The Binding Ability and Inclusion Complexation Behavior of Curcumin with Natural α-, β-, γ-Cyclodextrins and Organoselenium-Bridged Bis(β-cyclodextrin)s

Abstract

Abstract: Aim To investigate quantitatively the binding ability and inclusion complexation behavior of curcumin with natural α-, β-, γ-cyclodextrins (1-3) and a series of organoselenium-bridged bis (β-cyclodextrin) s with simple spacer (4-6). Methods The spectrophotometric titrations have been performed in KCl-HC1 buffer solution (pH = 2.0) at 25 °C to calculate the complex stability constants (Ks) and Gibbs free energy changes (ΔG°) for the stoichiometric 1: 1 inclusion complexation of 1-6 with curcumin. Results The binding ability of β-cyclodextrin for inclusion complexation with guestcurcumin is higher than that of a-and γ-cyclodextrins. As compared with parent β-cyclodextrin, the organoselenium bridged bis (β-cyclodextrin) s tethered by some functional groups can further enhance the original molecular binding ability through cooperative binding of one curcumin molecule in the closely located two cyclodextrin cavities, showing the enhanced binding abilities of parent β-cyclodextrin by a factor 2.8-17.1. Conclusion Size/shape fit and hydrophobic interaction between host cyclodextrins and guest curcumin molecule are the important factors affecting the binding ability and inclusion complexation behavior of these cyclodextrins 1- 6.

Key words: curcumin, curcumin, modified cyclodextrin, modified cyclodextrin, molecular recognition, molecular recognition, inclusion complexation, inclusion complexation

CLC Number:

R913

O648.2

Supporting:

QI Ai-di, LI Li, LIU Yu^*. The Binding Ability and Inclusion Complexation Behavior of Curcumin with Natural α-, β-, γ-Cyclodextrins and Organoselenium-Bridged Bis(β-cyclodextrin)s[J]. .

References

[1] Jovanovic SV, Steenken S, Boone CW, et al. H-atom transfer is a preferred antioxidant mechanism of curcumin [J]. J Am Chem Soc, 1999, 121 (41): 9677-9681.
[2] Xue Y, Xia T and Zhao JB. Progress in the anti-cancer mechanism of curcumin [J]. Chin Tradit Herb Drugs, 2000, 31 (2): 150-153.
[3] Hedges R. Industrial applications of cyclodextrins [J]. Chem Rev, 1998, 98 (5): 2035-2044.
[4] Harada A. Cyclodextrin2based molecular machines [J]. Acc Chem Res, 2001, 34 (6): 456-464.
[5] Liu Y, Chen Y, Li B, et al. Cooperative multipoint recognition of organic dyes by bis (β-cyclodextrin) s with 2,2’- bipyridine-4, 4’-dicarboxy tethers [J]. Chem Eur J, 2001, 7 (12): 2528-2535.
[6] Liu Y, Chen Y, Li L, et al. Cooperative multiple recognition by novel calix[4] arene-tetheredβ-cyclodextrin and calix[4] arene-bridged bis(β-cyclodextrin) [J]. J Org Chem, 2001, 66 (21): 7209-7215.
[7] Liu Y, Chen Y, Li L, et al. Bridged bis(β-cyclodextrin) s possessing coordinated metal center (s) and their inclusion complexation behavior with model substrates : enhanced molecular binding ability by multiple recognition [J]. J Org Chem, 2001, 66 (25): 8518-8527.
[8] Liu Y, You CC, Wada T, et al. Molecular recognition studies on supramolecular systems. 22. Size, shape, and chiral recognition of aliphatic alcohols by organoselenium-modified cyclodextrins [J]. J Org Chem, 1999, 64 (10): 3630-3634.
[9] Clark JL and Stezowski JJ. Molecular recognition in cyclodextrin complexes of amino acid derivatives. 1. Crystallographic studies of β-cyclodextrin complexes with N-acetyl-L-phenylalanine methyl ester and N-acetyl-L-phenylalanine amide pseudopeptides [J]. J Am Chem Soc, 2001, 123 (40): 9880-9888.
[10] Liu Y and Kang SZ. Molecular recognition on supramolecular systems (XXXV)-systhesis ofβ-cyclodextrin derivative bearing pyridinio group and its chiral discrimination of amino acids [J]. Sci Chin Ser B: Chem, 2001, 44 (3): 260-267.
[11] Liu Y, Li B, Wada T, et al. Fluorometric studies on inclusion complexation of L/D-tryptophan byβ-cyclodextrin 6-O-pyridinecarboxylates [J]. Bioorg Chem, 2001, 29: 19-26.
[12] Uekama K, Hirayama F and Irie T. Cyclodextrin drug carrier systems [J]. Chem Rev, 1998, 98 (5): 2045-2076.
[13] Szente L, Mikuni K, Hashimoto H, et al. Stabilization and solubilization of lipophilic natural colorants with cyclodextrins [J]. J Inclusion Phenom Mol Recognit Chem, 1998, 32 (1): 81-89.
[14] Liu Y, Li B, Wada T, et al. The novel o-phenylenediseleno bridged β-cyclodextrins complexes with platinum (IV) and palladium (II) ions [J]. Supramol Chem, 1999, 10 (4): 279-285.
[15] Liu Y, You CC, Chen Y, et al. Molecular recognition studies on supramolecular systems. 25. Inclusion complexation by organoselenium-bridged bis (β-cyclodextrin) s and their platinum (IV) complexes [J]. J Org Chem, 1999, 64 (21): 7781-7787.
[16] Liu Y, Li B, You CC, et al. Molecular recognition studies on supramolecular systems. 32. Molecular recognition of dyes by organoselenium-bridged bis (β-cyclodextrin) s [J]. J Org Chem, 2001, 66 (1): 225-232.
[17] Petter RC, Salek JS, Sikorski CT, et al. Cooperative binding by aggregated mono-6-(alkylamino)-β-cyclodextrins [J]. J Am Chem Soc, 1990, 112 (10): 3860-3868.
[18] Sandman DJ, Allen GW, Acampora LA, et al. Nickel, cobalt, and copper complexes of o-benzenediselenolate : synthesis and structural and magnetic properties [J]. Inorg Chem, 1987, 26 (11): 1664-1669.
[19] (a) Kajtár M, Horvath-Toro C, Kuthi E, et al. A simple rule for predicting circular dichroism induced in aromatic guests by cyclodextrin hosts in inclusion complexes [J]. Acta Chim Acad Sci Hung, 1982, 110: 327-355. (b) Harata K, Uedaira H. The circular dichroism spectra of theβ-cyclodextrin complex with naphthalene derivatives [J]. Bull Chem Soc Jpn,1975, 48 (2): 375-378.
[20] Inoue Y, Yamamoto K, Wada T, et al. Inclusion complexation of (cyclo) alkanes and (cyclo) alkanols with 6-O-modified cyclodextrins [J]. J Chem Soc Perkin Trans 2, 1998, 1807-1816.