發(fā)布時間：2018-06-19 05:10

  本文選題：電致化學(xué)發(fā)光 + 功能化雙金屬納米材料�。� 參考：《西南大學(xué)》2017年碩士論文

【摘要】：隨著納米技術(shù)的迅速發(fā)展,基于金屬納米材料的信號放大方法對提高免疫傳感器的靈敏度和選擇性表現(xiàn)出巨大的潛力。其中雙金屬納米材料在電催化活性等方面比相應(yīng)的單金屬擁有更優(yōu)越的性質(zhì)。但目前如何賦予雙金屬納米材料更多的功能,從而簡化實驗操作、提高作用效率仍然存在挑戰(zhàn)。本論文的工作主要集中在制備多種功能性雙金屬納米復(fù)合材料、發(fā)光試劑功能化殼核納米材料,結(jié)合電致化學(xué)發(fā)光(ECL)傳感技術(shù)和生物技術(shù),構(gòu)建新型、高靈敏的免疫傳感器。成功合成了共反應(yīng)試劑功能化的六八面體殼核材料、異魯米諾功能化多面體狀殼核納米粒子和自催化型魯米諾衍生物功能化的鈀銅納米立方@碳納米角復(fù)合物,也提出了共反應(yīng)試劑或催化劑對發(fā)光物可能的作用機理�；�于上述多功能化納米復(fù)合材料,發(fā)展了一系列新型ECL生物分析新方法,實現(xiàn)了對多種蛋白質(zhì)的靈敏檢測。本論文的研究工作主要分為以下幾部分:1.基于共反應(yīng)試劑功能化的六八面體殼核納米材料構(gòu)建電致化學(xué)發(fā)光免疫傳感器將共反應(yīng)試劑置于檢測底液中不但會增加試劑用量,而且也會帶來測量誤差。本研究利用六八面體殼核納米材料作為載體成功實現(xiàn)了共反應(yīng)試劑的大量固載以及ECL的信號放大,在簡化實驗操作的同時也提高了傳感器檢測的靈敏度。研究證明當(dāng)測試底液中有諾氟沙星(NFLX)存在時S2O82-能產(chǎn)生非常強的ECL信號,強度約是S2O82-單獨存在時的350倍。為了實現(xiàn)NFLX在電極表面的的大量固載,利用聚酰胺樹枝狀高分子的大量的端氨基,通過酰胺鍵將NFLX修飾在聚酰胺聚合物(PAMAM)表面從而形成PAMAM-NFLX復(fù)合物。該復(fù)合物作為新穎的共反應(yīng)試劑能有效放大S2O82--O2體系的ECL信號。同時,合成了凸?fàn)畹臍ず薖d@Au六八面體納米顆粒(Pd@AuHOHs),該粒子不僅擁有良好的生物相容性和電子傳導(dǎo)能力等優(yōu)點,通過促進S2O82--O2體系ECL反應(yīng)過程中中間自由基的產(chǎn)生,Pd@AuHOHs還能進一步提高ECL信號。此外,由于具有大的比表面積,Pd@AuHOHs作為納米載體能用來大量固載第二抗體以及PAMAM-NFLX復(fù)合物�；�于此,構(gòu)建夾心型ECL免疫傳感器用于檢測促甲狀腺激素(TSH)。該傳感器具有高的靈敏度和特異性,成功地實現(xiàn)了對臨床血清樣本中TSH的檢測。2.基于發(fā)光功能化殼核納米顆粒和二茂鐵衍生物的電致化學(xué)發(fā)光免疫傳感器的研究傳統(tǒng)的直接合成魯米諾或其衍生物功能化納米材料的方法得到的發(fā)光功能化納米材料常為單金屬且大多需要高溫煮沸的條件。研究表明雙金屬納米材料在電催化活性等方面比相應(yīng)的單金屬擁有更優(yōu)越的性質(zhì)。鑒于此,本研究采用魯米諾的一種衍生物N-4-氨基丁基-N-乙基異魯米諾(ABEI)作為還原劑和發(fā)光試劑在常溫下成功合成了ABEI功能化的Pd@Au殼核納米顆粒(ABEI-Pd@AuNPs)。該法成功實現(xiàn)了ABEI分子的固載,這樣就避免了后期修飾。此外,由于雙金屬納米顆粒對H2O2良好的催化性質(zhì),ABEI-Pd@AuNPs能夠增強ABEI-H2O2體系的ECL信號。為了進一步提高發(fā)光效率,利用L-半胱氨酸將催化劑羧基二茂鐵(Fc)連接在ABEI-Pd@AuNPs的表面。ABEI和Fc同時修飾在Pd@Au納米顆粒上意味著在納米顆粒表面二者的實際濃度遠高于將它們置于溶液中,從而能更好地實現(xiàn)催化。將該雙功能化的Pd@Au殼核納米顆粒作為載體固載第二抗體,利用夾心法構(gòu)建了信號增強型的ECL免疫傳感器,實現(xiàn)了對糖尿病腎病潛在標志物IV-型膠原(Col IV)的檢測。最終該傳感器達到了1 pg·mL-1到10 ng·mL-1的寬檢測范圍。該工作提供了一種新穎的信號放大方法,也拓寬了ABEI-H2O2體系在生物分析中的應(yīng)用。3.自催化型發(fā)光體與PdCu@碳納米角雜化物構(gòu)建電致化學(xué)發(fā)光免疫傳感器通�；�于魯米諾(luminol)的ECL反應(yīng)中,催化劑對luminol的信號放大是通過分子間的相互作用實現(xiàn)的。然而這種分子間的作用通常伴有較大的能量損失,限制了luminol與其催化劑之間的作用效率。為了實現(xiàn)將發(fā)光物luminol固載的同時提高其與催化劑之間的作用效率,本研究首次提出了基于自催化型發(fā)光衍生物和碳納米角雜化物放大luminol/H2O2體系ECL信號的放大策略,并成功構(gòu)建了用于檢測心衰標志物的超靈敏ECL免疫傳感器。將3,4,9,10-傒四甲酸(PTCA)與luminol偶聯(lián)起來形成自催化的發(fā)光體PTC-Lu,由于PTCA強的增強效果,該發(fā)光體具有極好的ECL性質(zhì);且由于芳香性,使得PTC-Lu更容易實現(xiàn)固載。通過π-π堆積作用將該自催化發(fā)光體組裝在PdCu@SWCNHs納米雜化物上,得到PTC-Lu功能化的PdCu@SWCNHs(PTC-Lu/PdCu@SWCNHs)。通過這種方式明顯提高了SWCNHs的水溶性和穩(wěn)定性。同時,PdCu@SWCNHs雜化物作為模擬酶對H2O2展現(xiàn)出電催化性質(zhì),因此能進一步放大luminol/H2O2體系的ECL信號。此外,由于PdCu納米立方的高比表面積和良好的生物相容性,能夠?qū)崿F(xiàn)對二抗蛋白的大量固載。基于此,構(gòu)建了信號增強型的免疫傳感器,并成功實現(xiàn)了對臨床人體血清樣本中N-末端B型鈉尿肽(NT-proBNP)的檢測。本工作在解決luminol固載問題的同時,在提高催化劑作用效率方面也得到突破。此外,該發(fā)光功能化納米材料的合成不僅改善了SWCNHs的水溶性和穩(wěn)定性,其中PdCu@SWCNHs也展示出良好的催化活性,該新穎的納米雜化物作為模擬酶在生物技術(shù)和臨床診斷有著潛在應(yīng)用價值。
[Abstract]:With the rapid development of nanotechnology, the signal amplification based on metal nanomaterials has shown great potential to improve the sensitivity and selectivity of the immunosensor. In which the electrocatalytic activity of bimetallic nanomaterials is more superior than that of the corresponding monometallic metal. The work of this paper is mainly focused on the preparation of functional bimetal nanocomposites, luminescent reagent functionalized shell nanomaterials, electrochemiluminescence (ECL) sensing technology and biological technology, to construct a new and highly sensitive immune sensor. The functionalized 68 hedral shell material, the functionalized polyhedron shell nanoparticles and the autocatalytic luminol derivative functionalized palladium copper nanomaterials, also proposed the possible mechanism of the co reaction reagent or catalyst on the luminescence. Based on the above functionalization, the function of the co reacting reagent was synthesized. Nanocomposites have developed a new series of new methods for ECL bioanalysis to achieve sensitive detection of various proteins. The research work of this paper is divided into the following parts: 1. an electrochemically immunized sensor based on the functionalized 68 surface shell nanomaterials of CO reacting reagents for the detection of CO reagents In this study, the dosage of reagents will not only increase the amount of reagents, but also the measurement error. In this study, a large number of solid loading of the co reagents and the signal amplification of ECL were successfully realized by using the 68 surface shell core nanomaterials as a carrier. The sensitivity of the sensor was also improved while the experimental operation was simplified. When norfloxacin (NFLX) exists, S2O82- can produce a very strong ECL signal, which is about 350 times as strong as S2O82- alone. In order to achieve a large amount of immobilization of NFLX on the surface of the electrode, a large number of amino terminated amino groups of polyamide dendrimers are used to modify the NFLX on the surface of polyamide polymer (PAMAM) through the amide bond to form a PAMAM-NFLX complex. The compound can effectively amplify the ECL signal of the S2O82--O2 system as a novel co reacting reagent. At the same time, the protruded shell of the shell Pd@Au 68 surface nanoparticle (Pd@AuHOHs) has been synthesized. The particle not only has the advantages of good biocompatibility and electron conduction, but also through the intermediate freedom to promote the ECL reaction in the S2O82--O2 system. The Pd@AuHOHs can further improve the ECL signal. In addition, because of the large specific surface area, Pd@AuHOHs can be used as a nanoscale to immobilizing second antibodies and PAMAM-NFLX complexes. Based on this, the sandwich ECL immune sensor is constructed for the detection of thyroid stimulating hormone (TSH). The sensor has high sensitivity and specificity. A successful implementation of the detection of TSH in clinical serum samples.2. based on electrochemiluminescent immunosensor based on luminescent functionalized putamen nanoparticles and two ferrocene derivatives, the traditional direct synthesis of Lumino or its derivative functionalized nanomaterials is usually single metal and large In this study, a derivative of Lumino's N-4- amino butyl -N- ethyl ISO Lumino (ABEI) was used as a reducing agent and luminescent reagent to synthesize ABEI function successfully at normal temperature. The modified Pd@Au shell nanoparticles (ABEI-Pd@AuNPs). This method successfully realized the immobilization of ABEI molecules, thus avoiding the later modification. In addition, because of the good catalytic properties of the bimetal nanoparticles on H2O2, ABEI-Pd@AuNPs can enhance the ECL signal of the ABEI-H2O2 system. In order to improve the luminous efficiency, L- cysteine will be used as the catalyst. Carboxyl two ferrocene (Fc) is connected to the surface of the ABEI-Pd@AuNPs on the surface.ABEI and Fc simultaneously on the Pd@Au nanoparticles, which means that the actual concentration of the two of the nanoparticles is much higher than that in the solution and thus can be better catalyzed. The dual functionalized Pd@Au shell nanoparticles are used as the carrier to immobilizing second antibodies and using the sandwich. A signal enhanced ECL immunosensor was constructed and the detection of IV- type collagen (Col IV) of the potential marker of diabetic nephropathy was realized. The sensor finally reached a wide detection range of 1 pg. ML-1 to 10 ng. ML-1. This work provides a novel signal amplification method and also widens the application of.3 in the biological analysis of.3. The electrochemiluminescence immunosensor of the autocatalytic luminescence and the PdCu@ carbon nanohybrids is usually based on the ECL reaction of Lumino (luminol), and the signal amplification of the catalyst to luminol is realized by intermolecular interaction. However, the interaction of these molecules is usually accompanied by greater energy loss, limiting the luminol and its effect. In order to improve the efficiency between the luminol and the catalyst, the amplification strategy based on the autocatalytic luminescent derivatives and carbon nano corner hybrids to amplify the ECL signal of the luminol/H2O2 system was first proposed, and a successful construction of the markers for the detection of heart failure was successfully constructed. The ultra sensitive ECL immunosensor is coupled with 3,4,9,10- four formic acid (PTCA) and luminol to form a self catalyzed luminescent body PTC-Lu. Due to the strong enhancement effect of PTCA, the luminescent body has excellent ECL properties. And because of its aromatic property, the PTC-Lu is more easily immobilized. The autocatalytic luminescent body is assembled in PdCu@SWCNH by pion pion accumulation. The PTC-Lu functionalized PdCu@SWCNHs (PTC-Lu/PdCu@SWCNHs) was obtained on the s nanohybrids. By this way, the solubility and stability of SWCNHs was obviously improved. At the same time, PdCu@SWCNHs hybrids were used as analog enzymes to exhibit the electrocatalytic properties of H2O2, thus further amplifying ECL signals of the luminol /H2O2 system. In addition, PdCu nanometers were used. The high specific surface area and good biocompatibility can achieve a large amount of immobilization of two anti protein. Based on this, a signal enhanced immunosensor is constructed and the detection of B type natriuretic peptide (NT-proBNP) of the N- terminal in the serum samples of the clinical human body is successfully realized. This work improves the catalyst at the same time to improve the luminol immobilization problem and improve the catalyst. In addition, the synthesis of the luminescent functionalized nanomaterials not only improves the water solubility and stability of SWCNHs, but also PdCu@SWCNHs shows good catalytic activity. The novel nano hybrid as a mimic enzyme has potential application value in biological technology and clinical diagnosis.
【學(xué)位授予單位】：西南大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TB383.1;TP212

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