A series of five coordinated iron bis(dithiolene)complexes[Fe(NHC)(S_(2)C_(2)R_(2))_(2)](R=C_(6)H_(5)or C_(6)H_(4)-p-OCH_(3))containing N-heterocyclic carbene(NHC)(NHC=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene ...A series of five coordinated iron bis(dithiolene)complexes[Fe(NHC)(S_(2)C_(2)R_(2))_(2)](R=C_(6)H_(5)or C_(6)H_(4)-p-OCH_(3))containing N-heterocyclic carbene(NHC)(NHC=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene or 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene)were isolated in high yield(84–92%).The iron complexes were characterized by NMR spectroscopy and confirmed by single crystal X-ray diffraction studies.展开更多
Alkenes are ubiquitous,and the difunctionalization of alkenes represents one of the most practical approaches for the construction of value-added compounds.Dicarbonylation of alkenes provides direct access to value-ad...Alkenes are ubiquitous,and the difunctionalization of alkenes represents one of the most practical approaches for the construction of value-added compounds.Dicarbonylation of alkenes provides direct access to value-added 1,4-dicarbonyl compounds.However,selectivity control for unsymmetric 1,2-dicarbonylation is of great challenge.We herein describe NHCs and photocatalysis co-catalyzed three-component radical 1,2-dicarbonylation of alkenes by distinguishing two carbonyl groups,providing structurally diversified 1,4-diketones.Distinct properties of acyl radical and NHCs-stabilized ketyl radical contributed to selectivity control.Acyl radicals are rapidly added to alkenes delivering alkyl radicals,which undergo subsequent radicalradical cross-coupling with NHCs-stabilized ketyl-type radicals,affording 1,2-dicarbonylation products.This transformation features mild reaction conditions,broad substrate scope,and excellent selectivity,providing a general and practical approach for the dicarbonylation of olefins.展开更多
Superior neutral or cationic dinuclear gold(Ⅰ)N-heterocyclic carbene(NHC)complexes with antitumor and tumor microenvironment regulation functions were developed by introducing an additional gold atom.The novel cation...Superior neutral or cationic dinuclear gold(Ⅰ)N-heterocyclic carbene(NHC)complexes with antitumor and tumor microenvironment regulation functions were developed by introducing an additional gold atom.The novel cationic dinuclear gold(Ⅰ)complex 4a(BF5-Au)with bis-NHC ligands exhibited potent anti-liver cancer capacity in vitro and in vivo.The Hyper7 sensor was first used to analyze the sites of reactive oxygen species(ROS)generation by BF5-Au,showing that ROS were preferably generated in mitochondria and endoplasmic reticulum.Mechanism studies showed that BF5-Au could induce immunogenic cell death(ICD)via ROS-driven endoplasmic reticulum stress(ERS).However,targeting a single type of immune cell seems insufficient to reverse the immunosuppressive circumstances.Further investigation indicated that BF5-Au could enhance antitumor immune responses by inducing ferroptosis and polarizing macrophages to M1-like types.Overall,BF5-Au could inhibit tumor growth and remodel the tumor microenvironment via ROS-driven ERS and ferroptosis,which is expected to be a promising chemoimmunotherapy for cancer treatment.展开更多
采用改进Stober法-化学沉淀法制备了Ni(OH)_(2)/氮掺杂空心碳球复合材料(Ni(OH)_(2)/NHCS)。通过X射线衍射(XRD)、透射电镜(TEM)和N 2吸附-脱附等手段对复合材料进行表征和分析,并采用电化学工作站对复合材料的电化学性能进行测试。研...采用改进Stober法-化学沉淀法制备了Ni(OH)_(2)/氮掺杂空心碳球复合材料(Ni(OH)_(2)/NHCS)。通过X射线衍射(XRD)、透射电镜(TEM)和N 2吸附-脱附等手段对复合材料进行表征和分析,并采用电化学工作站对复合材料的电化学性能进行测试。研究结果表明:相比于纯Ni(OH)_(2)而言,NHCS有效抑制了Ni(OH)_(2)的聚集,从而提高了活性材料的利用率。同时,复合材料的中空结构有利于电解质离子的渗入而缩短电解质离子的传输路径,且降低界面电阻,从而有效提高了复合材料Ni(OH)_(2)/NHCS的电化学性能。Ni(OH)_(2)/NHCS在2 M KOH电解质中,电流密度为0.5 A g^(-1)时可表现出1085 F g^(-1)的高比电容。展开更多
基金support by funds from the Army Research Office(Department of DefenseW911NF-16-1-0197)+1 种基金funds from The American Chemical Society Petroleum Research Fund(PRF-59893-UR7)Support by funds from Chemistry Department,Wright State University,College of Science and Mathematics for the purchase of the X-ray instrument is greatly acknowledged.The authors would like to acknowledge Dr Grossie,Wright State University and Dr Fratini,University of Dayton for help with low temperature single crystal X-ray diffraction measurements.S.S.acknowledges the donors of the American Chemical Society Petroleum Research Fund(PRF-58954-UNI5)and the National Science Foundation(Award#1904825)for support of this research.
文摘A series of five coordinated iron bis(dithiolene)complexes[Fe(NHC)(S_(2)C_(2)R_(2))_(2)](R=C_(6)H_(5)or C_(6)H_(4)-p-OCH_(3))containing N-heterocyclic carbene(NHC)(NHC=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene or 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene)were isolated in high yield(84–92%).The iron complexes were characterized by NMR spectroscopy and confirmed by single crystal X-ray diffraction studies.
基金supported by the National Natural Science Foundation of China (22001157,21831002,22193012)the Ten Thousand Talents Program+2 种基金the Fundamental Research Funds for the Central Universities (2412022QD016,2412021QD007)the Natural Science Foundation of Jilin Province (YDZJ202201ZYTS338)the Natural Science Foundation of Shaanxi Province (2020JQ-404)
文摘Alkenes are ubiquitous,and the difunctionalization of alkenes represents one of the most practical approaches for the construction of value-added compounds.Dicarbonylation of alkenes provides direct access to value-added 1,4-dicarbonyl compounds.However,selectivity control for unsymmetric 1,2-dicarbonylation is of great challenge.We herein describe NHCs and photocatalysis co-catalyzed three-component radical 1,2-dicarbonylation of alkenes by distinguishing two carbonyl groups,providing structurally diversified 1,4-diketones.Distinct properties of acyl radical and NHCs-stabilized ketyl radical contributed to selectivity control.Acyl radicals are rapidly added to alkenes delivering alkyl radicals,which undergo subsequent radicalradical cross-coupling with NHCs-stabilized ketyl-type radicals,affording 1,2-dicarbonylation products.This transformation features mild reaction conditions,broad substrate scope,and excellent selectivity,providing a general and practical approach for the dicarbonylation of olefins.
基金supported by the National Natural Science Foundation of China(No.82173684)the Priority Academic Program Development of Jiangsu Higher Education Institutions(Integration of Chinese and Western Medicine),High level key discipline construction project of the National Administration of Traditional Chinese Medicine-Resource Chemistry of Chinese Medicinal Materials(No.zyyzdxk-2023083)+1 种基金the Key R&D Program of Jiangsu Province(No.BE2023840)Yunnan Provincial Science and Technology Talent and Platform Program(No.202405AF140031)。
文摘Superior neutral or cationic dinuclear gold(Ⅰ)N-heterocyclic carbene(NHC)complexes with antitumor and tumor microenvironment regulation functions were developed by introducing an additional gold atom.The novel cationic dinuclear gold(Ⅰ)complex 4a(BF5-Au)with bis-NHC ligands exhibited potent anti-liver cancer capacity in vitro and in vivo.The Hyper7 sensor was first used to analyze the sites of reactive oxygen species(ROS)generation by BF5-Au,showing that ROS were preferably generated in mitochondria and endoplasmic reticulum.Mechanism studies showed that BF5-Au could induce immunogenic cell death(ICD)via ROS-driven endoplasmic reticulum stress(ERS).However,targeting a single type of immune cell seems insufficient to reverse the immunosuppressive circumstances.Further investigation indicated that BF5-Au could enhance antitumor immune responses by inducing ferroptosis and polarizing macrophages to M1-like types.Overall,BF5-Au could inhibit tumor growth and remodel the tumor microenvironment via ROS-driven ERS and ferroptosis,which is expected to be a promising chemoimmunotherapy for cancer treatment.
文摘采用改进Stober法-化学沉淀法制备了Ni(OH)_(2)/氮掺杂空心碳球复合材料(Ni(OH)_(2)/NHCS)。通过X射线衍射(XRD)、透射电镜(TEM)和N 2吸附-脱附等手段对复合材料进行表征和分析,并采用电化学工作站对复合材料的电化学性能进行测试。研究结果表明:相比于纯Ni(OH)_(2)而言,NHCS有效抑制了Ni(OH)_(2)的聚集,从而提高了活性材料的利用率。同时,复合材料的中空结构有利于电解质离子的渗入而缩短电解质离子的传输路径,且降低界面电阻,从而有效提高了复合材料Ni(OH)_(2)/NHCS的电化学性能。Ni(OH)_(2)/NHCS在2 M KOH电解质中,电流密度为0.5 A g^(-1)时可表现出1085 F g^(-1)的高比电容。
