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  1. NTU Theses and Dissertations Repository
  2. 理學院
  3. 化學系
請用此 Handle URI 來引用此文件: http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/29499
完整後設資料紀錄
DC 欄位值語言
dc.contributor.advisor邱勝賢(Sheng-Hsien Chiu)
dc.contributor.authorNai-Chia Chenen
dc.contributor.author陳乃嘉zh_TW
dc.date.accessioned2021-06-13T01:08:41Z-
dc.date.available2009-07-26
dc.date.copyright2007-07-26
dc.date.issued2007
dc.date.submitted2007-07-23
dc.identifier.citation1. Muller-Dethlefs, K.; Hobza, P. Chem. Rev. 2000, 100, 143–167.
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K.; Yoshizawa, M.; Fujita, N.; Kusukawa, T.; Biradha, K. Chem. Commun.
2001, 509–518. (c) Kim, K. Chem. Soc. Rev. 2002, 31, 96–107.
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Royal Society of Chemistry: Cambridge, 2000. (c) Whitesides, G. M.;
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D. A.; Whitesides, G. M. Pure Appl. Chem. 2003, 75, 621–630.
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Crown Ethers and Cryptands, Royal Society of Chemistry: London, 1991 (c)
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15. Moonen, N. N. P.; Flood, A. H.; Ferna'ndez, J. M.; Stoddart, J. F. Top. Curr.
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5131–5133.
17. For a definition of the term ‘ co-conformers’, see: Fyfe, M. C. T.; Glink, P. T.;
Menzer, S.; Stoddart, J. F.; White, A. J. P.; Williams, D. J. Angew Chem. Int. Ed.
Engl. 1997, 36, 2068-2070.
18. Bissell, R. A.; Co'rdova, E.; Kaifer, A. E.; Stoddart, J. F. Nature 1994, 369,
133-137.
19. Badjic, J. D.; Nelson, A.; Cantrill, S. J.; Turnbull, W. B.; Stoddart, J. F. Acc.
Chem. Res. 2005, 38, 723-732.
20. Ashton, P. R.; Ballardini, R.;Balzani, V.; Baxter, I.; Credi, A.;Fyfe, M. C. T.;
Gandolfi, M. T.; Gomez-Lopez, M.; Martinez-Diaz, M. V.; Piersanti, A.;
Spencer, N.; Stoddart, J. F.; Venturi, M.; White, A. J. P.; Williams D. J. J. Am.
Chem. Soc. 1998, 120, 11932–11942.
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22. Raymo, F. M.; Stoddart, J.F. in Molecular Switches (Ed.: Feringa, B. L.),
Wiley-VCH, Weinheim, 2001, pp. 219-248
23. (a) Jime'nez, C.; Dietrich-Buchecker, C.; Sauvage, J.-P.; Cian, A. D. Angew.
Chem. Int. Ed. 2000, 39, 1295-1298; (b) Jime'nez, M. C.; Dietrich-Buchecker,
C.; Sauvage, J.-P. Angew. Chem. Int. Ed. 2000, 39, 3284-3287; (c)
Jimenez-Molero, M. C.; Dietrich-Buchecker, C.; Sauvage, J.-P. Chem. Eur. J.
2002, 8, 1456-1466.
24. (a) Lehninger, A. L. Principles of Biochemistry, CBS Publishers, Delhi, 1984;
(b) Stryer, L. Biochemistry, 3rd ed., W. H. Freeman and Co., New York, 1988.
25. (a) Burguera, J. L.; Burguera, M. Talanta 2004, 64, 1099−1108; (b) Marco, V. B.
D.; Bombi, G. G.; Mass Spectrom. Rev. 2006, 25, 347−379.
26. (a) Carroll, M. K.; Bright, F. V.; Hieftje, G. M. Anal. Chem. 1989, 61,
1768−1772; (b) Tewari, P. K.; Singh, A. K. Analyst 1999, 124, 1847−1851; (c)
Safavi, A.; Abdollahi, H.; Mirzajani, R. Spectrochim. Acta, Part A: Mol. Biomol.
Spectrosc. 2006, 63A, 196−199.
27. (a) Robards, K.; Starr, P.; Patsalides, E. Analyst 1991, 116, 1247−1273; (b)
Zeng, W.; Chen, Y.; Cui, H.; Zhu, Y.; Fritz, J. S. J. Chromatogr. A 2006, 1118,
68−72.
28. (a) Vogt, C.; Klunder, G. L. Fresenius’ J. Anal. Chem. 2001, 370, 316−331; (b)
Padarauskas, A. Anal. Bioanal. Chem. 2006, 384, 132−144.
29. (a) Rohman, M. A.; Won, M.-S.; Shim, Y.-B. Anal. Chem. 2003, 75, 1123−1129;
(b) Bakker, E. Anal. Chem. 2004, 76, 3285−3298; (c) Rezaei, B.; Rezaei, E. J.
Anal. Chem. 2006, 61, 262−265.
30. (a) Prodi, L.; Bolletta, F.; Montalti, M.; Zaccheroni, N. Coord. Chem. Rev. 2000,
205, 59−83; (b) Callan, J. F.; de Silva, A. P.; Magri, D. C. Tetrahedron 2005, 61,
8551−8588; (c) Mancin, F.; Rampazzo, E.; Tecilla, P.; Tonellato, U. Chem. Eur.
J. 2006, 12, 1844−1854.
31. 2,2´-Bipyridine and phenanthroline derivatives have been applied to the
- 54 -
construction of many elegant interlocked molecules with the assistance of metal
ions; see: (a) Collin, J.-P.; Dietrich-Buchecker, C.; Gavina, P.; Jimenez-Molero,
M. C.; Sauvage, J.-P. Acc. Chem. Res. 2001, 34, 477−487; (b) Collin, J.-P.;
Heitz, V.; Sauvage, J.-P. Top. Curr. Chem. 2005, 262, 29−62; (c) Kraus, T.;
Budesinksy, M.; Cvacka, J.; Sauvage, J.-P. Angew. Chem. 2006, 118, 264−267;
Angew. Chem. Int. Ed. 2006, 45, 258−261.
32. 在此所指的「中性」,並非表示該車輪烷分子是一個中性分子,而是指相
對於被酸化的車輪烷分子而言,其bipyridine中心呈現「中性」的情形。
33. (a) Cheng, P.-N.; Hung, W.-C.; Chiu, S.-H. Tetrahedron Lett. 2005, 46,
4239−4242; (b) Cheng, P.-N.; Huang, P.-Y.; Li, W.-S.; Ueng, S.-H.; Hung,
W.-C.; Liu, Y.-H.; Lai, C.-C.; Peng, S.-M.; Chao, I.; Chiu, S.-H. J. Org. Chem.
2006, 71, 2373−2375.
34. Angeloni, A.; Crawford, P. C.; Orpen, A. G.; Podesta, T. J.; Shore, B. J. Chem.
Eur. J. 2004, 10, 3783−3791.
35. Cheng, P.-N.; Lin, C.-F.; Liu, Y.-H.; Lai, C.-C.; Peng, S.-M.; Chiu, S.-H. Org.
Lett. 2006, 8, 435−438.
36. Connors, K. A. Binding Constants, Wiley, New York, 1987.
37. For examples of acid/base-controllable molecular switches, see: (a) Elizarov, A.
M.; Chiu, S.-H.; Stoddart, J. F. J. Org. Chem. 2002, 67, 9175−9181; (b) Lee, J.
W.; Kim, K.; Kim, K. Chem. Commun. 2001, 1042–1043; (c) Jones, J. W.;
Bryant, W. S.; Bosman, A. W.; Janssen, R. A. J.; Meijer, E. W.; Gibson, H. W. J.
Org. Chem. 2003, 68, 2385–2389; (d) Huang, F.; Switek, K. A.; Gibson, H. W.
Chem. Commun. 2005, 3655−3657; (e) Yen, M.-L.; Li, W.-S.; Lai, C.-C.; Chao,
I.; Chiu, S.-H. Org. Lett. 2006, 8, 3223–3226.
38. Xing, B.; Yu, C.-W.; Ho, P.-L.; Chow, K.-H.; Cheung, T.; Gu, H.; Cai, Z.; Xu, B.
J. Med. Chem. 2003, 46, 4904−4909.
39. For more details regarding this stoppering method, see: (a) Rowan, S. J.;
Cantrill, S. J.; Stoddart, J. F. Org. Lett. 1999, 1, 129 −132; (b) Chiu, S.-H.;
Rowan, S. J.; Cantrill, S. J.; Stoddart, J. F.; White, A. J. P.; Williams, D. J. Chem.
Eur. J. 2002, 8, 5170−5183.
40 加入各種金屬離子的方法為:先將金屬離子鹽類溶於CD3CN 溶液中,再
注入7·2PF6 分子的CD3CN 中,充分混合。
41 當我們使用離子半徑尺寸更大的Cs+離子,在相同的條件下與[2]車輪烷分
子7·2PF6 錯合時,同樣可以得到「快交換」的1H NMR 光譜。
42. Crystallographic data (excluding structure factors) for [(7⊃Na)·MeCN][3PF6]
has been deposited with the Cambridge Crystallographic Data Centre as
supplementary publication nos. CCDC-640451. Copies of the data can be
obtained free of charge upon application to CCDC, 12 Union Road, Cambridge
CB21EZ, UK [fax: (+44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk].
43 . Crystal data for [(7⊃Na)·MeCN][3PF6]: [C74H75O6N3P2Na][PF6]3; Mr =
1647.24; triclinic; space group P1; a = 10.2597(2); b = 14.8941(2); c =
26.3207(4) A; V = 3885.98 (11) A3; ρcalcd = 1.408 g cm–3; μ(MoKα) = 0.221
mm–1; T = 200(2) K; colorless plates; 13666 independent measured reflections;
F2 refinement; R1 = 0.1196; wR2 = 0.3203.
44 在這些條件下,無論是自由車輪烷分子或其與金屬離子的錯合物之溶液
中,我們沒有觀察到肉眼可見的顏色變化。
dc.identifier.urihttp://tdr.lib.ntu.edu.tw/jspui/handle/123456789/29499-
dc.description.abstract我們發現實驗室過去所發展的類冠醚大環分子可以辨識2,2’-bipyridine的衍生物,並以此新型分子辨識系統合成出新型的車輪烷分子。此一車輪烷分子對人體中的多種重要金屬離子皆表現出良好的鍵結能力,由於其對生理重要之金屬離子的錯合與解離的動力行為在1H NMR的實驗中為「慢交換」(slow-exchange)的情形,且不同錯合物之間亦具有可茲分辨的不同訊號。如此一來,在一次1H NMR實驗的光譜中即可同時偵測溶液中Li+, Na+, K+, Mg2+, Ca2+等人體重要金屬離子的存在與否。zh_TW
dc.description.abstractHerein, we describe a new rotaxane-based molecular recognition
system incorporating 2,2´-bipyridinium ions and crown ether-like
macrocycles. The 1H NMR spectra of the corresponding “neutral”
[2]rotaxane recorded in the presence of a mixture of the physiologically
important Li+, Na+, Mg2+, and Ca2+ ions feature distinct signals for each
of the complexes, with the chemical shifts of pertinent probe protons
identifying the chemical nature of each metal ion. That is to say, the
identification of these metal ions in solution is possible from the analysis
of a single 1H NMR spectrum of a single molecular sensor.
en
dc.description.provenanceMade available in DSpace on 2021-06-13T01:08:41Z (GMT). No. of bitstreams: 1
ntu-96-R94223068-1.pdf: 3555502 bytes, checksum: f2fb195b72ec58df1de79f6bf550104c (MD5)
Previous issue date: 2007
en
dc.description.tableofcontents目次
謝誌 I
摘要 II
Abstract III
論文發表 IV
目次 V
圖表 VII
流程 IX
表格 X
壹、導論 1
1.1 前言 1
1.2 超分子化學的起源 4
1.2.1 Pedersen的冠醚 4
1.2.2 Lehn的穴窩體 7
1.2.3 Cram的球形體 8
1.3 內鎖分子的歷史沿革 10
1.3.1 內鎖分子的定義 10
1.3.2 內鎖分子的合成方法 12
1.3.2.1 以統計法合成內鎖分子 12
1.3.2.2 以模版導引法合成內鎖分子 13
1.4 超分子系統的發展與應用 17
1.4.1 多電子的芳香環與缺電子的巴拉刈衍生物之超分子系統 17
1.4.2 二級胺鹽與冠醚之超分子系統 23
1.4.3 利用過渡金屬離子與有機配位基錯合之超分子系統 26
貳、結果與討論 31
2.1 研究動機 31
2.2 利用酸/鹼控制的分子開關 34
2.3 [2]車輪烷分子的合成 40
2.4 以[2]車輪烷分子為基礎的金屬離子感測器 41
參、結論 46
肆、實驗部份 47
伍、參考文獻 52
陸、附錄 55
dc.language.isozh-TW
dc.subject金屬離子感測器zh_TW
dc.subject車輪烷zh_TW
dc.subject超分子化學zh_TW
dc.subjectmetal ion sensoren
dc.subjectsupramolecular chemistryen
dc.subjectrotaxaneen
dc.title利用NMR以單一[2]車輪烷分子同時鑑定多種生理上
重要金屬離子之研究
zh_TW
dc.titleA [2]Rotaxane-based 1H NMR Spectroscopic Probe
for the Simultaneous Determination of
Physiologically Important Metal Ions in Solution
en
dc.typeThesis
dc.date.schoolyear95-2
dc.description.degree碩士
dc.contributor.oralexamcommittee徐秀福,賴建成
dc.subject.keyword超分子化學,車輪烷,金屬離子感測器,zh_TW
dc.subject.keywordsupramolecular chemistry,rotaxane,metal ion sensor,en
dc.relation.page55
dc.rights.note有償授權
dc.date.accepted2007-07-23
dc.contributor.author-college理學院zh_TW
dc.contributor.author-dept化學研究所zh_TW
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