Please use this identifier to cite or link to this item:
http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/51416
Title: | 3-羥基黃酮衍生物應用於氫離子/氟離子雙分析物螢光探針以及分子內氫鍵之探測 3-Hydroxy Flavone Derivatives for Developing a H+/F- Dual Analyte Fluorescent Probe and Probing Intramolecular hydrogen Bonds |
Authors: | Yu-Kun Hsu 許鈺琨 |
Advisor: | 陳昭岑(Chao-Tsen Chen) |
Keyword: | 3-羥基黃酮,雙分析物螢光探針,分子內氫鍵, 3-hydroxy flavone,dual analyte probe,intramolecular hydrogen bond, |
Publication Year : | 2016 |
Degree: | 碩士 |
Abstract: | 本論文利用3-羥基黃酮之3號羥基在激發態質子轉移反應中作為質子予體且較一般醇類為酸之性質,在3號羥基進行衍生化,以發展氫離子/氟離子雙分析物螢光探針;或於2’位置上進行衍生化,以探測分子內氫鍵。
論文第一部分針對雙分析物螢光探針 3-TBSFE 與 3-TBSFA 進行研究,透過在3號羥基上修飾氫離子/氟離子敏感之矽醚基團、在2’位置修飾在氫離子催化下會與3號羥基形成內酯之羰基衍生物,而能達到一螢光探針對兩分析物有不同螢光行為。本研究並進一步以高效能液相層析、電灑法質譜及核磁共振觀察反應之時間過程,以佐證雙分析物螢光探針 3-TBSFE 與 3-TBSFA 之作用機制。 論文第二部分則是設計在2’位置衍生酚基,此酚基可能和環中之氧原子形成準六員環氫鍵而造成氧原子之電子供給能力下降使得吸收光譜藍移;或和3號羥基形成準七員環氫鍵而使得3號羥基酸性提升使得吸收光譜產生較長波長之陰離子訊號。透過系列衍生物的溶劑效應和酸性比較,較長波長之吸收應是來自形成準七員環氫鍵,但吸收光譜之藍移應來自立體障礙使得2苯基與分子其他部分之共平面性下降。透過x-ray晶體結構鑑定,證明2’酚基和3羥基確實形成準七員環氫鍵,亦可由溶劑之質子受體能力對吸收光譜進行分析,而得準八員環離子性氫鍵與準七員環離子性氫鍵之自由能差。 The thesis is focused on 3-hydroxyflavone derivatives serving as a H+/F- dual analyte fluorescent probe and intramolecular hydrogen bond probe, via its special 3-hydroxyl properties, which serves as the proton donor in the ESIPT process and is more acidic than normal alcohols. In the first part of the thesis, two 3-sily ether derivatives, namely 3-TBSFE and 3-TBSFA, were designed and synthesized. Upon addition of H+/F- the silyl ether is removed, while only in the present of H+ is the second step lactone product formed. The characteristic photo physical properties of each compound realized the goal to tell apart the concentration of H+/F- using one probe. With the help of HPLC, ESI-MS, and NMR, the working mechanism of 3-TBSFA was confirmed. In the second part of the thesis a serial 2’ phenol derivatives were designed and synthesized. The 2’ phenol may form 6-membered intramolecular H-bond and decrease the e- donating ability of the O atom in the ring, thus cause blue-shift in absorption spectrum. While when the 7-membered intramolecular H-bond formed, the acidity of 3-hydroxy increase which attribute to the long wavelength anion signal in absorption spectrum. Thought careful slovatochromism and acidity discussion of 2’ phenol derivatives, we conclude that the long wavelength absorption was related to the 7-membered intramolecular H-bond, while the blue-shift of absorption spectrum was due to steric-caused coplanarity decreasing. Via X-ray diffraction structure the formation of 7-membered intramolecular H-bond was confirmed. The free energy difference between 7- and 8-membered intramolecular ionic H-bond was also deduced from correlation of solvent H acceptor ability and absorbance. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/51416 |
Fulltext Rights: | 有償授權 |
Appears in Collections: | 化學系 |
Files in This Item:
File | Size | Format | |
---|---|---|---|
ntu-105-1.pdf Restricted Access | 20.67 MB | Adobe PDF |
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.