Attaining the selective oxidation of isochroman into isochromanone in a molecular oxygen(O_(2))environment without any additives,via a heterogeneous oxidation process,is highly desirable and challenging work.Herein,we...Attaining the selective oxidation of isochroman into isochromanone in a molecular oxygen(O_(2))environment without any additives,via a heterogeneous oxidation process,is highly desirable and challenging work.Herein,we prepare two mixed-addendum polyoxometalate-based coordination polymers of the general formula[H_(x)M_(1-x)(i-PrIm)_(4)][H_(2)N(CH_(3))_(2)]_(4)[HPMo_(8)V_(6)O_(42)](M=Co 1,Ni,2;i-PrIm=1-isopropyl-1H-imidazole).Needing no additives,they can catalyze the selective oxidation of isochroman to isochromanone with O_(2)as an oxidant,with yields of 91.5%(1)and 46.8%(2),respectively.Mechanistic studies indicate that the excellent performance of catalyst 1 is attributed to the synergistic operation of[Co(i-Pr-Im)_(4))]complex and PMo_(8)V_(6)unit,and that the catalytic reaction is a radical pathway involving superoxide radicals.Additionally,the catalyst 1 can be recycled and reused at least four times with uncompromised performance.These results provide fundamental guidelines for designing efficient and multi-site heterogeneous catalysts for the selective oxidation of benzyl C(sp^(3))-H bonds by activating O_(2).展开更多
In order to overcome the limitation of traditional active nano-therapeutic drugs on tumor targeting efficiency which cannot reach the receptor/target in sufficient amount in the body,in this work,we developed a monocl...In order to overcome the limitation of traditional active nano-therapeutic drugs on tumor targeting efficiency which cannot reach the receptor/target in sufficient amount in the body,in this work,we developed a monoclonal antibody(mAb)and a polymer-hyd-doxorubicin prodrug conjugate,which enables the self-assembled nanoparticles to have precise targeting,tumor tissue aggregation and pH-sensitive drug release.We first prepared an amphiphilic polymer prodrug,abbreviated as H2N-PEEP-b-PBYP-hyd-DOX,via a combination of ring-opening polymerization(ROP)and"click"chemistry,in which PEEP and PBYP represent two kinds of phosphoester segmemts,-hyd-is hydrazone bond.After self-assembly into prodrug nanoparticles(PDNPs)with a diameter of about 93 nm,CD147 mAb was conjugated onto the PDNPs by EDC/NHS chemistry to form mAb-PDNPs.For the PDNPs and mAb-PDNPs,we also investigated their stability,in vitro drug release behavior and cellular uptake.The results showed that the pH-responsive PDNPs can remain relatively stable under the condition of PB 7.4 buffer solution.However,under acidic conditions or in the presence of phosphodiesterase I(PDE I),both the amount and rate of DOX release increased at the same incubation period.Cytotoxicity assay showed that mAb-PDNPs exhibited higher cytotoxicity(IC50:1.12 mg·L^(-1))against HepG2 cells than PDNPs(IC50:2.62 mg·L^(-1))without monoclonal antibody.The nanoparticles with antibodies mAb-PDNPs have relatively better stability and can directly achieve the targeting drug delivery through CD147 mAb.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.22171122 and 22201123)Liaoning Revitalization Talents Program(No.XLYC 2007130)+1 种基金Fundamental Research Project(No.LJ212410148038)of the Educational Department of Liaoning ProvinceTalent Scientific Research Fund of Liaoning Petrochemical University(No.2016XJJL–019)。
文摘Attaining the selective oxidation of isochroman into isochromanone in a molecular oxygen(O_(2))environment without any additives,via a heterogeneous oxidation process,is highly desirable and challenging work.Herein,we prepare two mixed-addendum polyoxometalate-based coordination polymers of the general formula[H_(x)M_(1-x)(i-PrIm)_(4)][H_(2)N(CH_(3))_(2)]_(4)[HPMo_(8)V_(6)O_(42)](M=Co 1,Ni,2;i-PrIm=1-isopropyl-1H-imidazole).Needing no additives,they can catalyze the selective oxidation of isochroman to isochromanone with O_(2)as an oxidant,with yields of 91.5%(1)and 46.8%(2),respectively.Mechanistic studies indicate that the excellent performance of catalyst 1 is attributed to the synergistic operation of[Co(i-Pr-Im)_(4))]complex and PMo_(8)V_(6)unit,and that the catalytic reaction is a radical pathway involving superoxide radicals.Additionally,the catalyst 1 can be recycled and reused at least four times with uncompromised performance.These results provide fundamental guidelines for designing efficient and multi-site heterogeneous catalysts for the selective oxidation of benzyl C(sp^(3))-H bonds by activating O_(2).
基金financial supports from the National Natural Science Foundation of China(Nos.21975169 and 21374066)the Natural Science Foundation of Jiangsu Province(No.BK20171212)Funded by the Priority Academic Program Development(PAPD)of Jiangsu Higher Education Institutions。
文摘In order to overcome the limitation of traditional active nano-therapeutic drugs on tumor targeting efficiency which cannot reach the receptor/target in sufficient amount in the body,in this work,we developed a monoclonal antibody(mAb)and a polymer-hyd-doxorubicin prodrug conjugate,which enables the self-assembled nanoparticles to have precise targeting,tumor tissue aggregation and pH-sensitive drug release.We first prepared an amphiphilic polymer prodrug,abbreviated as H2N-PEEP-b-PBYP-hyd-DOX,via a combination of ring-opening polymerization(ROP)and"click"chemistry,in which PEEP and PBYP represent two kinds of phosphoester segmemts,-hyd-is hydrazone bond.After self-assembly into prodrug nanoparticles(PDNPs)with a diameter of about 93 nm,CD147 mAb was conjugated onto the PDNPs by EDC/NHS chemistry to form mAb-PDNPs.For the PDNPs and mAb-PDNPs,we also investigated their stability,in vitro drug release behavior and cellular uptake.The results showed that the pH-responsive PDNPs can remain relatively stable under the condition of PB 7.4 buffer solution.However,under acidic conditions or in the presence of phosphodiesterase I(PDE I),both the amount and rate of DOX release increased at the same incubation period.Cytotoxicity assay showed that mAb-PDNPs exhibited higher cytotoxicity(IC50:1.12 mg·L^(-1))against HepG2 cells than PDNPs(IC50:2.62 mg·L^(-1))without monoclonal antibody.The nanoparticles with antibodies mAb-PDNPs have relatively better stability and can directly achieve the targeting drug delivery through CD147 mAb.
