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ArticleFirst-principles Study on the Properties of CaO(100) Surface Adsorbing Carbon Dioxide
LI Ming-Yang, LI Jia-Yu, WU Miao-Miao* and WANG Xiao-Lin
Chin. J. Struct. Chem. 2021, 40, 973-984 DOI: 10.14102/j.cnki.0254-5861.2011-3072
August 15, 2021
density functional theory, CO2 adsorption, surface chemistry, CaO(100) surface, mono-dentate ligands
ABSTRACT
The increasing carbon dioxide emissions have a huge impact on the global environment. Carbonation reaction of CaO is regarded as a potential method to capture carbon dioxide. The density functional theory calculations have been performed to investigate the adsorption of CO2 on CaO(100) surface. This paper systematically studied the adsorption of CO2 at different adsorption sites on CaO(100) surface and the influence of adsorption angle on adsorption energy. Based on the studying of adsorption sites, adsorption energy and electronic structure of the CO2/CaO(100) systems, chemical adsorption mainly happens when CO2 molecules are absorbed on the CaO(100) surfaces, but physical adsorption may also happen. The research found that CO2 molecules reacted with surface O atom through C, forming monodentate surface carbonate species and tridentate carbonate. Among them, low-coordinated monodentate ligands have a higher stability than tridentate ligands due to the shorter C–OS bond length of monodentate ligands. -
ArticleConsensus Hologram QSAR Model Studying on the Aqueous Hydroxyl Radical Oxidation Reaction Rate Constants of Organic MicropollutantsJIAO Long*, LEI Bin, QU Le, LI Rui, YAN Chun-Hua and LI Hong
Chin. J. Struct. Chem. 2021, 40, 985-993 DOI: 10.14102/j.cnki.0254-5861.2011-3083
August 15, 2021
QSPR, hologram QSAR, consensus modeling, organic micropollutants, hydroxyl radical, rate constant
ABSTRACT
The combination of hologram quantitative structure-activity relationship (HQSAR) and consensus modeling was employed to study the quantitative structure-property relationship (QSPR) model for calculating the aqueous hydroxyl radical oxidation reaction rate constants (kOH) of organic micropollutants (OMPs). Firstly, individual HQSAR model were established by using standard HQSAR method. The optimal individual HQSAR model was obtained while setting the parameter of fragment distinction and fragment size to “B” and “3~6” respectively. Secondly, consensus HQSAR model was established by building the regression model between the kOH and the hologram descriptors with consensus partial least-squares (cPLS) approach. The obtained individual and consensus HQSAR model were validated with a randomly selected external test set. The result of external test set validation demonstrates that both individual and consensus HQSAR model are available for predicting the kOH of OMPs. Compared with the optimal individual HQSAR model, the established consensus HQSAR model shows higher prediction accuracy and robustness. It is shown that the combination of HQSAR and consensus modeling is a practicable and promising method for studying and predicting the kOH of OMPs. -
ArticlePolyoxovanadate-based MOFs Microsphere Constructed from 3-DDiscrete Nano-sheets as Supercapacitor
WU Xue-Min, LIU Min-Min, GUO Hong-Xu*, YING Shao-Ming and CHEN Zhang-Xu
Chin. J. Struct. Chem. 2021, 40, 994-998 DOI: 10.14102/j.cnki.0254-5861.2011-3053
August 15, 2021
MOFs microsphere, polyoxovanadate, discrete nano-sheets, supercapacitor
ABSTRACT
A novel polyoxovanadate-based MOFs microsphere, [Ni(phen)V2O7]·H2O (phen = 1,10- phenanthroline), constructed from 3-D discrete nano-sheets has been prepared and characterized by XRD, FT-IR, SEM and TEM. Electrochemical properties as supercapacitor of the as-prepared sample, such as CV, EIS, GCD and the cycle life test have also been studied. The as-prepared MOF (V, Ni) showed a high specific capacitance of 178.09 F×g-1 at 1 A×g-1 as well as good cycling stability and coulombic efficiency. This work proved that the novel MOFs based on polyoxovanadate hybrid material may serve as a promising electrode material for high-performance supercapacitor. -
ArticleOne-pot Synthesis and Formation Mechanism of Prisms-built VO2(M) with Hypersensitive Phase-transition HysteresisLI Xiong-Jian* and YANG Shui-Jin
Chin. J. Struct. Chem. 2021, 40, 999-1004 DOI: 10.14102/j.cnki.0254-5861.2011-3086
August 15, 2021
VO2(M), optical properties, hysteresis width, one-pot synthesis
ABSTRACT
Prisms-built VO2(M) micro-nanostructures with narrow hysteresis width of 2.7 ℃ were successfully synthesized using V2O5-H2C2O4-H2O system by one-pot hydrothermal approach. The structure, composition, phase transition and optical properties were characterized by XRD, SEM, DSC, and variable-temperature UV-vis. The results revealed the prism had well-defined six facets and entire smooth surface with lengths of about 500 nm and thicknesses of around 100 nm. Several prisms were connected to each other through the apical growth. The prismatic VO2(M) showed excellent phase transition and optical switching properties that would be beneficial for highly sensitive electrical/optical devices or other applications. The possible formation mechanism of prismatic VO2(M) was proposed via time-dependent SEM images and XRD patterns. Furthermore, the influence of the amount of H2O on the final product was discussed in detail. -
ArticleEnhanced Supercapacitance with Porous Single-crystalline GaN ElectrodeLI Hao and XIE Kui*
Chin. J. Struct. Chem. 2021, 40, 1005-1011 DOI: 10.14102/j.cnki.0254-5861.2011-3093
August 15, 2021
supercapacitance, GaN single crystal, Cu–CAT nanowire arrays, single-crystalline electrode
ABSTRACT
Capacitance is generally determined by the porous microstructure, electron conduction and the synergy effect of active sites in the porous electrode. In this work, we grew centimeter-scale metallic porous GaN single crystals with conductivity up to 18 S/cm at room temperature. The Cu-catecholates (Cu–CAT) nanowire arrays were grown on porous GaN single crystal to form porous single-crystalline electrode with enhanced supercapacitor performance. The Cu–CAT/GaN single crystalline electrode exhibits specific capacitance of 216 F/g and normalized capacitance of 40 µF/cm2. After 5000 cycles, it retains 80% of its initial capacitance. The porous single-crystalline GaN electrode has high porosity and excellent conductivity showing high surface capacitance. -
ArticleConjugation of Disassembled Zincphthalocyanine-based Nanocomposites and the Synergistic Effect on Visible-light Photosensitive ActivityZHAO Wen-Bo, ZHANG Ya-Lan, XU Guang-Yu, JIA Xiao* and XUE Jin-Ping*
Chin. J. Struct. Chem. 2021, 40, 1012-1022 DOI: 10.14102/j.cnki.0254-5861.2011-3104
August 15, 2021
metal-organic frameworks, zinc phthalocyanine, photosensitive activity, synergistic effect
ABSTRACT
In this research, a conjugated Pc-MIL-88B (Fe) nanoplatform was constructed via a condensation process between modified zinc phthalocyanine and MIL-88B (Fe) for the removal of organic pollutants. The as-prepared material was fully characterized by TEM, XPS, ICP, FTIR, UV-Vis, N2 adsorption-desorption isotherm, etc. The results indicate that Pc-MIL-88B (Fe) preserved the topological structure of MIL-88B (Fe), and the micropores of framework could effectively prevent the aggregation of Pc in water. Meanwhile, the conjugated Pc-MIL-88B (Fe) basically maintains the singlet oxygen quantum yield of Pc, and behaves a much higher photocurrent intensity compared to NH2-MIL-88B (Fe). Additionally, the photosensitive activity and reusability of Pc-MIL-88B (Fe) were evaluated by the degradation of methylene blue in aqueous solution under visible light irradiation, and the degradation mechanism was also investigated in detail. -
ArticleDesign and Synthesis of Tb3+-doped KGW Crystal for the Exploration of Scintillation Performance with X-ray Imaging
XU Hui, XU Wei-Wei, XU Liu-Wei, WANG Zhi-Lin, WANG Shuai-Hua*, SU Qing, ZHANG Bi-Sheng, ZENG Qing-You and WU Shao-Fan
Chin. J. Struct. Chem. 2021, 40, 1023-1030 DOI: 10.14102/j.cnki.0254-5861.2011-3134
August 15, 2021
KGW, X-ray scintillators, light yield, high stability, X-ray imaging
ABSTRACT
X-ray scintillators have been widely used in many fields owing to their strong penetrating ability, including security inspection, medical imaging, nuclear cameras, high energy physics and so forth. To explore new scintillation materials, we designed and synthesized KGW:Tb bulk scintillation crystals with monoclinic phase structure. We explored the fluorescence performance of KGW:Tb by testing the photoluminescence spectrum and fluorescence decay curve and observed strong green light emission in the visible light range at room temperature. Moreover, our crystal has a high stability under X-ray irradiation, a good sensitivity response and an appreciable light output (3424 ph/MeV) that is approximately twenty times more than PbWO4. Moreover, we used a 0.98 mm thickness polished crystal sheet for X-ray imaging applications and observed excellent results. Therefore, KGW:Tb crystal may be an important direction for X-ray scintillation detection. -
ArticleThree New Isostructural Metal-organic Coordination Polymers from Triangular Pyridinedicarboxylate Ligand: Syntheses, Structures and PropertiesZHU Ling-Bin, LI Fei, SUN Ming-Ling, QIN Ye-Yan and YAO Yuan-Gen*
Chin. J. Struct. Chem. 2021, 40, 1031-1038 DOI: 10.14102/j.cnki.0254-5861.2011-3078
August 15, 2021
isostructural polymer, 2D layers, 3D framework, hydrogen bonds, luminescence, magnetism
ABSTRACT
Three new isostructural coordination polymers, namely, [Mg(cpna)(H2O)2]n (1), [Mn(cpna)(H2O)2]n (2) and [Co(cpna)(H2O)2]n (3) (H2cpna = 5-(3-carboxylphenyl)nicotic acid) are reported. They were synthesized by hydrothermal reactions of transition metal or alkaline earth metal chloride with 5-(3-carboxylphenyl)nicotic acid, respectively. Complexes 1～3 exhibit 2D layers with a 3,3-connected topology with Schläfli symbol {4.82}. Such layers including hexagonal rings and a quadrangular ring are further extended into an ordered 3D framework by hydrogen bonds between the cpna2- ligands and water molecules. The rare complex 1 has excellent luminescence and can be used as luminescent materials, while 2 and 3 possess prominent magnetism with potential applications in magnetic materials. -
ArticleA New Pyridine-3,4-dicarboxylic Acid Bridged Zinc(II) Coordination Complex: Crystal Structure, Quantum Chemistry and Luminescence PropertyZHAN Pei-Ying, FENG Wan-Zhong, LI Xiu-Mei* and LIU Bo*
Chin. J. Struct. Chem. 2021, 40, 1039-1046 DOI: 10.14102/j.cnki.0254-5861.2011-3092
August 15, 2021
coordination polymers, hydrothermal synthesis, crystal structure, luminescence property
ABSTRACT
A new 2D metal coordination polymer, [Zn(pydc)(L)(H2O)]n·5nH2O (1, H2pydc = pyridine- 3,4-dicarboxylic acid, L = 3-(2-pyridyl)pyrazole), was synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, powder XRD, FT-IR, thermogravimetric, fluorescence spectrum and elemental analysis techniques. Complex 1 belongs to the monoclinic system, P21/c space group, with a = 10.707(5), b = 14.221(5), c = 13.278(5) Å, β = 102.071(5)°, V = 1977.1(14) Å3 and Z = 2. It features a 2D network constructed by pydc2- and L ligand. In addition, the quantum-chemical calculations were accomplished on ‘molecular fragments’ extracted from the crystal structure of 1 using the PBE0/LANL2DZ method built in Gaussian 16 Program. The calculation values denoted the distinct covalent interaction between the coordinated atoms and Zn(II) ion. -
ArticleEfficient C2 Hydrocarbons and CO2 Adsorption and Separation in a Multi-site Functionalized MOF
LI Gao-Peng, LI Zhen-Zhen, XIE Hong-Fang, FU Yun-Long* and WANG Yao-Yu*
Chin. J. Struct. Chem. 2021, 40, 1047-1054 DOI: 10.14102/j.cnki.0254-5861.2011-3094
August 15, 2021
multifunctional sites, metal-organic framework, selective gas adsorption, molecular simulations
ABSTRACT
A multi-site functionalized microporous metal-organic framework (MOF), H[Zn2(BDP)0.5(ATZ)3]·0.5H2O·0.5DMF (1), was synthesized through mixed ligands strategy. The pore surface of complex 1 was modified by uncoordinated carboxylate O atoms, phenyl and pyridyl rings as well as -NH2 groups, which strengthen interactions with C2H6, C2H4 and CO2 molecules and lead to efficiently selective C2H6, C2H4 and CO2 uptake over CH4. The selective adsorption mechanism was discussed deeply based on Grand Canonical Monte Carlo (GCMC) simulations. It is expected that this study will provide a new perspective for the rational design and synthesis of MOFs with efficient gas adsorption and separation performance.
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ArticleRare-earth Metal Dialkyl Complexes Supported by 1,3-Disubstituted Indolyl Ligand: Synthesis, Characterization and Catalytic Activity for Isoprene PolymerizationGUO Li-Ping and SONG Ren-Yuan*
Chin. J. Struct. Chem. 2021, 40, 1055-1060 DOI: 10.14102/j.cnki.0254-5861.2011-3172
August 15, 2021
indolyl ligand, rare-earth metal dialkyl complex, isoprene, polymerization
ABSTRACT
Rare-earth metal dialkyl complexes [1-Bn-3-(DippN=CH)C8H4N]RE(CH2SiMe3)2(thf)2 (Dipp = 2,6-iPr2C6H3, RE = Y (1) and Er (2)) were prepared through the cyclometalation reactions of the N-Bn-3- imino-functionalized indolyl ligand 1-Bn-3-(DippN=CH)C8H5N with one equivalent of rare-earth metal trialkyl precursors. The structures of compounds 1 and 2 were confirmed by X-ray crystal analyses and characterized by elemental analysis, IR, NMR spectroscopy wherein applicable. In the presence of cocatalysts, these rare-earth metal dialkyl complexes initiated isoprene polymerization with a high activity (95% conversion of 2000 equivalent of isoprene in 360 min), producing polymers with high regioselectivity (1,4-polymers up to 91%). -
ArticleCopper Carboxylate-phosphonates: Syntheses, Crystal Structures and Magnetic PropertiesXU Yan*
Chin. J. Struct. Chem. 2021, 40, 1061-1067 DOI: 10.14102/j.cnki.0254-5861.2011-3085
August 15, 2021
copper, carboxylate-phosphonate, crystal structure, magnetic properties
ABSTRACT
Two novel copper carboxyly-phosphonates, namely, Cu2.5(5-pnc)(SO4)0.5(OH)(H2O)0.5 (1) and Cu0.5(5-pncH2)(H2O)1.5 (2) (5-pncH3 = 5-phosphono-1-naphthalenecarboxylic acid), have been synthesized and characterized by X-ray diffraction, infrared spectroscopy, elemental analysis, and thermogravimetric analysis. In compound 1, each {PO3C} tetrahedron is corner-shared with two {Cu(1)O4}, two {Cu(2)O5} and one {Cu(3)O5}, thus forming a one-dimensional inorganic chain along the c axis containing 8-membered rings of [Cu3O4S] and 19-membered cages of [Cu5O10P4]. The inorganic chains are further connected by a 5-pnc3- ligand to generate a three-dimensional framework. Compound 2 exhibits a one-dimensional structure, in which the inorganic chains of [Cu-O-Cu]n are connected by the organic ligands through hydrogen bonding interactions, forming an infinite two-dimensional layer. Magnetic measurements of 1 indicate that dominant antiferromagnetic interactions are mediated between the Cu2+ centers. -
ArticleSynthesis, Crystal Structure and Fungicidal Activity of 3-Chloro-4-(3,4-dichloroisothiazol-5-yl)- 5-hydroxy-7-methyl-2H-chromen-2-onesLV You, LI Kun, HAO Ze-Sheng, KALININA Tatiana A., GLUKHAREVA Tatiana V.* and FAN Zhi-Jin*
Chin. J. Struct. Chem. 2021, 40, 1068-1074 DOI: 10.14102/j.cnki.0254-5861.2011-3108
August 15, 2021
coumarin, synthesis, crystal structure, fungicidal activity
ABSTRACT
3-Chloro-4-(3,4-dichloroisothiazol-5-yl)-5-hydroxy-7-methyl-2H-chromen-2-ones, a kind of coumarin derivatives, were synthesized by β-ketoester formation and cyclization. Target compound 5e was crystallized from methanol for structural identification as monoclinic crystal system, space group C2/c with a = 16.2700(6), b = 7.1801(5), c = 23.4861(10) Å, V = 2742.6(2) Å3, Z = 8, Dc = 1.756 g/cm3, F(000) = 1456 and μ = 0.827 mm-1. 8308 Reflections were collected (6.01≤2θ≤50.05°), of which 2428 were unique (Rint = 0.0432) and used in all calculations. The final R = 0.0408 (I > 2σ(I)) and wR = 0.1056 (reflections). In vitro bioassay indicated that compounds 5d & 5e possessed good activity against Botrytis cinerea, Physalospora piricola, Rhizoctonia solani, and Sclerotinia sclerotiorum with lower EC50 values falling between 0.50 and 4.85 µg/mL than that of positive control osthole with its EC50 values between 7.38 and 74.59 µg/mL. In vivo screening showed that 5e exhibited 98% and 95% efficacy against Pseudoperonospora cubensis (Berk. & Curt.) Rostov. at 100 and 50 µg/mL, respectively. Our studies discovered that the combination of bioactive substructures of isothiazole with coumarin was an effective way to novel fungicide development. -
CoMFA Model and Molecular Design of Anti-excitatory Activity for Benzodiazepinooxazole Derivatives against Mice
ZHU Li-Lan, QIN Zheng-Long and FENG Chang-Jun*
Chin. J. Struct. Chem. 2021, 40, 1075-1081 DOI: 10.14102/j.cnki.0254-5861.2011-3164
August 15, 2021
benzodiazepinooxazole derivative, mice, anti-excitatory activity, 3D-QSAR, comparative molecular field analysis
ABSTRACT
A 3D-QSAR study was conducted to analyze the anti-excitatory activity (pE) of benzodiaze- pinooxazole derivatives to mice by the comparative molecular field analysis (CoMFA) method. Among the 54 active molecules, a training set of 46 compounds was randomly selected to construct the CoMFA model; the remaining compounds, together with template molecule (No. 54) and two newly designed molecules constitute a test set of 17 compounds to validate the model. The obtained cross-validation coefficient (Rcv2), the non-cross validation coefficient (R2), and the test value F of the CoMFA model for training set are 0.516, 0.899, and 57.57, respectively. The model was used to predict the activities of all compounds in the training and testing sets, and the results indicated that the model had good correlation, strong stability and good predictability. Based on the 3D contour maps, eight novel benzodiazepinooxazole derivatives with higher anti-excitatory activity were designed. However, the effectiveness of these novel benzodiazepinooxazole derivatives is still needed to be verified by the experimental results. -
ArticleSynthesis, Crystal Structure and Characterization of a New Hydrogen-bonded Organic FrameworkSUN Jing, LIU Hai-Xiong* and LIU Tian-Fu*
Chin. J. Struct. Chem. 2021, 40, 1082-1087 DOI: 10.14102/j.cnki.0254-5861.2011-3113
August 15, 2021
tetrahydroyquinone, diethylamine, hydrogen-bonded organic framework
ABSTRACT
The hydrogen-bonded organic framework (PFC-32), constructed by tetrahydroxyquinone (THQN) and diethylamine (DEA), was readily prepared via hydrothermal synthesis in DEF (N,N-diethylformamide). PFC-32 was characterized by PXRD, IR, UV-Vis, TGA and photoluminescence (PL). Single crystal analysis reveals that PFC-32 shows a three-dimensional (3D) framework, where the THQN anions are coplanar and separated by DEA cations. PFC-32 displays intrinsic photoluminescence property owing to the alleviation of the aggregation-caused quenching (ACQ) effect caused by π-π stacking. -
ArticleSyntheses and Crystal Studies of Novel C-3΄-N-sulfonyl and 7-O-acyl Modified Paclitaxel Analogues
XIAO Shang-Qing, CUI Yong-Mei, QIU Wei-Qing, CUI Ye-Sha and LIN Hai-Xia*
Chin. J. Struct. Chem. 2021, 40, 1088-1097 DOI: 10.14102/j.cnki.0254-5861.2011-3116
August 15, 2021
paclitaxel, 3΄-N-sulfonyl, crystal structure, bioactivity, conformation
ABSTRACT
Three C-3΄-N-sulfonyl and C-7-O-acyl paclitaxel analogues were synthesized from 10-deacetyl baccatin III (10-DAB) and their structures were confirmed by 1H NMR, 13C NMR and HR-MS. Among them, the crystal structure of compound 9b was determined by single-crystal X-ray diffraction. Compound 9b crystallizes in monoclinic system, space group P21 with a = 12.395(4), b = 15.215(5), c = 14.905(5) Å, β = 105.559(4)° and Z = 2. In the structure, the introduction of the hydrophobic 3-fluorobenzoyl group at C(7) has little effect on the conformation of tetracyclic system. However, the conformation of the side-chain at C(13) in 9b is quite different from that of paclitaxel and docetaxel. -
ArticleExploration of a Library of Triazolothiadiazines as Potent Plant Growth Promoters: Design, Synthesis, X-ray Diffraction Analysis and Bioactivity StudiesDING Qi-Chun*, CAI Yi-Min, WANG Si-Lei, YAO Pei-Pao and YANG Ru-Ya
Chin. J. Struct. Chem. 2021, 40, 1098-1106 DOI: 10.14102/j.cnki.0254-5861.2011-3225
August 15, 2021
synthesis, 1,2,4-triazole, triazolothiadiazine, crystal structure, antiproliferative, plant growth regulation, bioactivity
ABSTRACT
A series of novel 3-methyl-6-aryl-7-aroyl-6,7-dihydro-5H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazines were designed, synthesized and tested for their antiproliferative activity against HepG2 cell lines in vitro by the standard SRB assay and plant growth regulation activities on wheat (amonocotyledon) and radish (adicotyledon). The results indicated all the title compounds exhibited a very weak antiproliferative activity against HepG2 cell lines in vitro unexpectedly, while showed potent plant growth-regulating activities on both wheat and radish. The crystal structure of trans-4d was obtained from X-ray diffraction: C18H13N4OSCl3, Mr = 439.75, monoclinic system, space group P21/n, a = 5.3224(7), b = 14.3578(18), c = 24.442(3) Å, β = 94.180(2)°, V = 1862.8(4) Å3, F(000) = 899, Z = 4, Dc = 1.5679 g/cm3, λ = 0.71073 Å, μ = 0.621 mm‑1 and the final R = 0.0382 for 3274 unique reflections with 2851 observed ones (I > 2σ(I)).
- Address: Fuzhou High & New Technology Industrial Zone, Shangjie, Minhou, Fuzhou, Fujian 350108, China
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