Supramolecular Complex of Cytochrome c with a Polyanionic β‐Cyclodextrin

Self Cite

Heat-capacity changes (deltaC(p)0) were determined for the complexation of 1-alkanecarboxylates with protonated hexakis(6-amino-6-deoxy)-alpha-cyclodextrin (per-NH3(+)-alpha-CD) and heptakis(6-amino-6-deoxy)-beta-cyclodextrin (per-NH3(+)-beta-CD). DeltaC(p)0 decreased with an increase in the binding constant (K) and plateaued at K = 4000 M(-1). The complexes of 1-pentanoate, 1-hexanoate, and 1-heptanoate with per-NH3(+)-alpha-CD are classified as the host-guest system in which the size of the guest fits the CD cavity well. In such a system, van der Waals interaction is the major force for complexation, leading to a negative deltaH0 value. Simultaneously, the water molecules around the hydrophobic alkyl chain of the guest and inside the CD cavity are released to the aqueous bulk phase, leading to a positive deltaS0 value. The negative deltaC(p)0 value in such complexation is ascribed to dehydration of the hydrophobic alkyl chain of the guest and extrusion of the water molecules inside the CD cavity. Meanwhile, the complexes that show positive deltaC(p)0 values are characterized by complexation in which the guest molecules are significantly smaller than the CD cavities. In such a case, the complexation is endothermic and driven by the entropy gain. When the guest is much smaller than the CD cavity, the main binding force should be Coulomb interaction. To form an ionic bond, dehydration of the charged groups must occur. This process is endothermic and leads to positive deltaH0 and deltaS0 values. As the top of the CD cavity is capped by a small but hydrophobic alkyl chain, the water molecules inside the CD cavity may form the iceberg structure. This process must be accompanied by a positive deltaC(p)0 value. Hence, the complexation of a small guest with the CD with a large cavity through Coulomb interactions shows positive and large deltaC(p)0 values. These conclusions were applied to the electrostatic binding of proteins with an anionic ligand.

Section: Resultssupporting

confidence: 78%

Section: Resultsmentioning

confidence: 99%

Heat‐Capacity Changes in Host–Guest Complexation by Coulomb Interactions in Aqueous Solution

Kawasaki¹,

Ishida²,

Kitagawa³

et al. 2007

Self Cite

“…Complex formation through electrostatic interaction in aqueous solution is usually driven by a favorable entropy term owing to dehydration from both host and guest. [15] These findings suggest that electrostatic interaction is not the sole binding force for the P1-V3 Ba-L and Fe III P1-V3 Ba-L systems. Although coordination of imidazole to iron porphyrins is an enthalpically favorable process, [16] the DH 0 (À62 kJ mol À1 ) for the Fe III P1-V3 Ba-L system was almost the same as that (À63 kJ mol À1 ) for the P1-V3 Ba-L system.…”

Section: Thermodynamic Parametersmentioning

confidence: 92%

“…Complexation of multivalent organic ions with oppositely charged ligands in aqueous solution commonly shows positive entropy changes. [15] Extended dehydration from both ions upon association is the origin of the positive DS 0 . As the complexation of both the anionic porphyrins with V3 IIIB having a net charge of +8 is still enthalpically dominated, van der Waals interaction also plays an important role.…”

Section: Thermodynamic Parametersmentioning

confidence: 99%

Binding of Multivalent Anionic Porphyrins to V3 Loop Fragments of an HIV‐1 Envelope and Their Antiviral Activity

Watanabe

Negi

Kiriyama

et al. 2010

Self Cite

Interactions of multivalent anionic porphyrins and their iron(III) complexes with cationic peptides, V3(Ba-L) and V3(IIIB), which correspond to those of the V3 loop regions of the gp120 envelope proteins of the HIV-1(Ba-L) and HIV-1(IIIB) strains, respectively, are studied by UV/Vis, circular dichroism, (1)H NMR, and EPR spectroscopy, a microcalorimetric titration method, and anti-HIV assays. Tetrakis(3,5-dicarboxylatophenyl)porphyrin (P1), tetrakis[4-(3,5-dicarboxylatophenylmethoxy)phenyl]porphyrin (P2), and their ferric complexes (Fe(III)P1 and Fe(III)P2) were used as the multivalent anionic porphyrins. P1 and Fe(III)P1 formed stable complexes with both V3 peptides (binding constant K>10(6) M(-1)) through combined electrostatic and van der Waals interactions. Coordination of the His residues in V3(Ba-L) to the iron center of Fe(III)P1 also played an important role in the complex stabilization. As P2 and Fe(III)P2 form self-aggregates in aqueous solution even at low concentrations, detailed analysis of their interactions with the V3 peptides could not be performed. To ascertain whether the results obtained in the model system are applicable to a real biological system, anti-HIV-1(BA-L) and HIV-1(IIIB) activity of the porphyrins is examined by multiple nuclear activation of a galactosidase indicator (MAGI) and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assays. There is little correlation between chemical analysis and actual anti-HIV activity, and the size rather than the number of the anionic groups of the porphyrin is important for anti-HIV activity. All the porphyrins show high selectivity, low cytotoxicity, and high viral activity. Fe(III)P1 and Fe(III)P2 are used for the pharmacokinetic study. Half-lives of these iron porphyrins in serum of male Wistar rats are around 4 to 6 h owing to strong interaction of these porphyrins with serum albumin.

Solubilization of Polycyclic Aromatics in Water by γ‐Cyclodextrin Derivatives

Wang

Wenz

2011

A series of hydrophilic per-6-thio-6-deoxy-γ-cyclodextrins (CDs) were synthesized from per-6-iodo-6-deoxy-γ-CD. These new hosts are able to solubilize polycyclic aromatic guests in aqueous solution to much higher extents than native CDs. Phase-solubility diagrams were mostly linear in accordance with both 1:1 and 1:2 CD-guest complexes in aqueous solution. The stoichiometry of the inclusion complexes was further investigated by fluorescence spectroscopy, which revealed very pronounced Stokes shifts typical for 1:2 complexes. This finding was further consolidated by quantum mechanical calculations of dimer formation of the guests and space-filling considerations by using the cross-sectional areas of the CDs and guests. The calculated dimerization energies correlated well with the binding free energies measured for the 1:2 complexes, and provided the main contribution to the driving force of complexation in the γ-CD cavity.