請用此 Handle URI 來引用此文件：
http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/33969完整後設資料紀錄
| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 周必泰 | |
| dc.contributor.author | Yu-Shan Yeh | en |
| dc.contributor.author | 葉育姍 | zh_TW |
| dc.date.accessioned | 2021-06-13T05:50:19Z | - |
| dc.date.available | 2006-07-07 | |
| dc.date.copyright | 2006-07-07 | |
| dc.date.issued | 2006 | |
| dc.date.submitted | 2006-07-07 | |
| dc.identifier.citation | Chapter 1
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Circular Dichroism: Principles and Applications, VCH, New York, 1994. (b) Rodger, A.; Nordén, B. Circular Dichroism and Linear Dichroism, Oxford University Press, New York, 1997. 16. Gawron´ski, J.; Grajewski, J. Org. Lett., 2003, 5, 3301. 17. (a) Tamaru, S. I.; Shinkai, S.; Khasanov, A. B.; Bell, T. W. Proc. Natl. Acad. Sci. USA , 2002, 99, 4972. (b) Mizuno, T.; Yamamoto, M.; Takeuchi, M.; Shinkai, S. Tetrahedron, 2000, 56, 6193. 18. Topiol, S. Chirality 1989, 1, 69. 19. (a) Turner, D. H.; Tinoco, I. Jr.; Maestre, M. J. Am. Chem. Soc. 1974, 96, 4340. (b) Tinoco, I. Jr.; Turner, D. H. J. Am. Chem. Soc. 1976, 98, 6453. | |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/33969 | - |
| dc.description.abstract | 中文摘要
分子辨識在化學、生物醫學等領域皆已有廣泛的應用，本論文即利用經由有機合成方法設計出模擬蛋白質立體結構的V型分子來與尿素及醣類分子作鍵結，並利用不同光譜技術觀察分子間鍵結前後產生的光譜變化來作為分子辨識的依據。 內容分成四章來討論。首章簡介主-客分子複合物之定義及其形成條件及其應用，並討論結合常數的量測與計算方法。第二章介紹暫穩態光譜技術的基本原理與實驗量測及校正方法。第三章介紹激發態質子轉移的基本原理與光譜現象在分子辨識上的應用。簡介3, 4, 5, 6-Tetrahydro-bis-(pyrido[3, 2-g]indolo)[2,3-a:3’, 2’–j]acridine的基本性質與其在含質子溶劑與非含質子溶劑中不同的光物理行為及所造成的放光機制。利用兩種不同質子轉移機制(catalytic/non-catalytic)對分子放光帶產生的消長關係，使主題討論分子可對尿素分子在醇/水混合溶劑中達到微量偵測的效果。第四章主要在介紹光學活性的偵測方法與應用，介紹並討論Circular Dichroism(CD)/Fluorescence-Detected Circular Dichroism (FDCD)之光譜技術及其優缺點，並利用理論計算方法計算Electronic Circular Dichroism(ECD)光譜來與實驗值作比較。利用前述的V型分子與具有不同光學活性的醣類分子鍵結，經由氫鍵鍵結與激發態質子轉移反應後產生具不同光學活性的複合物，再以光譜方法作為辨別光學異構物的依據。 | zh_TW |
| dc.description.abstract | Abstract
The concept of molecular recognition has been applied extensively in the field of biochemistry and many other fields. Here, designed and synthesized cleft-like host molecule, which mimics protein structure and its binding abilities, is used in binding with biomolecules such as urea and glucopyranosides. Spectroscopic methods act as powerful tool in discriminating between free and complexed molecules and evaluating their association entities quantitatively. This thesis is organized into four chapters. We start with a brief introduction of the concept of molecular recognition. Some basic principles and experimental setups of steady-state spectrometry, the general errors and correction methods are discussed in chapter 2. In the two successive chapters, utilizing excited state proton transfer reaction, 3, 4, 5, 6-Tetrahydro-bis-(pyrido[3, 2-g]indolo)[2,3-a:3’, 2’–j]acridine acts as an ideal host molecule to bind with different biomolecules efficiently in both protic and aprotic solvents. High sensitivity and selectivity are achieved via fluorescent detection method, and the association constants are deduced accordingly. In addition, to accomplish chiral recognition, circular dichroism (CD), fluorescence-detected circular dichroism (FDCD) and theoretical approach are performed in differentiation of optical isomers. The extension of these applications into aqueous environments is still the topic of endeavor. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-13T05:50:19Z (GMT). No. of bitstreams: 1 ntu-95-R93223010-1.pdf: 2271711 bytes, checksum: 473f101484bb76ea2e50c8f04bd12196 (MD5) Previous issue date: 2006 | en |
| dc.description.tableofcontents | Contents
Abstract 1 Chapter 1 Introduction of molecular recognition 2 1.1 Terminology.……………………………………………………………………..2 1.2 Structures…………………………………………………………………………4 1.3 Solvent effect……………………………………………………………………..5 1.4 Authentic molecular recognition cases…………………………………………...6 1.5 Calculation of association constants……………………………………………...7 1.6 Reference………………………………………………………………………...10 Chapter 2 Principles of operation and instrumentation 12 2.1 UV-vis absorption and the Beer-Lambert Law………………………………….12 2.2 Steady-state fluorescence………………………………………………………..16 2.2.1 Steady-state fluorescence intensity………………………………………...16 2.2.2 Emission spectra…………………………………………………………...18 Excitation inner filter effect…………………………………………………21 Emission inner filter effect (self-absorption)………………………………..21 Inner filter effects due to the presence of other substances…………………21 2.2.3 Excitation spectra…………………………………………………………..22 2.3 Principles of steady-state fluorometric techniques………………………………23 2.3.1 Steady-state spectrofluorometry……………………………………………23 2.3.2 Correction of emission spectra………………………………………….….26 2.3.3 Correction of excitation spectra……………………………………………27 2.4 Measurement of fluorescence quantum yields…………………………………...28 2.5 Time-correlated single photon counting………………………………………….32 2.5.1 Basic principles…………………………………………………………….32 2.5.2 Data analysis……………………………………………………………….34 Convolution…………………………………………………………………34 Deconvolution………………………………………………………………35 2.5.3 Light source………………………………………………………………...37 Operarion…………………………………………………………………...37 Choosing the filler gas……………………………………………………...40 2.5.4 Detection systems…………………………………………………………..42 2.6 Figures……………………………………………………………………………45 2.7 Reference…………………………………………………………………………59 Chapter 3 Protic Solvent Catalyzed Excited-state Proton Transfer in 3, 4, 5, 6-Tetrahydro-bis(pyrido[3, 2-g]indolo)[2,3-a:3’, 2’-j] acridine and its analogues; The Application Toward Urea Recognition in Aqueous Media. 60 Abstract………………………………………………………………………………60 3.1. Introduction……………………………………………………….……………..61 3.2 Experimental Section…………………………………………………………….65 3.2.1 Measurements………………………………………………………………65 3.2.2 Computational methods…………………………………………………….66 3.3. Results and Discussion…………………………………………………………..67 3.3.1 Photophysical properties in aprotic solvents………………………………67 3.3.2 Protic solvents catalyzed ESPT reaction…………………………………...70 3.3.3 Deuterium isotope effect……………………………………………………75 3.3.4 Toward sensing authentic urea…………………………………………….77 3.3.5 Molecular modeling………………………………………………………..81 3.3.6 Parameters tuning based on urea recognition…………………………….84 3.4 Conclusion……………………………………………………………………….85 3.5 Tables and figures………………………………………………………………..87 3.6 Reference………………………………………………………………………..104 Chapter 4 Recognition of Monosaccharides via Guest/Host Excited-State Proton Transfer Reaction; Ratiometric Fluorescence, Circular Dichroism and Fluorescence-detected Circular Dichroism 108 Abstract……………………………………………………………………………..108 4.1 General Introduction…………………………………………………………….108 4.2 Introduction of polarized light and CD/FDCD spectroscopy…………………...109 4.2.1 Polarized light…………………………………………………………….109 Linearly polarized light……………………………………………………109 Circularly polarized light………………………………………………….110 4.2.2 Circular dichroism spectroscopy………………………………………….112 4.2.3 Fluorescence-detected circular dichroism………………………………..116 4.3 Experimental section……………………………………………………………118 General………………………………………………………………………….119 UV-vis and Fluorescent Titration Studies……………………………………….119 Computational methodolog……………………………………………………..120 4.4 Results and discussion…………………………………………………………..120 Steady-state absorption and emission titration experiments……………………..120 Application of CD spectrum…………………………………………………….122 Application of FDCD spectrum…………………………………………………124 Calculations of ECD spectra……………………………………………………124 4.5 Conclusion……………………………………………………………………….125 4.6 Tables and figures……………………………………………………………….127 4.7 Reference………………………………………………………………………..142 | |
| dc.language.iso | en | |
| dc.subject | 分子辨識 | zh_TW |
| dc.subject | molecular recognition | en |
| dc.title | 分子辨識之基礎與應用— 以3, 4, 5, 6-Tetra hydro-bis-(pyrido[3,2-g]indolo)[2,3-a:3’,2’–j] acridine為受體分子之研究 | zh_TW |
| dc.title | Fundamentals and Applications of molecular recognition using 3, 4, 5, 6-Tetrahydro-bis-(pyrido [3, 2-g]indolo)[2, 3-a: 3’,2’–j]acridine as host molecule | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 94-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 張鎮平,季昀 | |
| dc.subject.keyword | 分子辨識, | zh_TW |
| dc.subject.keyword | molecular recognition, | en |
| dc.relation.page | 144 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2006-07-07 | |
| dc.contributor.author-college | 理學院 | zh_TW |
| dc.contributor.author-dept | 化學研究所 | zh_TW |
| 顯示於系所單位： | 化學系 | |
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