메뉴 건너뛰기




Volumn 121, Issue 35, 1999, Pages 8022-8032

An exceedingly long-lived fluorescent state as a distinct structural and dynamic probe for supramolecular association: An exploratory study of host- guest complexation by cyclodextrins

Author keywords

[No Author keywords available]

Indexed keywords

CYCLODEXTRIN DERIVATIVE;

EID: 0033536469     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja990626t     Document Type: Article
Times cited : (124)

References (62)
  • 2
    • 85001931066 scopus 로고    scopus 로고
    • Ramamurthy, V., Schanze, K. S., Eds.; Marcel Dekker Inc.: New York
    • Kleinman, M. H.; Bohne, C. In Molecular and Supramolecular Photochemistry; Ramamurthy, V., Schanze, K. S., Eds.; Marcel Dekker Inc.: New York, 1997; Vol. 1, pp 391-466.
    • (1997) Molecular and Supramolecular Photochemistry , vol.1 , pp. 391-466
    • Kleinman, M.H.1    Bohne, C.2
  • 4
    • 85069249073 scopus 로고    scopus 로고
    • note
    • Fluorescence quenching of pyrene and other polyaromatics has been extensively employed, however, for the indirect determination of micellar kinetics by using the method of external quenchers (cf. ref 2).
  • 14
    • 0033474997 scopus 로고    scopus 로고
    • Nau, W. M. Chimia 1999, 53, 217.
    • (1999) Chimia , vol.53 , pp. 217
    • Nau, W.M.1
  • 17
    • 0009153013 scopus 로고    scopus 로고
    • November Cologne
    • Presented in part at the Jahrestagung der GDCh-Fachgruppe Photochemie, November 1997, Cologne. Talk in print: Nau, W. M. J. Inf. Recording 1998, 24, 105-114.
    • (1997) Jahrestagung der GDCh-Fachgruppe Photochemie
  • 18
    • 0009153013 scopus 로고    scopus 로고
    • Presented in part at the Jahrestagung der GDCh-Fachgruppe Photochemie, November 1997, Cologne. Talk in print: Nau, W. M. J. Inf. Recording 1998, 24, 105-114.
    • (1998) J. Inf. Recording , vol.24 , pp. 105-114
    • Nau, W.M.1
  • 19
    • 0001753363 scopus 로고
    • Askani, R. Chem. Ber. 1965, 98, 2551-2555.
    • (1965) Chem. Ber. , vol.98 , pp. 2551-2555
    • Askani, R.1
  • 26
    • 0004297834 scopus 로고    scopus 로고
    • Hypercube, Inc.
    • HyperChem 5.0, Hypercube, Inc., 1996.
    • (1996) HyperChem 5.0
  • 38
    • 0010317917 scopus 로고
    • Horspool, W. M., Song, P.-S., Eds.; CRC Press: Boca Raton, FL
    • Weiss, R. G. In Organic Photochemistry and Photobiology; Horspool, W. M., Song, P.-S., Eds.; CRC Press: Boca Raton, FL, 1995; pp 471-483.
    • (1995) Organic Photochemistry and Photobiology , pp. 471-483
    • Weiss, R.G.1
  • 42
    • 84985451678 scopus 로고
    • DBO has been employed twice in the context of supramolecular chemistry, but the previous studies have nothing in common with the present application of DBO as a structural and dynamic fluorescent probe. In one study, singlet energy transfer from dimethylnaphthalene was examined in micelles (Aikawa, M.; Yekta, A.; Liu, J.-M.; Turro, N. J. Photochem. Photobiol. 1980, 32, 297-303), and in the second study photoproduct distributions in zeolites were analyzed (ref 23).
    • (1980) Photochem. Photobiol. , vol.32 , pp. 297-303
    • Aikawa, M.1    Yekta, A.2    Liu, J.-M.3    Turro, N.J.4
  • 43
    • 0004186990 scopus 로고
    • Wiley: London
    • Although pyrene is one of the few molecules whose fluorescence lifetime (ca. 435 ns in hexane, ref 40) approaches that of DBO, its application for the direct measurement of association rate constants has several disadvantages. These include its low water solubility (ref 15), its competitive excimer emission at concentrations above ca. 10 μM (ref 40), and a significant drop of the fluorescence lifetime upon derivatization due to the elevation of symmetry constraints (Birks, J. B. Photophysics of Aromatic Molecules; Wiley: London, 1970), e.g., to 120 ns in deaerated water for pyrene-1-butyrate (ref 15).
    • (1970) Photophysics of Aromatic Molecules
    • Birks, J.B.1
  • 48
    • 85069240706 scopus 로고    scopus 로고
    • note
    • A short survey of the literature is in order to substantiate this point. First, although the fluorescence of n,π*-excited ketones is generally too short-lived and too weak to allow practical exploitation, the steady-state fluorescence of n,π*-excited xanthone has been employed in one case to determine binding constants with cyclodextrins (ref 5). However, the short fluorescence lifetime of xanthone (ca. 0.6-0.8 ns in water, ref 9) precludes dynamic information and, moreover, the solvent dependence is not well understood (Bohne, C., personal communication). Second, compounds with n,π* configuration have been previously employed as fluorescent probes (ref 1), but in the reported examples it is actually not the n,π* state which is fluorescent, but a close-lying π,π* state; the latter becomes the lowest excited state in polar environments ("state switching").
  • 50
    • 0004283758 scopus 로고
    • Bertelsmann Universitätsverlag: Düsseldorf, Germany
    • Mauser, H. Formale Kinetik; Bertelsmann Universitätsverlag: Düsseldorf, Germany, 1974; p 88.
    • (1974) Formale Kinetik , pp. 88
    • Mauser, H.1
  • 51
    • 85069244336 scopus 로고    scopus 로고
    • note
    • Counterintuitively, although the association pathway for model 1 increases the concentration of CD·DBO* complexes, it reduces the apparent static preexponential factor associated with the decay of the CD·DBO* complexes.
  • 54
    • 33746190548 scopus 로고
    • 0] holds in a very good approximation. Note that low guest concentrations are often adjusted on purpose to allow simplified (since linearized) quantitative treatments, e.g., the so-called double-reciprocal Benesi- Hildebrand plots (Benesi, H. A.; Hildebrand, J. H. J. Am. Chem. Soc. 1949, 71, 2703-2710).
    • (1949) J. Am. Chem. Soc. , vol.71 , pp. 2703-2710
    • Benesi, H.A.1    Hildebrand, J.H.2
  • 55
    • 85069245409 scopus 로고    scopus 로고
    • note
    • 0) complex fluorescence (third term). The contributions due to the fluorescence from excited-state complexes (last two terms) need to be further multiplied by the efficiency factor R when dissociation of the excited-complexes becomes important (model 3); otherwise, R is unity.
  • 58
    • 85069244825 scopus 로고    scopus 로고
    • note
    • 2O solvent) and, thus, should display a significantly reduced reactivity. Moreover, the hydroxyl groups are located at the rim of the cavity, while DBO is deeply included in the cavity, as suggested by the NMR data.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.