Three cadmium（II）-halide complexes with 5-（ethylthio）-1H-tetrazole（Hett） as ligand, namely [Cd_7Cl_2（ett）_（12）（H_2O）_2]_n（1）, [Cd_2（OH）Br（ett）_2]_n（2） and [Cd_2（OH）I（ett）_2]_n（3）, have been h...Three cadmium（II）-halide complexes with 5-（ethylthio）-1H-tetrazole（Hett） as ligand, namely [Cd_7Cl_2（ett）_（12）（H_2O）_2]_n（1）, [Cd_2（OH）Br（ett）_2]_n（2） and [Cd_2（OH）I（ett）_2]_n（3）, have been hydrothermally synthesized and characterized. Complex 1 was synthesized at pH = 7 and exhibits a 3D supramolecular framework, where the adjacent Cd ions form a tetrahedron unit by ett ligands bridge and the tetrahedron units share vertices to connect each other by ett bridges to form a 2D layer architecture, which is further interlinked by μ_2-Cl to form 3D structures. Complexes 2 and 3 are isostructural, generated at pH = 8.0~9.0, displaying similar 2D networks via ett ligands and different halide ions（Br-in 2, I-in 3, respectively）. In addition, thermal stabilities and luminescent properties of new complexes 1~3 have been studied.展开更多
A Zn（Ⅱ） coordination polymer [Zn（NIP）（3,3＇-bpt）].H20 （1, NIP = 5-nitroisophtha- late, 3,3＂-bpt = 1H-3,5-bis（3-pyridyl）-l,2,4-triazolate） has been synthesized by the hydrothermal reaction at 140 ℃ and str...A Zn（Ⅱ） coordination polymer [Zn（NIP）（3,3＇-bpt）].H20 （1, NIP = 5-nitroisophtha- late, 3,3＂-bpt = 1H-3,5-bis（3-pyridyl）-l,2,4-triazolate） has been synthesized by the hydrothermal reaction at 140 ℃ and structurally characterized by IR spectroscopy, X-ray diffraction, thermal analysis, single-crystal X-ray diffraction and luminescent properties. In complex 1, the zinc atom is five-coordinated with three carboxylate oxygen atoms from three H2NIP and two nitrogen atoms from two 3,3＇-bpt, respectively, forming a distorted trigonal bipyramidal geometry and showing a 1D chain structure, which is further bridged by NIP to form a 3D supramolecular network via self-assembly of hydrogen bonds.展开更多
A novel Cd（Ⅱ） coordination polymer with diacylhydrazide ligand N,N？-bis（3-methoxysalicyl）-2,6-pyridinedicarbohydrazide（H_6msphz）,[Cd_2（H_2msphz）（Py）_4]_n（1,Py = pyridine） has been synthesized through sol...A novel Cd（Ⅱ） coordination polymer with diacylhydrazide ligand N,N？-bis（3-methoxysalicyl）-2,6-pyridinedicarbohydrazide（H_6msphz）,[Cd_2（H_2msphz）（Py）_4]_n（1,Py = pyridine） has been synthesized through solvothermal reaction and structurally characterized by single-crystal X-ray diffraction,IR,TGA and PXRD investigations. It crystallizes in triclinic system,space group P1,with a = 11.0230（11）,b = 11.7264（15）,c = 17.3395（14） ？,α = 70.520（9）,β = 84.806（7）,γ = 81.965（9）°,V = 2089.9（4） ？~3,Dc = 1.638 gcm^（–3）,μ = 1.083 mm^（-1）,F（000） = 1032,Z = 2 and S = 1.040. In complex 1,the H_2msphz4-ligand uses not only its coordinated pocket to catch one Cd（Ⅱ） ion,but also its two terminal groups to chelate other two Cd（Ⅱ） ions,leading to the formation of a chain structure. The adjacent chains are further assembled together by two kinds of π-π interactions between the Py rings,resulting in the finial double layered supramolecular structure. In addition,complex 1 is found to show photoluminescence in the solid state at room temperature,which can be ascribed to the intraligand π→π＊ transitions.展开更多
Based on the bent ligand 1 H-3-(3-pyridyl)-5-(4-pyridyl)-1,2,4-triazole(3,4?-Hbpt) with Co(Ⅱ) ions as well as a series of polycarboxylate co-ligands, three new coordination polymers were yielded, namely, {[Co(op)(3,4...Based on the bent ligand 1 H-3-(3-pyridyl)-5-(4-pyridyl)-1,2,4-triazole(3,4?-Hbpt) with Co(Ⅱ) ions as well as a series of polycarboxylate co-ligands, three new coordination polymers were yielded, namely, {[Co(op)(3,4?-Hbpt)(H_2O)_3]?2 H_2O}n(1), [Co(cyc)(3,4′-Hbpt)(H_2O)]n(2) and [Co(pro)(3,4′-Hbpt)(H_2O)]n(3)(here, op = o-phthalic anion, cyc = 1,1-cyclobutanedicarboxylic anion, pro = propanedioic anion). In cooperation with the auxiliary polycarboxylate co-ligands, a variety of Co(Ⅱ) coordination networks, such as 1-D chain 1 and 2-D layer 2 and 3 have been assembled. The magnetic behaviors of compounds 1～3 were studied. All of them indicated the existence of interesting spin-canting behavior.展开更多
Based on a 3-（pyridine-2-yl）-4H-1,2,4-triazole ligand（Hpytr）, one 2D Cd（Ⅱ） coordination polymer [Cd I（pytr）]n（1） and one 2D Mn（Ⅱ） coordination polymer [Mn（N3）（pytr）（H2O）]n（2） have been synthesize...Based on a 3-（pyridine-2-yl）-4H-1,2,4-triazole ligand（Hpytr）, one 2D Cd（Ⅱ） coordination polymer [Cd I（pytr）]n（1） and one 2D Mn（Ⅱ） coordination polymer [Mn（N3）（pytr）（H2O）]n（2） have been synthesized and characterized by X-ray crystallography, elemental analysis, and fluorescence spectroscopy. 1 shows a layer coordination architecture linked by pytr ligand, and the Cd（Ⅱ） centers display slightly distorted square pyramid coordination geometries. Complex 2 shows a 2D pillared-layer coordination architecture bridged by N3-and pytr, and the Mn（Ⅱ） centers display slightly distorted octahedral geometries. The luminescent properties of 1 and the PXRD and thermal stability of complexes 1 and 2 were measured briefly.展开更多
In this paper,the difunctionalizative perfluoroalkyloximation of alkenes has been developed for the first time.This photochemical method allows for the synthesis of various perfluoroalkyl ethanone oximes with excellen...In this paper,the difunctionalizative perfluoroalkyloximation of alkenes has been developed for the first time.This photochemical method allows for the synthesis of various perfluoroalkyl ethanone oximes with excellent regioselectivity and good functional group tolerance.Our method employs the most common perfluoroalkyl source,perfluoroalkyl iodides,as Rf reagents.Besides long-chain perfluoroalkyl groups,this approach could be extended to incorporating additional groups,including trifluoromethyl,difluoromethyl,sulfonyl,and malonate,selectively into olefins,resulting in a range ofβ-substituted ethanone oximes.Notably,the potential of this method in the Fukuyama indole synthesis,generating novel 2-perfluoroalkylated 3-(α-oximidobenzyl)indoles via a radical cascade mechanism with 2-vinylphenylacryloyl isocyanate as the radical acceptor,presents a compelling avenue for drug synthesis.The protocol is efficient,scalable,and useful for late-stage modification of bioactive molecules.展开更多
We report here a cocrystal with artesunate as the active pharmaceutical ingredient(API)and a pharmaceutical intermediate 4,4?-bipyridine as the cocrystal former(CCF).The analysis of single-crystal X-ray diffraction de...We report here a cocrystal with artesunate as the active pharmaceutical ingredient(API)and a pharmaceutical intermediate 4,4?-bipyridine as the cocrystal former(CCF).The analysis of single-crystal X-ray diffraction demonstrates that the eutectic structural unit consists of two artesunate molecules and one 4,4?-bipyridine molecule with their ratio to be 2:1.The carboxyl group on artesunate acts as a donor,and the acceptor is N on 4,4?-bipyridine,forming an O–H···N hydrogen bond.The appearance of new diffraction peaks in the X-ray powder diffraction pattern also indicates the formation of new phases.The PXRD results indicated a pure phase for the synthesized sample.The cocrystal is slightly soluble in water.Antimicrobial activities showed that the cocrystal displayed effective inhibition of different bacteria.展开更多
Four new sesquiterpenoids, 4,8-dioxo-6βhydroxyl-7β,l 1-epoxycarabrane （1）, 4,8-dioxo-6βhydroxyl- 7β,11-epoxycarabrane （2）, wenyujinins Q and R （3-4）, and nine known sesquiterpenoids （5-13） were isolated fr...Four new sesquiterpenoids, 4,8-dioxo-6βhydroxyl-7β,l 1-epoxycarabrane （1）, 4,8-dioxo-6βhydroxyl- 7β,11-epoxycarabrane （2）, wenyujinins Q and R （3-4）, and nine known sesquiterpenoids （5-13） were isolated from the Curcuma wenyujin （C wenyujin） dreg. Their structures and relative configurations wereelucidated using 1D, 2D NMR, and HR-ESI-MS data. All the compounds were isolated for the first time from the C wenyujin dreg and evaluated for their antibacterial and antifungal activities. Compounds 3, 5- 8 exhibited strong broad-spectrum antifungal activities against tested nine pathogenic fungi.展开更多
Nonplatinummetal complexes of[Pd(L^(1))Cl_(2)](C1),[Rh(L^(1))Cl_(3)(DMSO)](C2),[Pd(L^(2))Cl_(2)](C3),and[Rh(L^(3))Cl_(3)(DMSO)](C4)with isoquinoline derivatives have been prepared and characterized.C1-C4 exhibited hig...Nonplatinummetal complexes of[Pd(L^(1))Cl_(2)](C1),[Rh(L^(1))Cl_(3)(DMSO)](C2),[Pd(L^(2))Cl_(2)](C3),and[Rh(L^(3))Cl_(3)(DMSO)](C4)with isoquinoline derivatives have been prepared and characterized.C1-C4 exhibited higher in vitro anticancer activity and lower toxicity than the corresponding ligands and cisplatin against HepG2 cells.The mechanistic studies revealed that C1 arrested the cell cycle at S-phase by regulation of cyclin and cyclin-dependent kinases.C1 was accumulated in mitochondria,which increased the generation of reactive oxygen species(ROS)and endoplasmic reticulum(ER)-stress response through mitochondrial dysfunction.Moreover,C1 stimulated Ca^(2+)release,activated the caspase cascade,and triggered mitochondria-mediated apoptosis.The in vivo studies of C1 demonstrated higher safety than cisplatin and effective tumor growth inhibition.C1 is a potential anticancer drug candidate.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21361003 and 21461003)the Natural Science Foundation of Guangxi Province(Nos.2016GXNSFFA380010 and 2014GXNSFBA118056)
文摘Three cadmium（II）-halide complexes with 5-（ethylthio）-1H-tetrazole（Hett） as ligand, namely [Cd_7Cl_2（ett）_（12）（H_2O）_2]_n（1）, [Cd_2（OH）Br（ett）_2]_n（2） and [Cd_2（OH）I（ett）_2]_n（3）, have been hydrothermally synthesized and characterized. Complex 1 was synthesized at pH = 7 and exhibits a 3D supramolecular framework, where the adjacent Cd ions form a tetrahedron unit by ett ligands bridge and the tetrahedron units share vertices to connect each other by ett bridges to form a 2D layer architecture, which is further interlinked by μ_2-Cl to form 3D structures. Complexes 2 and 3 are isostructural, generated at pH = 8.0~9.0, displaying similar 2D networks via ett ligands and different halide ions（Br-in 2, I-in 3, respectively）. In addition, thermal stabilities and luminescent properties of new complexes 1~3 have been studied.
基金Supported by the National Natural Science Foundattion of China(21101035)Natural Science Foundattion of Guangxi province(2012GXNSFBA053017)+1 种基金the Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources,Ministry of Education of China(CMEMR2013-A05)the Natural Science Foundation of Guangxi Normal University
文摘A Zn（Ⅱ） coordination polymer [Zn（NIP）（3,3＇-bpt）].H20 （1, NIP = 5-nitroisophtha- late, 3,3＂-bpt = 1H-3,5-bis（3-pyridyl）-l,2,4-triazolate） has been synthesized by the hydrothermal reaction at 140 ℃ and structurally characterized by IR spectroscopy, X-ray diffraction, thermal analysis, single-crystal X-ray diffraction and luminescent properties. In complex 1, the zinc atom is five-coordinated with three carboxylate oxygen atoms from three H2NIP and two nitrogen atoms from two 3,3＇-bpt, respectively, forming a distorted trigonal bipyramidal geometry and showing a 1D chain structure, which is further bridged by NIP to form a 3D supramolecular network via self-assembly of hydrogen bonds.
基金Supported by the National Natural Science Foundation of China(Nos.51572050,21271050 and 21261004)the Guangxi Natural Science Foundation(Nos.2015GXNSFDA139007,2014GXNSFBA118055 and 2013GXNSFGA019008)
文摘A novel Cd（Ⅱ） coordination polymer with diacylhydrazide ligand N,N？-bis（3-methoxysalicyl）-2,6-pyridinedicarbohydrazide（H_6msphz）,[Cd_2（H_2msphz）（Py）_4]_n（1,Py = pyridine） has been synthesized through solvothermal reaction and structurally characterized by single-crystal X-ray diffraction,IR,TGA and PXRD investigations. It crystallizes in triclinic system,space group P1,with a = 11.0230（11）,b = 11.7264（15）,c = 17.3395（14） ？,α = 70.520（9）,β = 84.806（7）,γ = 81.965（9）°,V = 2089.9（4） ？~3,Dc = 1.638 gcm^（–3）,μ = 1.083 mm^（-1）,F（000） = 1032,Z = 2 and S = 1.040. In complex 1,the H_2msphz4-ligand uses not only its coordinated pocket to catch one Cd（Ⅱ） ion,but also its two terminal groups to chelate other two Cd（Ⅱ） ions,leading to the formation of a chain structure. The adjacent chains are further assembled together by two kinds of π-π interactions between the Py rings,resulting in the finial double layered supramolecular structure. In addition,complex 1 is found to show photoluminescence in the solid state at room temperature,which can be ascribed to the intraligand π→π＊ transitions.
基金The project was supported by the National Natural Science Foundation of China(21461003)the Guangxi Natural Science Foundation of China(2016GXNSFFA380010 and 2016GXNSFAA380206)the Project of Guangxi Education Department(KY2016LX235)
文摘Based on the bent ligand 1 H-3-(3-pyridyl)-5-(4-pyridyl)-1,2,4-triazole(3,4?-Hbpt) with Co(Ⅱ) ions as well as a series of polycarboxylate co-ligands, three new coordination polymers were yielded, namely, {[Co(op)(3,4?-Hbpt)(H_2O)_3]?2 H_2O}n(1), [Co(cyc)(3,4′-Hbpt)(H_2O)]n(2) and [Co(pro)(3,4′-Hbpt)(H_2O)]n(3)(here, op = o-phthalic anion, cyc = 1,1-cyclobutanedicarboxylic anion, pro = propanedioic anion). In cooperation with the auxiliary polycarboxylate co-ligands, a variety of Co(Ⅱ) coordination networks, such as 1-D chain 1 and 2-D layer 2 and 3 have been assembled. The magnetic behaviors of compounds 1～3 were studied. All of them indicated the existence of interesting spin-canting behavior.
基金Supported by the National Natural Science Foundation of China(No.21461003)Natural Science Foundation of Guangxi Province(No.2016GXNSFFA380010,2016GXNSFAA380206,2014GXNSFBA118056)the Foundation of Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources,Ministry of Education of China(CMEMR2015-A11,CMEMR2016-A11)
文摘Based on a 3-（pyridine-2-yl）-4H-1,2,4-triazole ligand（Hpytr）, one 2D Cd（Ⅱ） coordination polymer [Cd I（pytr）]n（1） and one 2D Mn（Ⅱ） coordination polymer [Mn（N3）（pytr）（H2O）]n（2） have been synthesized and characterized by X-ray crystallography, elemental analysis, and fluorescence spectroscopy. 1 shows a layer coordination architecture linked by pytr ligand, and the Cd（Ⅱ） centers display slightly distorted square pyramid coordination geometries. Complex 2 shows a 2D pillared-layer coordination architecture bridged by N3-and pytr, and the Mn（Ⅱ） centers display slightly distorted octahedral geometries. The luminescent properties of 1 and the PXRD and thermal stability of complexes 1 and 2 were measured briefly.
基金support of this work by the Guangxi Natural Science Foundation of China(2020GXNSFAA297213)the Guangxi Science and Technology Base and Special Talents(AD21075017)+1 种基金the National Natural Science Foundation of China(22161006)the Natural Science Foundation of Shandong Province(ZR2020MB016)isgratefully acknowledged。
文摘In this paper,the difunctionalizative perfluoroalkyloximation of alkenes has been developed for the first time.This photochemical method allows for the synthesis of various perfluoroalkyl ethanone oximes with excellent regioselectivity and good functional group tolerance.Our method employs the most common perfluoroalkyl source,perfluoroalkyl iodides,as Rf reagents.Besides long-chain perfluoroalkyl groups,this approach could be extended to incorporating additional groups,including trifluoromethyl,difluoromethyl,sulfonyl,and malonate,selectively into olefins,resulting in a range ofβ-substituted ethanone oximes.Notably,the potential of this method in the Fukuyama indole synthesis,generating novel 2-perfluoroalkylated 3-(α-oximidobenzyl)indoles via a radical cascade mechanism with 2-vinylphenylacryloyl isocyanate as the radical acceptor,presents a compelling avenue for drug synthesis.The protocol is efficient,scalable,and useful for late-stage modification of bioactive molecules.
基金supported by the National Natural Science Foundation of China(No.21861005)the Foundation of Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources(CMEMR2018-C15 and CMEMR2016-A11)。
文摘We report here a cocrystal with artesunate as the active pharmaceutical ingredient(API)and a pharmaceutical intermediate 4,4?-bipyridine as the cocrystal former(CCF).The analysis of single-crystal X-ray diffraction demonstrates that the eutectic structural unit consists of two artesunate molecules and one 4,4?-bipyridine molecule with their ratio to be 2:1.The carboxyl group on artesunate acts as a donor,and the acceptor is N on 4,4?-bipyridine,forming an O–H···N hydrogen bond.The appearance of new diffraction peaks in the X-ray powder diffraction pattern also indicates the formation of new phases.The PXRD results indicated a pure phase for the synthesized sample.The cocrystal is slightly soluble in water.Antimicrobial activities showed that the cocrystal displayed effective inhibition of different bacteria.
基金supported by the Program of Hainan provincial key science and technology(No.ZDXM20130059)the Natural Science Foundation of Hainan Province(No.213020)
文摘Four new sesquiterpenoids, 4,8-dioxo-6βhydroxyl-7β,l 1-epoxycarabrane （1）, 4,8-dioxo-6βhydroxyl- 7β,11-epoxycarabrane （2）, wenyujinins Q and R （3-4）, and nine known sesquiterpenoids （5-13） were isolated from the Curcuma wenyujin （C wenyujin） dreg. Their structures and relative configurations wereelucidated using 1D, 2D NMR, and HR-ESI-MS data. All the compounds were isolated for the first time from the C wenyujin dreg and evaluated for their antibacterial and antifungal activities. Compounds 3, 5- 8 exhibited strong broad-spectrum antifungal activities against tested nine pathogenic fungi.
基金This work was supported by the National Natural Science Foundation of China(grant no.21431001)IRT_16R15,and Natural Science Foundation of Guangxi Province of China(grant nos.2016GXNSFGA380005 and AD17129007)as well as the“BAGUI Scholar”program of Guangxi Province of China.
文摘Nonplatinummetal complexes of[Pd(L^(1))Cl_(2)](C1),[Rh(L^(1))Cl_(3)(DMSO)](C2),[Pd(L^(2))Cl_(2)](C3),and[Rh(L^(3))Cl_(3)(DMSO)](C4)with isoquinoline derivatives have been prepared and characterized.C1-C4 exhibited higher in vitro anticancer activity and lower toxicity than the corresponding ligands and cisplatin against HepG2 cells.The mechanistic studies revealed that C1 arrested the cell cycle at S-phase by regulation of cyclin and cyclin-dependent kinases.C1 was accumulated in mitochondria,which increased the generation of reactive oxygen species(ROS)and endoplasmic reticulum(ER)-stress response through mitochondrial dysfunction.Moreover,C1 stimulated Ca^(2+)release,activated the caspase cascade,and triggered mitochondria-mediated apoptosis.The in vivo studies of C1 demonstrated higher safety than cisplatin and effective tumor growth inhibition.C1 is a potential anticancer drug candidate.
