Synthesis,CO Sustained-Release And Bioactivity Of Water-Soluble Mn,Ru Carbonyl CORMs And Mn-CORMs@ Nanomotors

As an important cellular signaling molecule,Carbon Monoxide Releasing Molecules(CORMs)in vivo have attracted much research interest in the past decades for their capacity of regulating cellular functions and tumor micro-environment in many aspects.In addition,the micro/nano motors,as a newly-developing carrier,can undertake the arduous assignments of transporting goods from one side to the other side in which condition with or without fuels.It can move into the cell environment through self-propel and penetrate mode at the speed of surpass Brownian Motion,and has primarily application prospects in biomedicine fields such as biosensing,cell manipulation,and drug delivery.Transition metal carbonyl compounds,which contain numerous carbanyl groups,have good degree of stability and can provide CO through partly directed p Harmaceutical preparations.They have the advantages of easy control of dosing interval timing,dose dependency and dose rate,so often used in CORMs research.Aminoacid,as the building blocks of proteins,have good biocompatibility.Base on the above,a series of water-soluble Mn and Ru carbonyl CORMs were prepared by introducing small molecule aminoacid ligands into Mn and Ru carbonyl complexes.Combined with micro/nano motors,the CO slow-release and biological activity of CORMs@nanomoters composite system were investigated.The main work in this paper is as follows:In this study,D-glutamic acid(L1),D-aspartic acid(L2),L-serine(L3)and L-methoserine(L4)were used as ligand to react with manganese bromide pentacarbonyl and ruthenium chloride,respectively,to synthesize 8 Mn and Ru carbonyl complexes MnL1,MnL2,MnL3,MnL4,RuL1,RuL2,RuL3 and RuL4.The structures of these complexes were characterized by Fourier transform infrared spectra,¹H NMR and UV-Vis absorption spectra.It was also found that the prepared complexes had good water solubility.The CO slow-release properties of these complexes were studied by UV-Vis absorption spectra via myoglobin experiment using 365 nm UV light,465 nm blue light,520 nm green light as irradiation source.The results show that eight water-soluble CORMs are able to show good CO release properties,including MnL3 under blue light,release most CO 55.02?M has a half-life of 2025 s.Secondly,MTT was used to study the biocompatibility of Mn carbonyl complex.The results showed that MnL2 showed a relatively good tumor cell inhibition rate at 120?M.Finally,two different kinds of nanomotors,Pt-HSiO₂ motor and Au-UCNPs@SiO₂ motor were prepared.Their structures were characterized by scanning electron microscopy(SEM),transmission electron microscopy(TEM)and particle size analyzer.MnL1 and MnL2 CORMs were selected to load on the prepared motor,and the biocompatibility of the two kinds of loaded CORMs motors was also tested by MTT.The Pt-HSiO₂ motor driven by hydrogen peroxide can move at a speed of 9.085?m?s^-1 at 1.5%hydrogen peroxide,and the p Hotothermal driven Au-UCNPs@SiO₂ motor can move at a speed of 7.355?m?s^-1.CORM@Pt-HSiO₂,Na@SiO₂ and Na@SiO₂ all showed excellent killing effect on cancer cells,which may be due to the introduction of nanomotor to improve the distribution range of CO in cancer cells.