A model for sequential threading of alpha-cyclodextrin onto a guest: a complete thermodynamic and kinetic study in water.
The first variable-temperature and variable-pressure stopped-flow spectrophotometric study of the sequential threading of alpha-cyclodextrin (alpha-CD) onto the guest dye Mordant Orange 10, S, is reported. Complementary (1)H one-dimensional (1D) variable-temperature kinetic studies and two-dimensional (2D) rotating-frame nuclear Overhauser effect spectroscopy (ROESY) and EXSY NMR studies are also reported. In aqueous solution at 298.2 K, the first alpha-CD threads onto S to form a 1:1 complex S.alpha-CD with a forward rate constant k(1,f) = 15 200 +/- 200 M(-1) s(-1) and dethreads with a reverse rate constant k(1,r) = 4.4 +/- 0.3 s(-1). Subsequently, S.alpha-CD isomerizes to S.alpha-CD (k(3,f) = 0.158 +/- 0.006 s(-1), k(3,f) = 0.148 +/- 0.006 s(-1)). This process can be viewed as a thermodynamically controlled molecular shuttle. A second alpha-CD threads onto S.alpha-CD to form a 1:2 complex, S.(alpha-CD)(2), with k(2,f) = 98 +/- 2 M(-1) s(-1) and k(2,r) = 0.032 +/- 0.002 s(-1). A second alpha-CD also threads onto S.alpha-CD to form another 1:2 complex, S.(alpha-CD)(2), characterized by k(4,f) = 9640 +/- 1800 M(-1) s(-1) and k(4,r) = 61 +/- 6 s(-1). Direct interconvertion between S.(alpha-CD)(2) and S.(alpha-CD)(2) was not detected; instead, they interconvert by dethreading the second alpha-CD and through the isomerization equilibrium between S.alpha-CD and S.alpha-CD. The reaction volumes, DeltaV(0), were found to be negative for the first three equilibria and positive for the fourth equilibrium. For the first three forward and reverse reactions, the volumes of activation are substantially more negative, indicating a compression of the transition state in comparison with the ground states. These data were used in conjunction with DeltaH, DeltaH degrees, DeltaS, and DeltaS degrees data to deduce the dominant mechanistic threading processes, which appear to be largely controlled by changes in hydration and van der Waals interactions, and possibly by conformational changes in both S and alpha-CD. The structure of the four complexes were deduced from (1)H 2D ROESY NMR studies.
Saudan
C
C
Institut de Chimie Minérale et Analytique, Université de Lausanne, CH-1015 Lausanne, Switzerland.
Dunand
F A
FA
Abou-Hamdan
A
A
Bugnon
P
P
Lye
P G
PG
Lincoln
S F
SF
Merbach
A E
AE
D001391:Azo Compounds / Q000737:chemistry*; D001555:Benzene Derivatives / Q000737:chemistry*; D004396:Coloring Agents / Q000737:chemistry*; D003505:Cyclodextrins / Q000737:chemistry*; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D013053:Spectrophotometry / Q000379:methods; D013816:Thermodynamics; D047391:alpha-Cyclodextrins
D001391:Azo Compounds; D001555:Benzene Derivatives; D004396:Coloring Agents; D003505:Cyclodextrins; C442774:Mordant Orange 10; D047391:alpha-Cyclodextrins; C032613:alpha-cyclodextrin