With the continuous improvement of permanent magnet(PM)wind generators'capacity and power density,the design of reasonable and efficient cooling structures has become a focus.This paper proposes a fully enclosed s...With the continuous improvement of permanent magnet(PM)wind generators'capacity and power density,the design of reasonable and efficient cooling structures has become a focus.This paper proposes a fully enclosed self-circulating hydrogen cooling structure for a originally forced-air-cooled direct-drive PM wind generator.The proposed hydrogen cooling system uses the rotor panel supports that hold the rotor core as the radial blades,and the hydrogen flow is driven by the rotating plates to flow through the axial and radial vents to realize the efficient cooling of the generator.According to the structural parameters of the cooling system,the Taguchi method is used to decouple the structural variables.The influence of the size of each cooling structure on the heat dissipation characteristic is analyzed,and the appropriate cooling structure scheme is determined.展开更多
Objective To investigate the protective effects of hydrogen peroxide preconditioning (HPP) on the pheochromocytoma (PC12) cells treated with 1-methyl-4-phenylpyridinium (MPP^+) and to explore the potential mech...Objective To investigate the protective effects of hydrogen peroxide preconditioning (HPP) on the pheochromocytoma (PC12) cells treated with 1-methyl-4-phenylpyridinium (MPP^+) and to explore the potential mechanisms. Methods The viability and apoptosis of PC 12 cells were determinded by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay and 4′,6′-diamidino-2-phenylindole (DAPI) staining, respectively. The expressions of 14-3-3 protein and phospholylated p38 mitogen-activated protein kinase (MAPK) were determined by Western blot. Enzyme-linked immunosorbent assay (ELISA) was used to measure the activity of extracellular signal-regulated protein kinase 1/2 (ERK1/2). Results The cell viability decreased and the number of apoptotic cells increased dramatically in MPP^+ group compared with that in Control group. HPP induced a significant increase in cell viability and a marked decrease in population of apoptotic cells of the MPP^+- treated PC 12 cells, accompanied with up-regulation of 14-3-3 protein and increase of ERK 1/2 and p38 MAPK activities. The 14-3-3 protein expression was positively correlated with the phosphorylation of ERK1/2. Furthermore, inhibition of the ERK1/2 with PD98059 abolished the 14-3-3 protein up-regulation in PC 12 cells induced by HPP. Conclusion HPP protects PC 12 cells against MPP+ toxicity by up-regulating 14-3-3 protein expression through the ERK1/2 and p38 MAPK signaling pathways.展开更多
Hydrogenation modification is one of the most important ways to produce high-quality petroleum resin. The col- orless C9 petroleum resin (CgPR) was obtained by two-stage catalytic hydrogenation over NiWS/?-A1203 ca...Hydrogenation modification is one of the most important ways to produce high-quality petroleum resin. The col- orless C9 petroleum resin (CgPR) was obtained by two-stage catalytic hydrogenation over NiWS/?-A1203 catalyst and PdRu/ y-A1203 catalyst connected in series. Via the hydrogenation reaction, aromatic rings in C9PR were converted to alicyclic rings, and its color was reduced from Gardner color grade No. 11 to Gardner color grade No. 0. The optimum Ni/W atomic ratio was found to be close to 0.23, while the optimum Pd/Ru atomic ratio was close to 3.80. The TEM results showed that the morphology and size of sulfide or metal particles of the two kinds of catalysts remained almost unchanged after the reac- tion was carried our for 1 204 hours, attesting to their good catalytic stability.展开更多
This paper presents an analytical solution for the thermoelastic stress in a typical in-plane's thin-film micro- thermoelectric cooling device under different operating con- ditions. The distributions of the permissi...This paper presents an analytical solution for the thermoelastic stress in a typical in-plane's thin-film micro- thermoelectric cooling device under different operating con- ditions. The distributions of the permissible temperature fields in multilayered thin-films are analytically obtained, and the characteristics, including maximum temperature dif- ference and maximum refrigerating output of the thermo- electric device, are discussed for two operating conditions. Analytical expressions of the thermoelastic stresses in the layered thermoelectric thin-films induced by the tempera- ture difference are formulated based on the theory of mul- tilayer system. The results demonstrate that, the geometric dimension is a significant factor which remarkably affects the thermoelastic stresses. The stress distributions in layers of semiconductor thermoelements, insulating and support- ing membrane show distinctly different features. The present work may profitably guide the optimization design of high- efficiency micro-thermoelectric cooling devices.展开更多
A new mono-nuclear CuII complex [Cu(DPP)(DP)Br](ClO4)H2O (DPP = 2-(3,5- dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline, DP = 3,5-dimethyl-1H-pyrazole) has been syn- thesized with 2-(3,5-dimethyl-1H-pyrazol-1...A new mono-nuclear CuII complex [Cu(DPP)(DP)Br](ClO4)H2O (DPP = 2-(3,5- dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline, DP = 3,5-dimethyl-1H-pyrazole) has been syn- thesized with 2-(3,5-dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline and 3,5-dimethyl-1H-pyrazole as ligands, and its crystal structure was determined by X-ray crystallography. The crystal is of monoclinic system, space group P21/c with a = 13.765(2), b = 17.044(3), c = 10.9044(16), β= 97.112(2)°, V = 2538.5(6)3, Z = 4, C22H24BrClCuN6O5, Mr = 631.37, Dc = 1.652 g/cm3, F(000) = 1276 and μ= 2.585 mm-1. In the crystal, DPP functions as a tridentate ligand and CuII ions assume a distorted square pyramidal geometry with Br atom lying on the apex, and at the same time, there is π-π stacking between adjacent complexes, which deals with two 1,10-phenanthroline plane rings. In addition to the π-π stacking, there are C-H···Br non-classic hydrogen bonds between adjacent complexes. The theoretical calculations reveal that the π-π stacking and C-H···Br non-classic hydrogen bond result in a weak anti-ferromagnetic interaction with 2J = -5.34 cm-1 and a weak ferromagnetic 2J = 5.92 cm-1, respectively. The magnetic coupling sign from the π-π stacking could be explained with McConnell I spin-polarization mechanism.展开更多
Enantioselective hydrogenation of ethyl 2-oxo-4-phenylbutyrate to ethyl (R)-2-hydroxy-4-phenyl- bu- tyrate on Pt/γ-Al2O3 modified by 10,11-dihydrocinchonidine was studied by investigating the influences of the amou...Enantioselective hydrogenation of ethyl 2-oxo-4-phenylbutyrate to ethyl (R)-2-hydroxy-4-phenyl- bu- tyrate on Pt/γ-Al2O3 modified by 10,11-dihydrocinchonidine was studied by investigating the influences of the amount of modifier, initial concentration of reactant, pressure and temperature on conversion and enantiometric excess in a stirred autoclave and the effects of the liquid velocity, gas velocity, modifier concentration and various catalytic beds in a trickle-bed reactor. The maximum optical yields were about 50% and 60% in the two types of reactors, respectively. It was assumed that the total hydrogenation rate included the reaction rates over the unmodified and modified active sites on platinum surface and a kinetic model, which fitted the experimental data well in autoclave, was obtained. A simplified plug-flow model was proposed to describe the bed average efficiency of trickle-bed reactor.展开更多
Photocatalytic H2 evolution reactions on pristine graphitic carbon nitrides(g-C3N4),as a promising approach for converting solar energy to fuel,are attractive for tackling global energy concerns but still suffer from ...Photocatalytic H2 evolution reactions on pristine graphitic carbon nitrides(g-C3N4),as a promising approach for converting solar energy to fuel,are attractive for tackling global energy concerns but still suffer from low efficiencies.In this article,we report a tractable approach to modifying g-C3N4 with vanadyl phthalocyanine(VOPc/CN)for efficient visible-light-driven hydrogen production.A non-covalent VOPc/CN hybrid photocatalyst formed viaπ-πstacking interactions between the two components,as confirmed by analysis of UV-vis absorption spectra.The VOPc/CN hybrid photocatalyst shows excellent visible-light-driven photocatalytic performance and good stability.Under optimal conditions,the corresponding H2 evolution rate is nearly 6 times higher than that of pure g-C3N4.The role of VOPc in promoting hydrogen evolution activity was to extend the visible light absorption range and prevent the recombination of photoexcited electron-hole pairs effectively.It is expected that this facile modification method could be a new inspiration for the rational design and exploration of g-C3N4-based hybrid systems with strong light absorption and high-efficiency carrier separation.展开更多
Asymmetric hydrogenation of (6-methoxyl-2-naphthyl)-2-acrylic acid catalyzed by cinchona modified Pd(0)-a-FeOOH was reported and ee抯 of (S)-(+)-2-(6′-methoxyl-2-naphthyl) propionic acid ((S)-(+)-naproxen) up to 98% ...Asymmetric hydrogenation of (6-methoxyl-2-naphthyl)-2-acrylic acid catalyzed by cinchona modified Pd(0)-a-FeOOH was reported and ee抯 of (S)-(+)-2-(6′-methoxyl-2-naphthyl) propionic acid ((S)-(+)-naproxen) up to 98% was achieved firstly.展开更多
The reformation of (Bi,Pb)-2223 from the liquid or melt is very important for a melting process of (Bi,Pb)-2223 tape. By combination of quenching experiment with X-ray diffraction (XRD) analysis, the effect of cooling...The reformation of (Bi,Pb)-2223 from the liquid or melt is very important for a melting process of (Bi,Pb)-2223 tape. By combination of quenching experiment with X-ray diffraction (XRD) analysis, the effect of cooling rate on the evolution of three superconducting phases in the (Bi,Pb)-2223 core of Ag-sheathed tape was investigated. The results show that (Bi,Pb)-2223 reformation from the melt seems to experience different routes during slowly cooling at different rates. One is that (Bi,Pb)-2223 phase reformed directly from the melt, and no Bi-2212 participate in this process. The other is that (Bi,Pb)-2223 is converted from the intermediate product, Bi-2212, which formed from the melt during the first cooling stage. Due to the inherent sluggish formation kinetics of (Bi,Pb)-2223 from Bi-2212, only partial (Bi,Pb)-2223 can finally be reformed with the second route.展开更多
A new coordination polymer, {[Cd(OPY)(tdc)(HO)]·H2 O}n(OPY = 4,4?-(oxybis(4,1-phenylene))dipyridine, H2 tdc = thiophene-2,5-dicarboxylic acid), has been synthesized hydrothermally based on a V-shaped ligand OPY. ...A new coordination polymer, {[Cd(OPY)(tdc)(HO)]·H2 O}n(OPY = 4,4?-(oxybis(4,1-phenylene))dipyridine, H2 tdc = thiophene-2,5-dicarboxylic acid), has been synthesized hydrothermally based on a V-shaped ligand OPY. The structure was fully characterized by elemental analysis, FT-IR spectroscopy, and X-ray single-crystal diffraction analysis. In1, two OPY ligands and one water molecule acted as terminal ligands coordinating to Cdcation to form [Cd(OPY)HO]units, which are then linked by tdc2-ligands to generate a one-dimensional chain. Every two adjacent chains linked by extensive O–H···O hydrogen bonds constitute one-dimensional double-chains, and such chains are extended into two-dimensional layers via O–H···N hydrogen bonds. These layers are further connected to form a three-dimensional supramolecular architecture via π-π stacking interactions. In addition, the thermal stability and solid state fluorescence property of 1 were also investigated.展开更多
A novel three-dimensional(3D) supramolecular architecture, {[Nd(OH-BDC)(OH-HBDC)(H2O)2]·2HaO)n(1) (OH-H2BDC=5-hydroxyisophthalic acid), which was formed through hydrogen bonds and π-π stacking betw...A novel three-dimensional(3D) supramolecular architecture, {[Nd(OH-BDC)(OH-HBDC)(H2O)2]·2HaO)n(1) (OH-H2BDC=5-hydroxyisophthalic acid), which was formed through hydrogen bonds and π-π stacking between two-dimensional(2D) layers, was hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Windmill building blocks, which consist of two nine-coordinated metal centers and four OH-H2BDC groups are connected through two carboxyl groups, to lead to a one-dimensional infinite inorganic chain(… M--O--C--O--M…) along the [100] direction. An observed intense blue luminescence with an emission band peaked at 390 nm for compound 1 may results from ligand-to-metal charge transfer(LMCT). Variable-temperature magnetic susceptibility of compound 1 was investigated and the value was deviated from the Curie-Weiss law.展开更多
Co-crystallization of 2,3,6,7,10,11-hexahydroxytriphenylene(L)with nicotinic acid(3-pyaH)and isonicotinic acid(4-pyaH)offers L·(3-pyaH)·5 H2O(1)and L·2(4-pya H)·5 H2O(2),respectively.In 1,each L li...Co-crystallization of 2,3,6,7,10,11-hexahydroxytriphenylene(L)with nicotinic acid(3-pyaH)and isonicotinic acid(4-pyaH)offers L·(3-pyaH)·5 H2O(1)and L·2(4-pya H)·5 H2O(2),respectively.In 1,each L links three neighboring L molecules via O-H···O and C-H···O hydrogen bonds,furnishing a 1 D chain.The hydrogen bonding and p-p stacking deriving from 3-pyaH and L extend the chains to a 2D layer.Lattice water molecules are interconnected to 3-pyaH via hydrogen bonds into a 1 D[(3-pya H)×5 H2O]¥chain.While in 2,Hydrogen bonding between L and 4-pyaH produces a 2D net with triangle and parallelogram grids.Water molecules locate in interlayer and grids,and O(1 w)and O(2 w)link 4-pyaH into a 1 D[(4-pyaH)×2 H2O]∞ chain.展开更多
A three-dimensional complex [Cu(3-ampy)(HEO)4](SO4)·(H2O) (3-ampy = 3-amino- pyridine) has been synthesized. Crystallographic data: C5H16CuN2O9S, Mr = 343.80, triclinic, space group P1, a = 7.675(2),...A three-dimensional complex [Cu(3-ampy)(HEO)4](SO4)·(H2O) (3-ampy = 3-amino- pyridine) has been synthesized. Crystallographic data: C5H16CuN2O9S, Mr = 343.80, triclinic, space group P1, a = 7.675(2), b = 8.225(3), c = 10.845(3)A, α= 86.996(4), β = 76.292(4), γ= 68.890(4)°, V = 620.0(3)A^3, Z = 2, Dc = 1.841 g/cm^3, F(000) = 354 and μ = 1.971 mm^-1. The structure was refined to R = 0.0269 and wR = 0.0659 for 1838 observed reflections (I 〉 2a(/)). The structure consists of [Cu(3-ampy)(H2O)4]^2+ cations, SO4^2- anions and lattice water molecules. 3-Ampy acting as a bidentate bridging ligand generates a 1D covalent chain. A supramolecular 2D framework is formed through π-π stacking of pyridine rings. The lattice water molecules and SO4^2- anions are located between the adjacent 2D frameworks. The hydrogen bonding interactions from lattice water molecules and SO4^2- anions to coordinate water extend the 2D framework into a 3D network.展开更多
A new complex C(18)H(24)CoF6N(12)Si has been synthesized by the reaction of cobalt(II) fluoride tetrahydrate with imidazole in a glass vessel. SiF62-was generated by in situ reaction of fluoride on silica. Thi...A new complex C(18)H(24)CoF6N(12)Si has been synthesized by the reaction of cobalt(II) fluoride tetrahydrate with imidazole in a glass vessel. SiF62-was generated by in situ reaction of fluoride on silica. This complex has been characterized by different techniques such as elemental analysis, IR studies, magnetic measurements, electronic absorption measurements and single-crystal X-ray structure determination. The crystals are hexagonal in the R-3 space group, with a = 13.225(6), b = 13.225(6), c = 12.517(11) A, and g = 120°. In complex [Co(im)6]SiF6, the cobalt atom is six-coordinated to adopt a regular octahedral geometry and the SiF62-ion acts as the counter anion. The crystal displays a network structure and SiF62- bridging hexagram formation by N-(39)···F-Si interactions between imdazole and SiF62-. SiF62-plays an important role in assembling the supramolecular aggregates.展开更多
A series of polymer- supported Pd -Fe2O3 composite catalysts were prepared and their hydrogenation property mas investigated. It was found that the above catalysts have good catalytic hydrogenation activity for carbon...A series of polymer- supported Pd -Fe2O3 composite catalysts were prepared and their hydrogenation property mas investigated. It was found that the above catalysts have good catalytic hydrogenation activity for carbon - carbon double bonds systems and reusability. Furthermore, XPS and IR spectra shouted that active component in the composite catalysts is atomic Pd(0). An addition of a small amount of Fe2O3 has a promotive action upon hydrogenation activity of the catalysts, which indicated that there are some strong interactions (electron transfer) between Pd(0) and Fe(Ⅲ) species. Based on these results, a possible catalytic hydrogenation mechanism was also suggested.展开更多
Two new C2-symmetrical bidentate phosphoramidite ligands were synthesized and employed in the Rh-catalyzed asymmetric hydrogenation of β-(acylamino)acrylates, up to 89% ee with full conversions was obtained.
A new double betaine 1,1′-(propane-1,3-diyl)dipyridinium-4-carboxylate L has been synthesized. Reaction of 1, 1′-(propane-1,3-diyl)dipyridinium-4-carboxylate tetrahydrate 1 with Co(ClO4)2-6H2O leads to the for...A new double betaine 1,1′-(propane-1,3-diyl)dipyridinium-4-carboxylate L has been synthesized. Reaction of 1, 1′-(propane-1,3-diyl)dipyridinium-4-carboxylate tetrahydrate 1 with Co(ClO4)2-6H2O leads to the formation of a new Co(Ⅱ) coordination compound, namely [Co(H2O)6]-2H2O-2L-2ClO4 2. The crystal structures of 1 and 2 have been determined by single-crystal X-ray diffraction method. Crystal data for 1. monoclinic, space group C2/c, a = 18.945(4), b = 7.700(2), c = l 1.888(2)A,β = 101.67(3)°, V = 1698.3(6) A^3, Z = 4, F(000) = 760.0, Dc = 1.402 g/cm^3, the final R = 0.0607 and wR = 0.1607 for 950 observed reflections (1 〉 2σ(I)); and those for 2: monoclinic, space group P21/c, a = 17.982(1), b = 15.879 (1), c = 7.0716(5)/A,β= 100.675(1)°, V= 1984.3(3) ,A^3 Z= 4, F(000) = 1010.0, Dc = 1.631 g/cm^3, the final R = 0.0316 and wR = 0.0896 for 3784 observed reflections (1 〉20(I)). Crystal structure analysis indicates that in 1, molecules of L in a "V-shaped" conformation are linked to chains sustained by O-H…O hydrogen bonds between carboxylate groups and solvent water molecules. The chains are joined by O-H…O and C-H…O hydrogen bonds to further expand into a three-dimensional structure. For 2, molecules of L in a "Z-shaped" conformation are linked by hydrogen bonds between carboxylate groups and aqua ligands to form a chain of loops running down the b axis. The (2D→2D) polythreading in compound 2 represents the mode of parallel interpenetration of 2D sheets, having polyrotaxane character.展开更多
Nano-NiO and bulk NiO were prepared from Ni(AC)_2·4 H_2O by coordination precipitation using aqueous ammonia and by a solid state reaction, respectively. The nickel oxide particles were characterized by X-ray Dif...Nano-NiO and bulk NiO were prepared from Ni(AC)_2·4 H_2O by coordination precipitation using aqueous ammonia and by a solid state reaction, respectively. The nickel oxide particles were characterized by X-ray Diffraction(XRD) and scanning electron microscopy(SEM). The results indicate that nano-sized NiO has a crystal phase with a standard face-centered cubic lattice structure, with a mean particle diameter of about 10 nm. The evaluation of the activity of nickel oxide nanoparticles in the catalytic hydrogenation of 7-methoxy-1-naphthylacetonitrile was carried out. The results demonstrate the efficient synthesis of the title compound by a one-pot catalytic hydrogenation and acetylation with NiO. The NiO nanoparticles displayed superior catalytic activity in the synthesis of agomelatine in the one-pot reaction.The total yield of agomelatine is over 81.8% with a purity of 99.2%, as determined by HPLC. The structure of agomelatine was confirmed by IR, MS, and 1 H NMR analysis.展开更多
基金supported in part by the“Chunhui Plan”Collaborative Research Project of Chinese Ministry of Education under Grant HZKY20220604by the National Natural Science Foundation of China under Grant 52107007。
文摘With the continuous improvement of permanent magnet(PM)wind generators'capacity and power density,the design of reasonable and efficient cooling structures has become a focus.This paper proposes a fully enclosed self-circulating hydrogen cooling structure for a originally forced-air-cooled direct-drive PM wind generator.The proposed hydrogen cooling system uses the rotor panel supports that hold the rotor core as the radial blades,and the hydrogen flow is driven by the rotating plates to flow through the axial and radial vents to realize the efficient cooling of the generator.According to the structural parameters of the cooling system,the Taguchi method is used to decouple the structural variables.The influence of the size of each cooling structure on the heat dissipation characteristic is analyzed,and the appropriate cooling structure scheme is determined.
基金the National Natural Science Foundation of China (No. 30570627)
文摘Objective To investigate the protective effects of hydrogen peroxide preconditioning (HPP) on the pheochromocytoma (PC12) cells treated with 1-methyl-4-phenylpyridinium (MPP^+) and to explore the potential mechanisms. Methods The viability and apoptosis of PC 12 cells were determinded by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay and 4′,6′-diamidino-2-phenylindole (DAPI) staining, respectively. The expressions of 14-3-3 protein and phospholylated p38 mitogen-activated protein kinase (MAPK) were determined by Western blot. Enzyme-linked immunosorbent assay (ELISA) was used to measure the activity of extracellular signal-regulated protein kinase 1/2 (ERK1/2). Results The cell viability decreased and the number of apoptotic cells increased dramatically in MPP^+ group compared with that in Control group. HPP induced a significant increase in cell viability and a marked decrease in population of apoptotic cells of the MPP^+- treated PC 12 cells, accompanied with up-regulation of 14-3-3 protein and increase of ERK 1/2 and p38 MAPK activities. The 14-3-3 protein expression was positively correlated with the phosphorylation of ERK1/2. Furthermore, inhibition of the ERK1/2 with PD98059 abolished the 14-3-3 protein up-regulation in PC 12 cells induced by HPP. Conclusion HPP protects PC 12 cells against MPP+ toxicity by up-regulating 14-3-3 protein expression through the ERK1/2 and p38 MAPK signaling pathways.
基金financially supported by the Scientific Research Fund of Zhejiang Provincial Education Department (Y201018517)
文摘Hydrogenation modification is one of the most important ways to produce high-quality petroleum resin. The col- orless C9 petroleum resin (CgPR) was obtained by two-stage catalytic hydrogenation over NiWS/?-A1203 catalyst and PdRu/ y-A1203 catalyst connected in series. Via the hydrogenation reaction, aromatic rings in C9PR were converted to alicyclic rings, and its color was reduced from Gardner color grade No. 11 to Gardner color grade No. 0. The optimum Ni/W atomic ratio was found to be close to 0.23, while the optimum Pd/Ru atomic ratio was close to 3.80. The TEM results showed that the morphology and size of sulfide or metal particles of the two kinds of catalysts remained almost unchanged after the reac- tion was carried our for 1 204 hours, attesting to their good catalytic stability.
基金supported by the National Basic Research Program of China(2007CB607506)the Fok Ying-Tong Education Foundation for Young Teachers in the Higher Education Institutions of China(111005)the Foundation for Innovative Research Groups of the National Natural Science Foundation of China(11121202)
文摘This paper presents an analytical solution for the thermoelastic stress in a typical in-plane's thin-film micro- thermoelectric cooling device under different operating con- ditions. The distributions of the permissible temperature fields in multilayered thin-films are analytically obtained, and the characteristics, including maximum temperature dif- ference and maximum refrigerating output of the thermo- electric device, are discussed for two operating conditions. Analytical expressions of the thermoelastic stresses in the layered thermoelectric thin-films induced by the tempera- ture difference are formulated based on the theory of mul- tilayer system. The results demonstrate that, the geometric dimension is a significant factor which remarkably affects the thermoelastic stresses. The stress distributions in layers of semiconductor thermoelements, insulating and support- ing membrane show distinctly different features. The present work may profitably guide the optimization design of high- efficiency micro-thermoelectric cooling devices.
基金supported by the National Natural Science Foundation of China (No. 20971080)the Natural Science Foundation of Shandong Province (No. ZR2009BM026 and ZR2009BL002)
文摘A new mono-nuclear CuII complex [Cu(DPP)(DP)Br](ClO4)H2O (DPP = 2-(3,5- dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline, DP = 3,5-dimethyl-1H-pyrazole) has been syn- thesized with 2-(3,5-dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline and 3,5-dimethyl-1H-pyrazole as ligands, and its crystal structure was determined by X-ray crystallography. The crystal is of monoclinic system, space group P21/c with a = 13.765(2), b = 17.044(3), c = 10.9044(16), β= 97.112(2)°, V = 2538.5(6)3, Z = 4, C22H24BrClCuN6O5, Mr = 631.37, Dc = 1.652 g/cm3, F(000) = 1276 and μ= 2.585 mm-1. In the crystal, DPP functions as a tridentate ligand and CuII ions assume a distorted square pyramidal geometry with Br atom lying on the apex, and at the same time, there is π-π stacking between adjacent complexes, which deals with two 1,10-phenanthroline plane rings. In addition to the π-π stacking, there are C-H···Br non-classic hydrogen bonds between adjacent complexes. The theoretical calculations reveal that the π-π stacking and C-H···Br non-classic hydrogen bond result in a weak anti-ferromagnetic interaction with 2J = -5.34 cm-1 and a weak ferromagnetic 2J = 5.92 cm-1, respectively. The magnetic coupling sign from the π-π stacking could be explained with McConnell I spin-polarization mechanism.
文摘Enantioselective hydrogenation of ethyl 2-oxo-4-phenylbutyrate to ethyl (R)-2-hydroxy-4-phenyl- bu- tyrate on Pt/γ-Al2O3 modified by 10,11-dihydrocinchonidine was studied by investigating the influences of the amount of modifier, initial concentration of reactant, pressure and temperature on conversion and enantiometric excess in a stirred autoclave and the effects of the liquid velocity, gas velocity, modifier concentration and various catalytic beds in a trickle-bed reactor. The maximum optical yields were about 50% and 60% in the two types of reactors, respectively. It was assumed that the total hydrogenation rate included the reaction rates over the unmodified and modified active sites on platinum surface and a kinetic model, which fitted the experimental data well in autoclave, was obtained. A simplified plug-flow model was proposed to describe the bed average efficiency of trickle-bed reactor.
基金supported by the National Natural Science Foundation of China(51572253,21771171)Scientific Research Grant of Hefei National Synchrotron Radiation Laboratory(UN2017LHJJ)+1 种基金the Fundamental Research Funds for the Central Universitiescooperation between NSFC and Netherlands Organization for Scientific Research(51561135011)~~
文摘Photocatalytic H2 evolution reactions on pristine graphitic carbon nitrides(g-C3N4),as a promising approach for converting solar energy to fuel,are attractive for tackling global energy concerns but still suffer from low efficiencies.In this article,we report a tractable approach to modifying g-C3N4 with vanadyl phthalocyanine(VOPc/CN)for efficient visible-light-driven hydrogen production.A non-covalent VOPc/CN hybrid photocatalyst formed viaπ-πstacking interactions between the two components,as confirmed by analysis of UV-vis absorption spectra.The VOPc/CN hybrid photocatalyst shows excellent visible-light-driven photocatalytic performance and good stability.Under optimal conditions,the corresponding H2 evolution rate is nearly 6 times higher than that of pure g-C3N4.The role of VOPc in promoting hydrogen evolution activity was to extend the visible light absorption range and prevent the recombination of photoexcited electron-hole pairs effectively.It is expected that this facile modification method could be a new inspiration for the rational design and exploration of g-C3N4-based hybrid systems with strong light absorption and high-efficiency carrier separation.
文摘Asymmetric hydrogenation of (6-methoxyl-2-naphthyl)-2-acrylic acid catalyzed by cinchona modified Pd(0)-a-FeOOH was reported and ee抯 of (S)-(+)-2-(6′-methoxyl-2-naphthyl) propionic acid ((S)-(+)-naproxen) up to 98% was achieved firstly.
文摘The reformation of (Bi,Pb)-2223 from the liquid or melt is very important for a melting process of (Bi,Pb)-2223 tape. By combination of quenching experiment with X-ray diffraction (XRD) analysis, the effect of cooling rate on the evolution of three superconducting phases in the (Bi,Pb)-2223 core of Ag-sheathed tape was investigated. The results show that (Bi,Pb)-2223 reformation from the melt seems to experience different routes during slowly cooling at different rates. One is that (Bi,Pb)-2223 phase reformed directly from the melt, and no Bi-2212 participate in this process. The other is that (Bi,Pb)-2223 is converted from the intermediate product, Bi-2212, which formed from the melt during the first cooling stage. Due to the inherent sluggish formation kinetics of (Bi,Pb)-2223 from Bi-2212, only partial (Bi,Pb)-2223 can finally be reformed with the second route.
基金Supported by the National Natural Science Foundation of China(Nos.21361023 and 21461023)
文摘A new coordination polymer, {[Cd(OPY)(tdc)(HO)]·H2 O}n(OPY = 4,4?-(oxybis(4,1-phenylene))dipyridine, H2 tdc = thiophene-2,5-dicarboxylic acid), has been synthesized hydrothermally based on a V-shaped ligand OPY. The structure was fully characterized by elemental analysis, FT-IR spectroscopy, and X-ray single-crystal diffraction analysis. In1, two OPY ligands and one water molecule acted as terminal ligands coordinating to Cdcation to form [Cd(OPY)HO]units, which are then linked by tdc2-ligands to generate a one-dimensional chain. Every two adjacent chains linked by extensive O–H···O hydrogen bonds constitute one-dimensional double-chains, and such chains are extended into two-dimensional layers via O–H···N hydrogen bonds. These layers are further connected to form a three-dimensional supramolecular architecture via π-π stacking interactions. In addition, the thermal stability and solid state fluorescence property of 1 were also investigated.
基金the National Natural Science Foundation of China(Nos.20371007 and 20476011)
文摘A novel three-dimensional(3D) supramolecular architecture, {[Nd(OH-BDC)(OH-HBDC)(H2O)2]·2HaO)n(1) (OH-H2BDC=5-hydroxyisophthalic acid), which was formed through hydrogen bonds and π-π stacking between two-dimensional(2D) layers, was hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Windmill building blocks, which consist of two nine-coordinated metal centers and four OH-H2BDC groups are connected through two carboxyl groups, to lead to a one-dimensional infinite inorganic chain(… M--O--C--O--M…) along the [100] direction. An observed intense blue luminescence with an emission band peaked at 390 nm for compound 1 may results from ligand-to-metal charge transfer(LMCT). Variable-temperature magnetic susceptibility of compound 1 was investigated and the value was deviated from the Curie-Weiss law.
基金Supported by the Scientific Research Project of Guangzhou Municipal Universities(1201620100)the Natural Science Foundation of Guangdong Province(2017A030313072,2016A030313619)
文摘Co-crystallization of 2,3,6,7,10,11-hexahydroxytriphenylene(L)with nicotinic acid(3-pyaH)and isonicotinic acid(4-pyaH)offers L·(3-pyaH)·5 H2O(1)and L·2(4-pya H)·5 H2O(2),respectively.In 1,each L links three neighboring L molecules via O-H···O and C-H···O hydrogen bonds,furnishing a 1 D chain.The hydrogen bonding and p-p stacking deriving from 3-pyaH and L extend the chains to a 2D layer.Lattice water molecules are interconnected to 3-pyaH via hydrogen bonds into a 1 D[(3-pya H)×5 H2O]¥chain.While in 2,Hydrogen bonding between L and 4-pyaH produces a 2D net with triangle and parallelogram grids.Water molecules locate in interlayer and grids,and O(1 w)and O(2 w)link 4-pyaH into a 1 D[(4-pyaH)×2 H2O]∞ chain.
基金the Natural Science Found Council of China (Nos. 20671011, 20331010, 90406002 and 90406024) the Key Laboratory of Structural Chemistry Foundation (No. 060017)
文摘A three-dimensional complex [Cu(3-ampy)(HEO)4](SO4)·(H2O) (3-ampy = 3-amino- pyridine) has been synthesized. Crystallographic data: C5H16CuN2O9S, Mr = 343.80, triclinic, space group P1, a = 7.675(2), b = 8.225(3), c = 10.845(3)A, α= 86.996(4), β = 76.292(4), γ= 68.890(4)°, V = 620.0(3)A^3, Z = 2, Dc = 1.841 g/cm^3, F(000) = 354 and μ = 1.971 mm^-1. The structure was refined to R = 0.0269 and wR = 0.0659 for 1838 observed reflections (I 〉 2a(/)). The structure consists of [Cu(3-ampy)(H2O)4]^2+ cations, SO4^2- anions and lattice water molecules. 3-Ampy acting as a bidentate bridging ligand generates a 1D covalent chain. A supramolecular 2D framework is formed through π-π stacking of pyridine rings. The lattice water molecules and SO4^2- anions are located between the adjacent 2D frameworks. The hydrogen bonding interactions from lattice water molecules and SO4^2- anions to coordinate water extend the 2D framework into a 3D network.
基金financially supported by Higher Education Commission of Pakistan under Indigenous PhD 5000 Fellowship Program and International Research Support Initiative Program(IRSIP)
文摘A new complex C(18)H(24)CoF6N(12)Si has been synthesized by the reaction of cobalt(II) fluoride tetrahydrate with imidazole in a glass vessel. SiF62-was generated by in situ reaction of fluoride on silica. This complex has been characterized by different techniques such as elemental analysis, IR studies, magnetic measurements, electronic absorption measurements and single-crystal X-ray structure determination. The crystals are hexagonal in the R-3 space group, with a = 13.225(6), b = 13.225(6), c = 12.517(11) A, and g = 120°. In complex [Co(im)6]SiF6, the cobalt atom is six-coordinated to adopt a regular octahedral geometry and the SiF62-ion acts as the counter anion. The crystal displays a network structure and SiF62- bridging hexagram formation by N-(39)···F-Si interactions between imdazole and SiF62-. SiF62-plays an important role in assembling the supramolecular aggregates.
文摘A series of polymer- supported Pd -Fe2O3 composite catalysts were prepared and their hydrogenation property mas investigated. It was found that the above catalysts have good catalytic hydrogenation activity for carbon - carbon double bonds systems and reusability. Furthermore, XPS and IR spectra shouted that active component in the composite catalysts is atomic Pd(0). An addition of a small amount of Fe2O3 has a promotive action upon hydrogenation activity of the catalysts, which indicated that there are some strong interactions (electron transfer) between Pd(0) and Fe(Ⅲ) species. Based on these results, a possible catalytic hydrogenation mechanism was also suggested.
基金The authors would like to thank the National Natural Science Foundation of China (No. 20472083) for financial support of this work.
文摘Two new C2-symmetrical bidentate phosphoramidite ligands were synthesized and employed in the Rh-catalyzed asymmetric hydrogenation of β-(acylamino)acrylates, up to 89% ee with full conversions was obtained.
基金This work was financially supported by Liuhui Center for Applied Mathematics, Nankai University and Tianjin University (No. H10114)
文摘A new double betaine 1,1′-(propane-1,3-diyl)dipyridinium-4-carboxylate L has been synthesized. Reaction of 1, 1′-(propane-1,3-diyl)dipyridinium-4-carboxylate tetrahydrate 1 with Co(ClO4)2-6H2O leads to the formation of a new Co(Ⅱ) coordination compound, namely [Co(H2O)6]-2H2O-2L-2ClO4 2. The crystal structures of 1 and 2 have been determined by single-crystal X-ray diffraction method. Crystal data for 1. monoclinic, space group C2/c, a = 18.945(4), b = 7.700(2), c = l 1.888(2)A,β = 101.67(3)°, V = 1698.3(6) A^3, Z = 4, F(000) = 760.0, Dc = 1.402 g/cm^3, the final R = 0.0607 and wR = 0.1607 for 950 observed reflections (1 〉 2σ(I)); and those for 2: monoclinic, space group P21/c, a = 17.982(1), b = 15.879 (1), c = 7.0716(5)/A,β= 100.675(1)°, V= 1984.3(3) ,A^3 Z= 4, F(000) = 1010.0, Dc = 1.631 g/cm^3, the final R = 0.0316 and wR = 0.0896 for 3784 observed reflections (1 〉20(I)). Crystal structure analysis indicates that in 1, molecules of L in a "V-shaped" conformation are linked to chains sustained by O-H…O hydrogen bonds between carboxylate groups and solvent water molecules. The chains are joined by O-H…O and C-H…O hydrogen bonds to further expand into a three-dimensional structure. For 2, molecules of L in a "Z-shaped" conformation are linked by hydrogen bonds between carboxylate groups and aqua ligands to form a chain of loops running down the b axis. The (2D→2D) polythreading in compound 2 represents the mode of parallel interpenetration of 2D sheets, having polyrotaxane character.
基金Funded by the Natural Science Foundation of Hubei Province(2017CFB680)the Hubei University of Science and Technology Nuclear Technology Special Project(2018-19KZ06)+1 种基金the Open Fund of the State Key Laboratory of Refractories and Metallurgy(Wuhan University of Science and Technology)of China(G201703)the Key Laboratory of Measurement and Control System for Offshore Environment,Fuqing Branch of Fujian Normal University,Fujian Province University(S1-KF1604)
文摘Nano-NiO and bulk NiO were prepared from Ni(AC)_2·4 H_2O by coordination precipitation using aqueous ammonia and by a solid state reaction, respectively. The nickel oxide particles were characterized by X-ray Diffraction(XRD) and scanning electron microscopy(SEM). The results indicate that nano-sized NiO has a crystal phase with a standard face-centered cubic lattice structure, with a mean particle diameter of about 10 nm. The evaluation of the activity of nickel oxide nanoparticles in the catalytic hydrogenation of 7-methoxy-1-naphthylacetonitrile was carried out. The results demonstrate the efficient synthesis of the title compound by a one-pot catalytic hydrogenation and acetylation with NiO. The NiO nanoparticles displayed superior catalytic activity in the synthesis of agomelatine in the one-pot reaction.The total yield of agomelatine is over 81.8% with a purity of 99.2%, as determined by HPLC. The structure of agomelatine was confirmed by IR, MS, and 1 H NMR analysis.