DNA, amino acid enantiomer molecule, enzyme, etc. Hormones and complex structure of natural organic macromolecules and so on. Chiral enantiomers usually exhibit different physiological activities, especially chiral drugs. Chiral recognition is an important phenomenon of life. Therefore, the analysis, recognition and detection of chiral molecules are of great significance in modern pharmaceutical, medical, life sciences, food nutrition, pesticide and other fields. Electrochemical chiral recognition is an analytical method for the recognition of chiral enantiomers by electrochemical measurement. Compared with chromatography, fluorescence, capillary electrophoresis and ultraviolet absorption spectrometry, electrochemical method has high sensitivity. It has the advantages of quick response, good selectivity, easy preparation and repeatability. In electrochemical analysis methods, chiral surfaces are often constructed by means of nano-materials. These nanomaterials have good electrical conductivity, which is more favorable to improve the sensitivity of chiral analysis than the surface. In this paper, three chiral sensing interfaces were constructed by using electrochemical polymeric films, carbon nanotubes, metal nanoparticles and DNA. The interaction between the sensing interfaces and electroactive enantiomers of small molecules was studied. The main research contents include the following three parts: 1. The chiral surface of oxidized glutathione (GSSG) and L-lysine multilayer electrochemical polymerization film was studied. The interaction between ascorbic acid (AA) and isoascorbic acid (IAA) was studied. GSSG and L-lysine were polymerized on the surface of glassy carbon electrode by cyclic voltammetry. The morphology of the film was observed by scanning electron microscope (SEM). Electrochemical behavior of different modified electrodes was investigated by electrochemical cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The current changes of polymer films interacting with AA and IAA were investigated by differential pulse voltammetry (DPV). The experimental results show that the chiral surface can act on both AA and IAA, but more strongly with AA, and the resulting current signal is larger than that of IAA,. 2. In this experiment, carbon nanotubes (MWCNT),) were modified on the surface of glassy carbon electrode and then electropolymerized L-arginine (p-L-Arg) by cyclic voltammetry. Then the gold nanoparticles (Au NPs), were deposited by potentiostatic method. Finally, the Au-S bond was used to bind the chiral selector N- isobutylol-L-semi-N- isobutylol. The NILC modified sensing interface was obtained by cystine (NILC),. The morphology of the modified materials was observed by scanning electron microscopy (SEM). The selective interaction between the chiral interface and tyrosine (Tyr) enantiomers was investigated by square wave voltammetry (SWV). The experimental results show that the effect of the chiral interface modified by D-Tyr on D-Tyr is stronger than that on L-Tyr, and the difference between D-Tyr and L-Tyr current is obvious, thus realizing amperometric recognition of tyrosine enantiomers .3. The glassy carbon electrode was modified with carbon nanotubes and platinum-palladium nanoalloy composites (MWCNT/Pt-Pd NPs) and the chiral selective molecular calf thymus DNA, was modified to obtain the chiral sensor. The selective interaction between the sensor and tryptophan enantiomer (Trp) was studied. The surface morphology and component elements of the modified materials were observed by SEM and X-ray energy spectrometer (EDX). The electrochemical properties of the modified materials were investigated by CV and the selective interaction between the modified interface and tryptophan enantiomers was discussed by DPV. The experimental results show that the current response of the sensing interface to L-Trp is stronger than that of D-Trp.
【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】：2017
【分類號(hào)】：O657.1
本文編號(hào)：2224495
[Abstract]:Chirality, also known as asymmetry, is a specialized term widely used in chemistry and medicine. It belongs to the basic properties of three-dimensional space objects. When a substance does not coincide with its mirror image, it is called a chiral substance. Chirality is also the basic characteristic of biological system. Many molecules that make up biological system are chiral. The common ones include basic nutrients such as carbohydrate and protein, DNA, amino acid enantiomer molecule, enzyme, etc. Hormones and complex structure of natural organic macromolecules and so on. Chiral enantiomers usually exhibit different physiological activities, especially chiral drugs. Chiral recognition is an important phenomenon of life. Therefore, the analysis, recognition and detection of chiral molecules are of great significance in modern pharmaceutical, medical, life sciences, food nutrition, pesticide and other fields. Electrochemical chiral recognition is an analytical method for the recognition of chiral enantiomers by electrochemical measurement. Compared with chromatography, fluorescence, capillary electrophoresis and ultraviolet absorption spectrometry, electrochemical method has high sensitivity. It has the advantages of quick response, good selectivity, easy preparation and repeatability. In electrochemical analysis methods, chiral surfaces are often constructed by means of nano-materials. These nanomaterials have good electrical conductivity, which is more favorable to improve the sensitivity of chiral analysis than the surface. In this paper, three chiral sensing interfaces were constructed by using electrochemical polymeric films, carbon nanotubes, metal nanoparticles and DNA. The interaction between the sensing interfaces and electroactive enantiomers of small molecules was studied. The main research contents include the following three parts: 1. The chiral surface of oxidized glutathione (GSSG) and L-lysine multilayer electrochemical polymerization film was studied. The interaction between ascorbic acid (AA) and isoascorbic acid (IAA) was studied. GSSG and L-lysine were polymerized on the surface of glassy carbon electrode by cyclic voltammetry. The morphology of the film was observed by scanning electron microscope (SEM). Electrochemical behavior of different modified electrodes was investigated by electrochemical cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The current changes of polymer films interacting with AA and IAA were investigated by differential pulse voltammetry (DPV). The experimental results show that the chiral surface can act on both AA and IAA, but more strongly with AA, and the resulting current signal is larger than that of IAA,. 2. In this experiment, carbon nanotubes (MWCNT),) were modified on the surface of glassy carbon electrode and then electropolymerized L-arginine (p-L-Arg) by cyclic voltammetry. Then the gold nanoparticles (Au NPs), were deposited by potentiostatic method. Finally, the Au-S bond was used to bind the chiral selector N- isobutylol-L-semi-N- isobutylol. The NILC modified sensing interface was obtained by cystine (NILC),. The morphology of the modified materials was observed by scanning electron microscopy (SEM). The selective interaction between the chiral interface and tyrosine (Tyr) enantiomers was investigated by square wave voltammetry (SWV). The experimental results show that the effect of the chiral interface modified by D-Tyr on D-Tyr is stronger than that on L-Tyr, and the difference between D-Tyr and L-Tyr current is obvious, thus realizing amperometric recognition of tyrosine enantiomers .3. The glassy carbon electrode was modified with carbon nanotubes and platinum-palladium nanoalloy composites (MWCNT/Pt-Pd NPs) and the chiral selective molecular calf thymus DNA, was modified to obtain the chiral sensor. The selective interaction between the sensor and tryptophan enantiomer (Trp) was studied. The surface morphology and component elements of the modified materials were observed by SEM and X-ray energy spectrometer (EDX). The electrochemical properties of the modified materials were investigated by CV and the selective interaction between the modified interface and tryptophan enantiomers was discussed by DPV. The experimental results show that the current response of the sensing interface to L-Trp is stronger than that of D-Trp.
【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】：2017
【分類號(hào)】：O657.1
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