本文選題：微納結(jié)構(gòu) + 可控組裝　； 參考：《浙江大學(xué)》2017年博士論文

【摘要】：水產(chǎn)品質(zhì)量安全是社會(huì)關(guān)注的熱點(diǎn)之一。針對(duì)常見(jiàn)的危害因素,應(yīng)尋找靈敏、準(zhǔn)確、快速的檢測(cè)技術(shù)。電化學(xué)傳感器具有靈敏度好、選擇性好、操作簡(jiǎn)單等優(yōu)點(diǎn),是最有前景的快速檢測(cè)技術(shù)之一。其性能取決于電極材料及界面結(jié)構(gòu)。對(duì)于不同目標(biāo)分析物,應(yīng)選擇何種功能性材料以及如何控制納米結(jié)構(gòu)單元的組裝,以獲得預(yù)期的電極性能,是需要解決的關(guān)鍵問(wèn)題。本論文分別以一維單壁碳納米管(SWCNTs)、二維石墨烯和三維納米多孔金(NPG)作為電極的基礎(chǔ)組裝材料,根據(jù)不同分析物,選擇合適的功能性材料和可控的合成、組裝方法,分別構(gòu)建具有微納結(jié)構(gòu)電極界面的高性能傳感器,并開(kāi)展水產(chǎn)品質(zhì)量安全檢測(cè)的研究工作。主要的研究?jī)?nèi)容、結(jié)果和結(jié)論如下:(1)針對(duì)水產(chǎn)品新鮮度快速檢測(cè)問(wèn)題,首次提出基于介電泳(DEP)組裝技術(shù)的等離子體氧化SWCNTs與聚(3,4-乙烯二氧噻吩)/聚苯乙烯磺酸(PEDOT/PSS)氣敏薄膜的制備方法。結(jié)果表明,等離子體氧化處理能改善碳管的分散性,PEDOT/PSS可提高碳管的氣敏性。經(jīng)組裝后碳管和聚合物鏈重新排序形成新的有序微納結(jié)構(gòu),顯著提高薄膜的導(dǎo)電性和氣敏性。該傳感器可檢測(cè)魚類腐敗所釋放的ppm級(jí)NH_3以及ppb級(jí)TMA和H_2S。(2)針對(duì)水產(chǎn)品Pb~(2+)快速檢測(cè)問(wèn)題,制備了電化學(xué)還原氧化石墨烯(ERGO)薄膜修飾的絲印電極。ERGO可改善電極的比表面積和電化學(xué)性能。該電極可線性檢測(cè)5-200 μg/L Pb~(2+),靈敏度為93.36 μA μM-1 cm-2,檢測(cè)下限為0.54μg/L(S/N=3)。(3)針對(duì)水產(chǎn)品Hg~(2+)快速檢測(cè)問(wèn)題,制備了基于電化學(xué)合金/去合金化法的NPG電極。合金/去合金化循環(huán)圈數(shù)決定電極的多孔結(jié)構(gòu)及其對(duì)Hg~(2+)的溶出響應(yīng)。該電極可線性測(cè)出1-030μg/LHg~(2+)。自組裝硫醇化修飾電極表面可提高電極的靈敏度(32.92 μA/μM)和檢測(cè)下限(0.098 μg/L,S/N=3)。(4)針對(duì)水產(chǎn)品NO_2~-快速檢測(cè)問(wèn)題,制備了基于電化學(xué)循環(huán)共沉積法的ERGO/金納米顆粒(AuNPs)薄膜電極。ERGO可增大電極的比表面積,均勻分散在ERGO片之間的AuNPs可提高電極表面的導(dǎo)電性和電催化活性。電極對(duì)水產(chǎn)品中NO_2~-具有良好的線性響應(yīng)區(qū)間(1-6000μM、6-20mM)、較高的靈敏度(0.3029、0.1522 μAμM-1 cm-2)以及較低的檢測(cè)下限(0.13 μM,S/N=3)。(5)針對(duì)水產(chǎn)品單增李斯特菌(LM)靈敏檢測(cè)問(wèn)題,首次提出基于DEP組裝羧基化石墨烯(CGR)/AuNPs薄膜免疫傳感器的制備方法。DEP組裝可控制CGR和AuNPs在電極表面的定位與排布,所得的CGR/AuNPs薄膜利于大量抗體的穩(wěn)定固定。優(yōu)化后的傳感器可線性檢測(cè)2-2×105 CFU/mL的LM,檢測(cè)下限為 1CFU/mL(S/N=3)。上述研究成果為構(gòu)建基于微納結(jié)構(gòu)電極界面的高性能傳感器提供了新思路,也為食品質(zhì)量安全快速檢測(cè)提供技術(shù)支持。
[Abstract]:The quality and safety of aquatic products is one of the hot spots of social concern. In view of common hazard factors, sensitive, accurate and rapid detection techniques should be found. Electrochemical sensor has the advantages of good sensitivity, good selectivity and simple operation. It is one of the most promising rapid detection techniques. Its performance depends on the electrode material and interface structure. How to select the functional materials and how to control the assembly of nanostructure units to obtain the expected electrode performance are the key problems to be solved for different target analytes. In this thesis, one-dimensional single-walled carbon nanotubes (SWCNTsN), two-dimensional graphene and three-dimensional nano-porous gold (NPG) were used as the basic assembly materials of the electrode. According to the different analysis materials, suitable functional materials and controllable synthesis and assembly methods were selected. High performance sensors with micro / nano electrode interface were constructed, and the quality and safety of aquatic products were studied. The main research contents, results and conclusions are as follows: (1) aiming at the problem of rapid detection of freshness of aquatic products, The preparation method of plasma oxidized SWCNTs and PEDOT / PSSs based on dielectric electrophoresis (DEP) assembly technique is proposed for the first time. The results show that plasma oxidation can improve the dispersion of carbon tubes and PEDOT / PSS can improve the gas sensitivity of carbon tubes. After assembly, carbon tubes and polymer chains were rearranged to form a new ordered micro-nano structure, which significantly improved the conductivity and gas sensitivity of the films. The sensor detects ppm level NH_3 released by fish corruption and ppb class TMA and HSZ 2) for rapid detection of aquatic product Pb~(2. The electroreduction graphene oxide (ERG) film modified screen printing electrode. Ergo can improve the specific surface area and electrochemical performance of the electrode. The electrode can be used to detect 5-200 渭 g / L Pb~(2 with a sensitivity of 93.36 渭 A 渭 M-1 cm-2 and a detection limit of 0.54 渭 g / L ~ (-1) / N ~ (3). The NPG electrode based on electrochemical alloy / dealloying method has been prepared for rapid detection of Hg~(2 in aquatic products. The alloy / dealloying cycle circle number determines the porous structure of the electrode and its dissolution response to Hg~(2. The linear measurement of 1-030 渭 g/LHg~(2 can be obtained by this electrode. The self-assembled thiol modified electrode surface can improve the sensitivity of the electrode (32.92 渭 A / 渭 M) and the detection limit of 0.098 渭 g / L / N ~ (3) N ~ (3 +) for the problem of NO2- rapid detection of aquatic products. The ERGO/ gold nanoparticles AuNPs thin film electrode based on electrochemical cyclic co-deposition was prepared. The specific surface area of the electrode was increased, and the conductivity and electrocatalytic activity of the electrode surface were improved by AuNPs dispersed uniformly between the ERGO sheets. The electrode has a good linear response range of 1-6000 渭 M ~ (-1) -20 mm ~ (-1), a higher sensitivity of 0.3029 ~ 0.1522 渭 A 渭 M ~ (-1) cm ~ (-2) and a lower detection limit of 0.13 渭 M ~ (-1) N ~ (3 +) ~ (5) for the detection of Listeria monocytogenes (LM) in aquatic products. For the first time, the preparation method of carboxylated graphene / AuNPs thin film immunosensor based on DEP was proposed. DEP assembly can control the location and placement of CGR and AuNPs on the electrode surface. The obtained CGR/AuNPs film is conducive to the stable fixation of a large number of antibodies. The optimized sensor can be linearly detected for 2-2 脳 10 ~ 5 CFU/mL, and the detection limit is 1 CFU / m ~ (-1) L ~ (-1) S / N ~ (3 +). These results provide a new idea for the construction of high performance sensors based on micro-nano structure electrode interface, and also provide technical support for rapid detection of food quality and safety.
【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TS254.7;O657.1
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本文編號(hào)：1967900