本文關(guān)鍵詞：功能化石墨烯電化學(xué)傳感器檢測煙堿類農(nóng)藥的研究　出處：《哈爾濱工業(yè)大學(xué)》2017年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 石墨烯 煙堿類農(nóng)藥檢測 電化學(xué)傳感器 β-環(huán)糊精 表面分子印跡 殼寡糖-三維石墨烯

【摘要】：煙堿農(nóng)藥是世界上銷售量最大的殺蟲劑之一,但是長期濫用和違規(guī)使用導(dǎo)致農(nóng)產(chǎn)品中低毒低殘留農(nóng)藥嚴重超標(biāo),引起人們潛在健康問題以及“綠色貿(mào)易壁壘”。中國作為農(nóng)業(yè)大國,亟需建立快速、靈敏、價格低廉的煙堿農(nóng)藥大規(guī)模現(xiàn)場檢驗監(jiān)測技術(shù)。電化學(xué)傳感器技術(shù)憑借響應(yīng)快速、設(shè)備便攜、成本低、操作簡單等優(yōu)點,逐漸成為農(nóng)藥殘留現(xiàn)場偵測中最具有活力的手段之一。隨著超分子識別技術(shù)、表面分子印跡技術(shù)及三維多孔材料的快速發(fā)展,將其與高電催化活性的石墨烯結(jié)合,應(yīng)用于電化學(xué)傳感器的核心元件——工作電極,以提高電化學(xué)檢測方法的靈敏度、選擇性和線性范圍,是煙堿農(nóng)殘電化學(xué)檢測的重要研究方向,也是分析工作者面臨的巨大挑戰(zhàn)�；谶@樣的研究目的,本文的主要研究內(nèi)容如下:采用簡單的濕法合成路線合成了β-環(huán)糊精-還原氧化石墨烯(β-CD-r GO),并將其修飾于玻碳電極表面,構(gòu)建了β-環(huán)糊精-石墨烯電化學(xué)傳感器。β-CD不僅作為還原氧化石墨烯(r GO)的穩(wěn)定劑,同時也作為超分子主體識別客體分子哌蟲啶(IPP),通過形成超分子包絡(luò)物而將IPP帶到石墨烯表面,從而增強電化學(xué)響應(yīng)信號。與裸電極(GCE)和石墨烯修飾電極(r GO/GCE)相比,我國自主研發(fā)的新型煙堿農(nóng)藥哌蟲啶(IPP)在β-CD-r GO/GCE上的不可逆還原峰電流值分別增加了14倍和2倍,顯著提高了IPP檢測靈敏度。為了進一步提高煙堿類農(nóng)藥的檢測特異性,在石墨烯載體表面成功嫁接了分子印跡聚合物薄膜。構(gòu)建的石墨烯表面分子印跡電化學(xué)傳感器顯著提高了煙堿農(nóng)藥電化學(xué)檢測的電化學(xué)響應(yīng)信號、識別特異性,縮短了響應(yīng)平衡時間。試驗創(chuàng)新性地采用對乙烯基苯甲酸(VBA,具有連接交聯(lián)劑的烯基單元、結(jié)合模板分子的識別基團以及與石墨烯通過π-π相互作用而連接的苯環(huán)),在石墨烯(GN)表面成功負載單層均一的分子印跡(MIPs)膜,制備了石墨烯表面分子印跡聚合物(MIPs/GN)。分子印跡膜厚僅1.9nm,遠低于文獻中報道的石墨烯表面的分子印跡膜厚度17nm。GN/MIPs/GCE對吡蟲啉的印跡因子達到2.3,顯著高于同類煙堿農(nóng)藥,表明特異性良好。由于β-CD-r GO和MIPs/GN僅修飾于玻碳電極表面,識別位點有限,使得線性范圍較窄,因此,本文采用水熱法合成了殼寡糖-三維石墨烯,增加電極有效表面積,據(jù)此構(gòu)建了殼寡糖-三維石墨烯電化學(xué)傳感器。首先考察了影響三維石墨烯前驅(qū)體氧化石墨烯的超聲剝離頻率、超聲剝離時間、氧化石墨烯片徑。隨后,利用殼寡糖帶正電荷的特性,使其與帶負電荷的氧化石墨烯結(jié)合,制備了孔洞均勻、結(jié)構(gòu)穩(wěn)定的殼寡糖修飾三維石墨烯。與未修飾的三維石墨烯相比較,殼寡糖-三維石墨烯電極在磷酸鹽緩沖溶液(PBS)中平衡時循環(huán)伏安(CV)曲線明顯變得連續(xù)且平滑,吡蟲啉(IDP)不可逆還原峰電流顯著增加。將制備的β-CD-r GO/GCE、MIP/GN/GCE和OCS-GF三種電極作為工作電極,應(yīng)用于實際糙米樣品中煙堿農(nóng)藥的檢測。結(jié)果表明,β-CD-r GO/GCE具有通用性,對五種煙堿農(nóng)藥均有顯著的電催化活性,檢出限為0.10~0.11μM。GN/MIPs/GCE在提高煙堿農(nóng)藥檢測靈敏度的同時,通過嫁接分子印跡薄膜,提高了煙堿農(nóng)藥的檢測特異性,檢出限為0.10μM。OCS-GF充分利用了三維石墨烯電極的立體結(jié)構(gòu),大大擴大了吡蟲啉檢測的線性范圍,使線性范圍從GN/MIPs/GCE的0.5μM~15.0μM增加到了1.0μM~50.0μM。此外,針對五種煙堿農(nóng)藥各自的物理化學(xué)特性,建立了適用于不同煙堿農(nóng)藥的前處理方法,與新型電化學(xué)傳感器相結(jié)合,回收率達到70%~120%,且與液相檢測結(jié)果一致,表明在實際樣品中的可行性。
[Abstract]:Nicotine pesticide is one of the world's largest pesticide sales, but the long-term abuse and illegal use of lead in agricultural products and low toxicity pesticide residue seriously exceed the standard, cause potential health problems for people as well as the "green trade barrier". China as an agricultural country, need to establish a rapid, sensitive, large-scale field inspection and monitoring technology of neonicotinoid electrochemical technology with low price. The sensor with fast response, portable equipment, low cost, simple operation and other advantages, has gradually become one of the most vigorous means of detection of pesticide residues in the scene. With the rapid development of supramolecular recognition technology, surface molecular imprinting technique and three-dimensional porous material, with the high electrocatalytic activity of graphene with working electrode element application in the electrochemical sensor core, in order to improve the sensitivity and selectivity of the electrochemical detection method, linear range, nicotine An important research direction of the electrochemical detection of pesticide residues, but also a great challenge for analytical workers. Based on this study, the main contents of this paper are as follows: beta cyclodextrin redox Shi Moxi synthesized by using simple synthetic route (beta -CD-r, GO) and on the surface of glassy carbon electrode modified and constructed beta cyclodextrin / graphene based electrochemical sensor. Beta -CD not only as a reduction of graphene oxide (R GO) stabilizer, as well as supramolecular recognition of guest molecules paichongding (IPP), through the formation of supramolecular inclusion and bringing IPP to the graphene surface, thereby enhancing the electrochemical response signal with the bare electrode (GCE.) and graphene modified electrode (R GO/GCE) compared to China's independent research and development of new neonicotinoid paichongding (IPP) in beta -CD-r on GO/GCE irreversible reduction peak current value increased by 14 times and 2 times, significantly increased IPP. In order to further improve the detection sensitivity. The specificity of neonicotinoid pesticides, successfully grafted on the molecular imprinted polymer film on the surface of graphene carrier. The graphene surface molecular imprinted electrochemical sensor constructed significantly improves the electrochemical electrochemical detection of neonicotinoid response signal recognition specificity, shorten the response time. The balance test uses innovative p-vinyl benzoic acid (VBA, with alkenyl unit connected with crosslinking agent and template molecular recognition group and graphene by pi pi interactions and the connection of the benzene ring), Shi Moxi (GN) molecular imprinted monolayer surface successfully loaded uniform (MIPs) film, the graphene surface molecular imprinting polymer preparation of molecularly imprinted membrane (MIPs/GN). The thickness of only 1.9nm, far lower than reported in the literature of graphene surface molecular imprinting film thickness 17nm.GN/MIPs/GCE of imidacloprid imprinted factor at 2.3, significantly higher than that of similar nicotine pesticides, showed good specificity. The -CD-r GO beta and MIPs/GN only modified on the glassy carbon electrode surface, the recognition site is limited, the linear range is narrow, so the chitosan three-dimensional graphene was synthesized by hydrothermal method, increase the effective surface area of the electrode, then build the chitosan oligosaccharide the 3D graphene electrochemical sensor. The effects of ultrasonic stripping frequency of three-dimensional graphene graphene oxide precursor, ultrasonic stripping time, graphene oxide sheet size. Then, based on the characteristics of chitosan oligosaccharide with positive charge, which combined with the negatively charged graphene oxide, preparation of uniform holes, shell the structural stability of the modified oligosaccharide three-dimensional graphene. Compared with three-dimensional graphene modified chitosan, three-dimensional graphene electrode in phosphate buffer solution (PBS) CV at equilibrium (CV) curve became flat and continuous Slide, imidacloprid (IDP) irreversible reduction peak current increased significantly. The preparation of beta -CD-r GO/GCE, MIP/GN/GCE and OCS-GF three electrode as the working electrode, applied to the actual detection of nicotine pesticides in brown rice samples. The results showed that beta -CD-r GO/GCE is universal, the electrocatalytic activity of five kinds of pesticide nicotine significantly have a detection limit of 0.10~0.11 M.GN/MIPs/GCE in improving the detection sensitivity of nicotine pesticides at the same time, by grafting the molecularly imprinted film, improve the detection specificity of neonicotinoid, a detection limit of 0.10 M.OCS-GF make full use of the three-dimensional structure of graphene electrode, greatly extends the linear range of detection of imidacloprid, the linear range from GN/MIPs/GCE 0.5 mu M~15.0 mu M to 1 mu M~50.0 mu M. in addition, according to the physical and chemical properties of five kinds of pesticide nicotine respectively. The pretreatment method was established for different nicotine pesticides, and new Combined with the electrochemical sensor, the recovery rate is up to 70%~120%, which is consistent with the liquid phase detection results, indicating the feasibility in the actual sample.

【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O657.1;TP212.2;TQ450.263

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