Aliphatic Organoimido Derivatives of Polyoxometalates Containing a Bioactive Ligand

Abstract

A series of aliphatic organoimido derivatives of hexamolybdate based on amantadine, namely (nBu4 N)2 [Mo6 O18 (NC10 H15 )] (1), (nBu4 N)2 {cis-[Mo6 O17 (NC10 H15 )2 ]} (2), (nBu4 N)2 {trans-[Mo6 O17 (NC10 H15 )2 ]} (3), and (nBu4 N)2 [Mo6 O16 (NC10 H15 )3 ] (4), was synthesized in reasonable yield by dehydration with N,N'-dicyclohexylcarbodiimide (DCC). They were characterized by IR and UV/Vis spectroscopy, elemental analysis, ESI mass spectrometry, and single-crystal X-ray structure analysis. The spectral and structural similarities and differences between monosubstituted, cis-disubstituted, and trans-disubstituted organoimido derivatives were elucidated and may provide guidance for related work on organoimido-functionalized Lindqvist-type polyoxometalates. In addition, trans-disubstituted and polysubstituted derivatives containing aliphatic organoimido ligands have not yet been reported, and the crystal structure of the trans isomer may lead us to a deeper understanding of disubstituted derivatives. Furthermore, proliferation and morphology of MCF-7 cells were studied with compound 1. The present results show that the DCC-dehydrating protocol could be an efficient approach to covalently graft bioactive ligands such as amantadine onto POMs and enhance their application in clinical cancer treatment.

The Synthesis and Biological Function of a Novel Sandwich‐Type Complex Based on {SbW9} and Flexible bpp Ligand

“…Some inorganic polyxotungstates (POM) such as [Mo 7 O 24 ] 6− , [V 15 O 36 (CO 3 )] 7− , [PTi 2 W 10 O 40 ] 9− , [P 2 W 18 O 62 ] 6− , [(VO) 3 (SbW 9 O 33 ) 2 ] 9− , and [(WO 2 ) 4 (AsW 9 O 33 ) 4 ] 28− were summarized by Yamase and listed in Table S1 (Supporting Information). With the development of POM and modified chemistry, POM could be covalently linked with the organic groups or biological macromolecules, which have the targeting recognition on human body, resulting in changes of POM surface charge distribution to enhance the target recognition and drug activities . Isopoly Mo series modified by orgnaophosphorus could inhibit the growth of lung cancer NCI‐H460 cells, breast cancer MCF‐7 cells, and nervous central cancer SF‐268 cells, leading to being interested by many researchers .…”

Nanocomposites of Polyoxometalates and Chitosan‐Based Polymers as Tuneable Anticancer Agents

“…Despite the growing number of such bio‐active POMs, their clinical applications still remain to be explored, because their selectivity, toxicity and stability at physiological conditions need to be controlled individually. Drug carriers, such as liposomes or biocompatible polymeric matrices made of starch, chitosan,, and – as in our recent study – its derivative carboxymethyl chitosan were applied to reduce POM toxicity while enhancing their selectivity.…”

Non‐Aqueous Microwave‐Assisted Syntheses of Deca‐ and Hexa‐Molybdovanadates

“…[3][4][5][6][7][8][9][10][11] Historically the compositional diversification of POMs has been achieved via:reaction of stoichiometric mixtures of the desired constituents in pH controlled media;the addition of electrophiles to preformed plenary or lacunary POMs;o r the covalent functionalization of the POM surface by organic moieties. [12][13][14][15][16][17][18][19][20][21][22][23][24] Often the precise atomic ratios of early transition metals in the products can be controlled, however, occasionally the solution chemistry is sufficiently complex that separation and structural characterization of all products is not possible.[ 3À species". Furthermore,t he resulting arrangement of heteroatoms in POMs bearing oxo ligands of varying basicity and hence propensities for protonation has been utilized over many years.T his enables the direct functionalization of the molecular metal oxide surface by av ariety of alkoxo species resulting in inorganic-organic hybrids with ahost of applications.…”