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ArticleTwo Novel {Ti6P2} Clusters Decorated with Inorganic Acids
ZHENG Ai-Ping, GAO Mei-Yan, FANG Wei-Hui* and KANG Yao*
Chin. J. Struct. Chem. 2021, 40, 277-282 DOI: 10.14102/j.cnki.0254-5861.2011-2853
March 15, 2021
polyoxo-titanium clusters, inorganic acid, labile coordination sites, water-splitting
ABSTRACT
Two inorganic acids decorating titanium-oxo clusters (PTCs), Ti6O4(OiPr)10(O3P-Phen)2(NO3)2 (PTC-251) and Ti6O4(OiPr)10(O3P-Phen)2(HSO4)2 (PTC-252) (H2O3P-Phen = phenylphosphinic acid) have been synthesized under solvothermal conditions. As a result of the labile coordination sites of the {Ti6P2} unit, nitrite and sulfate adopt different capping mode. Besides, they also present different space packing. The photocatalytic H2 evolution activities of these obtained PTCs have been studied, with sulfate decorating PTC-252 presenting a maximum H2 production rate up to 110.95 μmol·g-1·h-1. -
ArticleSynthesis of High-purity Fe2AlB2 and the Effect as Sintering Additive for ZrB2
WANG Rui, XU Wen-Tao, QIN Zi-Xuan, LING Jun-Rong and ZHOU You-Fu*
Chin. J. Struct. Chem. 2021, 40, 283-290 DOI: 10.14102/j.cnki.0254-5861.2011-2882
March 15, 2021
MAB phase, ternary layered structure, high purity, ZrB2
ABSTRACT
Fe2AlB2 powder material was prepared by the direct reaction of iron, aluminum and boron powders in a tubular furnace. The effects of different Al contents, temperature and raw material pretreatment on the purity of product were studied. The mixed powder with the stoichiometric ratio of 1.5Al/2Fe/2B was processed by CIP (Cold Isostatic Pressing), and then calcined at 1150 ℃ for 120 min. The product containing a small amount of impurities is treated with alkaline solution to obtain high-purity Fe2AlB2 powder. ZrB2-Fe2AlB2 composite ceramic was successfully prepared at 1250 ℃ by hot pressing sintering. The density, hardness and fracture toughness were 96.2%, 22 ± 0.3 GPa and 5.78 ± 0.5 MPa·m1/2, respectively. -
ArticleSynthesis, Characterization, Biological and Docking Simulations of 4-(Benzylideneamino) Benzoic Acids
HAMID Aziz, AAMER Saeed*, FARUKH Jabeen, ABDUL Basit, IRFAN Zia Qureshi, ABDUL Aziz, ATIF Haroon and ASHFAQ Ur Rehman
Chin. J. Struct. Chem. 2021, 40, 291-300 DOI: 10.14102/j.cnki.0254-5861.2011-2871
March 15, 2021
antidiabetic, biochemical, cholesterol, glibenclamide, simulations
ABSTRACT
The present research paper presents the synthesis, characterization, biological and computational studies of 4-(benzylideneamino) benzoic acid derivatives (3a～3g). Derivatives 3a～3c displayed best antidiabetic potential with a glucose-lowering effect compared to the reference drug Glibenclamide. Biochemical parameters including plasma glucose, serum triglycerides, cholesterol, alanine amino transferase and aspartate amino transferase levels showed significant alterations in concentrations relative to the control. Similarly, the derivatives 3a, 3d and 3e displayed potent in vitro antibacterial potential. Molecular docking simulations delineated that the ligands and complexes were stabilized at the active site by electrostatic and hydrophobic forces, consistent with the corresponding experimental results. In silico study of the binding pattern predicted that the synthesized ligands, 3d and 3a could serve as a potential surrogate for hit-to-lead generation and the design of novel antibacterial drugs. -
ArticleOne Novel Ag(I) Compound Generated from Double Schiff-base Ligand with Quinoxaline-N-oxide as Terminal Binding Sites
WANG Dong-Xiao, WANG Peng* and CHENG Jun-Yan*
Chin. J. Struct. Chem. 2021, 40, 301-305 DOI: 10.14102/j.cnki.0254-5861.2011-2843
March 15, 2021
crystal structure, double Schiff-base ligand, discrete coordination compound, hydrogen bond
ABSTRACT
One novel discrete coordination molecule with AgI centers, namely [Ag3(L)3(ClO4)3]∙3CH2Cl2∙6CH3OH∙1.5H2O (1), has been synthesized based on the double Schiff-base ligand, 3,6-bis[2-(4-oxide- quinoxaline)-yl]-4,5-diaza-3,5-octadiene (L) and AgClO4. The obtained Ag(I) compound was fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. 1 is of trigonal system space group P-31c with a = 16.320(2), b = 16.320(2), c = 20.108(6) Å, T = 173(2) K, V = 4638.2(16) Å3, Dc = 1.645 g/cm3, Mr = 2297.33, Z = 2, F(000) = 2334, μ = 0.970 mm–1, Goodness-of-fit = 1.109, the final R = 0.0776, wR = 0.1813, R indices (all data) = 0.1196, wR = 0.2011. The compound exhibits a triple-helical [Ag3L3]3+ crown-like trimer, in which three Ag(I) atoms form an equilateral triangle with the Ag···Ag distance of 4.7 Å. Uncoordinated counterions ClO4– and solvent molecules methanol generate the hydrogen-bonded frameworks based on discrete molecular complex building blocks.
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ArticleA Manganese(II) Coordination Polymer Constructed from Phosphonate Ligand: Synthesis, Crystal Structure and Magnetic Properties
XU Yan*, LIU Bin, LI Jie and GAO Li
Chin. J. Struct. Chem. 2021, 40, 306-310 DOI: 10.14102/j.cnki.0254-5861.2011-2852
March 15, 2021
manganese, phosphonate ligand, crystal structure, magnetic properties
ABSTRACT
A coordination polymer formulated as [Mn(5-pncH2)2H2O] (1, 5-pncH3 = 5-phosphono-1- naphthalenecarboxylic acid), was hydrothermally synthesized and magnetically characterized. Compound 1 features a three-dimensional structure in which the inorganic chains of [Mn(O-P-O)]n are cross-linked by the organic groups of phosphonate ligands. Magnetic measurements of 1 indicate that dominant antiferromagnetic interactions are mediated between the MnII centers. -
ArticleSynthesis, Crystal Structure and Gas Adsorption Properties of Metal-organic Supercontainer Based 2,6-Naphthalenedicarboxylate Linker
SHENG Tian-Pu, DAI Feng-Rong*, ZHENG Guo-Zong* and CHEN Zhong-Ning
Chin. J. Struct. Chem. 2021, 40, 311-316 DOI: 10.14102/j.cnki.0254-5861.2011-2855
March 15, 2021
coordination container, sulfonylcalix[4]arene, gas separation, self-assembly
ABSTRACT
A new sulfonylcalixarene-based coordination container 1 was designed and synthesized from the self-assembly reaction of p-tert-butylsulfonylcalix[4]arene (TBSC), Co(II) ion, and 2,6-naphthalenedicarboxylic acid (NDC). It crystallizes in tetragonal system, space group I4/m with a = b = 30.9119(19) Å, c = 43.565(3) Å, V = 41628(6) Å3, Dc = 0.731 g/cm3, Mr = 9162.36, C384H348Co24O126S24, Z = 2, F(000) = 9384, μ = 0.566 mm–1, the final GOOF = 1.027, R = 0.0987 and wR = 0.2474 for 7240 observed reflections with I > 2σ(I). Structural analyses indicate that 1 adopts an edge-directed octahedral geometry and consists of six TBSC-supported Co4 tetranuclear units locating on the vertices and twelve NDC bridging ligands occupying the edges. The new compound exhibits outstanding performance for the C2 hydrocarbons separation over CH4. -
ArticleLI Xiu-Ying, GAO Lin, CHE Guang-Bo*, YAN Yong-Sheng and LI Chun-Xiang*
Chin. J. Struct. Chem. 2021, 40, 317-323 DOI: 10.14102/j.cnki.0254-5861.2011-2857
March 15, 2021
Fe-based coordination polymer, hydrothermal synthesis, crystal structure, photocatalytic activity
ABSTRACT
A Fe-based coordination polymer, [Fe(C2O4)0.5(4-NCP)]n·2nH2O (1, 4-HNCP = 2-(4-carboxy- phenyl)-1H-imidazo(4,5-f)-(1,10)phenanthroline, H -
ArticleSynthesis, Crystal Structure and Antitumor Activity of a Ca(II) Coordination Polymer Based on 4-Acetylphenoxyacetate LigandsCAO Shu-Hua, TAI Xi-Shi* and XIN Chun-Ling
Chin. J. Struct. Chem. 2021, 40, 324-328 DOI: 10.14102/j.cnki.0254-5861.2011-2860
March 15, 2021
4-acetylphenoxyacetic acid, Ca(II) coordination polymer, synthesis, crystal structure, antitumor activity
ABSTRACT
A novel Ca(II) coordination polymer, [CaL2(H2O)2]n (1, HL = 4-acetylphenoxyacetic acid) has been synthesized with 4-acetylphenoxyacetic acid, Ca(ClO4)2·4H2O and NaOH as raw materials. Complex 1 was characterized by elemental analysis and single-crystal X-ray diffraction analysis. The results show that the Ca(II) ion is eight-coordinated in a distorted triangular dodecahedral geometric configuration with six carboxylate O atoms of four L ligands and two O atoms of two coordinated water molecules. Complex 1 forms a one-dimensional chained structure by the bridging effect of carboxylate O atoms. The antitumor activity of HL ligand and complex 1 has also been investigated. -
ArticleSynthesis, Crystal Structure, Theoretical Calculation, and Photophysical Property of a New Cd(II) Complex Based on N-heterocyclic Ligand and Isophthalic Acid
YAN Li*, MENG Xue, XU Yue and LIU Wei*
Chin. J. Struct. Chem. 2021, 40, 329-335 DOI: 10.14102/j.cnki.0254-5861.2011-2864
March 15, 2021
Cd(II) complex, crystal structure, fluorescence, theoretical calculation
ABSTRACT
A new metal-organic coordination complex [Cd(imp)(m-bdc)]n (1, ipm = 5-(1H-imidazo[4,5-f][1,10] phenanthrolin-2-yl)-2-methoxyphenol, m-bdc = isophthalic acid) has been synthesized by hydrothermal reaction and characterized by elemental analysis, thermogravimetric (TG) analysis, infrared spectrum (IR) and single-crystal X-ray diffraction. Complex 1 crystallizes in monoclinic, space group C2/c with a = 15.373(5), b = 16.719(5), c = 19.406(6) Å, β = 106.995(5)°, V = 4770(2) Å3, C28H18CdN4O6, Mr = 618.86, Dc = 1.724 g/cm3, μ(MoKα) = 0.971 mm–1, F(000) = 2480, Z = 8, the final R = 0.0391 and wR = 0.1044 for 4701 observed reflections (I > 2σ(I)). Single-crystal X-ray diffraction reveals that 1 exhibits a one-dimensional (1D) double-chain architecture, and the H-bond intersections link the 1D double-chain architecture into a 2D layer structure. TG analysis shows clear courses of weight loss, which corresponds to the decomposition of different ligands. We also study the luminescent properties of complex 1. In addition, to elucidate the essential electronic characters of this complex, theoretical calculation analysis was performed by the PBE0/LANL2DZ method in Gaussian 03 Program.
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ArticleSyntheses, Crystal Structures and Properties of Mn(II) and Co(II) Coordination Complexes Based on 1,10-Phenanthroline Derivative
ZHANG Hua, JI Liu-Qing, SONG Yu-Zhu, KONG Zhi-Guo, LI Cong and WANG Xiu-Yan*
Chin. J. Struct. Chem. 2021, 40, 336-342 DOI: 10.14102/j.cnki.0254-5861.2011-2901
March 15, 2021
crystal structure, coordination complex, 1,10-phenanthroline derivative, thermal behavior
ABSTRACT
Two new coordination complexes [Mn(L)2(DNSA)] (1) and [Co(L)(1,4-bdc)]n (2) have been achieved under hydrothermal conditions (H2DNSA = 3,5-dinitro-salicylic acid, 1,4-bdc = 1,4-benzenedicarboxylic acid and L = 2-(2-fluoro-6-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline). 1 crystallizes in monoclinic, space group P21/c with a = 15.871(3), b = 17.274(4), c = 16.078(3) Å, β = 113.03(3)o, V = 4056.6(16) Å3, Z = 4, C45H22Cl2F2MnN10O7, Mr = 978.57, Dc = 1.602 g/cm3, F(000) = 1980, μ(MoKa) = 0.536 mm–1, R = 0.0437 and wR = 0.1065. 2 belongs to the monoclinic system, space group C2/c with a = 14.665(2), b = 30.856(4), c = 11.237(2) Å, β = 111.166(2)o, V = 4742.0(12) Å3, Z = 8, C27H14ClCoFN4O4, Mr = 517.80, Dc = 1.602 g/cm3, F(000) = 2312, μ(MoKa) = 0.889 mm–1, R = 0.0364 and wR = 0.0862. The central Mn(II) ion in 1 is six-coordinated by four nitrogen atoms from two L ligands and two oxygen atoms from one DNSA anion. In 2, the two kinds of 1,4-bdc ligands link neighboring Co(II) atoms to yield a two-dimensional layer structure. The luminescence of 1 has been studied in detail. Moreover, thermal behaviors of 1 and 2 are also investigated. -
ArticleSynthesis, Structure, and Characterization of a Novel Coordination Polymer with Polythreading Feature
YANG Shi, JIANG Hong, ZHANG Wen-Qiang, TANG Xian-Hui, JIN Yao and LIU Yan*
Chin. J. Struct. Chem. 2021, 40, 343-348 DOI: 10.14102/j.cnki.0254-5861.2011-2877
March 15, 2021
coordination polymer, polythreading, single crystal, photoluminescence
ABSTRACT
A novel coordination polymer 1 with formula of Zn2(BDC)2(TPPA) was built from 1,4-dicarboxy- benzene (H2BDC), tris(4-(pyridin-3-yl)phenyl)amine (TPPA), and Zn(II) ion. It was characterized by single-crystal and powder X-ray diffraction, Fourier-transform infrared spectra (FT-IR), thermal gravimetric analysis (TGA), and UV-vis. 1 crystallizes in triclinic space group P
with a = 14.589, b = 14.606, c = 16.108 Å, α = 115.635o, β = 90.328o, γ = 114.662o, V = 2738.6 Å3, Z = 2, Mr = 935.52 g/mol, Dc = 1.134 g/cm3, F(000) = 956, GOOF = 1.062, the final R = 0.0685 and wR = 0.1817 for 7701 observed reflections with (I > 2σ(I)), and R = 0.0717 and wR =
0.1843 for all data. In 1, Zn(II) is
coordinated with H2BDC to form a 2D square grid, and TPPA ligands were arranged above and beneath the
2D layer. Two neighbor layers are interpenetrated
each other by π-π interactions to
generate a polythreading framework structure. Moreover, the photoluminescence
of 1 was also studied.
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ArticleTwo New Copper Complexes by H4AQTC (Anthraquinone-1,4,5,8-tetracarboxylic Acid): Syntheses, Structures and Properties
YAN Wei-Hong* and ZENG Xian-Cai
Chin. J. Struct. Chem. 2021, 40, 349-356 DOI: 10.14102/j.cnki.0254-5861.2011-2923
March 15, 2021
anthraquinone-1,4,5,8-tetracarboxylic acid, di-2-pyridyl ketone, syntheses, crystal structure
ABSTRACT
Two new complexes [Cu(AQTC)0.5(H2O)3]·3H2O}n (1, H4AQTC = anthraquinone-1,4,5,8-tetracar- boxylic acid) and Cu[(Py)2C(OH)2]2(H2AQTC)·2H2O (2, (Py)2CO = di-2-pyridyl ketone) have been prepared and characterized by elemental analyses and IR spectroscopy. X-ray crystallographic studies show that complex 1 crystallizes in monoclinic space group C2/m and complex 2 in monoclinic space group P21/c. Complex 1 features a 1D chain structure by carboxyl oxygen atoms. Complex 2 displays a mononuclear structure and anions and cations are separated. What's interesting is that the ligand of H4AQTC with eight carboxyl oxygen atoms and two quinone oxygen atoms does not directly coordinate with metals, and only exist as a counter-anion in complex 2. Three-dimensional structures of two complexes are formed by intermolecular interactions. The thermogravimetric analyses of two complexes are investigated. The luminescent properties of complex 1 are investigated as well. -
ArticleSolvothermal Synthesis, Crystal Structure and Photocurrent Property of a Ti6-Core-based Titanium Oxo ClusterGUO Yu-Hua, YU You-Zhu*, NIU Yong-Sheng, WANG Zhen, SHI Wei-Yun and WU Xian-Li
Chin. J. Struct. Chem. 2021, 40, 357-362 DOI: 10.14102/j.cnki.0254-5861.2011-2921
March 15, 2021
titanium oxo cluster, crystal structure, band gap, photocurrent response
ABSTRACT
A Ti6-core-based titanium oxo cluster (TOC) [Ti6(m2-O)2(m3-O)2(Bpo)2(PhCOO)8(OiPr)4] assembled by 2,2΄-biphenol (H2Bpo) and benzoic acid has been synthesized and characterized by IR, elemental analyses, thermogravimetric analysis and X-ray diffraction technique. Single-crystal X-ray diffraction analysis revealed that the complex crystallizes in monoclinic system, space group P21/n. The structure contains two Ti3(m3-O) units featuring a flat mode as building blocks. Solid-state UV/Vis absorption spectrum reveals that complex 1 shows a wide range from 240 to 650 nm. Moreover, the optical band gap of 1 is estimated to be 2.35 eV. Additionally, the Ti6-TOC exhibits good photocurrent response. -
ArticleHydrothermal Synthesis, Crystal Structure and Properties of a New Binuclear Nickel(III) Complex with 3-(Pyridin-2-yl)-1,2,4-triazole
LI Chang-Hong*, LI Yu-Lin*, LI Wei* and KUANG Yun-Fei
Chin. J. Struct. Chem. 2021, 40, 363-368 DOI: 10.14102/j.cnki.0254-5861.2011-2931
March 15, 2021
binuclear nickel(II) complex, thermal stability, fluorescent and magnetic properties
ABSTRACT
A new binuclear nickel(II) complex Ni2(HPT)4(H2O)3 (1) has been hydrothermally synthesized with nickel hydroxide, 3,4-pyridine dicarboxylic acid and 3-(pyridin-2-yl)-1,2,4-triazole (HPT) in the mixed solution (the volume ratio of methanol and water is 1:4). It crystallizes in tetragonal space group P42/n, with a = 20.844(1), b = 20.844(1), c = 7.2463(7) Å, V = 3148.2(5) Å3, Dc = 1.587 g/cm3, Z = 4, μ(MoKa) = 1.257, F(000) = 1544, the final GOOF = 1.043, R = 0.0437 and wR = 0.1297. The crystal structure shows that the whole molecule consists of two nickel ions which are bridged by four μ2-η1:η0-3-(pyridin-2-yl)-1,2,4-triazole anions. The coordination environment of Ni(II) ion is NiN6, giving a distorted octahedral geometry. The thermal stability and fluorescent and magnetic properties of the complex were investigated. -
ArticleDetection of Diethyl Ether by a Europium MOF through Fluorescence Enhancement
WANG Xue-Ting, WEI Wei, ZHANG Kai and DU Shao-Wu*
Chin. J. Struct. Chem. 2021, 40, 369-375 DOI: 10.14102/j.cnki.0254-5861.2011-2917
March 15, 2021
lanthanide MOF, water stable, fluorescence enhancement, diethyl ether detection
ABSTRACT
A new water-stable europium MOF, (Me2NH2)[Eu(abtc)(phen)]·2H2O (1), has been synthesized from Eu(NO3)3·6H2O with 1,10-phenanthroline (phen) and 3,3′,5,5′-azobenzenetetracarboxylic acid (H4abtc) ligands under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction analysis, IR, TGA and PXRD. It crystallizes in monoclinic system, C2/c space group, with a = 16.278(3), b = 14.261(3), c = 27.936(5) Å, b = 103.464(3)°, V = 6307(2) Å3, Z = 8, C30H26EuN5O10, Mr = 768.5, Dc = 1.543 g/cm3, F(000) = 2912, m(MoKa) = 2.044 mm‒1, R = 0.0315 and wR = 0.0663. In the structure of 1, the EuO7N2 polyhedra are assembled into a 2D layer with rhombic windows and these layers are further condensed to form a 3D framework. It can be used as selective and sensitive fluorescence sensors capable of detecting diethyl ether vapor. -
ArticleEnhancing Electrochemical Reduction of CO2 to Formate by Regulating the Support Morphology
ZHAO Xiu-Hui, ZHUO De-Huang, CHEN Qing-Song* and GUO Guo-Cong*
Chin. J. Struct. Chem. 2021, 40, 376-382 DOI: 10.14102/j.cnki.0254-5861.2011-2903
March 15, 2021
CO2ER, morphology, electrochemistry, formate
ABSTRACT
Electroreduction of CO2 to formic acid has attracted extensive attention, because it is a promising strategy to re-utilize CO2 and reduce greenhouse gas emissions that may favor the mitigation of energy and environment issues. Although great efforts have been made to tune the structure and composition of catalysts aiming to improve CO2 conversion efficiency, seldom studies have been focused on the support regulation. In this work, ordered, porous TiO2 nanotube arrays have been used as model support to study the impact of pore structure for CO2 electrochemical reduction. It has been revealed that Pd supported on TiO2 nanotube arrays substrate exhibits enhanced performance towards CO2 reduction, showing a higher formate Faradaic efficiency of 20% over than Pd supported on TiO2 film substrate. This study will shed new light on the design and synthesis of efficient catalysts by tuning the morphology of support for CO2 conversion. -
ArticleOligo(aromatic ether sulfone)-F as a Nonlinear Polarized Polymeric Material: an Experiment and DFT Study
GAN Dong-Er, ZHANG Zhang, LI Qiao-Hong and LI Wen-Mu*
Chin. J. Struct. Chem. 2021, 40, 383-393 DOI: 10.14102/j.cnki.0254-5861.2011-2878
March 15, 2021
DFT method, NLO properties, oligo(aromatic ether sulfone)-F, sum-over-states method
ABSTRACT
Polymeric membranes with diverse structures have attracted much attention as new materials for nonlinear optical devices. In this report, a novel oligomer of poly (aromatic ether sulfone) (OAES) has been synthesized and characterized. The electronic structure as well as linear and nonlinear optical properties has been studied by density function theory. The effect for general nonlinear optical polarizability of various condition has been further researched such as absence of side chains and introduction of phenyl substituent on side chains. The static and frequency-dependent hyperpolarizabilities of OAES and its derivatives have been calculated. This work interprets an efficient adjustment for the frequency response and the intensity of nonlinear optical polarizability can be achieved by regulating the structure of system, which provides a new potential for the application of oligomeric materials on nonlinear optical field. -
ArticleStudy on the Different Photocatalytic Performances for Tetracycline Hydrochloride Degradation of p-block Metal Composite Oxides Sr1.36Sb2O6 and Sr2Sb2O7HUANG Yi-Wei, MAO Jing-Yun, QIAN Qing-Rong, XUE Hun* and LIU Yan-Ru*
Chin. J. Struct. Chem. 2021, 40, 394-402 DOI: 10.14102/j.cnki.0254-5861.2011-3105
March 14, 2021
p-block metal composite oxide, Sr1.36Sb2O6, Sr2Sb2O7, photocatalytic, tetracycline hydrochloride
ABSTRACT
p-block metal composite oxides Sr1.36Sb2O6 and Sr2Sb2O7 synthesized by a hydrothermal method as photocatalysts in the degradation of tetracycline hydrochloride under UV light irradiation have been extensively studied. The effects of synthesis conditions on the photocatalytic activity were discussed. The Sr1.36Sb2O6-100 °C-24 h-5 and Sr2Sb2O7-150°C-24 h-2 samples prepared under optimal conditions exhibited remarkably different photocatalytic activities. The essential factors influencing the difference of photocatalytic performance were revealed. The results showed that the different photocatalytic activities observed for Sr1.36Sb2O6 and Sr2Sb2O7 could be attributed to their different electronic and crystal structures. Our work will provide a new perspective for the screening and design of p-block metal composite oxide photocatalysts to enhance the removal of organic pollutants in the environment.
- Address: Fuzhou High & New Technology Industrial Zone, Shangjie, Minhou, Fuzhou, Fujian 350108, China
- Tel: (86)-591-63173769, 63173770
- E-mail: cjsc@fjirsm.ac.cn