【摘要】：金屬離子是環(huán)境化學(xué)、生命和醫(yī)療等科學(xué)領(lǐng)域的重點(diǎn)研究內(nèi)容,對水溶液中金屬離子的檢測更是分析化學(xué)的熱點(diǎn)研究問題。近年來,金屬離子熒光探針因具有選擇性好,靈敏度高、反應(yīng)迅速等特征成為研究熱點(diǎn)。水楊醛席夫堿因具有C=N-,-OH結(jié)構(gòu)單元,使其與金屬具有良好的配位能力,同時(shí),由于這類分子具有較大共軛體系,也表現(xiàn)出優(yōu)異的熒光性能。但由于其金屬絡(luò)合物在水相和有機(jī)相中較低的溶解度使其作為熒光探針在金屬離子檢測領(lǐng)域的應(yīng)用受到限制。本論文的主要工作是對水楊醛分子進(jìn)行結(jié)構(gòu)修飾,具體為在水楊醛分子中引入油溶性基團(tuán),增加其金屬絡(luò)合物在有機(jī)溶劑中的溶解度,考察金屬配合物的熒光性能及其作為金屬離子熒光探針的可能性。本論文主要研究工作如下:從烷基酚出發(fā),經(jīng)付克氏烷基化反應(yīng)、甲�；磻�(yīng)合成出3種水楊醛衍生物5-甲基-3-α,α-二甲基-α-苯基水楊醛(3a)、3,5-二-α,α-二甲基-α-苯基水楊醛(3b)和5-特辛基-3-α,α-二甲基-α-苯基水楊醛(3c);3種水楊醛衍生物分別與鄰氨基苯酚縮合,合成了三種具有平面共軛體系結(jié)構(gòu)特點(diǎn)的新型席夫堿熒光探針(4a,4b,4c),3種熒光探針分別與Zn~(2+)、Cu~(2+)、Mn~(2+)、Ni~(2+)、Co~(2+)形成絡(luò)合物。對所合成的配體及絡(luò)合物進(jìn)行了結(jié)構(gòu)表征和熒光性質(zhì)研究,結(jié)果表明,所制備的3種熒光探針對Zn~(2+)表現(xiàn)出良好的識別性能,其中4b與Zn~(2+)絡(luò)合物的熒光強(qiáng)度是配體的5倍左右,4a和4c分別為2倍和2.5倍左右。與Zn~(2+)相比,Cu~(2+)、Mn~(2+)、Ni~(2+)、Co~(2+)與3種配體形成的絡(luò)合物熒光強(qiáng)度均低于配體。3a-c分別與三種天然氨基酸發(fā)生縮合反應(yīng),制備出9種新型L-氨基酸水楊醛席夫堿(7a-i),9種新型L-氨基酸席夫堿分別與Zn~(2+)、Cu~(2+)、Mn~(2+)、Ni~(2+)、Co~(2+)絡(luò)合生成相應(yīng)的金屬絡(luò)合物。對所合成的熒光探針及金屬絡(luò)合物進(jìn)行了結(jié)構(gòu)表征和熒光性質(zhì)研究,結(jié)果表明,9種配體與Zn~(2+)的絡(luò)合物有較強(qiáng)的熒光發(fā)射,絡(luò)合物的熒光強(qiáng)度是配體的1.5倍以上,其中7f達(dá)到10倍左右。與Zn~(2+)相比,Cu~(2+)、Mn~(2+)、Ni~(2+)、Co~(2+)與9種配體形成的絡(luò)合物熒光強(qiáng)度均低于配體,表明這9種配體作為Zn~(2+)的熒光探針具有極好的選擇性。研究了Cu~(2+)、Mn~(2+)、Ni~(2+)、Co~(2+)4種金屬離子對7f配體作為熒光探針檢測鋅離子影響,結(jié)果表明Cu~(2+)對7f和Zn~(2+)絡(luò)合物的熒光發(fā)射表現(xiàn)出明顯的猝滅作用,而其他離子及其混合物則幾乎沒有影響。研究了7b與Cu~(2+)偶合物的晶體結(jié)構(gòu),單晶X-衍射檢測顯示,該絡(luò)合物晶體屬正交晶系,P21空間群。本文共合成了3種水楊醛衍生物,12種水楊醛席夫堿配體,60種金屬絡(luò)合物,全部為文獻(xiàn)未見報(bào)道的新化合物。
[Abstract]:Metal ions are the focus of environmental chemistry, life and medical science, and the detection of metal ions in aqueous solution is a hot issue in analytical chemistry. In recent years, metal ion fluorescence probes have become a hot research area because of their good selectivity, high sensitivity and rapid reaction. The Schiff base of salicylidene has good coordination ability with metals because of its Cn- (N-OH-OH) structure unit. At the same time, it also exhibits excellent fluorescence properties because of its large conjugated system. However, its low solubility in aqueous and organic phases limits its application as a fluorescent probe in the field of metal ion detection. The main work of this thesis is to modify the structure of salicylic aldehyde molecules by introducing oil-soluble groups into salicylaldehyde molecules to increase the solubility of its metal complexes in organic solvents. The fluorescence properties of metal complexes and the possibility of using them as metal ion fluorescence probes were investigated. The main work of this thesis is as follows: starting from alkylphenol, three salicylic aldehyde derivatives 5-methyl-3- 偽, 偽 -dimethyl- 偽 -phenylsalicylic aldehyde (3a), 3- (5-di- 偽) -diphenylsalicylaldehyde (3a) were synthesized by formylation of alkylphenol and formylation. 偽 -dimethyl- 偽 -phenylsalicylidene (3b) and 5-tert-octyl-3- 偽, 偽 -dimethyl- 偽 -phenylsalicylaldehyde (3c); Three novel Schiff base fluorescent probes (4aAc) with planar conjugation system were synthesized by condensation of three salicylaldehyde derivatives with o-aminophenol, respectively. Three kinds of fluorescent probes were synthesized with Zn~ (2) and Cu~ (2), respectively. Mn~ (2), Ni~ (2), Co~ (2) form complex. The structure and fluorescence properties of the synthesized ligands and complexes were studied. The results show that the three fluorescent probes have good recognition performance for Zn~ (2). The fluorescence intensity of 4b / Zn~ (2) complexes is about 5 times of that of ligands, and the fluorescence intensities of 4a and 4c complexes are 2 and 2. 5 times, respectively. Compared with Zn~ (2), the fluorescence intensity of Cu~ (2), Mn~ (2), Ni~ (2), Co~ (2) complexes with three ligands was lower than that of ligands. 3a-c condensed with three natural amino acids. Nine novel L-amino acid salicylaldehyde Schiff bases (7a-i) and nine novel L-amino acid Schiff bases were synthesized by complexing with Zn~ (2), Cu~ (2), Mn~ (2), Ni~ (2), Co~ (2) to form corresponding metal complexes. The structure and fluorescence properties of the synthesized fluorescent probes and metal complexes have been studied. The results show that the complexes of 9 ligands with Zn~ (2) have strong fluorescence emission, and the fluorescence intensity of the complexes is more than 1.5 times that of the ligands. Among them, 7 f is about 10 times. Compared with Zn~ (2), the fluorescence intensities of Cu~ (2), Mn~ (2), Ni~ (2), Co~ (2) complexes with 9 ligands were lower than those of ligands, which indicated that these ligands had excellent selectivity as fluorescence probes for Zn~ (2). The effects of four metal ions, Cu~ (2), Mn~ (2), Ni~ (2), Co~ (2), on the detection of zinc ions by using 7f ligands as fluorescence probes were studied. The results show that Cu~ (2) has obvious quenching effect on fluorescence emission of 7f and Zn~ (2) complexes, while other ions and their mixtures have little effect. The crystal structure of the coupling compound 7b with Cu~ (2) has been studied. The X-ray diffraction analysis shows that the complex crystal belongs to the orthogonal crystal system and P21 space group. In this paper, three salicylaldehyde derivatives, 12 salicylaldehyde Schiff base ligands and 60 metal complexes have been synthesized, all of which are new compounds not reported in literature.
【學(xué)位授予單位】：哈爾濱理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O657.3

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