基于納米材料增敏技術的β-受體激動劑分子印跡傳感器的研究
發(fā)布時間：2019-01-30 13:06
【摘要】：β-受體激動劑類藥物在畜牧生產(chǎn)中具有促進動物生長及減少脂肪沉積的作用,但其易在動物體內(nèi)殘留,影響動物產(chǎn)品安全并危害人類健康。目前我國對此類藥物的監(jiān)管是先使用免疫速測技術對樣品進行篩查,而后對可疑樣品進行儀器確證分析。免疫速測技術易出現(xiàn)假陽性和假陰性,儀器確證前處理時間長,因此有必要開發(fā)高效靈敏的分析技術以滿足對此類藥物的分析要求。分子印跡傳感器能夠結合分子印跡聚合物專一性吸附的特性及傳感器快速靈敏分析的特點,提高了檢測分析效率,但也存在對β-受體激動劑等小分子物質分析檢測信號響應差,靈敏度不足的缺點。納米材料具有比表面積大和表面反應活性高等特點,可作為分子印跡傳感器的增敏材料�；诖�,本研究中將分子印跡技術與納米技術相結合,通過不同方式修飾納米材料和印跡聚合物,得出了以下結論:(1)采用石墨烯/納米金雜化納米材料修飾玻碳電極,在此基礎上以鄰苯二胺為功能單體,萊克多巴胺為模板分子,采用電聚合法制備了分子印跡電化學傳感器。研究結果表明,當石墨烯采用滴涂法、納米金采用電聚合法;聚合介質為乙酸銨緩沖液(pH=5.2),聚合電位為0-2.0V,聚合圈數(shù)為10圈,模板與功能單體比例為1:3,模板洗脫溶液為pH=7.0PBS且采用電洗脫的方式時,可以制得性能較好的分子印跡傳感器。在優(yōu)化后的條件下進行分析時,檢測限為0.0244ng/mL,尿液基質回收率高于80%。研究制得的納米材料分子印跡傳感器比同類電化學傳感器有著更高的靈敏度,石墨烯納米金能夠對分子印跡傳感器起到增敏作用。(2)在現(xiàn)有文獻報道基礎上通過優(yōu)化交聯(lián)劑和致孔劑的用量制備了萊克多巴胺分子印跡聚合物微球,結合石墨烯/納米金復合納米材料采用直接旋涂法制備得到分子印跡SPR傳感器。結果顯示,制得的SPR傳感器表面分子印跡聚合物及復合納米材料能夠均勻分布,且厚度適中;使用PBS(pH=7.0)為緩沖溶液,樣品溶劑為PBS/乙腈(體積為9:1),再生液為乙酸/乙腈(體積比為3:7)時,僅需780s即可完成單個樣品分析過程,分析效率高,且對β-受體激動劑類藥物SAL及CL有著良好的選擇性和靈敏度,檢出限可達5ng/mL。對比現(xiàn)有研究報道中分子印跡SPR傳感器(檢出限一般為20-50ng/mL),研究中使用的復合納米材料能夠顯著的提高SPR傳感器的靈敏度,可為其他小分子物質使用此傳感器提供技術參考。本研究中,通過在玻碳電極和裸金芯片表面修飾石墨烯/納米金及印跡聚合物制備出了具高選擇性和高靈敏度、能夠快速準確分析β-受體激動劑的分子印跡電化學傳感器和分子印跡SPR傳感器,并建立相應的分析方法,研究結果可為其他物質制備分子印跡傳感器進行殘留分析提供參考。
[Abstract]:尾-receptor agonists can promote animal growth and reduce fat deposition in animal husbandry, but it is easy to remain in animals, which affects the safety of animal products and endangers human health. At present, the supervision of this kind of drugs in our country is to screen the samples by immunological rapid detection technique, and then to analyze the suspicious samples by means of instrument. Rapid immunoassay is prone to false-positive and false-negative, so it is necessary to develop an efficient and sensitive analytical technique to meet the requirements of this kind of drug analysis. The molecular imprinting sensor can improve the efficiency of detection and analysis by combining the characteristics of molecular imprinted polymer specific adsorption and fast sensitive analysis of the sensor. However, there are also shortcomings of poor response and low sensitivity to small molecular substances such as 尾-receptor agonists. Nanomaterials with large surface area and high surface reaction activity can be used as sensitizing materials for molecular imprinting sensors. Based on this, the molecular imprinting technology and nanotechnology were combined in this study, and the following conclusions were obtained by modifying nano-materials and imprinted polymers in different ways: (1) the glassy carbon electrode was modified by graphene / nano-gold hybrid nanomaterials. The molecularly imprinted electrochemical sensor was prepared by electropolymerization with o-phenylenediamine as functional monomer and ractopamine as template molecule. The results show that when graphene is dripped, nano-gold is electropolymerized. When the polymerization medium is ammonium acetate buffer (pH=5.2), the polymerization potential is 0-2.0 V, the number of polymerization cycles is 10 cycles, the ratio of template to functional monomer is 1: 3, the template elution solution is pH=7.0PBS and the electroelution method is used. Molecular imprinting sensor with better performance can be prepared. The detection limit was 0.0244 ng / mL and the recovery rate of urine matrix was higher than 80%. The molecular imprinting sensor of nanomaterials has higher sensitivity than the electrochemical sensor of the same kind. Graphene nanocrystalline gold can enhance the sensitivity of molecular imprinting sensor. (2) based on the existing literature, ractopamine molecularly imprinted polymer microspheres were prepared by optimizing the amount of crosslinking agent and pore-inducing agent. The molecularly imprinted SPR sensor was prepared by direct spin-coating method combined with graphene / nano-gold composite nanomaterials. The results show that the molecularly imprinted polymers and composite nanomaterials on the surface of SPR sensors can be evenly distributed and the thickness is moderate. When PBS (pH=7.0) was used as buffer solution, the sample solvent was PBS/ acetonitrile (9:1 in volume) and the regenerated solution was acetic acid / acetonitrile (3:7), the single sample analysis process could be completed in 780s, and the analysis efficiency was high. It has good selectivity and sensitivity for 尾 -receptor agonists SAL and CL, and the detection limit is up to 5 ng / mL. Compared with the molecularly imprinted SPR sensor (the detection limit is generally 20-50ng/mL), the composite nanomaterials used in the study can significantly improve the sensitivity of the SPR sensor. It can provide technical reference for other small molecular matter to use this sensor. In this study, high selectivity and high sensitivity were obtained by modifying graphene / nanocrystalline and imprinted polymer on glassy carbon electrode and bare gold chip. Molecularly imprinted electrochemical sensors and molecularly imprinted SPR sensors can be used to analyze 尾-receptor agonists quickly and accurately, and the corresponding analytical methods are established. The results can provide a reference for the residue analysis of molecularly imprinted sensors prepared by other substances.
【學位授予單位】：中國農(nóng)業(yè)科學院
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：S859.84
本文編號：2418158
[Abstract]:尾-receptor agonists can promote animal growth and reduce fat deposition in animal husbandry, but it is easy to remain in animals, which affects the safety of animal products and endangers human health. At present, the supervision of this kind of drugs in our country is to screen the samples by immunological rapid detection technique, and then to analyze the suspicious samples by means of instrument. Rapid immunoassay is prone to false-positive and false-negative, so it is necessary to develop an efficient and sensitive analytical technique to meet the requirements of this kind of drug analysis. The molecular imprinting sensor can improve the efficiency of detection and analysis by combining the characteristics of molecular imprinted polymer specific adsorption and fast sensitive analysis of the sensor. However, there are also shortcomings of poor response and low sensitivity to small molecular substances such as 尾-receptor agonists. Nanomaterials with large surface area and high surface reaction activity can be used as sensitizing materials for molecular imprinting sensors. Based on this, the molecular imprinting technology and nanotechnology were combined in this study, and the following conclusions were obtained by modifying nano-materials and imprinted polymers in different ways: (1) the glassy carbon electrode was modified by graphene / nano-gold hybrid nanomaterials. The molecularly imprinted electrochemical sensor was prepared by electropolymerization with o-phenylenediamine as functional monomer and ractopamine as template molecule. The results show that when graphene is dripped, nano-gold is electropolymerized. When the polymerization medium is ammonium acetate buffer (pH=5.2), the polymerization potential is 0-2.0 V, the number of polymerization cycles is 10 cycles, the ratio of template to functional monomer is 1: 3, the template elution solution is pH=7.0PBS and the electroelution method is used. Molecular imprinting sensor with better performance can be prepared. The detection limit was 0.0244 ng / mL and the recovery rate of urine matrix was higher than 80%. The molecular imprinting sensor of nanomaterials has higher sensitivity than the electrochemical sensor of the same kind. Graphene nanocrystalline gold can enhance the sensitivity of molecular imprinting sensor. (2) based on the existing literature, ractopamine molecularly imprinted polymer microspheres were prepared by optimizing the amount of crosslinking agent and pore-inducing agent. The molecularly imprinted SPR sensor was prepared by direct spin-coating method combined with graphene / nano-gold composite nanomaterials. The results show that the molecularly imprinted polymers and composite nanomaterials on the surface of SPR sensors can be evenly distributed and the thickness is moderate. When PBS (pH=7.0) was used as buffer solution, the sample solvent was PBS/ acetonitrile (9:1 in volume) and the regenerated solution was acetic acid / acetonitrile (3:7), the single sample analysis process could be completed in 780s, and the analysis efficiency was high. It has good selectivity and sensitivity for 尾 -receptor agonists SAL and CL, and the detection limit is up to 5 ng / mL. Compared with the molecularly imprinted SPR sensor (the detection limit is generally 20-50ng/mL), the composite nanomaterials used in the study can significantly improve the sensitivity of the SPR sensor. It can provide technical reference for other small molecular matter to use this sensor. In this study, high selectivity and high sensitivity were obtained by modifying graphene / nanocrystalline and imprinted polymer on glassy carbon electrode and bare gold chip. Molecularly imprinted electrochemical sensors and molecularly imprinted SPR sensors can be used to analyze 尾-receptor agonists quickly and accurately, and the corresponding analytical methods are established. The results can provide a reference for the residue analysis of molecularly imprinted sensors prepared by other substances.
【學位授予單位】：中國農(nóng)業(yè)科學院
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：S859.84
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