Ca. Haskard et al., FORMATION OF L)AMINO)ETHYL)AMINO)-6(A)-DEOXY-BETA-CYCLODEXTRINS AND THEIR COMPLEXATION OF TRYPTOPHAN IN AQUEOUS-SOLUTION, Inorganic chemistry, 35(4), 1996, pp. 1059-1064
A pH titration study shows that no)ethyl)amino)-6(A)-deoxy-beta-cyclod
extrin)(beta CDtren) forms binary metallocyclodextrins, [M(beta CDtren
)](2+), for which log(K/dm(3) mol(-1)) = 11.65 +/- 0.06, 17.29 +/- 0.0
5, and 12.25 +/- 0.03, respectively, when M(2+) = Ni2+, Cu2+, and Zn2, where K is the stability constant in aqueous solution at 298.2 K and
I = 0.10 mol dm(-3) (NaClO4). The ternary metallocyclodextrins [M(bet
a CDtren)Trp](+), where Trp(-) is the tryptophan anion, are characteri
zed by log(K/dm(3) mol(-1)) = 8.2 +/- 0.2 and 8.1 +/- 0.2, 9.5 +/- 0.3
and 9.4 +/- 0.2, and 8.1 +/- 0.1 and 8.3 +/- 0.1, respectively, where
the first and second values represent the stepwise stability constant
s for the complexation of (R)- and (S)-Trp(-), respectively, when M(2) = Ni2+, Cu2+, and Zn2+. From comparisons of stabilities and UV-visib
le spectra, the binary and ternary metallocyclodextrins appear to be s
ix-coordinate when M(2+) = Ni2+ and Zn2+ and five-coordinate when M(2) = Cu2+. The factors affecting the stoichiometries and stabilities of
the metallocyclodextrins, are discussed and comparisons are made with
related systems.