Kinetic analysis of superoxide anion radical-scavenging and hydroxyl radical-scavenging activities of platinum nanoparticles

There are few reports on the physiological effects of metal nanoparticles (nps), especially with respect to their functions as scavengers for superoxide anion radical (O2(.-)) and hydroxyl radical (.OH). We tried to detect the scavenging activity of Pt nps using a hypoxanthine-xanthine oxidase system for O2(.-) and using a Fenton and a UV/H2O2 system for .OH. Electron spin resonance analysis revealed that 2 nm particle size Pt nps have the ability to scavenge O2(.-) and .OH. The calculated rate constant for the O2(.-)-scavenging reaction was 5.03 +/- 0.03 x 10(7) M (-1) s (-1). However, the analysis of the Fenton and UV/H 2O 2 system in the presence of Pt nps suggested that the .OH-scavenging reaction cannot be determined in both systems. Among particle sizes tested from 1 to 5 nm, 1 nm Pt nps showed the highest O2(.-)-scavenging ability. Almost no cytotoxicity was observed even after adherent cells (TIG-1, HeLa, HepG2, WI-38, and MRC-5) were exposed to Pt nps at concentrations as high as 50 mg/L. Pt nps scavenged intrinsically generated reactive oxygen species (ROS) in HeLa cells. Additionally, Pt nps significantly reduced the levels of intracellular O2(.-) generated by UVA irradiation and subsequently protected HeLa cells from ROS damage-induced cell death. These findings suggest that Pt nps may be a new type of antioxidant capable of circumventing the paradoxical effects of conventional antioxidants.     

γ‐Cyclodextrin as Inhibitor of the Precipitation Reaction between Berberine and Glycyrrhizin in Decoctions of Natural Medicines: Interaction Studies of Cyclodextrins with Glycyrrhizin and Glycyrrhetic Acid by 1H‐NMR Spectroscopy and Molecular‐Dynamics Calculation

To prevent the precipitation reaction between glycyrrhizin ( 1 ) and berberine ( 3 ) in the decoctions of Glycyrrhiza/Coptis rhizome or Glycyrrhiza/Phellodendron bark, the presence of cyclodextrin (CD) in the mixture was proven to be effective. The preventing effect decreased in the order γ‐CD>β‐CD, and no effect was observed for α‐CD. On the other hand, the extraction degree of 1 from the natural medicine Glycyrrhia was considerably increased in the presence of γ‐CD, γ‐CD being much more effective than α‐ or β‐CD. Thus, the blocking effect of CD on the precipitate formation between 1 and 3 is suggested to be primarily dependent on the stability of the inclusion complex of the CD with 1 . To establish the structure of such a preferred inclusion complex, the interactions of 1 with β‐ and γ‐CDs were investigated by ¹H‐NMR spectroscopy and molecular‐dynamics (MD) calculations. The ¹H‐NMR measurements showed that the increase in solubility of 1 in H₂O is dependent on the degree of its inclusion into the CD, which depends on the molecular size of the CD. The MD calculations suggested that the H‐bond interactions are sufficiently strong to form a stable [ 1 /γ‐CD] complex, in which the lipophilic rings C, D, and E of 1 are fully inserted into the molecular cavity of γ‐CD, thus forming a kind of structure covered by a hydrophilic molecular capsule, while such an interaction mode is impossible for α‐ or β‐CD.     

Thermoresponsive shuttling of rotaxane containing trichloroacetate ion

A thermoresponsive rotaxane shuttling system was developed with a trichloroacetate counteranion of an ammonium/crown ether-type rotaxane. Chemoselective thermal decomposition of the ammonium trichloroacetate moiety on the rotaxane yielded the corresponding nonionic rotaxane accompanied by a positional change of the crown ether on the axle. The rotaxane skeleton facilitated effective dissociation of the acid, markedly lowering the thermal decomposition temperature.     

Reversible helix-random coil transition of poly(m-phenylenediethynylene) by a rotaxane switch

Pendant rotaxane switch-tethering poly(m-phenylene diethynylene) was synthesized by the polyoxidative coupling of a rotaxane containing an axle-terminal m-diethynylbenzene group and an optically active crown ether. The reversible helix-random coil transition of the polymer was successfully performed by the positional switching of the rotaxane wheel.     

Electronic structure and kinetic behavior of 4-(cycloheptatrienylidene)cyclohexa-2,5-dienone (or [6.7]Quinaren-9-one) and its derivatives)

The conjugative interaction between the two terminal groups in title quinarenone 2 and its chloro- and methoxy-derivatives were evaluated, proving that the diatropicity of the seven-membered ring is a little larger in 2 than in tropone. Some of these quinarenones are also found to exist in equilibrium with their oligomers and show unexpectedly low barriers of rotation about the intercyclic bond.