Polyesters,as a class of high-performance and versatile polymer materials,often suffer from some drawbacks,such as hydrophobicity and brittleness due to their single structure nature.Thus,modifications have attracted ...Polyesters,as a class of high-performance and versatile polymer materials,often suffer from some drawbacks,such as hydrophobicity and brittleness due to their single structure nature.Thus,modifications have attracted much attention for enhancing their desirable properties,of which one efficient way is incorporating the aliphatic polyether segment into the main chain of the polyester.However,this approach is of much challenge because the obtained polyesters are problematic in either low alternating degree or low molecular weight.Herein,we describe an efficient strategy to incorporate polyether fragment into polyester by developing a novel Co-Al based heterodinuclear complex for mediating the copolymerization of propylene oxide(PO)withε-caprolactone(CL).The tracking experiments reveal that PO and CL convert into the polymer chain throughout the polymerization process.Especially,the linear increase in the molecular weight with conversion of CL indicates the controllable nature of the copolymerization.The competition polymerization,offering the monomer reactivity ratios of rCL=0.96 and rPO=1.04,suggests that the tendency of self-propagation or incorporation of monomers is nearly identical.interestingly,the obtained polymers with different ether contents exhibit tunable thermal properties with enhanced decomposition temperature for the polymer with higher ether content.The newly developed heterodinuclear complex for new polymerization provides an idea to synthesize new functional polymeric materials.展开更多
Some reactions of R3SnM（CO）5 （M = Mn, Re） with CH3CN or pyridine were investigated to give complexes R3SnMn（CO）3LL＇ or R3SnMn（CO）4L by a facile mild method. X-ray diffractions analyses show that, in contrast ...Some reactions of R3SnM（CO）5 （M = Mn, Re） with CH3CN or pyridine were investigated to give complexes R3SnMn（CO）3LL＇ or R3SnMn（CO）4L by a facile mild method. X-ray diffractions analyses show that, in contrast to the phosphine ligand occupying in axial position, nitrogen ligands occupy equatorial position.展开更多
Photodynamic therapy is receiving increasing attention due to its versatile application in anticancer therapy.Ru(II)and Pt(II)complexes are among the most investigated compounds as potential photosensitizers for photo...Photodynamic therapy is receiving increasing attention due to its versatile application in anticancer therapy.Ru(II)and Pt(II)complexes are among the most investigated compounds as potential photosensitizers for photodynamic therapy based on their outstanding photophysical and biological properties(i.e.,strong emission,high intersystem crossing efficiency,large Stokes shift,high(photo-)stability,biological compatibility,good water solubility).While these classes of compounds have been widely studied separately or combined in derivatives that display a dual therapeutic effect,herein,a novel study on the conjugation of Ru(II)and Pt(II)fragments into a single bimetallic conjugate is proposed.It is assumed that this molecular design could undergo an intramolecular electron transfer from the Ru(II)moiety to the Pt(II)moiety upon irradiation to produce a highly efficient excited state.Capitalizing on the presence of both metals,the bimetallic conjugate was found to generate singlet oxygen with an outstanding efficiency in comparison to its individual components.To enhance the pharmacological profile,the bimetallic complex was encapsulated into polymeric nanoparticles.The nanoparticles were demonstrated to eradicate human breast adenocarcinoma monolayer cells as well as multicellular tumor spheroids upon light irradiation at nanomolar concentrations.We are confident that this approach will open new avenues towards the development of novel highly efficient photosensitizers.展开更多
A new dinucleating ligand consisting of a tetraphenylporphyrin derivative covalently linked with tris(2-benzimidazylmethyl)-amine and its homodinuclear Co-Co and heterodinuclear Co-Cu complexes were synthesized and ...A new dinucleating ligand consisting of a tetraphenylporphyrin derivative covalently linked with tris(2-benzimidazylmethyl)-amine and its homodinuclear Co-Co and heterodinuclear Co-Cu complexes were synthesized and spectroscopically characterized. The heterobimetallic cobalt-copper complex bearing three benzimidazole ligands for copper, as cytochrome c oxidase active site model, was applied to the surface of glassy carbon electrode to show electrocatalytic activity for O 2 reduction in aqueous solution at an acidity level close to physiological pH value. The kinetic parameters of this electrocatalytic process were obtained.展开更多
Two d-f heterodinuclear cryptates Eu(Ⅲ)-M(Ⅱ)(M=Zn 2+, Ni 2+) were synthesized and characterized by elemental analysis, IR and ES-MS. The fluorescence properties of the cyptates in acetonitrile solution show that inc...Two d-f heterodinuclear cryptates Eu(Ⅲ)-M(Ⅱ)(M=Zn 2+, Ni 2+) were synthesized and characterized by elemental analysis, IR and ES-MS. The fluorescence properties of the cyptates in acetonitrile solution show that inclusion of Zn 2+ in the mononuclear europium(Ⅲ) cryptate increases the energy transfer between cryptand and europium(Ⅲ) ion, while the inclusion of Ni 2+ in the cavity quenches the fluorescence of Eu(Ⅲ) cryptate.展开更多
The mononuclear cryptate [Eu(H 3L F)(NO 3)(H 2O)](NO 3) 2 and the heterodinuclear cryptate [EuZnL F(DMF)](ClO 4) 2 were synthesized and characterized. The triplet state energy of the cryptand (H 3L F) was ...The mononuclear cryptate [Eu(H 3L F)(NO 3)(H 2O)](NO 3) 2 and the heterodinuclear cryptate [EuZnL F(DMF)](ClO 4) 2 were synthesized and characterized. The triplet state energy of the cryptand (H 3L F) was studied by phosphorescence spectrum. The fluorescent properties of Eu(Ⅲ) cryptates in MeOH solution show that the cryptand (H 3L F) can sensitize the Eu(Ⅲ) ion to luminescence and the introduction of the Zn(Ⅱ) ion into the mononuclear Eu(Ⅲ) cryptate resulted in blue shift of three ligand centered bands, increase of molar absorption coefficient and increase of the luminescence intensity of Eu(Ⅲ).展开更多
基金the National Natural Science Foundation of China(Nos.21722402 and 21674015)the Fundamental Research Funds for the Central Universities(No.DUT18ZD105).
文摘Polyesters,as a class of high-performance and versatile polymer materials,often suffer from some drawbacks,such as hydrophobicity and brittleness due to their single structure nature.Thus,modifications have attracted much attention for enhancing their desirable properties,of which one efficient way is incorporating the aliphatic polyether segment into the main chain of the polyester.However,this approach is of much challenge because the obtained polyesters are problematic in either low alternating degree or low molecular weight.Herein,we describe an efficient strategy to incorporate polyether fragment into polyester by developing a novel Co-Al based heterodinuclear complex for mediating the copolymerization of propylene oxide(PO)withε-caprolactone(CL).The tracking experiments reveal that PO and CL convert into the polymer chain throughout the polymerization process.Especially,the linear increase in the molecular weight with conversion of CL indicates the controllable nature of the copolymerization.The competition polymerization,offering the monomer reactivity ratios of rCL=0.96 and rPO=1.04,suggests that the tendency of self-propagation or incorporation of monomers is nearly identical.interestingly,the obtained polymers with different ether contents exhibit tunable thermal properties with enhanced decomposition temperature for the polymer with higher ether content.The newly developed heterodinuclear complex for new polymerization provides an idea to synthesize new functional polymeric materials.
基金supported by the National Natural Science Foundation of China(No.29672018).
文摘Some reactions of R3SnM（CO）5 （M = Mn, Re） with CH3CN or pyridine were investigated to give complexes R3SnMn（CO）3LL＇ or R3SnMn（CO）4L by a facile mild method. X-ray diffractions analyses show that, in contrast to the phosphine ligand occupying in axial position, nitrogen ligands occupy equatorial position.
基金financial support provided by Ministerio de Ciencia e Innovación/Agencia Estatal de Investigación(MCIN/AEI)of Spain(PID2021-127187OB-C21)J.S.V.acknowledges his predoctoral grant to Universidad de Burgos(2019/00002/008/001)the PhD Exchange Scholarship provided by RUB Research School.J.V.C.V.acknowledges the financial support provided by Ministerio de Ciencia e Innovación/Agencia Estatal de Investigación(MCIN/AEI)of Spain(PID2022-142318NB-I00).
文摘Photodynamic therapy is receiving increasing attention due to its versatile application in anticancer therapy.Ru(II)and Pt(II)complexes are among the most investigated compounds as potential photosensitizers for photodynamic therapy based on their outstanding photophysical and biological properties(i.e.,strong emission,high intersystem crossing efficiency,large Stokes shift,high(photo-)stability,biological compatibility,good water solubility).While these classes of compounds have been widely studied separately or combined in derivatives that display a dual therapeutic effect,herein,a novel study on the conjugation of Ru(II)and Pt(II)fragments into a single bimetallic conjugate is proposed.It is assumed that this molecular design could undergo an intramolecular electron transfer from the Ru(II)moiety to the Pt(II)moiety upon irradiation to produce a highly efficient excited state.Capitalizing on the presence of both metals,the bimetallic conjugate was found to generate singlet oxygen with an outstanding efficiency in comparison to its individual components.To enhance the pharmacological profile,the bimetallic complex was encapsulated into polymeric nanoparticles.The nanoparticles were demonstrated to eradicate human breast adenocarcinoma monolayer cells as well as multicellular tumor spheroids upon light irradiation at nanomolar concentrations.We are confident that this approach will open new avenues towards the development of novel highly efficient photosensitizers.
文摘A new dinucleating ligand consisting of a tetraphenylporphyrin derivative covalently linked with tris(2-benzimidazylmethyl)-amine and its homodinuclear Co-Co and heterodinuclear Co-Cu complexes were synthesized and spectroscopically characterized. The heterobimetallic cobalt-copper complex bearing three benzimidazole ligands for copper, as cytochrome c oxidase active site model, was applied to the surface of glassy carbon electrode to show electrocatalytic activity for O 2 reduction in aqueous solution at an acidity level close to physiological pH value. The kinetic parameters of this electrocatalytic process were obtained.
文摘Two d-f heterodinuclear cryptates Eu(Ⅲ)-M(Ⅱ)(M=Zn 2+, Ni 2+) were synthesized and characterized by elemental analysis, IR and ES-MS. The fluorescence properties of the cyptates in acetonitrile solution show that inclusion of Zn 2+ in the mononuclear europium(Ⅲ) cryptate increases the energy transfer between cryptand and europium(Ⅲ) ion, while the inclusion of Ni 2+ in the cavity quenches the fluorescence of Eu(Ⅲ) cryptate.
文摘The mononuclear cryptate [Eu(H 3L F)(NO 3)(H 2O)](NO 3) 2 and the heterodinuclear cryptate [EuZnL F(DMF)](ClO 4) 2 were synthesized and characterized. The triplet state energy of the cryptand (H 3L F) was studied by phosphorescence spectrum. The fluorescent properties of Eu(Ⅲ) cryptates in MeOH solution show that the cryptand (H 3L F) can sensitize the Eu(Ⅲ) ion to luminescence and the introduction of the Zn(Ⅱ) ion into the mononuclear Eu(Ⅲ) cryptate resulted in blue shift of three ligand centered bands, increase of molar absorption coefficient and increase of the luminescence intensity of Eu(Ⅲ).
