水溶性卟啉的聚集行为及其金属配合物的光谱性质研究
发布时间：2018-09-16 20:57
【摘要】：卟啉是化合物卟吩(porphin, C20H40N4)中四个吡咯环的8个β位和4个中位(R位)的H原子被其他基团取代生成的各种各样的卟吩衍生物。由于卟啉类化合物较大的刚性空间结构,导致它的水溶性很差,给卟啉化合物的研究和应用带来了一定的限制。近年来,人们试图通过修饰和调整其取代基,增大水溶性,进而开展相关的学术研究已成为卟啉研究热点。本论文选取了三种水溶性卟啉meso-四(4-羧基苯基)卟啉(TCPP)、meso-四(4-磺酸基苯基)卟啉(TSPP)、meso-四(4-三甲铵基苯基)卟啉(TTAP),对其聚集行为和金属配合物的光谱特性进行了研究。具体内容如下：第一章：综述了卟啉的结构、性质及其应用,重点介绍了水溶性卟啉的结构、聚集行为研究现状及本选题的意义,对本论文的研究内容和创新点进行了概括。第二章：本章对阴离子卟啉TCPP的自聚条件进行了研究,发现在酸性溶液中发生自聚,在pH=1.0时,形成较为规则的棒状纳米材料；自聚集前后表现出了不同的紫外吸收光谱和荧光光谱性质；共振光散射研究表明卟啉自聚体的颗粒大小与时间正相关。电化学方法检测发现自聚体有良好的光电响应,并且可逆。推测TCPP自聚集是通过H-键作用力和π-π相互作用形成的。第三章：采用紫外吸收光谱、荧光光谱和共振光散射研究了阳离子卟啉TTAP与阴离子卟啉TCPP和阴离子卟啉TSPP的相互作用,发现在中性溶液中混合后即发生聚集,结合比分别为TTAP:TCPP=2:1和TTAP:TSPP=1:1;显微镜显示TTAP与TSPP混聚体为高度有序的花瓣晶状结构；原子力显微镜测定结果表明,聚集体为高160nm,宽0.48μm的纳米级材料。第四章：通过紫外和荧光分光光度法研究了阳离子卟啉TTAP在水溶液中与过渡金属Fe、Co、Ni之间的相互作用。结果发现TTAP与过渡金属Fe、Co、Ni形成金属配合物,它们的紫外吸收和荧光光谱与形成配合物前有较大的变化,并且与配位金属的性质有关。Fe-TTAP和Co-TTAP的最大吸收峰均发生了红移,而Ni-TTAP的最大吸收峰没有变化；荧光强度均降低或猝灭。对其光谱变化的机理进行讨论。
[Abstract]:Porphyrin is a variety of porphine derivatives formed by the substitution of H atoms of four pyrrole rings and eight 尾 sites and four median (R sites) of four pyrrole rings in porphine (porphin, C20H40N4) by other groups. Because of the large rigid space structure of porphyrin compounds, the water solubility of porphyrin compounds is very poor, which brings some limitations to the research and application of porphyrin compounds. In recent years, people try to increase the water solubility by modifying and adjusting their substituents, and then carry out related academic research has become a hot spot of porphyrin research. In this paper, the aggregation behavior of three water-soluble porphyrin meso- tetra (4-carboxyphenyl) porphyrin (TCPP) and meso- tetra (4-sulfophenyl) porphyrin (TSPP) tetra (4-trimethylammoniphenyl) porphyrin (TTAP), were investigated. The main contents are as follows: chapter 1: the structure, properties and applications of porphyrins are reviewed. The structure, aggregation behavior and significance of this topic are introduced, and the contents and innovations of this paper are summarized. Chapter 2: in this chapter, the self-polymerization conditions of anionic porphyrin TCPP were studied. It was found that self-polymerization occurred in acid solution and formed regular rod nanomaterials at pH= 1.0. The results of resonance light scattering (RLS) show that the particle size of porphyrin self-polymer is positively correlated with time. Electrochemical detection showed that the self-polymer had a good photoelectric response and was reversible. It is inferred that TCPP self-aggregation is formed by the interaction of H-bond and 蟺-蟺. Chapter 3: the interaction of cationic porphyrin TTAP with anionic porphyrin TCPP and anionic porphyrin TSPP was studied by ultraviolet absorption spectrum, fluorescence spectrum and resonance light scattering. The binding ratios of TTAP:TCPP=2:1 and TTAP:TSPP=1:1; showed that the mixture of TTAP and TSPP was a highly ordered petal crystal structure, and the atomic force microscope (AFM) showed that the aggregates were nanomaterials with a height of 160 nm and a width of 0.48 渭 m. Chapter 4: the interaction of cationic porphyrin TTAP with transition metal Fe,Co,Ni in aqueous solution was studied by UV and fluorescence spectrophotometry. The results showed that TTAP formed metal complexes with transition metal Fe,Co,Ni, their UV absorption and fluorescence spectra changed greatly before the formation of the complexes, and the maximum absorption peaks of both Fe-TTAP and Co-TTAP were red-shifted in relation to the properties of coordination metals. However, the maximum absorption peak of Ni-TTAP did not change, and the fluorescence intensity decreased or quenched. The mechanism of spectral variation is discussed.
【学位授予单位】：山西大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：R917;O657.3
本文编号：2244768
[Abstract]:Porphyrin is a variety of porphine derivatives formed by the substitution of H atoms of four pyrrole rings and eight 尾 sites and four median (R sites) of four pyrrole rings in porphine (porphin, C20H40N4) by other groups. Because of the large rigid space structure of porphyrin compounds, the water solubility of porphyrin compounds is very poor, which brings some limitations to the research and application of porphyrin compounds. In recent years, people try to increase the water solubility by modifying and adjusting their substituents, and then carry out related academic research has become a hot spot of porphyrin research. In this paper, the aggregation behavior of three water-soluble porphyrin meso- tetra (4-carboxyphenyl) porphyrin (TCPP) and meso- tetra (4-sulfophenyl) porphyrin (TSPP) tetra (4-trimethylammoniphenyl) porphyrin (TTAP), were investigated. The main contents are as follows: chapter 1: the structure, properties and applications of porphyrins are reviewed. The structure, aggregation behavior and significance of this topic are introduced, and the contents and innovations of this paper are summarized. Chapter 2: in this chapter, the self-polymerization conditions of anionic porphyrin TCPP were studied. It was found that self-polymerization occurred in acid solution and formed regular rod nanomaterials at pH= 1.0. The results of resonance light scattering (RLS) show that the particle size of porphyrin self-polymer is positively correlated with time. Electrochemical detection showed that the self-polymer had a good photoelectric response and was reversible. It is inferred that TCPP self-aggregation is formed by the interaction of H-bond and 蟺-蟺. Chapter 3: the interaction of cationic porphyrin TTAP with anionic porphyrin TCPP and anionic porphyrin TSPP was studied by ultraviolet absorption spectrum, fluorescence spectrum and resonance light scattering. The binding ratios of TTAP:TCPP=2:1 and TTAP:TSPP=1:1; showed that the mixture of TTAP and TSPP was a highly ordered petal crystal structure, and the atomic force microscope (AFM) showed that the aggregates were nanomaterials with a height of 160 nm and a width of 0.48 渭 m. Chapter 4: the interaction of cationic porphyrin TTAP with transition metal Fe,Co,Ni in aqueous solution was studied by UV and fluorescence spectrophotometry. The results showed that TTAP formed metal complexes with transition metal Fe,Co,Ni, their UV absorption and fluorescence spectra changed greatly before the formation of the complexes, and the maximum absorption peaks of both Fe-TTAP and Co-TTAP were red-shifted in relation to the properties of coordination metals. However, the maximum absorption peak of Ni-TTAP did not change, and the fluorescence intensity decreased or quenched. The mechanism of spectral variation is discussed.
【学位授予单位】：山西大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：R917;O657.3
【参考文献】
相关期刊论文 前1条
1 罗小刚;邱明礼;侯长军;霍丹群;;基于卟啉传感器的气体检测系统的设计[J];传感器与微系统;2010年12期
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