The Synthesis And Medical Activity Of Amino Acid Functionalized Polymolybdates

Polyoxometalates(POMs)are a class of large-sized anionic metal clusters formed by the transition metal in the highest oxidation state,which exhibit different topologies and adjustable properties that have been widely used in catalysis,materials science,magnetic and medical fields.The functionalization of polyoxometalates with organic ligands makes the structure and type of polyoxometalates more novel and diverse,and the change of the structure of polyoxometalates can bring about the change in property and can be better applied in various scientific fields.In this paper,?-alanine and glycine-functionalized heteropolymolybdates were synthesized,and metal cations were selectively introduced to obtain a series of new amino acid-functionalized inorganic-organic hybrid polyoxometalates.The compounds were characterized by elemental analysis,IR,UV,TG analysis,X-ray single crystal diffraction,and powder X-ray diffraction in order to confirm their composition and structure,and the inhibitory activity of these compounds against human tumor cells was studied.It mainly includes the following two parts:1.Four inorganic-organic hybrid compounds were successfully prepared by the combination of the ?-alanine-functionalized arsenomolybdates [As Mo6O21(Ala)3]3-as building block with rare earth ions Ce3+,Nd3+,Sm3+,and Gd3+:[Ce(Ala)(H2O)5][As Mo6O21(Ala)3]·11.5H2O(1)[Nd(Ala)(H2O)5][As Mo6O21(Ala)3]·11.5H2O(2)[Sm(Ala)(H2O)5][As Mo6O21(Ala)3]·12H2O(3)[Gd(Ala)(H2O)5][As Mo6O21(Ala)3]·12H2O(4)These four compounds are isostructural and are dimeric structures obtained by combining two [As Mo6O21(Ala)3]3-clusters with dinuclear [Ln2(Ala)2(H2O)10]6+.The results of anti-tumor experiments in vitro of these four compounds indicated that all these POM compounds enhanced the inhibitory activity of parent polyoxometalates on K562 cells,while the POMs compound containing Ce3+ exhibited the highist activity against human leukaemia cells K562;We further studied the inhibitory activity of these four compounds on human breast cancer cells MCF-7,the results showed that the compound 3 containing Sm3+ exhibited the best anticancer activity and was significantly better than the parent polyoxometalates compound.These results indicate that the anti-tumor activity of the parent POM compound can be effectively regulated by the interaction between rare earth ions and amino acid-functionalized polyoxometalates.2.Two inorganic-organic hybrid species were obtained by the combination of the?-alanine-functionalized [Se Mo6O21(Ala)3]2-and glycine-functionalized [Se Mo6O21(gly)3]2-as polyoxometalates precursors with metal cations:Cs1.5H2.5[SeMo6O21(O2C(CH2)2NH3)3SeMo6O21]·14.5H2O(5)Cs2Cu[SeMo6O21(O2C(CH2)NH3)3SeMo6O21]·9H2O(6).Compound 5 is a novel amino acid-functionalized polymolybdates formed by the covalent linking of alanine to the [Se2Mo12O42]4-unit;compound 6 is a new functionalized cluster which formed by the covalent attachment of glycine to the [Se2Mo12O42]4-anion.This kind of amino acid-functionalized polyoxometalates cluster was synthesized for the first time.The two compounds were characterized by elemental analysis,IR,UV,TG analysis,X-ray single crystal diffraction,and powder X-ray diffraction.