分级多孔纳米卟啉材料对鱼新鲜度可视化无损检测标志物的响应机理

Freshness is an important index to measure the quality of fish. The conventional detection methods of fish freshness are so time-consuming and tedious. They require expensive instruments, professional technical personnel, and the destruction of fish samples. Therefore, visualized, fast and nondestructive evaluation of fish freshness has a scientific and practical value to monitor the preservation and freshness of fish. Nano-porphyrin is a very ideal gas sensitive material, because it is characterized by diverse structure, good optical properties and high sensitivity. But the freshness detecting method used nano-porphyrin as gas sensing materials is seldom reported. Based on this, combining the subtle and complex framework of natural biological material with the gas sensing properties of nano-porphyrin, the project intends to prepare a nano-porphyrin visualized sensor with hierarchical porous structure. In this project, the action mechanism between volatile organic compounds in the corruption process of fish and nano-porphyrin materials has been theoretically and experimentally investigated by using the density functional theory together with spectrum techniques. And the new methods such as fluorescence spectroscopy and fluorescence microscopy are used to verify the effect of visual detection of fish freshness. We achieve fast, nondestructive qualitative and quantitative detection of fish freshness. The purpose of this study is to clarify the action mechanism between the gas marker detection in the corruption process of fish and the nano-porphyrin materials, which will provide new ideas and scientific basis for the next step of building visual array and intelligent detection.

新鲜度是鱼类最重要的品质指标之一。常规鱼新鲜度的检测方法存在费时费力，需昂贵的仪器和专业的技术人员，且对鱼体样品有破坏性等缺点。因此，可视化、快速、无损的检测方法对鱼类贮藏保鲜的监测具有极其重要的意义。纳米卟啉材料拥有多样的结构、良好的光学性质及较高的灵敏度，是非常理想的气敏材料，而以纳米卟啉为气敏材料的新鲜度检测方法却鲜有报道。鉴于此，本项目利用生物材料的精细微观结构以及纳米卟啉的气敏特性，构建具有分级多孔结构的纳米卟啉可视化传感器；采用密度泛函理论和光谱法从理论和实验两个角度研究纳米卟啉材料与鱼贮藏过程中的挥发性有机物的作用机理；运用能量转移原理，结合荧光光谱和荧光显微镜等手段，研究该传感器对鱼新鲜度的可视化检测效果，为鱼新鲜度快速、无损的定性和定量分析奠定理论基础。本研究旨在阐明纳米卟啉材料对鱼贮藏过程中标志性气体的响应机制，为下一步构建可视化阵列及实现智能化检测提供新的思路。

新鲜度是鱼类最重要的品质指标之一。常规鱼新鲜度的检测方法存在费时费力，需昂贵的仪器和专业的技术人员等缺点。因此，快速、无损的检测方法对鱼类贮藏保鲜的监测具有极其重要的意义。本项目利用纳米卟啉复合材料作为生物传感器用于鱼新鲜度的检测。具体开展工作包括以下几个方面：(1) 以油菜花粉为生物模板，硝酸锌为锌源，通过生物模板法制备分级多孔ZnO纳米材料。(2) 利用ZnO纳米材料和黄嘌呤氧化酶构建的荧光探针，建立了一种定量检测黄嘌呤的新方法，并且通过黄嘌呤的变化来确定鱼的新鲜度。(3) 基于ZnO纳米材料和磺酸基卟啉之间的荧光共振能量转移作用，制备一种新型的荧光生物传感器用来检测三甲胺(TMA)，并且通过TMA的变化来确定鱼的新鲜度。(4) 以氧化石墨烯和DMF为原料，通过一步溶剂热法合成了石墨烯量子点(GQDs)。(5) 基于GQDs和三种卟啉的非共价相互作用构建了荧光纳米组装体，利用紫外光谱和荧光光谱对其组装形式和能量转移进行了研究。(6) 基于GQDs和氨基卟啉之间的荧光共振能量转移作用，制备一种新型的荧光生物传感器用来检测TMA，并且通过TMA的变化来确定鱼的新鲜度。本研究成功制备了分级多孔ZnO纳米材料和GQDs，研究其与多种卟啉相互作用的机制，并将多种纳米卟啉复合物应用于检测鱼体内的黄嘌呤、TMA含量并确定鱼类的新鲜程度，为下一步构建智能化鱼新鲜度检测提供新的思路。