Static and Dynamic Behavior of 2:1 Inclusion Complexes of Cyclodextrins and Charged Porphyrins in Aqueous Organic Media

Abstract

Two heptakis(2,3,6-tri-O-methyl)-beta-cyclodextrin (TMe-beta-CD) molecules strongly include the peripheral substituents at the 5- and 15-positions of the charged meso-tetrasubstituted porphyrins, PorSub(4) [TPPS(4) (Sub = p-C(6)H(4)-SO(3)(-)), TPPOC3PS (p-C(6)H(4)-O-(CH(2))(3)-p-C(6)H(4)-SO(3)(-)), TCPP (Sub = p-C(6)H(4)-CO(2)(-)), and TPPOC3Py (p-C(6)H(4)-O-(CH(2))(3)-Py(+)Br(-)), where Py(+) = N-alkylpyridinium] in aqueous ethylene glycol. The binding constants (K(1) and K(2)) and the rate constants (k(1) and k(2)) for formation of the 1:1 and 2:1 complexes of TMe-beta-CD and PorSub(4) were determined. Both the binding constants and the rate constants for anionic TPPS(4), TCPP, and TPPOC3PS were much larger than those for cationic TPPOC3Py. The smaller k(1) and k(2) values for TPPOC3Py indicate a higher barrier for penetration of a cationic guest into the TMe-beta-CD cavity. The methyl groups at the rims and the cavity wall of the host are positively polarized due to the inductive effect of the ethereal oxygens. The positively polarized rims and interior of the host cavity should prevent the penetration of the cationic substituent of TPPOC3Py into the TMe-beta-CD cavity. The 2:1 TMe-beta-CD-PorSub(4) complexes are extraordinary stable in aqueous solutions, even in the case of cationic TPPOC3Py. Formation of both 1:1 and 2:1 complexes is promoted by negative and large enthalpy changes, suggesting a strong van der Waals interaction as the main binding force.

Iron(II)porphyrin–Cyclodextrin Supramolecular Complex as a Carbon Monoxide-Depleting Agent in Living Organisms

“…Per-O-methylated CD derivatives strongly interact with anionic porphyrins such as meso-tetrakis(4-sulfonatophenyl)-porphyrin (TPPS) to form 2 : 1 inclusion complexes in aqueous solution. [19][20][21] In 1996, Kano et al first reported the 1 : 2 inclusion complex of TPPS with 2,3,6-tri-O-methyl-β-cyclodextrin (TMe-β-CD, Fig. 2).…”

β-Cyclodextrin as a Metal-anionic Porphyrin Complexation Accelerator in Aqueous Media

“…rate constants between TPPS4 and β-CD in ethylene glycol-H2O (3:1) was previously reported). 56,57 The free-base TPPS4 was immediately incorporated by β-CD in aqueous solution to form the inclusion complex, TPPS4-(β-CD)2. The solubility of β-CD in water is lower than that of other CD (cf.…”

Poly(epsilon caprolactone)/clay nanocomposites via host–guest chemistry

“…The most important feature of such cyclic structures is a hydrophobic inner cavity and a hydrophilic outer surface, hence their ability to form non-covalent inclusion complexes with organic [34], inorganic [35], biological molecules [36] or supramolecular aggregates [37,38]. The main factors acting as driving force to form host-guest complexes and their stabilities are hydrophobic forces, the sizes of molecules/cavity and the guest properties.…”