基于卟啉酞菁金屬配合物的無酶電化學傳感器的構筑及性質研究
發(fā)布時間：2018-08-10 16:33
【摘要】：卟啉酞菁金屬配合物具有大環(huán)共軛體系,具有獨特的電學、光學和磁學性質。作為新型的功能材料,它們在分子熒光探針、分子信息存儲和電化學傳感器上具有潛在的應用價值,在材料科學領域擁有廣闊的應用前景。近年來,在傳感器領域,對基于卟啉酞菁金屬配合物的新型材料的開發(fā)和研究已經成為了熱點。本文內容主要包括以下幾個部分:1.卟啉酞菁三層稀土配合物與氧化石墨烯混雜膜的制備及對H_2O_2的電化學傳感性質研究設計合成了一種結構新穎的卟啉酞菁銪三層配合物(Pc)Eu(Pc)Eu[trans-T(COOCH3)2PP],并通過紫外可見吸收(UV-vis),核磁氫譜(1H NMR),質譜(MS)等對該三層配合物的分子結構進行了表征,通過電化學方法(DPV)測試配合物溶液發(fā)現(xiàn)該化合物具有優(yōu)異的雙極半導體性質,可以用于制備電化學傳感器。用一種低成本簡單方便可溶劑化處理的QLS方法制備了(Pc)Eu(Pc)Eu[trans-T(COOCH3)2PP]與氧化石墨烯(GO)的混雜多層膜。通過紫外可見吸收(UV-vis),偏振紫外可見吸收(Polarized UV-vis),X射線粉末衍射(XRD),原子力顯微鏡(AFM),掃描電子顯微鏡(SEM),電流-電壓曲線(I-V)等測試對混雜膜的表面形貌和聚集性質進行了表征,結果表明,該混雜膜中,由于GO的模板作用,三層配合物分子具有更好的結晶性和分散性,混雜膜具有明顯改善的表面形貌,聚集均勻且尺寸較小(大約70 nm),并且混雜膜具有更高的導電性,適合構筑電化學傳感器。一系列電化學傳感性質測試例如循環(huán)伏安曲線(CV),計時電流曲線(I-t)等表明,響應電流與H_2O_2的濃度呈極好的線性關系,且線性范圍較寬為0.05-1800μM,響應時間很短為0.03 s·μM-1,檢測限極低為0.017μM,靈敏度較好為7.4μA·m M-1。這個工作是迄今為止四吡咯基化合物無酶過氧化氫電化學傳感器最好的結果。更重要的是,(Pc)Eu(Pc)Eu[trans-T(COOCH3)2PP]/GO/ITO電極具有極好的穩(wěn)定性,重現(xiàn)性和選擇性,顯示了電化學活性的四吡咯基稀土三明治配合物與GO的結合在無酶電化學傳感器領域的巨大潛能。2.具有電化學超分子識別性質的卟啉酞菁三層稀土配合物與杯芳烴混雜膜的制備及電化學傳感性質研究設計合成了一種結構新穎的具有優(yōu)秀電化學活性的混雜卟啉酞菁三層銪配合物(Pc)Eu(Pc)Eu[T(OH)PP],并通過紫外可見吸收(UV-vis),核磁氫譜(1H NMR),質譜(MS)等對該三層配合物的分子結構進行了表征。將此三層配合物與具有卓越超分子識別性質的杯[4]芳烴或杯[8]芳烴的混合溶液以低成本簡單方便可溶劑化處理的QLS方法制備成混雜膜并構筑成化學修飾電極,通過紫外可見吸收(UV-vis),偏振紫外可見吸收(Polarized UV-vis),X射線粉末衍射(XRD)等測試對混雜膜的聚集性質進行了表征,(Pc)Eu(Pc)Eu[T(OH)PP]分子在純膜與混雜膜中的聚集方式都是J聚集,且混雜前后,分子與基片間的夾角沒有發(fā)生明顯的變化。另外,杯芳烴組分與三層配合物組分幾乎達到了分子程度的混合,這可以實現(xiàn)三層配合物良好電化學活性與杯芳烴很好超分子識別活性的結合,有利于基于超分子電化學識別的電化學傳感器的構筑。也通過一系列電化學測試例如循環(huán)伏安法(CV)等確定了此基于電化學超分子識別的混雜膜的傳感性質,發(fā)現(xiàn)杯芳烴的加入確實可以提高配合物對于一系列不同被檢測物的分析能力,這來源于三層配合物好的電化學活性和杯芳烴通過超分子相互作用對被檢測物的富集作用。這個工作拓寬了卟啉酞菁三層配合物在電化學傳感器中的應用范圍,并且對電化學傳感器性能的提高提供了嶄新的思路,為仿酶體系的設計提供了新的方向。
[Abstract]:Porphyrin-phthalocyanine metal complexes have unique electrical, optical and magnetic properties. As novel functional materials, they have potential applications in molecular fluorescence probes, molecular information storage and electrochemical sensors, and have broad application prospects in the field of materials science. In recent years, they have been widely used in the field of sensors. The research and development of new materials based on porphyrin phthalocyanine metal complexes have become a hot spot. This paper mainly includes the following parts: 1. Preparation of porphyrin phthalocyanine three-layer rare earth complexes and graphene oxide hybrid films and electrochemical sensing properties of H_2O_2 The molecular structure of the three-layer complex (Pc) Eu (Pc) Eu [trans-T (COOCH3) 2PP] was characterized by UV-vis, 1H NMR and MS. It was found that the complex solution had excellent bipolar semiconductor properties and could be used to prepare electrochemistry. Sensors. Hybrid multilayers of (Pc) Eu (Pc) Eu [trans-T (COOCH3) 2PP] and graphene oxide (GO) were prepared by a low-cost, simple and solvent-soluble QLS method. The hybrid multilayers were characterized by UV-vis, polarized UV-vis, X-ray powder diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM). The surface morphology and aggregation properties of the hybrid films were characterized by SEM, current-voltage curve (I-V) and other measurements. The results showed that the three-layer complex molecules had better crystallinity and dispersity due to the template effect of GO. The hybrid films had obviously improved surface morphology, uniform aggregation and small size (about 70 nm). A series of electrochemical sensing properties such as cyclic voltammetry (CV) and chronoamperometry (I-t) curves show that the response current has an excellent linear relationship with the concentration of H_2O_2, and the linear range is 0.05-1800 mu M, the response time is very short 0.03 s. This work is by far the best result of an enzyme-free hydrogen peroxide electrochemical sensor for tetrapyrrolyl compounds. More importantly, (Pc) Eu [trans-T (COOCH3) 2PP]/GO/ITO electrode has excellent stability, reproducibility and selectivity, showing electrochemical activity of the tetrapyrrolyl group. The combination of rare earth sandwich complexes with GO has great potential in the field of enzyme-free electrochemical sensors. 2. Preparation and electrochemical sensing properties of porphyrin phthalocyanine triple-layer rare earth complexes with calixarene hybrid membranes The molecular structure of the three-layer Eu (Pc) Eu (Pc) Eu [T (OH) PP] complex was characterized by UV-vis, 1H NMR and MS. The three-layer complexes were mixed with calix [4] aromatic hydrocarbons or calix [8] aromatic hydrocarbons with excellent supramolecular recognition properties in a low-cost, simple and convenient way. The hybrid films were prepared by solvent-treated QLS method and the chemically modified electrodes were fabricated. The aggregation properties of the hybrid films were characterized by UV-vis, Polarized UV-vis and XRD. The aggregation patterns of the (Pc) Eu [T (OH) PP] molecules in pure and hybrid films were investigated. It is J-aggregated, and the angle between the molecule and the substrate does not change significantly before and after mixing. In addition, the calixarene component and the three-layer complex component almost reach the molecular level of mixing, which can achieve the combination of the good electrochemical activity of the three-layer complex and the good supramolecular recognition activity of calixarene, which is conducive to the supramolecular electrochemistry based on the supramolecular electrochemistry. The sensing properties of the hybrid membranes based on electrochemical supramolecular recognition were also determined by a series of electrochemical tests such as cyclic voltammetry (CV). It was found that the addition of calixarene could improve the analytical ability of the complexes for a series of different detectable compounds, which originated from the three-layer complexes. This work broadens the application scope of porphyrin-phthalocyanine three-layer complexes in electrochemical sensors, and provides a new way to improve the performance of electrochemical sensors, and provides a new direction for the design of enzyme-mimetic systems.
【學位授予單位】：濟南大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O641.4;TP212
本文編號：2175481
[Abstract]:Porphyrin-phthalocyanine metal complexes have unique electrical, optical and magnetic properties. As novel functional materials, they have potential applications in molecular fluorescence probes, molecular information storage and electrochemical sensors, and have broad application prospects in the field of materials science. In recent years, they have been widely used in the field of sensors. The research and development of new materials based on porphyrin phthalocyanine metal complexes have become a hot spot. This paper mainly includes the following parts: 1. Preparation of porphyrin phthalocyanine three-layer rare earth complexes and graphene oxide hybrid films and electrochemical sensing properties of H_2O_2 The molecular structure of the three-layer complex (Pc) Eu (Pc) Eu [trans-T (COOCH3) 2PP] was characterized by UV-vis, 1H NMR and MS. It was found that the complex solution had excellent bipolar semiconductor properties and could be used to prepare electrochemistry. Sensors. Hybrid multilayers of (Pc) Eu (Pc) Eu [trans-T (COOCH3) 2PP] and graphene oxide (GO) were prepared by a low-cost, simple and solvent-soluble QLS method. The hybrid multilayers were characterized by UV-vis, polarized UV-vis, X-ray powder diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM). The surface morphology and aggregation properties of the hybrid films were characterized by SEM, current-voltage curve (I-V) and other measurements. The results showed that the three-layer complex molecules had better crystallinity and dispersity due to the template effect of GO. The hybrid films had obviously improved surface morphology, uniform aggregation and small size (about 70 nm). A series of electrochemical sensing properties such as cyclic voltammetry (CV) and chronoamperometry (I-t) curves show that the response current has an excellent linear relationship with the concentration of H_2O_2, and the linear range is 0.05-1800 mu M, the response time is very short 0.03 s. This work is by far the best result of an enzyme-free hydrogen peroxide electrochemical sensor for tetrapyrrolyl compounds. More importantly, (Pc) Eu [trans-T (COOCH3) 2PP]/GO/ITO electrode has excellent stability, reproducibility and selectivity, showing electrochemical activity of the tetrapyrrolyl group. The combination of rare earth sandwich complexes with GO has great potential in the field of enzyme-free electrochemical sensors. 2. Preparation and electrochemical sensing properties of porphyrin phthalocyanine triple-layer rare earth complexes with calixarene hybrid membranes The molecular structure of the three-layer Eu (Pc) Eu (Pc) Eu [T (OH) PP] complex was characterized by UV-vis, 1H NMR and MS. The three-layer complexes were mixed with calix [4] aromatic hydrocarbons or calix [8] aromatic hydrocarbons with excellent supramolecular recognition properties in a low-cost, simple and convenient way. The hybrid films were prepared by solvent-treated QLS method and the chemically modified electrodes were fabricated. The aggregation properties of the hybrid films were characterized by UV-vis, Polarized UV-vis and XRD. The aggregation patterns of the (Pc) Eu [T (OH) PP] molecules in pure and hybrid films were investigated. It is J-aggregated, and the angle between the molecule and the substrate does not change significantly before and after mixing. In addition, the calixarene component and the three-layer complex component almost reach the molecular level of mixing, which can achieve the combination of the good electrochemical activity of the three-layer complex and the good supramolecular recognition activity of calixarene, which is conducive to the supramolecular electrochemistry based on the supramolecular electrochemistry. The sensing properties of the hybrid membranes based on electrochemical supramolecular recognition were also determined by a series of electrochemical tests such as cyclic voltammetry (CV). It was found that the addition of calixarene could improve the analytical ability of the complexes for a series of different detectable compounds, which originated from the three-layer complexes. This work broadens the application scope of porphyrin-phthalocyanine three-layer complexes in electrochemical sensors, and provides a new way to improve the performance of electrochemical sensors, and provides a new direction for the design of enzyme-mimetic systems.
【學位授予單位】：濟南大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O641.4;TP212
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