Abstract:General synthetic methods for the grafting of peptide chains onto polyoxometalate clusters by the use of general activated precursors have been developed. Using a solution‐phase approach, pre‐synthesized peptides can be grafted to a metal oxide cluster to produce hybrids of unprecedented scale (up to 30 residues). An adapted solid‐phase method allows the incorporation of these clusters, which may be regarded as novel hybrid unnatural amino acids, during the peptide synthesis itself. These methods may open the … Show more
“…For increased specificity, click chemistry could be used 34 to conjugate cell-penetrating peptides to the POM to direct the payload to its desired location, further increasing the efficacy of the bioactive POM. 35 …”
The size and redox properties of molecular polyoxometalates (POMs) make them extremely relevant for bioapplications: from disrupting tumour growth and enzyme inhibition, to DNA-intercalating agents and antimicrobial applications. Their unique ability to reversibly dominate and receive electrons, coupled with their high anionic charge, also makes them suitable for the preparation of zero-valent state metal nanoparticles (NPs) from molecular precursors. Polyoxometalate-stabilised nanoparticles (NPs@POM) are therefore an ideal delivery vehicle for bioactive POMs. Here we show how POM-stabilised gold NPs (AuNPs@POM) are massively internalised into Vero (kidney epithelial) and B16 (skin melanoma) cell lines with variable cytotoxic effects. Cell viability assays and quantification of cytoplasmic membrane composition revealed that the Vero cell line was unaltered by the internalisation of these hybrid particles; while their internalisation in B16 tumour cells produced mild cytotoxic effects and an antiproliferative cell cycle arrest in the G0/G1 and G2/M phases. The observed perturbation of the tumour cell line combined with the high degree of internalisation means that these (or similar) NPs@POM could serve as candidates for a range of bioapplications in diagnostics or therapy.
“…For increased specificity, click chemistry could be used 34 to conjugate cell-penetrating peptides to the POM to direct the payload to its desired location, further increasing the efficacy of the bioactive POM. 35 …”
The size and redox properties of molecular polyoxometalates (POMs) make them extremely relevant for bioapplications: from disrupting tumour growth and enzyme inhibition, to DNA-intercalating agents and antimicrobial applications. Their unique ability to reversibly dominate and receive electrons, coupled with their high anionic charge, also makes them suitable for the preparation of zero-valent state metal nanoparticles (NPs) from molecular precursors. Polyoxometalate-stabilised nanoparticles (NPs@POM) are therefore an ideal delivery vehicle for bioactive POMs. Here we show how POM-stabilised gold NPs (AuNPs@POM) are massively internalised into Vero (kidney epithelial) and B16 (skin melanoma) cell lines with variable cytotoxic effects. Cell viability assays and quantification of cytoplasmic membrane composition revealed that the Vero cell line was unaltered by the internalisation of these hybrid particles; while their internalisation in B16 tumour cells produced mild cytotoxic effects and an antiproliferative cell cycle arrest in the G0/G1 and G2/M phases. The observed perturbation of the tumour cell line combined with the high degree of internalisation means that these (or similar) NPs@POM could serve as candidates for a range of bioapplications in diagnostics or therapy.
“…A Cu-catalyzed alkyne−azide cycloaddition reaction was then applied to link the clusters together forming linear oligomers in the nanometer range. Yvon et al [275] have reported the Mn III Mo 6 POM with 15 amino acids attached on each side of the POM. The modified properties of the inorganic diamine may be useful in both medical and nano-science research, in specific as recognition motifs and catalytically active sites where key amino acids may be replaced by POM amino acids.…”
Section: An Overview Of Tris-functionalized Hybrid Structuresmentioning
“…Among the various POMs, the organic derivatives of polyoxovanadates (POVs) have attracted increasing attentions due to their fascinating catalytic, magnetic properties as well as bioactivities [5][6][7][8]. The combination of POVs and amino acids may improve the bioactivities of the POVs and reduce their toxicity [9,10].…”
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