Synthesis,Characterization,CO Releasing Properties And Bioactivities Of Mn And Ru Metal Carbonyl Complexes With Nheterocyclic Ligand And The Composites Of Ru Carbonyl Complexes With Hydrogels And Upconversion Nanoparticles

Similar to NO,a suitable concentration of CO has good application prospects in inhibiting coronary vasoconstriction,lowering blood pressure,inhibiting tumor cell proliferation,treating cardiovascular,respiratory and digestive diseases and organ transplant protection.And N-containing heterocyclic compounds are widely used in anti-inflammatory and anti-cancer fields.In this work,7 organic ligands（L₁-L₇）were synthesized:bis（pyridin-2-yl）methane(L₁),bis（pyrazol-2-yl）methane（L₂）,2-[（1H-pyrazole-1-yl）methyl]pyridine（L₃）,5-methyl-2-1-（2-pyridyl）-1H-pyrazol-3-yl]phenol（L₄）,5-methoxy-2-[1-（2-Pyridyl）-1H-pyrazol-3-yl]phenol（L₅）,1-pyridine-3-（4-methoxyphenyl）pyrazole-5-carboxylic acid ethyl ester（L₆）,3-[3-（4-methoxy Phenyl）pyrazol-5-yl]-4-（4-nitrobenzylidene）imino-5-mercapto-1,2,4-triazole（L₇）.Secondly,we synthesized 14 new Ru,Mn carbonyl compounds 1-14 using hydrothermal or reflux methods to react L₁-L₇ with[Ru（CO）₃Cl₂]₂ and Mn（CO）₅Br,respectively.The structures of these compounds were investigated by FT-IR,(¹H/¹³C)NMR,and X-ray single crystal diffraction.The ultraviolet-visible spectra were used to explore the CO release properties and the results showed that the 14 compounds have good CO release properties.The results of MTT and Western blot showed that complexes 1,5,8 could inhibit the proliferation of tumor cells.The decrease of bax/bcl-2 ratio indicated that carbonyl compounds could induce apoptosis of cancer cells,and the apoptosis was caused by intrinsic factors.Finally,CS-PVA@CORM,UCNP@CORM were constructed by reactions Ru metal carbonyl complexes 1 and 5 with good CO release properties with CS-PVA and UCNP,respectively.The CO release ability and biological activity of these compounds were investigated to expand the application range of transition metal carbonyl compounds.It is found that the hydrogel loading system can improve the targeting and biocompatibility of drug release..The UCNP@CORM complex has the ability to release CO at 980nm,what can be applied to PDT collaborative therapy research.