發(fā)布時間：2018-03-05 22:10

  本文選題：碳納米材料　切入點：電化學(xué)傳感器　出處：《廣東藥科大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：化學(xué)修飾電極(Chemically Modified Electrodes,CMEs)作為電化學(xué)傳感的基礎(chǔ),是當(dāng)前電化學(xué)、電分析化學(xué)方面十分最活躍的研究領(lǐng)域。自問世以來,已經(jīng)成為藥物分析領(lǐng)域中的一個重要的研究方向。在分析應(yīng)用中,CMEs具有以下優(yōu)點:(1)在電極表面上可根據(jù)需要修飾特定的功能基團,制得一系列不同類型和特殊功能的修飾電極;(2)基底電極材料可為金屬、非金屬、有機物,也可以是導(dǎo)體、半導(dǎo)體,為開拓新的電分析化學(xué)方法提供基礎(chǔ);(3)根據(jù)電極修飾的功能基團不同,修飾電極對溶液中存在的物質(zhì)具有選擇性響應(yīng);(4)修飾電極能增強電極反應(yīng)的可逆性,為電極過程動力學(xué)的研究開辟新的途徑;(5)修飾電極的靈敏度與裸電極相比要大得多,為痕量分析的進一步發(fā)展提供有力的手段。基于上述優(yōu)點,CMEs在許多領(lǐng)域都具有廣闊的應(yīng)用前景。針對碳納米管和石墨烯擁有高的比表面積、獨特的空間結(jié)構(gòu)、易于功能化和修飾等特點,以及納米金屬材料具有增強電子傳遞速率的特點,二者對電化學(xué)效應(yīng)均有促進的作用。本研究構(gòu)建了三種納米金屬雜合碳納米材料修飾的電化學(xué)傳感器,應(yīng)用于中藥成分分析。論文的內(nèi)容主要分為以下三個部分:1.延胡索乙素在納米鎳雜合磺酸化石墨烯修飾的玻碳電極上的電化學(xué)行為及分析應(yīng)用。實驗制備了納米金屬鎳/磺酸化石墨烯修飾的玻碳電極(NiNPs/SGS/GCE)。通過掃描電鏡、能譜分析以及光電子能譜對修飾電極表面和金屬性質(zhì)進行表征,并用該修飾電極對延胡索乙素(Tetrahydropalmatine,THP)的電化學(xué)行為進行研究分析。研究表明磺酸化石墨對THP有良好的電化學(xué)效應(yīng),并且納米鎳能夠進一步增強THP的氧化峰電流,促進其在修飾電極表面的電子轉(zhuǎn)移效率。在最佳條件下THP氧化峰電流與濃度在5.0×10-7~2.0×10-5 mol/L呈線良好的線性關(guān)系,線性系數(shù)r為0.9988,檢出限LOD(S/N=3)達到1.7×10-7 mol/L。該修飾電極成功應(yīng)用在元胡止痛膠囊中THP的測定。2.芒果苷和淫羊藿苷在納米金銀合金-碳納米管磺酸化石墨烯修飾玻碳電極上的電化學(xué)行為及其應(yīng)用。實驗通過滴涂的方法將碳納米管磺酸化石墨烯混合分散液(MWNTs-SGSs)和金銀納米合金(Au-AgNPs)先后修飾在玻碳電極(GCE)表面,研制出了新電極。修飾電極結(jié)合了石墨烯的平面二維結(jié)構(gòu),碳納米管的管狀立體結(jié)構(gòu)和納米金屬的的特殊電化學(xué)效應(yīng),不僅增加了修飾電極的有效表面積,也增強了電極表面的電子傳遞速率,可實現(xiàn)芒果苷(MIN)和淫羊藿苷(IIN)的同時分析。實驗中通過掃描電子顯微鏡、紅外對修飾電極的表面形態(tài)進行研究表征,用循環(huán)伏安法(CV)、差示脈沖伏安法(DPV)、計時庫侖對MIN和IIN在修飾電極上的電化學(xué)行為進行考察。研究發(fā)現(xiàn),Au-AgNPs/MWNTs-SGSs/GCE對MIN和IIN的電化學(xué)行為表現(xiàn)出優(yōu)異的選擇性和催化性。通過循環(huán)伏安法對修飾量,pH,掃描速率等條件進行優(yōu)化,在最佳條件下循環(huán)伏安峰電位分別在0.56 V和0.95 V,MIN和IIN的氧化峰電流與濃度的線性范圍分別是5.0×10-8~5.0×10-4 mol/L和5.0×10-8~1.0×10-4 mol/L,r分別為0.9995和0.9991,LOD均為1.7×10-8 mol/L(S/N=3)。在實際樣品測定中,Au-AgNPs/MWNTs-SGSs/GCE可成功應(yīng)用在知母、茵陳、淫羊藿葉的測定,結(jié)果令人滿意。該方法具有試劑用量少、分析成本低、靈敏度高、重現(xiàn)性好等特點,是一種能同時測定藥物有效成分芒果苷和淫羊藿苷的新方法。3.納米金屬銀雜合羧基化碳納米管修飾的玻碳電極對敵百蟲的殘留分析及應(yīng)用研究。實驗通過恒電位沉積的方法,在滴涂有羧基化碳納米管(MWNTs-COOH)的玻碳電極上電沉積納米金屬銀,成功研制出AgNPs/MWNTs-COOH/GCE。相比裸GCE,AgNPs/GCE,MWNTs-COOH/GCE,雜合材料修飾電極具有更強的電催化效應(yīng)。實驗中研制的AgNPs/MWNTs-COOH/GCE對敵百蟲有更高的響應(yīng)電流,并表現(xiàn)出良好的選擇性、穩(wěn)定性、重復(fù)性。在1.9×10-9~3.77×10-6 mol/L范圍內(nèi)呈現(xiàn)良好的線性關(guān)系,r為0.9991。該測定方法對敵百蟲的LOD為6.2×10-10mol/L(S/N=3)。在測定實際樣品(金銀花和陳皮)中,結(jié)果表現(xiàn)出較高的靈敏度,回收率達到99.3%,在重復(fù)多次試驗中RSD均低于5%,令人滿意。
[Abstract]:Chemical modified electrode (Chemically Modified, Electrodes, CMEs) as the basis of electrochemical sensor, the electrochemical research field of electroanalytical chemistry is the most active. Since its inception, has become an important research direction in the field of drug analysis. In the analysis of application, CMEs has the following advantages: (1) in the electrode surface can be modified with specific functional groups, modified electrode prepared a series of different types and special functions; (2) material electrode substrate can be metal, nonmetal, organic matter, can also be a conductor, semiconductor, for the development of new electro analytical methods provide the basis; (3) according to the electrode modification of different functional groups, modified electrode has a selective response to solution in the presence of substances; (4) modified electrode can enhance the reversibility of electrode reaction, open up a new way to study the kinetics of electrode process; (5) modification The sensitivity of the electrodes is much larger compared with the bare electrode, provide a means for the further development of trace analysis. Based on the above advantages, CMEs has a broad application prospect in many fields. Based on carbon nanotubes and graphene have high surface area, unique structure, easy functionalization and modification etc. and the nano metal materials with enhanced characteristics of electron transfer rate, two on the electrochemical effect have promote role. This study constructed three kinds of nano metal complex electrochemical sensor and carbon nano materials modified and applied to the traditional Chinese medicine composition analysis. This thesis mainly consists of the following three parts: the electrochemical behavior and application of 1. Rhizoma Corydalis B in the glassy carbon electrode of nano nickel mixed sulfonated graphene modified glassy carbon electrode. The nano Ni / sulfonated graphene modified were prepared (NiNPs/SGS/ GCE) By scanning electron microscope, energy spectrum analysis and X-ray photoelectron spectroscopy were used to characterize the surface modification and properties of metals, and use the modified electrode to tetrahydropalmatine (Tetrahydropalmatine, THP) were analyzed. The results show that the electrochemical behavior of graphite has good electrochemical effect of sulfonic acid on THP, and can further enhance the oxidation peak of nano nickel the current THP, promote the electron transfer efficiency in the surface of the electrode. The oxidation peak current and the concentration of THP under the optimum conditions the linear relationship between the fine line in 5 * 10-7~2.0 * 10-5 mol/L, the linear coefficient of R is 0.9988, the detection limit of LOD (S/N=3) to 1.7 x 10-7 mol/L. electrochemical behavior of the modified electrode was successfully applied in the Yuanhuzhitong capsule THP.2. determination of mangiferin and icariin in nano silver alloys - carbon nanotubes sulfonated graphene modified glassy carbon electrode and its application. Through the experiment of drop The method of coated carbon nanotubes mixed sulfonated graphene dispersion (MWNTs-SGSs) and nano silver alloy (Au-AgNPs) has been modified on a glassy carbon electrode (GCE) surface, the development of new electrode. The modified electrode combined with the two-dimensional structure of Shi Moxi, carbon nanotubes and nano metal tubular structure special electrochemical effect that not only increases the effective surface area of electrode, but also enhance the electron transfer rate of the electrode surface, can realize the mangiferin (MIN) and icariin (IIN) at the same time. The experimental analysis by scanning electron microscopy, the surface morphology of modified electrode were studied by infrared characterization of cyclic voltammetry (CV), differential pulse voltammetry (DPV), chronocoulometry were investigated on the electrochemical behavior of MIN and IIN on the modified electrode. The study found that electro chemical behavior of Au-AgNPs/MWNTs-SGSs/GCE on MIN and IIN show excellent choice And catalysis. By cyclic voltammetry on modification, pH, scan rate and other conditions were optimized. Under the optimal conditions of cyclic voltammetry peak potential was 0.56 V and 0.95 V, the linear range of the oxidation peak current and the concentration of MIN and IIN were 5 mol/L and 5 * 10-8~5.0 * 10-4 * 10-8~1.0 * 10-4 mol/L and R were 0.9995 and 0.9991, LOD was 1.7 * 10-8 mol/L (S/N=3). In practical samples, Au-AgNPs/MWNTs-SGSs/GCE can be successfully applied in the determination of Anemarrhena, wormwood, Epimedium leaves, with satisfactory results. This method has less reagent, analysis of low cost, high sensitivity and good reproducibility. Is the glassy carbon electrode is a new method for simultaneously determination of drug active ingredient icariin mango glycosides and.3. nano silver hybrid carboxylated carbon nanotubes modified to trichlorfon residue analysis and application research. The experiment by potentiostatic deposition In the drop, coated with carboxylated carbon nanotubes (MWNTs-COOH) electrodeposition of nano silver on the glassy carbon electrode, successfully developed AgNPs/MWNTs-COOH/GCE. compared with bare GCE, AgNPs/GCE, MWNTs-COOH/GCE, electro catalytic effect of hybrid material modified electrode has stronger. AgNPs /MWNTs-COOH/GCE developed the response current higher for trichlorfon, and performance good selectivity, stability and reproducibility. There was a good linear relationship in 1.9 * 10-9~3.77 * 10-6 mol/L range, R 0.9991. for the determination of trichlorfon LOD 6.2 * 10-10mol/L (S/N=3). In the determination of practical samples (honeysuckle and tangerine peel), the results showed high sensitivity, recovery rate in 99.3%, repeat the experiment in RSD were lower than 5%, satisfactory.

【學(xué)位授予單位】：廣東藥科大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TB383.1;TP212.2

【參考文獻】

相關(guān)期刊論文 前10條

1 陳紅艷;胡海洋;胡偉武;;碳納米管/石墨烯修飾電極的制備及在槲皮素檢測中的應(yīng)用[J];中國農(nóng)業(yè)大學(xué)學(xué)報;2016年09期

2 牛佳鈺;肖純凌;;有機磷農(nóng)藥的殘留危害及檢測方法研究[J];安徽農(nóng)業(yè)科學(xué);2016年16期

3 王藝蘭;包曉玉;楊妍;鮑克燕;劉夢菲;;電沉積Cu_2O在無酶葡萄糖傳感器中的應(yīng)用[J];分析科學(xué)學(xué)報;2016年01期

4 張亞;鄭建斌;;石墨烯修飾玻碳電極在對苯二酚存在下選擇性測定米吐爾[J];應(yīng)用化學(xué);2016年01期

5 韓恩;潘超;曹曉梅;蔡健榮;;基于酪氨酸酶抑制作用的莠去津農(nóng)藥殘留電化學(xué)快速檢測[J];食品科技;2015年05期

6 張宇童;楊兆娜;謝飛;馬雪梅;王明連;;有機磷農(nóng)藥神經(jīng)發(fā)育毒性作用機制研究進展[J];安徽農(nóng)業(yè)科學(xué);2014年12期

7 李叢叢;李曉霞;羅賢文;漆紅蘭;;以苯硼酸為識別物質(zhì)的電化學(xué)阻抗糖傳感器的制備[J];分析化學(xué);2013年10期

8 岳瑩;梁卿;郭勇;邵士俊;;介孔碳納米纖維修飾電極用于黃酮類化合物蘆丁的電化學(xué)測定[J];分析測試學(xué)報;2012年08期

9 黃美榮;谷國利;施鳳英;李新貴;;基于氧硫功能團載體的鉛離子電位傳感器的研究與進展[J];分析化學(xué);2012年01期

10 葉玫;余穎;賀學(xué)榮;姜琳琳;吳成業(yè);;氣相色譜法測定水產(chǎn)品中敵百蟲、敵敵畏殘留量[J];上海海洋大學(xué)學(xué)報;2010年04期

相關(guān)博士學(xué)位論文 前1條

1 朱作藝;新型功能化碳納米管修飾電極的制備及其在藥物分析中的應(yīng)用[D];浙江大學(xué);2014年

，

本文編號：1572099