论文总字数：31701字

摘 要

光气是一种剧毒性的重要化工生产原料，在生产及使用过程中具有巨大中毒危险，并且光气在军事上也被用作一种有毒武器使用。光气的吸入中毒可能 造成吸入者死亡，基于此严重的潜在威胁，工作或军事环境中的光气即时检测就显得非常重要。

本文首先对光气的一些传统检测方法作了简要介绍，例如，苯肼法、苯胺法、液相色谱法和有机荧光探针法等。但是苯肼法、苯胺法和液相色谱不能即时的检测所处环境中的光气暴露量，这些缺陷，限制了它们的应用。而荧光探针虽然可以对光气进行快速即时检测，但由于它对需要高能量的激发光源和高功率密度的激光器（10⁶W/cm），会对生物体造成损伤，因而难以应用于生物样本检测。而上转换材料由于其只需低功率密度激光器（10^1-3W/cm），在生物检测中具有重要的意义。因此本文中探究了一种基于罗丹明有机荧光探针和上转换发光材料的新型光气检测方法，这种方法对实现光气快速隐蔽检测具有重要意义。首先我们利用罗丹明B和邻苯二胺合成了一种结构中含有内酰胺环的罗丹明衍生物，并通过核磁共振谱图和质谱的对该有机物进行了表征。核磁谱图上的吸收峰和质谱图上的分子离子峰都表明该化合物结构正确。接着我们将这种有机物与稀土纳米晶上转换颗粒进行性自组装，得到罗丹明修饰的稀土纳米晶上转换光气探针。与上转换粒子结合后的探针同时结合了荧光团和上转换材料的优势，既具有罗丹明荧光探针肉眼可见的颜色变化，又具备上转换探针生物损伤小，穿透力强的优点。在合成了这种探针以后，我们利用毒性远小于光气的固体光气，即三光气，作为替代物来检测探针的性能，得到了加入不同量光气后探针的紫外-可见光和荧光光谱吸收峰的变化，其中紫外光谱中，位于543nm的吸光强度随光气浓度增加而增强，荧光强度则是随光气浓度增加而降低。而与有机荧光探针结合前的上转换探针则由于不具有吸收而无法应用这种光谱性质进行光气检测。除此之外，X射线衍射图的不同吸收峰和红外谱图上位于1155cm^-1和1028 cm^-1的新吸收峰都清晰表明了上转换探针与有机探针的区别。此外，如果利用比色卡作为此类探针反应介质，比率成像空气中的光气，将能够为环境和军事中光气的检测提供可靠且隐蔽的纳米化学探针工具。

关键词：光气 光气检测 三光气 罗丹明衍生物制备 上转换 荧光探针

Rhodamine-Modified Upconversion Nanophosphors for Ratiometric Detection of Phosgene

Abstract

1. Phosgene is an important toxic and important chemical raw material. It has great toxicity in the production and use, and it is also used as a poisonous weapon in military. Inhalation of phosgene poisoning could directly lead to suffocation of poisoning deaths. Based on the serious consequences of phosgene poisoning, phosgene detection in the workplace or military environment is very important.
2. Firstly, some traditional phosgene detection methods are briefly introduced in this paper, such as 4-dinitrophenylhydrazine method, liquid chromatography and organic fluorescent probe, but the first two conventional detection methods cannot detect phosgene immediately, limiting the application of these methods. And the organic fluorescent probe is harmful to organism. Therefore, a new phosgene detection method based on rhodamine fluorescent chromospheres and up conversion luminescent materials is investigated. This method is of great significance for rapid detection of phosgene. We synthesized a rhodamine derivative containing an inner amide ring by using rhodamine B and o-diaminobenzene. The organic compounds were characterized by nuclear magnetic resonance spectroscopy and mass spectrometry. The absorption peaks on the NMR spectrum and the molecular ion peaks on the mass spectra show that the compounds are of the correct structure. Then, the organic compound was self-assembled with the rare earth Nano crystals to develop a rhodamine-modified up-conversion nanophosphors. The probes combine the advantages of fluorophores and up conversion materials, including the color changes that can be observed by naked eyes of rhodamine fluorescent probes, and the small biological damage, penetrating power of up-conversion probes. After the probe was synthesized, we use solid phosgene, triphosgene, whose toxicity is far less than that of phosgene, as a substitute for phosgene, to detect the performance of the probe. obtained by adding different amount of ultraviolet - visible light after phosgene probe and fluorescence spectrum absorption peak. The UV Vis and fluorescence absorption peaks of the probe were obtained after adding different amounts of phosgene. In the UV-Vis spectra the absorption intensity at 543nm increased with the increase of phosgene concentration. On the contrast, the fluorescent intensity is decreased with the increase of phosgene. However, the upconversion probe without organic fluorescent probes cannot be used to detect phosgene via these spectral properties. Besides, we also use x-ray diffraction and infrared spectrum to characterize the up-conversion probe. It demonstrated the structure of the upconversion probe and its differences from the organic probe. If we can use ratio-metric as a medium to imaging phosgene in air proportionately. It will provide a reliable and subtle Nano-chemical probe for the detection of phosgene in environment and military.
3. Keywords: phosgene; testing phosgene; triphosgene; preparation of the derivative of rhodamine ; up-conversion ; fluorescent probe

目 录

摘要 i

Abstract I

第一章 综述 1

1.1光气 1

1.1.1光气的概述 1

1.1.2光气的检测方法 3

1.2 自组装技术概述 5

1.3罗丹明类化合物及其衍生物的概述 6

1.3.1罗丹明类化合物的概述 6

1.3.2 罗丹明衍生物的概述 7

1.3.3 罗丹明衍生物的制备 8

1.3.4 罗丹明-邻苯二胺与光气的反应 8

1.4 有机荧光探针及罗丹明类荧光探针的概述 10

1.4.1有机荧光探针 10

1.4.2 罗丹明类有机荧光探针 10

1.4.3 嵌入式罗丹明聚合物纤维的概述 12

1.5 稀土纳米晶上转换材料概述 13

第二章 实验部分 15

2.1 实验仪器与实验试剂 15

2.1.1 实验仪器 15

2.1.2 实验试剂 15

2.2 罗丹明-邻苯二胺的合成及性能测试 16

2.2.1 合成步骤 16

2.2.2 有机物性质及结构表征 18

2.3 上转换探针的制备及性能测试 18

2.3.1 合成步骤 18

2.3.2上转换探针的性能测试 18

第三章 结果与讨论 21

3.1 有机物罗丹明B-邻苯二胺的结构表征 21

3.1.1 RB-OPD的核磁共振图 21

3.1.2 RB-OPD的质谱图 22

3.1.3 有机物的红外谱图 23

3.2 RB-OPD的对光气的响应机理 24

3.3 探针的紫外-可见光吸收光谱 24

3.4 探针的荧光吸收光谱 26

3.5 探针的XRD衍射图 28

3.6 探针的红外光谱图 29

第四章 结论与展望 31

4.1 结论 31

4.2 展望 32

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