【作者】 张磊；

【导师】 董永平；

【作者基本信息】 安徽工业大学 ， 分析化学， 2019， 硕士

【摘要】 本论文通过对黑磷电致化学发光性质的研究,开发出新的电致化学发光体系。主要包括以下三个方面:1.通过液相剥离法结合高速离心合成了黑磷量子点（BPQDs）。通过高分辨率透射显微镜（HRTEM）,原子力显微镜（AFM）和拉曼光谱表征BPQDs的表面形态和厚度,平均尺寸为8.2nm左右。在中性条件下,研究了BPQDs修饰的玻碳电极在Ru（bpy）₃²⁺中的电致化学发光（ECL）行为。没有共反应物的情况下,在修饰电极上获得强阳极ECL信号,与空白电极相比,修饰电极上的信号增强了近三个数量级。电化学结果表明BPQDs可以显著催化Ru（bpy）₃²⁺的氧化过程,这意味着BPQDs可以作为Ru（bpy）₃²⁺的共反应物并与其作用产生很强的光发射。多巴胺可与Ru（bpy）₃²⁺的氧化产物反应,并显示出对ECL发射的明显抑制作用。可以在0.1nM-50nM的范围内灵敏地检测多巴胺,检出限为0.022nM。目前的工作表明,BPQDs是一个潜在的ECL平台,并且有望用于制造新型ECL生物传感器。2.在水溶液中,通过液相剥离结合高速离心从BP晶体上剥离出黑磷纳米片（BPNS）。通过TEM,XPS,AFM,拉曼光谱,UV-vis吸收和荧光光谱表征合成的BPNS的形态。合成的BPNS呈现多层结构,横向长度约为300nm,可在380nm发出荧光。制备了BPNS修饰的玻碳电极（BPNS/GCE）,在中性条件下,以三丙胺（TPrA）为共反应物,在修饰电极上获得了强阳极电致化学发光（ECL）信号。过氧化氢对阳极ECL信号表现出明显的抑制作用,并且可以被灵敏地检测。在1-1000nM的范围内,ECL强度的降低值与H₂O₂浓度的对数呈线性关系,检出限为0.96nM（3σ）。所提出的修饰电极具有高灵敏性和良好的稳定性。结果揭示了BPNS在ECL研究中的新特征,以及2D纳米复合材料在ECL传感领域的潜在应用。3.黑磷量子点（BPQDs）可以与Ru（bpy）₃²⁺反应产生强阳极电致化学发光（ECL）信号。然而,BPQDs的不稳定性和缺乏功能基团限制了其在ECL生物传感器中的进一步应用。通过将BPQDs镶嵌到苯乙烯-丙烯酰胺（St-AAm）共聚物纳米球中来合成均匀尺寸的BPQDs-St-AAm纳米球（BSAN）。相当数量的BPQDs可嵌入纳米球中,并与Ru（bpy）₃²⁺反应生成强阳极ECL信号,与单独的BPQDs产生的信号强度相当。氨基聚合物赋予BPQDs与DNA连接的能力,并可用于制备能灵敏检测溶菌酶ECL适体传感器。所提出的适体传感器在0.1-100 pg mL^-1浓度范围内可以对溶菌酶进行灵敏检测,并且具有良好的选择性和稳定性,检出限为0.029 pg mL^-1（3σ）。这说明了BP纳米材料的ECL传感应用有望用于检测各种蛋白质。更多还原

【Abstract】 In this paper,new electrogenerated chemiluminescence systems were developed by studying the electrogenerated chemiluminescence properties of black phosphorus.It mainly includes the following three parts:1.Black phosphorus quantum dots（BPQDs）with an average size of 8.2 nm were synthesized through a liquid exfoliation coupled with ultrasonic methods.The surface morphology and the thickness of the BPQDs were identified by high-resolution transmission microscopy（HRTEM）,atomic force microscopy（AFM）,and Raman spectroscopy.The electrogenerated chemiluminescence（ECL）behavior of Ru（bpy）₃²⁺was investigated at a BPQDs modified glassy carbon electrode under neutral conditions.A strong anodic ECL signal was obtained at the modified electrode in the absence of a coreactant,which is nearly three orders of magnitude larger than that at the bare electrode.Electrochemical results revealed that the oxidation process of Ru（bpy）₃²⁺can be significantly catalyzed by BPQDs,suggesting that BPQDs can act as the coreactant of Ru（bpy）₃²⁺to generate strong light emission.Dopamine could react with the oxidation product of Ru（bpy）₃ ²⁺and exhibited an apparent inhibiting effect on ECL emission.As a result,it can be sensitively detected in the range of 0.1nM to 50 nM with a detection limit of 0.022 nM.The present work revealed that BPQDs are a potential ECL platform,and which are promising in the fabrication of a novel ECL biosensor.2.Black phosphorus nanosheets（BPNS）were synthesized from BP crystals through liquid exfoliation coupled with ultrasonic methods under aqueous conditions.The morphology of the synthesized BPNS was characterized by TEM,XPS,AFM,Raman spectroscopy,UV-vis absorption and fluorescence spectroscopy,respectively.The obtained BPNS exhibited a multilayer structure and the lateral length was around300 nm,and could emit fluorescence at 380 nm.A BPNS modified glassy carbon electrode（BPNS/GCE）was fabricated and a strong anodic electrogenerated chemiluminescence（ECL）signal was obtained at the modified electrode with tripropylamine（TPrA）as a coreactant under neutral conditions.Hydrogen peroxide exhibited an apparent inhibiting effect on the anodic ECL signal,and can be sensitively detected.In the range of 1–1000 nM,the decreased ECL intensities varied linearly with the logarithm of the H₂O₂ concentration,and the detection limit was calculated as 0.96 nM（3σ）.The proposed modified electrode exhibited high sensitivity and good stability.The results revealed a new character of BPNS in ECL investigation,and the potential application of 2D nanocomposites in the ECL sensing field.3.Black phosphorus quantum dots（BPQDs）can react with Ru（bpy）₃²⁺to generate strong anodic electrogenerated chemiluminescence（ECL）.However,the instability and the lack of functional groups on BPQDs limit its further application in the fabrication of ECL biosensor.In the present work,uniform BPQDs-styrene-acrylamide（St-AAm）nanospheres（BSAN）are synthesized by encapsulating BPQDs into St-AAm copolymer nanospheres.Sufficient amount of BPQDs can be embedded into nanospheres,and react with Ru（bpy）₃²⁺to generate strong anodic ECL which is comparable to that of pure BPQDs.Amino group of polymer endows BPQDs the ability to connect with DNA,and can be used to fabricate ECL aptasensor for the sensitive detection of lysozyme.The proposed aptasensor shows high sensitivity,good selectivity and stability for the detection of lysozyme in the range of 0.1–100 pg mL^-11 with a detection limit of 0.029 pg mL-1（3σ）.The proposed method reveals the promising ECL sensing application of BP nanomaterials in the detection of various proteins.更多还原