本文選題：聚對(duì)氨基苯磺酸 + 聚鄰巰基苯胺　； 參考：《廣東工業(yè)大學(xué)》2011年碩士論文

【摘要】：氨基酸是蛋白質(zhì)的基本結(jié)構(gòu)單位,是動(dòng)物體合成蛋白質(zhì)的原料來(lái)源,屬食品、飼料的營(yíng)養(yǎng)成分,也可作為營(yíng)養(yǎng)型化妝品的有效成分及表面活性劑、其他工業(yè)產(chǎn)品的化工原料。因此,氨基酸分析是工業(yè)、農(nóng)業(yè)生產(chǎn)及生命科學(xué)研究中最重要的技術(shù)之一。芳香族氨基酸包括苯丙氨酸、酪氨酸和色氨酸等。芳香族氨基酸的代謝情況在肝、腎、神經(jīng)精神疾病等疾病診斷中有重大意義。因此定量分析血液中的芳香族氨基酸不僅在蛋白質(zhì)化學(xué)和評(píng)價(jià)病人的營(yíng)養(yǎng)狀況方面十分重要,而且在多種疾病的診斷治療和病因?qū)W研究上十分關(guān)鍵。目前,臨床測(cè)定芳香族氨基酸的方法有許多,包括高效液相色譜法、毛細(xì)管電泳法、熒光法、紫外分光光度法、質(zhì)譜法等等。其中HPLC是分析芳香族氨基酸的常用方法,但是樣品處理復(fù)雜,需梯度洗脫,衍生產(chǎn)物不穩(wěn)定。也有研究人員利用芳香族氨基酸在一定的激發(fā)光照射下能產(chǎn)生自然熒光的特性來(lái)測(cè)定,獲得了較好的結(jié)果,但是由于它們熒光光譜嚴(yán)重重疊,熒光特性不一致而不能在同一波長(zhǎng)下同時(shí)進(jìn)行3種氨基酸的測(cè)定,因此不能滿足某些疾病的臨床診斷與監(jiān)測(cè)需要。色氨酸、酪氨酸和苯丙氨酸都是在紫外區(qū)有吸收的常見氨基酸,用紫外分光光度法測(cè)定時(shí),因其吸收光譜嚴(yán)重重疊,需要采用一定的數(shù)學(xué)方法。這些方法中所用儀器較貴,且三種氨基酸往往相互干擾。 電分析化學(xué)是根據(jù)物質(zhì)在溶液中的電化學(xué)性質(zhì)及其變化建立的一類分析方法,特別是現(xiàn)代儀器分析與計(jì)算機(jī)聯(lián)用實(shí)現(xiàn)了分析工作的自動(dòng)化。目前,在工業(yè)農(nóng)業(yè)、食品檢驗(yàn)、環(huán)境保護(hù)和醫(yī)學(xué)檢驗(yàn)等各領(lǐng)域獲得廣泛的應(yīng)用。氨基酸的電化學(xué)分析因簡(jiǎn)單、靈敏、無(wú)放射、無(wú)污染與各種現(xiàn)代化的分離方法相結(jié)合可以大大簡(jiǎn)化操作過(guò)程,節(jié)約分析時(shí)間,且靈敏度及準(zhǔn)確度都很高,選擇性好。氨基酸的電化學(xué)分析可分為直接電化學(xué)分析和間接電化學(xué)分析。直接電化學(xué)分析檢測(cè)要求被測(cè)物質(zhì)具有一定的電化學(xué)活性。在三種芳香烴氨基酸中,色氨酸(Trp)和酪氨酸(Tyr)都是電活性物質(zhì),是人和動(dòng)物必需的氨基酸,Trp又是限制性氨基酸,對(duì)其測(cè)定具有重要意義。采用電分析方法直接檢測(cè)是較理想的選擇。 化學(xué)修飾電極是通過(guò)化學(xué)修飾的方法在電極表面進(jìn)行分子設(shè)計(jì),將具有優(yōu)良化學(xué)性質(zhì)的分子、離子、聚合物固定在電極表面,造成某種微結(jié)構(gòu),利用微結(jié)構(gòu)所提供的多種能利用的勢(shì)場(chǎng),使待測(cè)物進(jìn)行有效的分離富集,并借控制電極電位,進(jìn)一步提高選擇性。 把電化學(xué)測(cè)定方法的靈敏性和修飾劑化學(xué)反應(yīng)的的選擇性相結(jié)合,成為分離、富集和選擇性三者合而為一的理想體系,廣泛應(yīng)用于選擇性富集與分離、電催化、選擇性滲透、媒介作用和化學(xué)傳感器。 本論文聚合物膜修飾電極的電化學(xué)法制備及其應(yīng)用從以下兩個(gè)方面進(jìn)行了探討,一方面電化學(xué)聚合法制備了對(duì)氨基苯磺酸聚合膜修飾玻碳電極(P-p-ABSA/GCE),系統(tǒng)而詳細(xì)地研究了色氨酸和酪氨酸在P-p-ABSA/GCE修飾電極上的電化學(xué)行為；另一方面對(duì)金電極上電化學(xué)法聚合鄰巰基苯胺進(jìn)行了初探。主要內(nèi)容包括： 1,采用循環(huán)伏安法在玻碳電極表面修飾聚對(duì)氨基苯磺酸,隨著循環(huán)掃描周數(shù)的增加,伏安圖上相應(yīng)蜂電流不斷增長(zhǎng)證明聚合物的形成。該制備方法簡(jiǎn)便、快捷,所制得的修飾膜均一穩(wěn)定,具有良好的重現(xiàn)性。 2,研究了L-色氨酸(L-Trp)在該電極上的電化學(xué)行為,以及支持電解質(zhì)、溶液pH、掃描速率等對(duì)L-Trp電化學(xué)行為的影響。該修飾電極明顯提高了L-Trp的氧化峰電流,參與電極反應(yīng)的質(zhì)子數(shù)和電子數(shù)相等,電極過(guò)程為吸附控制過(guò)程。在pH 3.0的NaH2PO4-Na2HPO4緩沖溶液中,氧化峰電流與濃度在5.0×10-8～2.0×10-5 mol/L范圍內(nèi)呈良好的線性關(guān)系,檢出限為1.5×10-8mol/L。連續(xù)測(cè)定5×10-6mol/L的L-Trp標(biāo)準(zhǔn)溶液,電流值的相對(duì)標(biāo)準(zhǔn)偏差(RSD)為3.13%(n=5),重現(xiàn)性良好。一些常見物質(zhì)對(duì)測(cè)定無(wú)干擾。 3,研究了L-酪氨酸(L-Tyr)在該電極上的電化學(xué)行為,并優(yōu)化了測(cè)定條件。該修飾電極明顯提高了L-Tyr的氧化峰電流,參與電極反應(yīng)的質(zhì)子數(shù)和電子數(shù)相等,電極過(guò)程為吸附控制過(guò)程。在0.2 mol/L H3PO4溶液中,氧化峰電流與濃度在2×10-7～2×10-5mol/L范圍內(nèi)呈良好的線性關(guān)系,檢出限為1.0×10-7 mol/L。連續(xù)測(cè)定5×10-6mol/L的L-Tyr標(biāo)準(zhǔn)溶液,電流值的相對(duì)標(biāo)準(zhǔn)偏差(RSD)為4.95%(n=5),具有較好的重現(xiàn)性。 4,色氨酸和酪氨酸在一般電極上完全不能分開,但在P-p-ABSA/GCE修飾電極上,采用差分脈沖伏安法,在2.0mol/L H2SO4溶液中,色氨酸和酪氨酸的氧化峰電位分別為0.912 V和1.016 V,可以完全分離,實(shí)現(xiàn)了色氨酸和酪氨酸共存時(shí)的選擇性測(cè)定。且該法用于醫(yī)院營(yíng)養(yǎng)輸液常用的復(fù)合氨基酸注射液中色氨酸和酪氨酸的同時(shí)測(cè)定,取得了滿意的結(jié)果。 5,另一方面,在對(duì)金電極上電化學(xué)法聚合鄰巰基苯胺的研究上,本論文采用恒電位法在金電極上電解合成了聚鄰巰基苯胺(PATP)膜。該聚合物兼有聚苯胺的導(dǎo)電性和-SH基團(tuán)的氧化還原性能,在巰代苯胺聚合物電極材料的研究與開發(fā)中具有重要前景,也可能在電池正極材料上得到應(yīng)用,如一次鋰電池的正極材料。另外,-SH基團(tuán)能與金形成穩(wěn)定Au-S鍵,可以作為用于石英晶體微天平分析時(shí)的分子印跡聚合物,用于分離手性氨基酸,在電化學(xué)傳感器方面得到應(yīng)用。初步探討了鄰巰基苯胺的電化學(xué)聚合過(guò)程及PATP的氧化還原機(jī)理。結(jié)果表明,鄰巰基苯胺的聚合反應(yīng)是通過(guò)陽(yáng)離子自由基中間體進(jìn)行的,且用恒電位法合成PATP膜時(shí),電位應(yīng)控制在1.38V～1.43V之間。在此基礎(chǔ)上用循環(huán)伏安法對(duì)PATP膜的電化學(xué)性質(zhì)進(jìn)行表征,研究了聚合電位、鹽酸濃度、聚合時(shí)間對(duì)PATP電化學(xué)行為的影響。
[Abstract]:Amino acid is the basic structural unit of protein. It is the source of raw material for protein synthesis in animal body. It belongs to food, feed nutrition, and can also be used as an effective component and surfactant of nutritional cosmetics and chemical raw materials for other industrial products. Therefore, amino acid analysis is the most important technology in industry, agricultural production and life science research. Aromatic amino acids include phenylalanine, tyrosine and tryptophan. The metabolism of aromatic amino acids is of great significance in the diagnosis of liver, kidney, and neuropsychiatric diseases. Therefore, the quantitative analysis of aromatic amino acids in the blood is important not only in protein chemistry and in evaluating the nutritional status of patients, but also in the evaluation of the nutritional status of the patients. At present, there are many methods for the clinical determination of aromatic amino acids, including high performance liquid chromatography, capillary electrophoresis, fluorescence, UV spectrophotometry, mass spectrometry and so on. HPLC is a common method for the analysis of aromatic aminoacids, but the sample treatment is complex and needs gradient. Elution, derivatives are unstable, and some researchers have obtained good results by using aromatic amino acids to produce natural fluorescence properties under certain excitation light, but they have obtained good results. But because of their serious overlapping of fluorescence spectra and the inconsistency of fluorescence characteristics, the determination of 3 kinds of amino acids can not be carried out simultaneously under the same wavelength. The clinical diagnosis and monitoring needs of certain diseases are not satisfied. Tryptophan, tyrosine and phenylalanine are common amino acids that are absorbed in the ultraviolet region. When the absorption spectra are seriously overlapped by ultraviolet spectrophotometry, some mathematical methods are needed. The instruments used in these methods are more expensive, and the three kinds of amino acids are often reciprocal. Interference.
Electroanalytical chemistry is a kind of analytical method based on the electrochemical properties and changes of substances in solutions, especially the automation of analytical work in conjunction with modern instrument analysis and computer. The electrochemistry of amino acids has been widely used in various fields, such as industrial agriculture, food inspection, environmental protection and medical inspection. The analysis of simple, sensitive, no radiation, no pollution and various modern separation methods can greatly simplify the operation process, save the analysis time, and the sensitivity and accuracy are high and the selectivity is good. The electrochemical analysis of amino acids can be divided into direct electrochemical analysis and indirect electrochemical analysis. Direct electrochemical analysis and detection requirements are required. In the three aromatic hydrocarbon amino acids, tryptophan (Trp) and tyrosine (Tyr) are both electroactive substances, which are essential amino acids for human and animal, and Trp is a restrictive amino acid. It is of great significance for the determination of the substance. Direct detection by electroanalysis is an ideal choice.
Chemically modified electrodes are chemically modified to carry out molecular design on the surface of the electrode. The molecules, ions and polymers with excellent chemical properties are fixed on the surface of the electrode to cause some micro structure, and a variety of potential fields provided by the microstructures are used to effectively separate and enrich the measured objects, and to control the potential of the electrode. One step to improve selectivity.
The sensitivity of electrochemical determination method and the selectivity of the modifier chemical reaction are combined to become an ideal system for separation, enrichment and selectivity, which are widely used in selective enrichment and separation, electrocatalysis, selective osmosis, media action and chemical sensing devices.
In this paper, the electrochemical preparation of polymer film modified electrode and its application are discussed in the following two aspects. On the one hand, the electrochemical polymerization of p-aminophenylsulfonic acid polymerized membrane modified glassy carbon electrode (P-p-ABSA/GCE) has been prepared, and the electrochemical behavior of tryptophan and tyrosine on the P-p-ABSA/GCE modified electrode has been studied in detail. On the other hand, the electrochemical polymerization of O - mercapto aniline on gold electrode was studied.
1, polyp-aminophene sulfonic acid was modified by cyclic voltammetry at the surface of glassy carbon electrode. With the increase of cycle scanning weeks, the corresponding bee current on the voltammetry proved the formation of polymer. The preparation method was simple and fast, and the modified membranes were stable and good reproducibility.
2, the electrochemical behavior of L- tryptophan (L-Trp) on this electrode and the effect of supporting electrolyte, solution pH, scanning rate on the electrochemical behavior of L-Trp were investigated. The modified electrode obviously improved the oxidation peak current of L-Trp, the number of protons and the electron number phase in the electrode reaction, and the electrode process as the adsorption control process. In the NaH2PO4- of pH 3 NaH2PO4- In the Na2HPO4 buffer solution, the peak current and concentration of oxidation peak are linear in the range of 5 x 10-8 to 2 x 10-5 mol/L. The detection limit is 1.5 x 10-8mol/L. for 5 x 10-6mol/L L-Trp standard solution. The relative standard deviation of current value (RSD) is 3.13% (n=5), and the reproducibility is good. Some common substances have no interference to the determination.
3, the electrochemical behavior of L- tyrosine (L-Tyr) on this electrode was studied and the determination conditions were optimized. The modified electrode improved the oxidation peak current of L-Tyr obviously, the number of protons and the number of electrons in the electrode reaction were equal, the electrode process was the adsorption control process. The peak current and concentration of oxidation peak in 0.2 mol/L H3PO4 solution were 2 x 10-7 ~ 2 x 10-5mo. There is a good linear relationship in the range of l/L. The detection limit is 1 x 10-7 mol/L. for the continuous determination of 5 x 10-6mol/L L-Tyr standard solution, the relative standard deviation of current value (RSD) is 4.95% (n=5), and it has good reproducibility.
4, tryptophan and tyrosine can not be separated completely on the general electrode, but on the P-p-ABSA/GCE modified electrode, the peak potential of tryptophan and tyrosine is 0.912 V and 1.016 V in 2.0mol/L H2SO4 solution, and the selective determination of tryptophan and tyrosine in the coexistence of tryptophan and tyrosine can be completely separated and the selective determination of tryptophan and tyrosine is achieved. The method has been applied to the simultaneous determination of tryptophan and tyrosine in compound Amino Acid Injection commonly used in hospital nutrition infusion. Satisfactory results have been obtained.
5, on the other hand, in the study of the electrochemical polymerization of O mercapto aniline on gold electrodes, the polyaniline (PATP) film was synthesized by electrolysis on gold electrode by potentiostatic method. The polymer has both the conductivity of Polyaniline and the redox property of the -SH group. It has been developed in the research and development of the polymer electrode material of thiol substituted aniline. In addition, the -SH group can form a stable Au-S bond with gold, which can be used as a molecularly imprinted polymer used in the analysis of quartz crystal microbalance, and is used to separate chiral amino acids and be applied in electrochemical sensors. The electrochemical polymerization process of O mercapto aniline and the oxidation reduction mechanism of PATP show that the polymerization of O mercapto aniline is carried out through the cationic radical intermediate, and the potential should be controlled between 1.38V and 1.43V when the PATP film is synthesized by constant potential method. On this basis, the electrochemical properties of the PATP membrane are carried out by cyclic voltammetry. The effects of polymerization potential, concentration of hydrochloric acid and polymerization time on Electrochemical Behavior of PATP were characterized.
【學(xué)位授予單位】：廣東工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2011
【分類號(hào)】：O646.5;O629.7

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