The interaction of beta-cyclodextrin(beta-CD), hydroxypropyl-beta-CD and gamma-CD with the drug rutin has been investigated by using fluorimetry. The stoichiometry of the complexes and their formation constants have b...The interaction of beta-cyclodextrin(beta-CD), hydroxypropyl-beta-CD and gamma-CD with the drug rutin has been investigated by using fluorimetry. The stoichiometry of the complexes and their formation constants have been estimated. The thermodynamic parameters for the formation of complexes were obtained. The complexing ability of HP-beta-CD is remarkably stronger than beta-CD and gamma-CD.展开更多
Organics present significant prospects as environmentally friendly and sustainable electrode materials for potassium ion batteries(PIBs)because of their abundant,recyclable and highly customizable characteristics.Howe...Organics present significant prospects as environmentally friendly and sustainable electrode materials for potassium ion batteries(PIBs)because of their abundant,recyclable and highly customizable characteristics.However,small molecular organics are easily solubilized in organic electrolytes,resulting in a low capacity and poor stability.Herein,the folic acid-based supermolecules(SM-FAs)are successfully prepared by a hydrothermal assisted self-assembly strategy.Due to multi-locus hydrogen bonds(HBs)and the cyclizedπ-conjugated interactions,the structural stability of SM-FAs has been significantly improved,and the solubility in carbonate electrolytes has been effectively inhibited.As an anode for PIB,the SM-FA-6sample exhibits a large capacity(206 mAh/g at 50 mA/g)and an outstanding cycle stability(capacity retention of 91%after 1000 cycles at 50 m A/g).More impressively,an integrative storage mechanism which combines both the general enolization reaction between C=O groups and K^(+),and the atypicalπ–K^(+)interaction within the assembled conjugation framework,is unraveled for potassium ion accumulation.It is envisioned that this facile self-assemble strategy opens up a promising avenue to modulate the stability of small molecular organic electrodes with enhanced storage capacity.展开更多
Dimethyl 4,6-bis(bromomethyl)isophthalate was synthesized by bromomethylation,oxidation,esterification and bromination of 1,3-dimethylbenzene.This was used to initiate the atom transfer radical polymerization of styre...Dimethyl 4,6-bis(bromomethyl)isophthalate was synthesized by bromomethylation,oxidation,esterification and bromination of 1,3-dimethylbenzene.This was used to initiate the atom transfer radical polymerization of styrene successfully.Results showed that the process had some of the good characteristics of controlled/living free radical poly-merization.The molecular weight of the obtained polymer increased linearly with monomer conversion,its molecular weight distribution was very narrow,and a linear relationship between ln([M]0/[M])and polymerization time was found.A well-defined novel structural polystyrene containing two ester groups in the mid-main chain was prepared with con-trolled molecular weight and narrow polydispersity.The structure of the polymer was confirmed by 1H-NMR spectra.After being hydrolyzed,dicarboxy polystyrene was obtained and used to form ionic-bonded supramolecules with 1-dodecanamine as a model of the star-shaped supramolecules.The supramolecules formed were characterized by Fourier transform infrared(FTIR)spectrum.展开更多
Two novel 3D supramolecular architectures with hexamolybdate and phosphotungstate anions were syn- thesized under ionothermal conditions. The structures were named as [Cut(L1)2]2L2[Mo6O19](1) and [Cur(L3)2]2.5...Two novel 3D supramolecular architectures with hexamolybdate and phosphotungstate anions were syn- thesized under ionothermal conditions. The structures were named as [Cut(L1)2]2L2[Mo6O19](1) and [Cur(L3)2]2.5· H0.5[PW12O40].H2O(2)(L1=2,2'-bipyridine, L2=4,4'-bipyridine, L3=2,2'-biimidazole) and characterized via Fourier transform infrared spectroscopy(FTIR) and FT-Raman spectroscopy analyses. Single-crystal X-ray diffraction analysis revealed that the two compounds crystallized in the space group P1 and were constructed through hydrogen bonding.展开更多
Amorphous carbons are promising anodes for high-rate potassium-ion batteries.Most low-temperature annealed amorphous carbons display unsatisfactory capacities.Heteroatom-induced defect engineering of amorphous carbons...Amorphous carbons are promising anodes for high-rate potassium-ion batteries.Most low-temperature annealed amorphous carbons display unsatisfactory capacities.Heteroatom-induced defect engineering of amorphous carbons could enhance their reversible capacities.Nevertheless,most lignocellulose biomasses lack heteroatoms,making it a challenge to design highly heteroatom-doped carbons(>10 at%).Herein,we report a new preparation strategy for amorphous carbon anodes.Nitrogen/sulfur co-doped lignin-derived porous carbons(NSLPC)with ultra-high nitrogen doping levels(21.6 at%of N and 0.8 at%of S)from renewable lignin biomacromolecule precursors were prepared through a supramolecule-mediated pyrolysis strategy.This supermolecule/lignin composite decomposes forming a covalently bonded graphitic carbon/amorphous carbon intermediate product,which induces the formation of high heteroatom doping in the obtained NSLPC.This unique pyrolysis chemistry and high heteroatom doping of NSLPC enable abundant defective active sites for the adsorption of K+and improved kinetics.The NSLPC anode delivered a high reversible capacity of 419 mAh g^(-1)and superior cycling stability(capacity retention of 96.6%at 1 A g^(-1)for 1000 cycles).Potassiumion hybrid capacitors assembled by NSLPC anode exhibited excellent cycling stability(91%capacity retention for 2000 cycles)and a high energy density of 71 Wh kg^(-1)at a power density of 92 W kg^(-1).展开更多
A novel supramolecular compound, [Co(IN)_2(H_2O)_4](1), was synthesized by means of the hydrothermal method and its structure was characterized with elemental analysis, FT-IR spectrum, TGA and X-ray diffraction. Thoug...A novel supramolecular compound, [Co(IN)_2(H_2O)_4](1), was synthesized by means of the hydrothermal method and its structure was characterized with elemental analysis, FT-IR spectrum, TGA and X-ray diffraction. Though the unit cell structure of the title compound is only monomeric, all these units as building blocks are assembled into a novel three-dimensional supramolecular network via the widely hydrogen-bonding and π-π stacking interactions.展开更多
Two three-dimensional complexes Ln(DMPA)3phen2(HDMPA=3,4-dimet hoxyphenylacetic acid,homoveratric acid;Ln=La,Y;phen=1,10-phenanthroline) were synthesized under hydrothermal conditions and characterized with IR and emi...Two three-dimensional complexes Ln(DMPA)3phen2(HDMPA=3,4-dimet hoxyphenylacetic acid,homoveratric acid;Ln=La,Y;phen=1,10-phenanthroline) were synthesized under hydrothermal conditions and characterized with IR and emission spectra.The crystal structures were determined with single crystal X-ray diffraction method.The two compounds were isostructural,and 3D supramolecule architectures were formed by hydrogen bonds and π-π stacking interactions.They strongly emitted upon excitation due to π→π transition of th...展开更多
A novel two-dimensional supramolecular complex [Mn(phen)(DPZDA)(H2O)]·2H2O has been synthesized by the reaction of Mn(CH3COO)2, 1,10-phenanthroline (phen) and H2DPZDA (3,5-dimethyl-pyrazine-2,6-dicarbo...A novel two-dimensional supramolecular complex [Mn(phen)(DPZDA)(H2O)]·2H2O has been synthesized by the reaction of Mn(CH3COO)2, 1,10-phenanthroline (phen) and H2DPZDA (3,5-dimethyl-pyrazine-2,6-dicarboxylic acid). Elemental analysis, IR spectra and X-ray singlecrystal diffraction were carried out to determine the composition and crystal structure of the title complex. Crystal data: triclinic system, space group P1, a = 7.7474(13), b = 9.3381(15), c = 15.146(3) A, α = 93.872(3), β= 102.451 (11 ), y = 105.261 ( 11)°, C20H20MnN4O7, Mr = 483.34, Z = 2, F(000) = 498, V=1023.2(3)A^3, Dc=1.569 g/cm^3,μ=0.697 mm^-1, -9≤h≤9, -11≤k≤10, -18≤l≤12, R = 0.0365 and wR=0.0901 for 3585 independent reflections (Rint= 0.0165) and 2923 observed reflections (I〉 2σ(I)). Structural analysis indicates that Mn(Ⅱ) adopts a distorted octahedral geometry. The 2-D framework supramolecular structure of the title complex is constructed from hydrogen bonds and π…π interactions.展开更多
The title complex [Cu(NO3)2(H2O)2(3,3-azpy)2] (3,3?azpy = 3,3?azobispyridine) has been synthesized and characterized, and its crystal belongs to the triclinic system, space group P with the following crystallographic ...The title complex [Cu(NO3)2(H2O)2(3,3-azpy)2] (3,3?azpy = 3,3?azobispyridine) has been synthesized and characterized, and its crystal belongs to the triclinic system, space group P with the following crystallographic parameters: a = 7.4161(2), b = 8.1754(3), c = 10.7545(4) ? a = 92.958(2), b = 109.978(1), g = 93.369(2)? V = 609.96(4) ?, C20H20N10CuO8, Mr = 592.00, Dc = 1.612 g/cm3, m(MoKa) = 0.964 mm-1, F(000) = 303, Z = 1, the final R = 0.0494 and wR = 0.1269 for 1945 observed reflections (I > 2s(I)). X-ray analysis reveals that the Cu atom adopts a distorted octahedral (4 + 2) coordination. The four closer donor atoms include two N atoms of 3,3?azpy and two O atoms of the coordination aqua with the CuN and CuO distances of 2.014(3) and 1.974(3) ? respectively. Two longer out-of-plane CuO bonds (2.450(3) ? from nitrate complete the strongly distorted octahedral coordination of the Cu atom. Hydrogen bonds are formed through H atoms of each coordination aqua with the remaining N atoms of 3,3?azpy and O atoms of nitrate. A two-dimensional network is constructed by hydrogen bonds and p-p interactions.展开更多
A binuclear complex [Cu2(phen)2(ip)(Hip)2].4H2O has been synthesized by the reaction of Cu(CH3COO)2.H2O, phen(1,10-phenanthroline) and isophthalic acid (H2ip) under hydrothermal condition. Elemental analys...A binuclear complex [Cu2(phen)2(ip)(Hip)2].4H2O has been synthesized by the reaction of Cu(CH3COO)2.H2O, phen(1,10-phenanthroline) and isophthalic acid (H2ip) under hydrothermal condition. Elemental analysis, IR spectra and X-ray single-crystal diffraction were carded out to determine the composition and crystal structure. Crystal data for this complex: monoclinic, space group C2/c, a = 19.214(3), b = 10.6973(14), c = 22.567(3) A, β = 105.081(2)°, C24H19N2O8Cu, Mr= 526.95, Z = 8, F(000) = 2160, V= 4478.6(10) A3, Dc = 1.563 g/cm^3,μ = 1.030 mm^-1, -24≤h≤ 16, -13≤k≤13, -28≤l≤28, R = 0.0369 and wR = 0.0819 for 4615 (Rint = 1.0357) independent reflections and 3290 observed ones (I 〉 2σ(I)). Structural analysis shows that coordination geometry of Cu( Ⅱ ) is a planar square, and the title complex exhibits a 2-D framework supramolecular structure by hydrogen bonds and π-π stacking interactions.展开更多
Based on the crystal engineering, six models of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX)/3-nitro-1,2,4-triazol-5-one(NTO) supramolecular explosive were designed. The probable formation of HMX/NTO supramol...Based on the crystal engineering, six models of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX)/3-nitro-1,2,4-triazol-5-one(NTO) supramolecular explosive were designed. The probable formation of HMX/NTO supramolecular explosive was investigated by the molecular dynamic (MD) method. Interaction between oxygen atoms in HMX and hydrogen atoms in NTO or between hydrogen atoms in HMX and oxygen atoms in NTO were studied by the radial distribution function (RDF). It shows that there are strong hydrogen bonds and Van Der Waals forces between HMX and NTO, in which the hydrogen bonds between oxygen atoms in the NTO and hydrogen atoms in HMX are the main host-guest interactions. The distributions of bond length, bond angle and dihedral angle were simulated by MD. It shows that the structure of HMX is seriously distorted. The binding energies and X-ray powder diffraction (XRD) patterns were calculated on the basis of the final HMX/NTO supramolecular structures. The results show that the binding energies of six supramolecular models are E binding (1 1 1-) >E binding (1 0 0)>E binding (0 2 0)>E binding (random)>E binding (1 0 2-)>Ebinding (0 1 1), and the XRD patterns of six supramolecular models are quite different from pure HMX or NTO. Based on the investigation for growth morphology, binding energies and RDF, the model of HMX supercell substituted by NTO along the (1 1 1-) surface of HMX is easier to form.展开更多
A new dinuclear centrosymmetric complex [LaL(HL)(H2O)3]2(2H2O (H2L = 3-nitrophthalic acid, NPA) was synthesized in water/ethanol solution and characterized by X-ray diffraction, IR spectrum and TGA-DTA. The com...A new dinuclear centrosymmetric complex [LaL(HL)(H2O)3]2(2H2O (H2L = 3-nitrophthalic acid, NPA) was synthesized in water/ethanol solution and characterized by X-ray diffraction, IR spectrum and TGA-DTA. The complex crystallizes in triclinic system, space group P1^- with a = 8.1549(16), b = 8.8856(18), c = 15.277(3)A,α= 100.93(3),α= 90.81(3), γ= 104.56(3)°, V = 1049.8(4)A^3, Z = 1,μ= 2.125 mm^-1, Dc=1.994 g/cm^3, R = 0.0259 and wR = 0.0679. Two 3-nitrophthalates(2-) coordinate with the La3+ ions in a bridging mode, and two monohydrogen- 3-nitrophthates(1-) and three waters in terminal ways, respectively. Each La^3+ ion is nine-coordinated to exhibit a distorted tricapped trigonal prism coordination polyhedron. Both the coordinated and crystal waters are involved in the inter- and intramolecular hydrogen bonds. The dinuclear units are linked into a 2D network structure in the ab plane via intermolecular hydrogen bonds along the axes a and b. Two crystal waters fill each rhombic pore of the network. The networks are further packed along the c axis forming a layered supramolecular structure through the C-H…O weak forces between the adjacent sheets. TGA analysis shows the complex undergoes the loss of waters of crystallization and coordination and the decomposition of ligands sequentially.展开更多
The title complex Co(DMSO)2(H2O)2(SCN)2 has been prepared and structurally characterized. It crystallizes in monoclinic, space group P21/n with a= 5.1981(9), b = 11.944(2), c = 12.646(2) A,β = 98.686(2)...The title complex Co(DMSO)2(H2O)2(SCN)2 has been prepared and structurally characterized. It crystallizes in monoclinic, space group P21/n with a= 5.1981(9), b = 11.944(2), c = 12.646(2) A,β = 98.686(2)°, V = 776.2(2) A^3, C6H16CoN2O4S4, Mr = 367.38, Z = 2, De = 1.572 g/cm^3, F(000) = 378 and μ(MoKa) = 1.646 mm^-1. The structure was refined to R= 0.0232 and wR = 0.0645 for 1241 observed reflections with I 〉 2σ(I). In the title complex, each Co(II) atom is octahedrally coordinated by four O atoms from two DMSO ligands and two water molecules as well as two N atoms from SCN^- ions. The title molecules are connected to each other through intermolecular hydrogen bonds to form a 1-D structure extended by eight-membered Co2O4H2 rings.展开更多
The title compound, bis( μ 2 aqua)(aqua)(3 carboxy acrylate) monosodium(Ⅰ), was synthesized in an ethanol water solution and its crystal structure was determined by means of X ray diffraction. The crystal is triclin...The title compound, bis( μ 2 aqua)(aqua)(3 carboxy acrylate) monosodium(Ⅰ), was synthesized in an ethanol water solution and its crystal structure was determined by means of X ray diffraction. The crystal is triclinic , space group P 1 with the cell parameters a =0 592 4(2) nm, b =0 635 7(3) nm, c =1 117 7(6) nm, α =104 18°, β =91 53°, γ =100 19°, V =0 400 6(3) nm 3, Z =2, the final R value is 0 033 5. The supramolecule is made up of coordination chains, which are further extended into a three dimensional network via the hydrogen bonding interactions.展开更多
With its long-term empirical clinical practice and increasing number of health benefits reported,Chinese Materia Medica(CMM)is gaining increasing global acceptance.Importantly,the identification of chemical constituen...With its long-term empirical clinical practice and increasing number of health benefits reported,Chinese Materia Medica(CMM)is gaining increasing global acceptance.Importantly,the identification of chemical constituents in vitro and exposed forms in vivo is a prerequisite for understanding how CMM formulae prevent and treat diseases.This review systematically summarizes the exciting and magical journey of CMM components from compound formulae to where they fight,the possible structural transformation of CMM components in vitro and in vivo,and their pharmacological contribution.When a decoction is prepared,significant chemical reactions are observed,including degradation and production of polymers and self-assembling supramolecules,leading to the construction of a component library with diverse decoction structures.After ingestion,compounds pass through the intestinal and blood-brain barriers and undergo a more wonderful journey involving the gut microbiota,microbial enzymes,and endogenous drug-metabolizing enzymes(mainly liver enzymes).At this stage,they are modified and assembled into novel and complex compounds,such as newly generated metabolites,conjugates,and self-assembling superamolecules.This review might provide a strategic orientation to explore the active compounds of CMM formulae in vivo.展开更多
The IR spectroscopic data indicate the tautomeric transformations of typical aprotonic organic fluids such as methane halides with gross formulas CHX3 (X = Cl, Br), CH2X2 (X = CI, Br, I) and CCl4 at normal conditi...The IR spectroscopic data indicate the tautomeric transformations of typical aprotonic organic fluids such as methane halides with gross formulas CHX3 (X = Cl, Br), CH2X2 (X = CI, Br, I) and CCl4 at normal conditions. These transformations lead to the appearance in molecules of activated hydrogen atoms similar in the spectral behaviour to the bounded proton. The classical analysis of IR bands in 5000-600 cm^-1 region, for studied samples and their deuterated derivatives, proves the existence in the presented organic fluids of hydrogen and dihydrogen bonds. This bonding promotes the formation of supramolecular structure in methane halides. The mechanism of unusual binding in liquid phase in terms of common knowledge for the basic chemical properties of the examined compounds is discussed.展开更多
A number of naphthalene derivatives containing adamantanamine binding moiety and an (CH2). (n = 2, 3, 4, 5, 6) spacer were prepared as electron donor. A supramolecular assembly was fabricated by the inclusion comp...A number of naphthalene derivatives containing adamantanamine binding moiety and an (CH2). (n = 2, 3, 4, 5, 6) spacer were prepared as electron donor. A supramolecular assembly was fabricated by the inclusion complexation of the donor substrates with the host molecules, mono-6-O-p-nitrobenzoyl-β-cyclodextrin (p-NBCD) and mono-6-O-m-nitrobenzoyl-β-cyclodextrin (m-NBCD), in water. The fluorescence quenching in these systems was studied and detailed Stern-Volmer constants were measured. It revealed that an efficient photoinduced electron transfers (PET) between the naphthalene donors and the cyclodextrin acceptors occurred.展开更多
A novel lanthanide coordination polymer formulated as [Nd(dpdo) 4(H 2O) 3] 3·4.5H 2O·dpdo 1(dpdo=4,4′-dipyrazine-dioxide) was synthesized and structurally characterized. The Nd 3+ ions are bridged b...A novel lanthanide coordination polymer formulated as [Nd(dpdo) 4(H 2O) 3] 3·4.5H 2O·dpdo 1(dpdo=4,4′-dipyrazine-dioxide) was synthesized and structurally characterized. The Nd 3+ ions are bridged by dpdo ligands in a cis-mode to form a zigzag chain along direction. Meanwhile, each Nd 3+ ion is coordinated with three terminal dpdo molecules. One of them is overlapped with the bridging one through π-π stackings, and the other two are bound to the opposite directions of the bridging ones, producing a ribbon-like motif with rectangular cavity. These adjacent ribbons are connected through inter-molecular π-π stackings to give parquet-like architecture with a large rectangular channel (1.108 nm×1.660 nm) in which the crystal lattice water molecules and ClO 4 - anions are included. Thermal analysis shows that the solvate dpdo and water molecules can be removed at lower temperature, while coordinated dpdo molecules are lost simultaneously at higher temperature.展开更多
A novel porous lanthanide-organic coordination polymer, [Nd(H2O)(HnicO)(TP)]·2H2O (1) (H2nicO=2-hydroxynicotinic acid, TP= terephthalate), was prepared under hydrothermal condition and characterized by ...A novel porous lanthanide-organic coordination polymer, [Nd(H2O)(HnicO)(TP)]·2H2O (1) (H2nicO=2-hydroxynicotinic acid, TP= terephthalate), was prepared under hydrothermal condition and characterized by single-crystal X-ray diffraction, thermogravimetric analysis and infrared spectroscopy. Compound 1 exhibited a flexible coordination geometry of lanthanide ions, which possessed a three-dimensional (3D) open framework with one-dimensional (1D) channels containing lattice water molecules. This framework structure exhibited a high stability up to 330℃ after removing free water molecules. A homometallic supramolecular framework (Zn(HnicO)2(H2O)2 (2)) was obtained due to the competitive reaction between organic ligands, Nd3+ and Zn2+ ions. The results showed that on the basis of the soft-hard/acid-base principle the coordination selection between metal ions and organic ligands played an essential role in the smart construction of lanthanide architectures.展开更多
文摘The interaction of beta-cyclodextrin(beta-CD), hydroxypropyl-beta-CD and gamma-CD with the drug rutin has been investigated by using fluorimetry. The stoichiometry of the complexes and their formation constants have been estimated. The thermodynamic parameters for the formation of complexes were obtained. The complexing ability of HP-beta-CD is remarkably stronger than beta-CD and gamma-CD.
基金the financially supported by the “Western Light”Foundation of Chinese Academy of Sciences(No.2019XBQNXZ-A-002)the Youth Innovation Promotion Association,Chinese Academy of Sciences(No.2019427)+1 种基金the Xinjiang Science Foundation for Distinguished Young Scholars(No.2019Q004)the Key Research and Development Projects of Xinjiang Uygur Autonomous Region(Nos.2022B02013 and 2022B01023)。
文摘Organics present significant prospects as environmentally friendly and sustainable electrode materials for potassium ion batteries(PIBs)because of their abundant,recyclable and highly customizable characteristics.However,small molecular organics are easily solubilized in organic electrolytes,resulting in a low capacity and poor stability.Herein,the folic acid-based supermolecules(SM-FAs)are successfully prepared by a hydrothermal assisted self-assembly strategy.Due to multi-locus hydrogen bonds(HBs)and the cyclizedπ-conjugated interactions,the structural stability of SM-FAs has been significantly improved,and the solubility in carbonate electrolytes has been effectively inhibited.As an anode for PIB,the SM-FA-6sample exhibits a large capacity(206 mAh/g at 50 mA/g)and an outstanding cycle stability(capacity retention of 91%after 1000 cycles at 50 m A/g).More impressively,an integrative storage mechanism which combines both the general enolization reaction between C=O groups and K^(+),and the atypicalπ–K^(+)interaction within the assembled conjugation framework,is unraveled for potassium ion accumulation.It is envisioned that this facile self-assemble strategy opens up a promising avenue to modulate the stability of small molecular organic electrodes with enhanced storage capacity.
基金supported by the National Natural Science Foundation of China(Grant No.20474059)Specialized Research Fund for the Doctoral Program of Higher Education(Grant No.20040358017).
文摘Dimethyl 4,6-bis(bromomethyl)isophthalate was synthesized by bromomethylation,oxidation,esterification and bromination of 1,3-dimethylbenzene.This was used to initiate the atom transfer radical polymerization of styrene successfully.Results showed that the process had some of the good characteristics of controlled/living free radical poly-merization.The molecular weight of the obtained polymer increased linearly with monomer conversion,its molecular weight distribution was very narrow,and a linear relationship between ln([M]0/[M])and polymerization time was found.A well-defined novel structural polystyrene containing two ester groups in the mid-main chain was prepared with con-trolled molecular weight and narrow polydispersity.The structure of the polymer was confirmed by 1H-NMR spectra.After being hydrolyzed,dicarboxy polystyrene was obtained and used to form ionic-bonded supramolecules with 1-dodecanamine as a model of the star-shaped supramolecules.The supramolecules formed were characterized by Fourier transform infrared(FTIR)spectrum.
基金Supported by the National Natural Science Foundation of China(No.21301019), the Youth Foundation of Science and Technology Department of Jilin Province, China(No.20130522129JH), the National Science Foundation for Post-doctoral Scientists of China(No. 2013 M530135 ) and the Proj ect of the Technology Department of Jilin Province, China(No. ZDZH2011003).
文摘Two novel 3D supramolecular architectures with hexamolybdate and phosphotungstate anions were syn- thesized under ionothermal conditions. The structures were named as [Cut(L1)2]2L2[Mo6O19](1) and [Cur(L3)2]2.5· H0.5[PW12O40].H2O(2)(L1=2,2'-bipyridine, L2=4,4'-bipyridine, L3=2,2'-biimidazole) and characterized via Fourier transform infrared spectroscopy(FTIR) and FT-Raman spectroscopy analyses. Single-crystal X-ray diffraction analysis revealed that the two compounds crystallized in the space group P1 and were constructed through hydrogen bonding.
基金the financial support from the National Natural Science Foundation of China(22108044,22208061)the Research and Development Program in Key Fields of Guangdong Province(2020B1111380002)+1 种基金the Basic Research and Applicable Basic Research in Guangzhou City(202201010290)the financial support from the Guangdong Provincial Key Laboratory of Plant Resources Biorefinery(2021GDKLPRB07)。
文摘Amorphous carbons are promising anodes for high-rate potassium-ion batteries.Most low-temperature annealed amorphous carbons display unsatisfactory capacities.Heteroatom-induced defect engineering of amorphous carbons could enhance their reversible capacities.Nevertheless,most lignocellulose biomasses lack heteroatoms,making it a challenge to design highly heteroatom-doped carbons(>10 at%).Herein,we report a new preparation strategy for amorphous carbon anodes.Nitrogen/sulfur co-doped lignin-derived porous carbons(NSLPC)with ultra-high nitrogen doping levels(21.6 at%of N and 0.8 at%of S)from renewable lignin biomacromolecule precursors were prepared through a supramolecule-mediated pyrolysis strategy.This supermolecule/lignin composite decomposes forming a covalently bonded graphitic carbon/amorphous carbon intermediate product,which induces the formation of high heteroatom doping in the obtained NSLPC.This unique pyrolysis chemistry and high heteroatom doping of NSLPC enable abundant defective active sites for the adsorption of K+and improved kinetics.The NSLPC anode delivered a high reversible capacity of 419 mAh g^(-1)and superior cycling stability(capacity retention of 96.6%at 1 A g^(-1)for 1000 cycles).Potassiumion hybrid capacitors assembled by NSLPC anode exhibited excellent cycling stability(91%capacity retention for 2000 cycles)and a high energy density of 71 Wh kg^(-1)at a power density of 92 W kg^(-1).
基金Supported by the National Natural Science Foundation of China( No.2 973 3 0 90 ),the Research Funds for the DoctoralProgram of Higher Education,the State Key L aboratory of Coordination ChemistryNanjing U niversity and the Funds ofInner Mongolia Edu
文摘A novel supramolecular compound, [Co(IN)_2(H_2O)_4](1), was synthesized by means of the hydrothermal method and its structure was characterized with elemental analysis, FT-IR spectrum, TGA and X-ray diffraction. Though the unit cell structure of the title compound is only monomeric, all these units as building blocks are assembled into a novel three-dimensional supramolecular network via the widely hydrogen-bonding and π-π stacking interactions.
文摘Two three-dimensional complexes Ln(DMPA)3phen2(HDMPA=3,4-dimet hoxyphenylacetic acid,homoveratric acid;Ln=La,Y;phen=1,10-phenanthroline) were synthesized under hydrothermal conditions and characterized with IR and emission spectra.The crystal structures were determined with single crystal X-ray diffraction method.The two compounds were isostructural,and 3D supramolecule architectures were formed by hydrogen bonds and π-π stacking interactions.They strongly emitted upon excitation due to π→π transition of th...
基金Project supported by the Natural Science Foundation of Liaoning Province (No. 20052014) and Doctor Foundation of Shenyang Institute of Chemical Technology (No. 20063204)
文摘A novel two-dimensional supramolecular complex [Mn(phen)(DPZDA)(H2O)]·2H2O has been synthesized by the reaction of Mn(CH3COO)2, 1,10-phenanthroline (phen) and H2DPZDA (3,5-dimethyl-pyrazine-2,6-dicarboxylic acid). Elemental analysis, IR spectra and X-ray singlecrystal diffraction were carried out to determine the composition and crystal structure of the title complex. Crystal data: triclinic system, space group P1, a = 7.7474(13), b = 9.3381(15), c = 15.146(3) A, α = 93.872(3), β= 102.451 (11 ), y = 105.261 ( 11)°, C20H20MnN4O7, Mr = 483.34, Z = 2, F(000) = 498, V=1023.2(3)A^3, Dc=1.569 g/cm^3,μ=0.697 mm^-1, -9≤h≤9, -11≤k≤10, -18≤l≤12, R = 0.0365 and wR=0.0901 for 3585 independent reflections (Rint= 0.0165) and 2923 observed reflections (I〉 2σ(I)). Structural analysis indicates that Mn(Ⅱ) adopts a distorted octahedral geometry. The 2-D framework supramolecular structure of the title complex is constructed from hydrogen bonds and π…π interactions.
基金the funds of the Key Laboratory of Organic Syntheses of Jiansu province, and the funds of the State Key Laboratory of Structural Chemistry
文摘The title complex [Cu(NO3)2(H2O)2(3,3-azpy)2] (3,3?azpy = 3,3?azobispyridine) has been synthesized and characterized, and its crystal belongs to the triclinic system, space group P with the following crystallographic parameters: a = 7.4161(2), b = 8.1754(3), c = 10.7545(4) ? a = 92.958(2), b = 109.978(1), g = 93.369(2)? V = 609.96(4) ?, C20H20N10CuO8, Mr = 592.00, Dc = 1.612 g/cm3, m(MoKa) = 0.964 mm-1, F(000) = 303, Z = 1, the final R = 0.0494 and wR = 0.1269 for 1945 observed reflections (I > 2s(I)). X-ray analysis reveals that the Cu atom adopts a distorted octahedral (4 + 2) coordination. The four closer donor atoms include two N atoms of 3,3?azpy and two O atoms of the coordination aqua with the CuN and CuO distances of 2.014(3) and 1.974(3) ? respectively. Two longer out-of-plane CuO bonds (2.450(3) ? from nitrate complete the strongly distorted octahedral coordination of the Cu atom. Hydrogen bonds are formed through H atoms of each coordination aqua with the remaining N atoms of 3,3?azpy and O atoms of nitrate. A two-dimensional network is constructed by hydrogen bonds and p-p interactions.
基金Project supported by the National Natural Science Foundation of China (No. 20671064)Foundation of Education Committee of Liaoning Province (No. 2005336)
文摘A binuclear complex [Cu2(phen)2(ip)(Hip)2].4H2O has been synthesized by the reaction of Cu(CH3COO)2.H2O, phen(1,10-phenanthroline) and isophthalic acid (H2ip) under hydrothermal condition. Elemental analysis, IR spectra and X-ray single-crystal diffraction were carded out to determine the composition and crystal structure. Crystal data for this complex: monoclinic, space group C2/c, a = 19.214(3), b = 10.6973(14), c = 22.567(3) A, β = 105.081(2)°, C24H19N2O8Cu, Mr= 526.95, Z = 8, F(000) = 2160, V= 4478.6(10) A3, Dc = 1.563 g/cm^3,μ = 1.030 mm^-1, -24≤h≤ 16, -13≤k≤13, -28≤l≤28, R = 0.0369 and wR = 0.0819 for 4615 (Rint = 1.0357) independent reflections and 3290 observed ones (I 〉 2σ(I)). Structural analysis shows that coordination geometry of Cu( Ⅱ ) is a planar square, and the title complex exhibits a 2-D framework supramolecular structure by hydrogen bonds and π-π stacking interactions.
基金Sponsored by the National Natural Science Foundation of China (61106078)NUST Research Funding (2011ZDJH28)
文摘Based on the crystal engineering, six models of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX)/3-nitro-1,2,4-triazol-5-one(NTO) supramolecular explosive were designed. The probable formation of HMX/NTO supramolecular explosive was investigated by the molecular dynamic (MD) method. Interaction between oxygen atoms in HMX and hydrogen atoms in NTO or between hydrogen atoms in HMX and oxygen atoms in NTO were studied by the radial distribution function (RDF). It shows that there are strong hydrogen bonds and Van Der Waals forces between HMX and NTO, in which the hydrogen bonds between oxygen atoms in the NTO and hydrogen atoms in HMX are the main host-guest interactions. The distributions of bond length, bond angle and dihedral angle were simulated by MD. It shows that the structure of HMX is seriously distorted. The binding energies and X-ray powder diffraction (XRD) patterns were calculated on the basis of the final HMX/NTO supramolecular structures. The results show that the binding energies of six supramolecular models are E binding (1 1 1-) >E binding (1 0 0)>E binding (0 2 0)>E binding (random)>E binding (1 0 2-)>Ebinding (0 1 1), and the XRD patterns of six supramolecular models are quite different from pure HMX or NTO. Based on the investigation for growth morphology, binding energies and RDF, the model of HMX supercell substituted by NTO along the (1 1 1-) surface of HMX is easier to form.
基金This work was supported by the Beijing Talent Fund for Young Sci-Tech Researchers (No. H013610050112)
文摘A new dinuclear centrosymmetric complex [LaL(HL)(H2O)3]2(2H2O (H2L = 3-nitrophthalic acid, NPA) was synthesized in water/ethanol solution and characterized by X-ray diffraction, IR spectrum and TGA-DTA. The complex crystallizes in triclinic system, space group P1^- with a = 8.1549(16), b = 8.8856(18), c = 15.277(3)A,α= 100.93(3),α= 90.81(3), γ= 104.56(3)°, V = 1049.8(4)A^3, Z = 1,μ= 2.125 mm^-1, Dc=1.994 g/cm^3, R = 0.0259 and wR = 0.0679. Two 3-nitrophthalates(2-) coordinate with the La3+ ions in a bridging mode, and two monohydrogen- 3-nitrophthates(1-) and three waters in terminal ways, respectively. Each La^3+ ion is nine-coordinated to exhibit a distorted tricapped trigonal prism coordination polyhedron. Both the coordinated and crystal waters are involved in the inter- and intramolecular hydrogen bonds. The dinuclear units are linked into a 2D network structure in the ab plane via intermolecular hydrogen bonds along the axes a and b. Two crystal waters fill each rhombic pore of the network. The networks are further packed along the c axis forming a layered supramolecular structure through the C-H…O weak forces between the adjacent sheets. TGA analysis shows the complex undergoes the loss of waters of crystallization and coordination and the decomposition of ligands sequentially.
基金This work was supported by the National Natural Science Foundation of China (No. 50572040)
文摘The title complex Co(DMSO)2(H2O)2(SCN)2 has been prepared and structurally characterized. It crystallizes in monoclinic, space group P21/n with a= 5.1981(9), b = 11.944(2), c = 12.646(2) A,β = 98.686(2)°, V = 776.2(2) A^3, C6H16CoN2O4S4, Mr = 367.38, Z = 2, De = 1.572 g/cm^3, F(000) = 378 and μ(MoKa) = 1.646 mm^-1. The structure was refined to R= 0.0232 and wR = 0.0645 for 1241 observed reflections with I 〉 2σ(I). In the title complex, each Co(II) atom is octahedrally coordinated by four O atoms from two DMSO ligands and two water molecules as well as two N atoms from SCN^- ions. The title molecules are connected to each other through intermolecular hydrogen bonds to form a 1-D structure extended by eight-membered Co2O4H2 rings.
基金Supported by the Education Comm ission of Zhejiang Province(No. 2 0 0 10 12 9) and " 5 5 1" Distinguished PersonFoundation of Wenzhou.
文摘The title compound, bis( μ 2 aqua)(aqua)(3 carboxy acrylate) monosodium(Ⅰ), was synthesized in an ethanol water solution and its crystal structure was determined by means of X ray diffraction. The crystal is triclinic , space group P 1 with the cell parameters a =0 592 4(2) nm, b =0 635 7(3) nm, c =1 117 7(6) nm, α =104 18°, β =91 53°, γ =100 19°, V =0 400 6(3) nm 3, Z =2, the final R value is 0 033 5. The supramolecule is made up of coordination chains, which are further extended into a three dimensional network via the hydrogen bonding interactions.
基金supported by the National Natural Science Foundation of China(81873192 and 81202877)Postgraduate Research and Innovation Project of Tianjin(2021YJSB288 and YJSKC-20211004)the Science and Technology Program of Tianjin(Grant No.20ZYJDJC00070)
文摘With its long-term empirical clinical practice and increasing number of health benefits reported,Chinese Materia Medica(CMM)is gaining increasing global acceptance.Importantly,the identification of chemical constituents in vitro and exposed forms in vivo is a prerequisite for understanding how CMM formulae prevent and treat diseases.This review systematically summarizes the exciting and magical journey of CMM components from compound formulae to where they fight,the possible structural transformation of CMM components in vitro and in vivo,and their pharmacological contribution.When a decoction is prepared,significant chemical reactions are observed,including degradation and production of polymers and self-assembling supramolecules,leading to the construction of a component library with diverse decoction structures.After ingestion,compounds pass through the intestinal and blood-brain barriers and undergo a more wonderful journey involving the gut microbiota,microbial enzymes,and endogenous drug-metabolizing enzymes(mainly liver enzymes).At this stage,they are modified and assembled into novel and complex compounds,such as newly generated metabolites,conjugates,and self-assembling superamolecules.This review might provide a strategic orientation to explore the active compounds of CMM formulae in vivo.
文摘The IR spectroscopic data indicate the tautomeric transformations of typical aprotonic organic fluids such as methane halides with gross formulas CHX3 (X = Cl, Br), CH2X2 (X = CI, Br, I) and CCl4 at normal conditions. These transformations lead to the appearance in molecules of activated hydrogen atoms similar in the spectral behaviour to the bounded proton. The classical analysis of IR bands in 5000-600 cm^-1 region, for studied samples and their deuterated derivatives, proves the existence in the presented organic fluids of hydrogen and dihydrogen bonds. This bonding promotes the formation of supramolecular structure in methane halides. The mechanism of unusual binding in liquid phase in terms of common knowledge for the basic chemical properties of the examined compounds is discussed.
基金the National Natural Science Foundation of China (No.20472079) for the financial support.
文摘A number of naphthalene derivatives containing adamantanamine binding moiety and an (CH2). (n = 2, 3, 4, 5, 6) spacer were prepared as electron donor. A supramolecular assembly was fabricated by the inclusion complexation of the donor substrates with the host molecules, mono-6-O-p-nitrobenzoyl-β-cyclodextrin (p-NBCD) and mono-6-O-m-nitrobenzoyl-β-cyclodextrin (m-NBCD), in water. The fluorescence quenching in these systems was studied and detailed Stern-Volmer constants were measured. It revealed that an efficient photoinduced electron transfers (PET) between the naphthalene donors and the cyclodextrin acceptors occurred.
文摘A novel lanthanide coordination polymer formulated as [Nd(dpdo) 4(H 2O) 3] 3·4.5H 2O·dpdo 1(dpdo=4,4′-dipyrazine-dioxide) was synthesized and structurally characterized. The Nd 3+ ions are bridged by dpdo ligands in a cis-mode to form a zigzag chain along direction. Meanwhile, each Nd 3+ ion is coordinated with three terminal dpdo molecules. One of them is overlapped with the bridging one through π-π stackings, and the other two are bound to the opposite directions of the bridging ones, producing a ribbon-like motif with rectangular cavity. These adjacent ribbons are connected through inter-molecular π-π stackings to give parquet-like architecture with a large rectangular channel (1.108 nm×1.660 nm) in which the crystal lattice water molecules and ClO 4 - anions are included. Thermal analysis shows that the solvate dpdo and water molecules can be removed at lower temperature, while coordinated dpdo molecules are lost simultaneously at higher temperature.
基金Program for New Century Excellent Talents in University (NCET-05-0278)the National Natural Science Foundation of China (50872016)the Foundation for the Author of National Excellent Doctoral Dissertation of China (200322)
文摘A novel porous lanthanide-organic coordination polymer, [Nd(H2O)(HnicO)(TP)]·2H2O (1) (H2nicO=2-hydroxynicotinic acid, TP= terephthalate), was prepared under hydrothermal condition and characterized by single-crystal X-ray diffraction, thermogravimetric analysis and infrared spectroscopy. Compound 1 exhibited a flexible coordination geometry of lanthanide ions, which possessed a three-dimensional (3D) open framework with one-dimensional (1D) channels containing lattice water molecules. This framework structure exhibited a high stability up to 330℃ after removing free water molecules. A homometallic supramolecular framework (Zn(HnicO)2(H2O)2 (2)) was obtained due to the competitive reaction between organic ligands, Nd3+ and Zn2+ ions. The results showed that on the basis of the soft-hard/acid-base principle the coordination selection between metal ions and organic ligands played an essential role in the smart construction of lanthanide architectures.