Antitumor activity and photoconductivity of photochemically-induced 12- and 28-electron reduced aggregates derived from [Mo7O24]6-

INOR 3

Toshihiro Yamase, tyamase@res.titech.ac.jp, Chemical Resources Laboratory, Tokyo Institute of Technology, R1-21 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503, Japan
ε-Keggin MoV12-core ({MoV12}) capped by four MoVIO3 units, prepared by the long-term photolysis of [Mo7O24]6- in aqueous solutions at pH 5-7, [H2MoV12O28(OH)12(MoVIO3)4]6- (1a), strongly inhibits human pancreatic cancer AsPC-1 cells with an involvement of both apoptosis and autophagy. Plausible pathways to 1a through conversion of four-electron reduced species, [MoV4Mo3O20(OH)4]6-, into six-electron reduced intermediate, {Mo9} (probably [MoV6Mo3O22(OH)6]2-), is proposed in terms of the dissociative aggregation of {Mo9} (2{Mo9}→{MoV12} + 2{MoVI3}). In conjunction with a good stability of 1a under the physiological condition, neither overt toxicity nor body weight loss for 1a -treated tumor-mice suggests that 1a is a promising candidate as a new type of antitumor agent. Furthermore, it is found that Mo-blue ring-derivatives ([MoV28MoVI114O429H10(H2O)49(MeCO2)5(EtCO2)]27-, for example), prepared by the photolysis of [Mo7O24]6- at pH <4, exhibit the photoconductivity due to d-band electrons in the lattice, which is interesting in construction of the nano-electronic device based on polyoxometalates.