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Volumn 69, Issue 13, 2004, Pages 4390-4402

Polyvalent interactions in unnatural recognition processes

Author keywords

[No Author keywords available]

Indexed keywords

ASSOCIATION REACTIONS; CHEMICAL BONDS; IONS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SYNTHESIS (CHEMICAL);

EID: 3042701770     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo030283o     Document Type: Article
Times cited : (29)

References (114)
  • 3
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    • Varki, A., Cummings, R., Esko, J., Freeze, H., Hart, G., Marth, J., Eds.; Cold Spring Harbor Laboratory Press: New York
    • (c) Essentials of Glycobiology; Varki, A., Cummings, R., Esko, J., Freeze, H., Hart, G., Marth, J., Eds.; Cold Spring Harbor Laboratory Press: New York, 1999.
    • (1999) Essentials of Glycobiology
  • 8
    • 0032769701 scopus 로고    scopus 로고
    • Statistical and chelate effects have been proposed to explain the "glycoside cluster effect" that has been observed in nature. See: (a) Pohl, N. L.; Kiessling, L. L. Synthesis 1999, 1515-1519.
    • (1999) Synthesis , pp. 1515-1519
    • Pohl, N.L.1    Kiessling, L.L.2
  • 13
    • 0001420002 scopus 로고    scopus 로고
    • (a) Roy, R. Polym. News 1996, 21, 226-232.
    • (1996) Polym. News , vol.21 , pp. 226-232
    • Roy, R.1
  • 33
    • 0037184773 scopus 로고    scopus 로고
    • For some of our recent publications in which the complexation of dibenzylammonium ions by DB24C8 has been exploited for the construction of mechanically interlocked molecules, see: (c) Elizarov, A. M.; Chiu, S.-H.; Stoddart, J. F. J. Org. Chem. 2002, 67, 9175-9181.
    • (2002) J. Org. Chem. , vol.67 , pp. 9175-9181
    • Elizarov, A.M.1    Chiu, S.-H.2    Stoddart, J.F.3
  • 76
    • 3042716260 scopus 로고    scopus 로고
    • note
    • Ion pairing was not taken into account for the calculation of all the association constants in this paper.
  • 86
    • 0000360638 scopus 로고    scopus 로고
    • Atwood, J. L., Davies, J. E. D., MacNicol, D. D., Vögtle, F., Eds.; Pergamon: Oxford, UK, Chapter 14
    • (b) MacNicol, D. D.; Downing, G. A. In Comprehensive Supramolecular Chemistry; Atwood, J. L., Davies, J. E. D., MacNicol, D. D., Vögtle, F., Eds.; Pergamon: Oxford, UK, 1996; Vol. 6, Chapter 14.
    • (1996) Comprehensive Supramolecular Chemistry , vol.6
    • MacNicol, D.D.1    Downing, G.A.2
  • 90
    • 3042800369 scopus 로고    scopus 로고
    • note
    • a cannot be determined easily by the single-point method.
  • 101
    • 3042713932 scopus 로고    scopus 로고
    • note
    • -1. See ref 11.
  • 103
    • 3042788715 scopus 로고    scopus 로고
    • note
    • Because of difficulties in integrating these spectra, we believe that the error limits are large. Additionally, there is probably some divergence from the ideal 1:1 binding isotherm because the δ values of some of the signals shift upon addition of increasing amounts of the crown ether. This divergence from the ideal behavior could be a consequence of competing equilibria, such as, for example, ion pairing between the dialkylammonium cation and its hexafluorophosphate anion.
  • 104
    • 3042759498 scopus 로고    scopus 로고
    • note
    • a, which results primarily from an assumed error of 10% in integrating signals in these complicated NMR spectra.
  • 105
    • 3042831475 scopus 로고    scopus 로고
    • note
    • AVE. The weakening of the ion-pairing interaction upon binding of the cationic centers could be a consequence of a bound cationic center having a more dispersed positive charge than an unbound one. This charge dispersal would result in reduced electrostatic charges between the hexacation and any anions. This changing strength of ion pairing may be a component of the effect of clustering multivalent cationic receptors.
  • 107
    • 0031585687 scopus 로고    scopus 로고
    • We have observed such interactions between dialkylammonium ions and hexafluorophosphate anions (usually [C-H⋯F] hydrogen bonds) in many solid-state structures of similar host-guest systems. See, for example: Ashton, P. R.; Fyfe, M. C. T.; Glink, P. T.; Menzer, S.; Stoddart, J. F.; White, A. J. P.; Williams, D. J. J. Am. Chem. Soc. 1997, 119, 12514-12524.
    • (1997) J. Am. Chem. Soc. , vol.119 , pp. 12514-12524
    • Ashton, P.R.1    Fyfe, M.C.T.2    Glink, P.T.3    Menzer, S.4    Stoddart, J.F.5    White, A.J.P.6    Williams, D.J.7
  • 108
    • 3042759497 scopus 로고    scopus 로고
    • note
    • + centers of the bis-(dialkylammonium) ion at a rate commensurate with that of the NMR time scale at 376 MHz. That is to say, the crown ether exists in discrete "bound" and "unbound" states (i.e., slow exchange) because its rate of passage over the 3,5-difluorophenyl units is slow, but within the 1:1 complex, the crown ether has less of a steric barrier for shuttling between the binding sites. This lower shuttling barrier, however, is not low enough to cause this process to be fast on the NMR time scale, and so at 376 MHz the two termini of the bis(dialkylammonium) ion are somewhat nonequivalent and, hence, their signals are broad.
  • 109
    • 3042757164 scopus 로고    scopus 로고
    • note
    • 2 (1:1) solvent mixture.
  • 110
    • 3042833842 scopus 로고    scopus 로고
    • note
    • -1). See ref 11.
  • 111
    • 3042716251 scopus 로고    scopus 로고
    • note
    • -1. See Table 1, entry 3.
  • 112
    • 3042838329 scopus 로고    scopus 로고
    • note
    • -1). See ref 11.
  • 113
    • 3042798045 scopus 로고    scopus 로고
    • note
    • 6), this effect does not change the conclusion that the binding strength of these systems differs only marginally.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.