水溶性卟啉的聚集行為及其金屬配合物的光譜性質(zhì)研究
發(fā)布時(shí)間：2018-09-16 20:57
【摘要】：卟啉是化合物卟吩(porphin, C20H40N4)中四個(gè)吡咯環(huán)的8個(gè)β位和4個(gè)中位(R位)的H原子被其他基團(tuán)取代生成的各種各樣的卟吩衍生物。由于卟啉類化合物較大的剛性空間結(jié)構(gòu),導(dǎo)致它的水溶性很差,給卟啉化合物的研究和應(yīng)用帶來(lái)了一定的限制。近年來(lái),人們?cè)噲D通過(guò)修飾和調(diào)整其取代基,增大水溶性,進(jìn)而開(kāi)展相關(guān)的學(xué)術(shù)研究已成為卟啉研究熱點(diǎn)。本論文選取了三種水溶性卟啉meso-四(4-羧基苯基)卟啉(TCPP)、meso-四(4-磺酸基苯基)卟啉(TSPP)、meso-四(4-三甲銨基苯基)卟啉(TTAP),對(duì)其聚集行為和金屬配合物的光譜特性進(jìn)行了研究。具體內(nèi)容如下：第一章：綜述了卟啉的結(jié)構(gòu)、性質(zhì)及其應(yīng)用,重點(diǎn)介紹了水溶性卟啉的結(jié)構(gòu)、聚集行為研究現(xiàn)狀及本選題的意義,對(duì)本論文的研究?jī)?nèi)容和創(chuàng)新點(diǎn)進(jìn)行了概括。第二章：本章對(duì)陰離子卟啉TCPP的自聚條件進(jìn)行了研究,發(fā)現(xiàn)在酸性溶液中發(fā)生自聚,在pH=1.0時(shí),形成較為規(guī)則的棒狀納米材料；自聚集前后表現(xiàn)出了不同的紫外吸收光譜和熒光光譜性質(zhì)；共振光散射研究表明卟啉自聚體的顆粒大小與時(shí)間正相關(guān)。電化學(xué)方法檢測(cè)發(fā)現(xiàn)自聚體有良好的光電響應(yīng),并且可逆。推測(cè)TCPP自聚集是通過(guò)H-鍵作用力和π-π相互作用形成的。第三章：采用紫外吸收光譜、熒光光譜和共振光散射研究了陽(yáng)離子卟啉TTAP與陰離子卟啉TCPP和陰離子卟啉TSPP的相互作用,發(fā)現(xiàn)在中性溶液中混合后即發(fā)生聚集,結(jié)合比分別為T(mén)TAP:TCPP=2:1和TTAP:TSPP=1:1;顯微鏡顯示TTAP與TSPP混聚體為高度有序的花瓣晶狀結(jié)構(gòu)；原子力顯微鏡測(cè)定結(jié)果表明,聚集體為高160nm,寬0.48μm的納米級(jí)材料。第四章：通過(guò)紫外和熒光分光光度法研究了陽(yáng)離子卟啉TTAP在水溶液中與過(guò)渡金屬Fe、Co、Ni之間的相互作用。結(jié)果發(fā)現(xiàn)TTAP與過(guò)渡金屬Fe、Co、Ni形成金屬配合物,它們的紫外吸收和熒光光譜與形成配合物前有較大的變化,并且與配位金屬的性質(zhì)有關(guān)。Fe-TTAP和Co-TTAP的最大吸收峰均發(fā)生了紅移,而Ni-TTAP的最大吸收峰沒(méi)有變化；熒光強(qiáng)度均降低或猝滅。對(duì)其光譜變化的機(jī)理進(jìn)行討論。
[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.
【學(xué)位授予單位】：山西大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2014
【分類號(hào)】：R917;O657.3
本文編號(hào)：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.
【學(xué)位授予單位】：山西大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2014
【分類號(hào)】：R917;O657.3
【參考文獻(xiàn)】
相關(guān)期刊論文 前1條
1 羅小剛;邱明禮;侯長(zhǎng)軍;霍丹群;;基于卟啉傳感器的氣體檢測(cè)系統(tǒng)的設(shè)計(jì)[J];傳感器與微系統(tǒng);2010年12期
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