期刊
JOURNAL OF PHYSICAL CHEMISTRY B
卷 110, 期 10, 页码 5132-5138出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp056411p
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The photophysical properties of the phenazine-based dye neutral red were investigated in aqueous solution in the presence of the macrocyclic host molecule cucurbit[7]uril (CB7) using ground-state absorption as well as steady-state and time-resolved fluorescence measurements. The results are contrasted to those previously obtained for beta-cyclodextrin (beta-CD; Singh et al. J. Phys. Chem. A 2004, 108, 1465). Both the neutral (NR) and cationic (NRH+) forms of the dye formed inclusion complexes with C137, with the larger binding constant for the latter (K = 6.5 x 10(3) M-1 versus 6.0 x 10(5) M-1). This result differed from that for -CD, where only the neutral form of the dye was reported to undergo sizable inclusion complex formation. From the difference in binding constants and the pK(a) value of protonated neutral red in the absence of CB7 (6.8), an increased pKa value of the dye when complexed by CB7 was projected (similar to 8.8). This shift differed again from the behavior of the dye with beta-CD, where a decreased pK(a) value (ca. 6.1) was reported. The photophysical properties of both NR and NRH+ forms showed significant changes in the presence of CB7. Fluorescence anisotropy studies indicated that the inclusion complexes of both forms of the dye rotate as a whole, giving rotational relaxation times much larger than that expected for the free dye in aqueous solution. The thermodynamic parameters for the NRH+-CB7 complex were investigated in temperature-dependent binding studies, suggesting an entropic driving force for complexation related to desolvation of the cation and the removal of high-energy water molecules from the CB7 cavity.
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