Two d10 metal complexes Zn(NCS)2(C14HI3NO2)2 (1) and [Cd(NO3)2(CI4HI3NO2)2]. 4H20 (2) assembled by 2-methoxy-6-(phenyliminiomethyl) phenolate ligand (C14H13NO2, HL) have been synthesized and characteri...Two d10 metal complexes Zn(NCS)2(C14HI3NO2)2 (1) and [Cd(NO3)2(CI4HI3NO2)2]. 4H20 (2) assembled by 2-methoxy-6-(phenyliminiomethyl) phenolate ligand (C14H13NO2, HL) have been synthesized and characterized by elemental analysis, IR and TG The single-crystal X-ray diffraction studies demonstrated that complex 1 crystallizes in monoclinic, P21/c space group with a = 17.321(7), b = 11.781(0), c = 15.593(2) A, fl = 110.273(6)°, V = 2984.95 A3, Z = 4, C30H26N404SzZn, Mr = 636.04, F(000) = 1312, Dc = 1.415 g/cm3,μ(MoKa) = 1.004 mm"1, the final R = 0.0403 and wR = 0.0900 for 21441 observed reflections with I 〉 20(/). Complex 2 is of monoclinic system, space group C2/c with a = 16.7767(2), b = 10.8989(2), c = 17.4928(2) A, fl = 90.614(9)°, V= 3198.37 A3, Z = 4, C28H34N4O14Cd, Mr= 731.25, F(000) = 1528, Dc = 1.568 g'cm^-3, μ(MoKa) = 0.757 mm-1, the final R = 0.0361 and wR = 0.0857 for 19811 observed reflections with I 〉 2σ(I). The two complexes were formed by Schiff base 2-methoxy-6-(phenyliminiomethyl) phenolate ligand and formed a 3D supramolecular architecture by π-πstacking interactions. Moreover, the complexes are luminescent in the solid state. These observations indicate that the complexes are promising system for the development of potential photoactive materials.展开更多
In order to improve the water solubility and bioavailability of 5-hydroxy-7-methoxyflavone,argentum 5-hydroxy-7-methoxy-2-phenyl-4H-chromen-4-one-6-sulfonate[Ag4(H2O)6](C(16)H(11)O4SO3)4·H2O(1,C(16)H(11)O4SO3=5-h...In order to improve the water solubility and bioavailability of 5-hydroxy-7-methoxyflavone,argentum 5-hydroxy-7-methoxy-2-phenyl-4H-chromen-4-one-6-sulfonate[Ag4(H2O)6](C(16)H(11)O4SO3)4·H2O(1,C(16)H(11)O4SO3=5-hydroxy-7-methoxy-2-phenyl-4H-chromen-4-one-6-sulfonate)was synthesized by sulfonation reaction.The structure of 1 was characterized by FT-IR,elemental analysis and X-ray single-crystal diffraction.Complex 1 belongs to the triclinic system,space group P1,a=8.077(4),b=12.365(4),c=17.735(7)A,V=1685.0(12)A3,Z=1,μ=1.372 mm^–1,Dc=1.936 g/cm^3,F(000)=984,the final R=0.0819 and wR=0.2332 with I>2σ(I).3D structure of 1 exhibits alternating organic and inorganic regions.O–H×××O hydrogen bonds and Ag–O coordination interactions exist among crystal water,coordinated water and sulfo group,which constructed an organic zone.Flavone skeletons form organic region of 1.Sulfo group is the bridge linking these two regions.The in vitro antitumor activity of 1 against human lymphoma cells U937 and human breast cancer cells MCF-7 were evaluated with CCK-8 assay.The result shows that 1 showed inhibitory activity against tumour cell U937 and MCF-7,and indicated that flavone sulfonate derivatives may be potential leads for further biological screenings and may generate drug-like molecules.展开更多
Cyclization of 2-methoxy-6-benzyloxy acetophenone hydrazone gave 3-methyl-4-meth- oxy indazole and 3-methyl-4-methoxy-7-benzyl indazole in the presence of polyphosphoric acid (PPA).The hydrazone was probably converted...Cyclization of 2-methoxy-6-benzyloxy acetophenone hydrazone gave 3-methyl-4-meth- oxy indazole and 3-methyl-4-methoxy-7-benzyl indazole in the presence of polyphosphoric acid (PPA).The hydrazone was probably converted to 2-hydroxy-6-methoxy acetophenone hydra- zone and 2-hydroxy-3-benzyl-6-methoxy acetophenone hydrazone followed by cyclization to the corresponding indazoles in acidic conditions.Cyelization of 2-methoxy-6-(halo or alkyl or aryl benzyloxy)acetophenone hydrazones gave similar products.Cyclization of 2-methoxy-6- (p-nitrobenzyloxy)acetophenone hydrazone gave 2-(p-nitrophenyl)-3-methyl-4-methoxy benzo- furan and 3-methyl-4-methoxy indazole while 2-methoxy-6-(m-nitrobenzyloxy)acetophenone hydrazone gave 3-methyl-4-methoxy indazole,3-methyl-4-methoxy-7-(m-nitrophenyl)indazole and 3-methyl-4-(m-nitrobenzyloxy)indazole.展开更多
Cultivation of an endophytic fungus Aspergillus niger EN-13 that was isolated from the inner tissue of the marine brown alga Colpomenia sinuosa resulted in the characterization of a new naphthoquinoneimine derivative,...Cultivation of an endophytic fungus Aspergillus niger EN-13 that was isolated from the inner tissue of the marine brown alga Colpomenia sinuosa resulted in the characterization of a new naphthoquinoneimine derivative, namely, 5,7-dihydroxy-2-[1-(4- methoxy-6-oxo-6H-pyran-2-yl)-2-phenylethylamino]-[ 1,4]naphthoquinone. The structure of the new compound was established on the basis of various NMR spectroscopic analyses including 2D NMR techniques, El-MS, and HR-ESI-MS. This compound displayed moderate antifungal activity.展开更多
The photo-controlled/living radical polymerization of methacrylic acid (MAA) was performed at room temperature by irradiation with a high-pressure mercury lamp using azo initiators and 4-methoxy-2,2,6,6-tetramethylpip...The photo-controlled/living radical polymerization of methacrylic acid (MAA) was performed at room temperature by irradiation with a high-pressure mercury lamp using azo initiators and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl as the mediator in the presence of (4-tert-butylphenyl)diphenylsulfonium triflate (tBuS) as the accelerator. Whereas the bulk polymerization yielded polymers with a bimodal molecular weight distribution in both the absence and presence of tBuS, the solution polymerization in methanol produced unimodal polymers with the molecular weight distribution of 2.0 - 2.3 in the presence of tBuS. The molecular weight distribution of the resulting poly (MAA) decreased with an in- crease in tBuS. The dilution of the monomer concentration also reduced the molecular weight distribution. The use of the initiator with a low 10-h half-life temperature also effectively controlled the molecular weight. The livingness of the polymerization was confirmed by obtaining linear increases in the first-order conversion versus time, the molecular weight versus the conversion, and the molecular weight versus the reciprocal of the initiator concentration.展开更多
The acceleration mechanisms by a photosensitive onium salt for the nitroxide-mediated photocontrolled/living radical polymerization (photo-NMP) were determined. The photo-NMP of methyl methacrylate was performed by ir...The acceleration mechanisms by a photosensitive onium salt for the nitroxide-mediated photocontrolled/living radical polymerization (photo-NMP) were determined. The photo-NMP of methyl methacrylate was performed by irradiation at room temperature using 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) as the mediator and (2RS, 2’RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) as the initiator. The polymerization was accelerated in the presence of (4-tertbutylphenyl)diphenylsulfonium triflate (tBuS) to produce a polymer with a molecular weight distribution as narrow as the polymerization in its absence. (±)-Camphor-10-sulfonic acid or 2-fluoro-1-methylpyridinium p-toluenesulfonate had no effect on the polymerization speed, suggesting that tBuS did not serve as the photo-acid generator for the photo-NMP. It was found that the acceleration of the polymerization was based on the electron transfer from MTEMPO into tBuS in the excited state to temporarily generate a free radical propagating chain end and an oxoaminium salt (OAS), the one-electron oxidant of MTEMPO. This electron transfer mechanism was verified on the basis of the fact that the photo-NMP in the presence of tBuS was still accelerated by triphenylamine, the electron transfer inhibitor, to partly produce a polymer with an uncontrolled molecular weight. The formation of an uncontrolled molecular weight polymer indicated the generation of a free radical propagating chain end due to the deactivation of the OAS by the triphenylamine. It was deduced that tBuS served as the electron acceptor from MTEMPO in the excited state to temporarily produce a free radical propagating chain end along with OAS, resulting in the acceleration of the polymerization.展开更多
基金supported by the Natural Science Foundation of Zhejiang Province (LY12B01003)
文摘Two d10 metal complexes Zn(NCS)2(C14HI3NO2)2 (1) and [Cd(NO3)2(CI4HI3NO2)2]. 4H20 (2) assembled by 2-methoxy-6-(phenyliminiomethyl) phenolate ligand (C14H13NO2, HL) have been synthesized and characterized by elemental analysis, IR and TG The single-crystal X-ray diffraction studies demonstrated that complex 1 crystallizes in monoclinic, P21/c space group with a = 17.321(7), b = 11.781(0), c = 15.593(2) A, fl = 110.273(6)°, V = 2984.95 A3, Z = 4, C30H26N404SzZn, Mr = 636.04, F(000) = 1312, Dc = 1.415 g/cm3,μ(MoKa) = 1.004 mm"1, the final R = 0.0403 and wR = 0.0900 for 21441 observed reflections with I 〉 20(/). Complex 2 is of monoclinic system, space group C2/c with a = 16.7767(2), b = 10.8989(2), c = 17.4928(2) A, fl = 90.614(9)°, V= 3198.37 A3, Z = 4, C28H34N4O14Cd, Mr= 731.25, F(000) = 1528, Dc = 1.568 g'cm^-3, μ(MoKa) = 0.757 mm-1, the final R = 0.0361 and wR = 0.0857 for 19811 observed reflections with I 〉 2σ(I). The two complexes were formed by Schiff base 2-methoxy-6-(phenyliminiomethyl) phenolate ligand and formed a 3D supramolecular architecture by π-πstacking interactions. Moreover, the complexes are luminescent in the solid state. These observations indicate that the complexes are promising system for the development of potential photoactive materials.
基金Scientific Research Program Funded by Shaanxi Provincial Education Department(No.18JK0837)Natural Science Basic Research Plan Funded by Shaanxi Province of China(No.2018JM2045)+2 种基金Science and Technology Projects of Xianyang City(No.2017k02-19)Scientific Research Project Funded by Xianyang Normal University(No.XSYK18006)Qing-Lan Talents Project Funded by Xianyang Normal University(No.XSYQL201904)。
文摘In order to improve the water solubility and bioavailability of 5-hydroxy-7-methoxyflavone,argentum 5-hydroxy-7-methoxy-2-phenyl-4H-chromen-4-one-6-sulfonate[Ag4(H2O)6](C(16)H(11)O4SO3)4·H2O(1,C(16)H(11)O4SO3=5-hydroxy-7-methoxy-2-phenyl-4H-chromen-4-one-6-sulfonate)was synthesized by sulfonation reaction.The structure of 1 was characterized by FT-IR,elemental analysis and X-ray single-crystal diffraction.Complex 1 belongs to the triclinic system,space group P1,a=8.077(4),b=12.365(4),c=17.735(7)A,V=1685.0(12)A3,Z=1,μ=1.372 mm^–1,Dc=1.936 g/cm^3,F(000)=984,the final R=0.0819 and wR=0.2332 with I>2σ(I).3D structure of 1 exhibits alternating organic and inorganic regions.O–H×××O hydrogen bonds and Ag–O coordination interactions exist among crystal water,coordinated water and sulfo group,which constructed an organic zone.Flavone skeletons form organic region of 1.Sulfo group is the bridge linking these two regions.The in vitro antitumor activity of 1 against human lymphoma cells U937 and human breast cancer cells MCF-7 were evaluated with CCK-8 assay.The result shows that 1 showed inhibitory activity against tumour cell U937 and MCF-7,and indicated that flavone sulfonate derivatives may be potential leads for further biological screenings and may generate drug-like molecules.
文摘Cyclization of 2-methoxy-6-benzyloxy acetophenone hydrazone gave 3-methyl-4-meth- oxy indazole and 3-methyl-4-methoxy-7-benzyl indazole in the presence of polyphosphoric acid (PPA).The hydrazone was probably converted to 2-hydroxy-6-methoxy acetophenone hydra- zone and 2-hydroxy-3-benzyl-6-methoxy acetophenone hydrazone followed by cyclization to the corresponding indazoles in acidic conditions.Cyelization of 2-methoxy-6-(halo or alkyl or aryl benzyloxy)acetophenone hydrazones gave similar products.Cyclization of 2-methoxy-6- (p-nitrobenzyloxy)acetophenone hydrazone gave 2-(p-nitrophenyl)-3-methyl-4-methoxy benzo- furan and 3-methyl-4-methoxy indazole while 2-methoxy-6-(m-nitrobenzyloxy)acetophenone hydrazone gave 3-methyl-4-methoxy indazole,3-methyl-4-methoxy-7-(m-nitrophenyl)indazole and 3-methyl-4-(m-nitrobenzyloxy)indazole.
基金partially supported by the fund of Key Laboratory of Marine Drugs(0cean University of China),Ministry of Education[KLMD(0UC)2004]by the National Natural Science Foundation of China(No.30530080)+1 种基金A program supported by the Department of Science and Technology of Shandong Province(No.2006GG2205023)by the Guangdong Key Laboratory of Marine Materia Medica is also gratefully acknowledged.
文摘Cultivation of an endophytic fungus Aspergillus niger EN-13 that was isolated from the inner tissue of the marine brown alga Colpomenia sinuosa resulted in the characterization of a new naphthoquinoneimine derivative, namely, 5,7-dihydroxy-2-[1-(4- methoxy-6-oxo-6H-pyran-2-yl)-2-phenylethylamino]-[ 1,4]naphthoquinone. The structure of the new compound was established on the basis of various NMR spectroscopic analyses including 2D NMR techniques, El-MS, and HR-ESI-MS. This compound displayed moderate antifungal activity.
文摘The photo-controlled/living radical polymerization of methacrylic acid (MAA) was performed at room temperature by irradiation with a high-pressure mercury lamp using azo initiators and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl as the mediator in the presence of (4-tert-butylphenyl)diphenylsulfonium triflate (tBuS) as the accelerator. Whereas the bulk polymerization yielded polymers with a bimodal molecular weight distribution in both the absence and presence of tBuS, the solution polymerization in methanol produced unimodal polymers with the molecular weight distribution of 2.0 - 2.3 in the presence of tBuS. The molecular weight distribution of the resulting poly (MAA) decreased with an in- crease in tBuS. The dilution of the monomer concentration also reduced the molecular weight distribution. The use of the initiator with a low 10-h half-life temperature also effectively controlled the molecular weight. The livingness of the polymerization was confirmed by obtaining linear increases in the first-order conversion versus time, the molecular weight versus the conversion, and the molecular weight versus the reciprocal of the initiator concentration.
文摘The acceleration mechanisms by a photosensitive onium salt for the nitroxide-mediated photocontrolled/living radical polymerization (photo-NMP) were determined. The photo-NMP of methyl methacrylate was performed by irradiation at room temperature using 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) as the mediator and (2RS, 2’RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) as the initiator. The polymerization was accelerated in the presence of (4-tertbutylphenyl)diphenylsulfonium triflate (tBuS) to produce a polymer with a molecular weight distribution as narrow as the polymerization in its absence. (±)-Camphor-10-sulfonic acid or 2-fluoro-1-methylpyridinium p-toluenesulfonate had no effect on the polymerization speed, suggesting that tBuS did not serve as the photo-acid generator for the photo-NMP. It was found that the acceleration of the polymerization was based on the electron transfer from MTEMPO into tBuS in the excited state to temporarily generate a free radical propagating chain end and an oxoaminium salt (OAS), the one-electron oxidant of MTEMPO. This electron transfer mechanism was verified on the basis of the fact that the photo-NMP in the presence of tBuS was still accelerated by triphenylamine, the electron transfer inhibitor, to partly produce a polymer with an uncontrolled molecular weight. The formation of an uncontrolled molecular weight polymer indicated the generation of a free radical propagating chain end due to the deactivation of the OAS by the triphenylamine. It was deduced that tBuS served as the electron acceptor from MTEMPO in the excited state to temporarily produce a free radical propagating chain end along with OAS, resulting in the acceleration of the polymerization.
基金supported by the National Natural Science Foundation of China(No.30830114)Young Academic and Technical Leader Raising Foundation of Yunnan Province to Y.-T.Di(No.2009CI072)~~