The application of amino acid-based surfactant in dishwasher detergent was studied in this paper. The foam and oil-removing performance of amino acid surfactants in alkaline condition were test to discuss feasibility ...The application of amino acid-based surfactant in dishwasher detergent was studied in this paper. The foam and oil-removing performance of amino acid surfactants in alkaline condition were test to discuss feasibility of amino acid-based surfactant from natural origin as the alternative to traditional nonionic surfactants from petroleum origin in dishwasher detergent. Comparative study was conducted through using various amino acid-based surfactants and nonionic surfactants respectively, together with enzymes and peroxide to formulate dishwasher detergents, and their application properties such as foam performance and detergency were also evaluated when washing different tableware in automatic dishwasher. The results showed that among all tested amino acid surfactants, glutamate surfactants showed low foaming and high oil-removing ability in alkaline condition, and excellent decontamination ability in dishwashing tests.展开更多
Two novel polymers (NJ-1 and N J-2) were synthesized by chemically modified a hypercrosslinked polymer NJ-0 with dimethylamine and trimethylamine, respectively. The comparison of the adsorption properties of the thr...Two novel polymers (NJ-1 and N J-2) were synthesized by chemically modified a hypercrosslinked polymer NJ-0 with dimethylamine and trimethylamine, respectively. The comparison of the adsorption properties of the three polymers toward phenol, resorcin and phloroglucin was made. The study focused on the static equilibrium adsorption behaviors and the adsorption thermodynamics. Freundlich equation was found to fit the adsorption results well. The effect of amino groups introduced onto the surface of the resin and the structure of phenolic compounds on the adsorption were also studied. The hydrogen-bonding interaction and electrostatic interaction could happen between the amino groups and the adsorbates. The adsorption impetus increased as quantity of hydroxyl groups increased, but the adsorption capacity decreased due to the drop of the matching degree of the aperture of resins and the diameter of adsorbate molecules.展开更多
The creation of a porous magnet is a long-sought academic goal since magnetism and porosity are hostile to one another. While long-range magnetic ordering needs spin carriers of short separation through short bridges,...The creation of a porous magnet is a long-sought academic goal since magnetism and porosity are hostile to one another. While long-range magnetic ordering needs spin carriers of short separation through short bridges, porosity relies on the use of extended connecting ligands. Here, we will give a survey of the cluster-based magnetic porous coordination polymers, i.e., 0-D MPCPs, according to their functional subunits: (1) nanoporous spin crossover materials with single metal nodes; (2) metal-radical approach with rigid organic radical ligands and single metal nodes; (C) PCPs with rigid organic ligands and metal oligomer nodes; (D) PCPs with metal complex linkers and polymetal cluster nodes; (E) PCPs with organo-polymetal cluster linkers and single metal nodes. The assembly from clusters can provide a reasonable route to resolve the hostility between magnetism and porosity. This assembly’s merits are obvious: the pore benefits from the big cluster according to "Scale Chemistry", and the functional framework inherits interesting physical properties from the clusters with a large ground spin S.展开更多
5-Hydroxymethylfurfural(5-HMF),as a key platform compound for the conversion of biomass to various biomass-derived chemicals and biofuels,has been attracted extensive attention.In this research,using Pickering high in...5-Hydroxymethylfurfural(5-HMF),as a key platform compound for the conversion of biomass to various biomass-derived chemicals and biofuels,has been attracted extensive attention.In this research,using Pickering high internal phase emulsions(Pickering HIPEs)as template and functional metal-organic frameworks(MOFs,UiO-66-SO;H and UiO-66-NH;)/Tween 85 as co-stabilizers to synthesis the dual acid-base bifunctional macroporous polymer catalyst by one-pot process,which has excellent catalytic activity in the cascade reaction of converting cellulose to 5-HMF.The effects of the emulsion parameters including the amount of surfactant(ranging from 0.5%to 2.0%(mass)),the internal phase volume fraction(ranging from 75%to 90%)and the acid/base Pickering particles mass ratio(ranging from 0:6 to 6:0)on the morphology and catalytic performance of solid catalyst were systematically researched.The results of catalytic experiments suggested that the connected large pore size of catalyst can effectively improve the cellulose conversion,and the synergistic effect of acid and base active sites can effectively improve the 5-HMF yield.The highest 5-HMF yield,about 40.5%,can be obtained by using polymer/MOFs composite as catalyst(Poly-P12,the pore size of(53.3±11.3)μm,the acid density of 1.99 mmol·g^(-1)and the base density of 1.13 mol·g^(-1))under the optimal reaction conditions(130℃,3 h).Herein,the polymer/MOFs composite with open-cell structure was prepared by the Pickering HIPEs templating method,which provided a favorable experimental basis and theoretical reference for achieving efficient production of high addedvalue product from abundant biomass.展开更多
Five new coordination polymers Cu(phen)(H2O)(phth)·CH3OH(1), [Cu(2,2′-bipy)(H2O)](phth)·3.5H2O(2), Zn(phen)(phth)(H2O)·1.125H2O(3) and [M(4,4′-bipy)(H2O)2](phth)·2H2...Five new coordination polymers Cu(phen)(H2O)(phth)·CH3OH(1), [Cu(2,2′-bipy)(H2O)](phth)·3.5H2O(2), Zn(phen)(phth)(H2O)·1.125H2O(3) and [M(4,4′-bipy)(H2O)2](phth)·2H2O[M=Zn(4), Mn(5)](H2phth=phthalic acid, bipy=bipyridine, phen=1,10-phenanthroline) have been synthesized from the amino acid derivatives(phthalyl-l- valine, H2L) and structurally characterized. H2L was hydrolyzed into phth2- group during the reaction, but the strucure feature was different from that of the complex directly synthesized from H2phth in the reported literature, revealing that H2L played an important role in composing the novel compounds. Compounds 1, 2 and 3 are all 1D chains, but the differences are that compound 1 is further hydrogen-bonded into 2D networks, and compound 2 is further extended into 3D supramolecular network through π-π stacking and hydrogen-bonding interactions. However, compound 3 is a 1D helix chain structure and further links into 2D networks through π-π stacking. Compounds 4 and 5 are isostructural and exhibit the same 2D layers, which are further connected by hydrogen-bonding interactions to form 3D supramolecular network. Antiferromagnetic superexchange was observed for compounds 1, 2 and 5.展开更多
Two N-donor ligands mediated Cd(Ⅱ) coordination polymers, namely,[Cd(L)(dmpz)2]n (1) and {[Cd(L)(atr)05(H20)](H2O)}n (2) (H2L = methyl-3-hydroxy-5-carboxy-2-thiophenecarboxylate, dmpz = 3,5-dimethy...Two N-donor ligands mediated Cd(Ⅱ) coordination polymers, namely,[Cd(L)(dmpz)2]n (1) and {[Cd(L)(atr)05(H20)](H2O)}n (2) (H2L = methyl-3-hydroxy-5-carboxy-2-thiophenecarboxylate, dmpz = 3,5-dimethylpyrazole, and atr= 4-amino-l,2,4-triazole), havebeen produced. Their structures were characterized by single-crystal X-ray diffraction analysis,elemental analyses and infrared spectra. Compound 1 possesses a one-dimensional (1D) chainstructure and is finally extended into a three-dimensional (3D) supramolecular architecturethough hydrogen bonding interactions. Compound 2 features a two-dimensional (2D) networkwith 4-connected sql topology based on dinuclear Cd(Ⅱ) clusters as nodes, which is alsoassembled into a 3D supramolecular architecture through hydrogen bonding interactions.Furthermore, compounds 1 and 2 exhibit high thermal stabilities and intense fluorescent emissionin the solid, and can be explored as potential luminescent materials.展开更多
Abstract A novel polyglycidylmethacrylate (PGMA) microspheres with high adsorption capacity of Cr(VI) was prepared by cerium(IV) initiated graft polymerization of tentacle-type polymer chains with amino group on...Abstract A novel polyglycidylmethacrylate (PGMA) microspheres with high adsorption capacity of Cr(VI) was prepared by cerium(IV) initiated graft polymerization of tentacle-type polymer chains with amino group on polymer microspheres with hydroxyl groups. The micron-sized PGMA microspheres were prepared by a dispersion polym erization method and subsequently modified by ring-opening reaction to introduce functional hydroxyl groups. The polymer microspheres were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The results indicated that the polymer microspheres had an average diameter of 5 m with uniform size distribution. The free amino group content was determined to be 5.13 mmol·g^-1 for g;PGMA-NH2 microspheres by potentiometric and conductometric titration methods. The Cr(VI) adsorption results indicated that the graft polymerization of tentacle-type polymer chains on the polymer microspheres could produce adsorbents with high adsorption capacity (500 mg-g-l). The polymer microspheres with grafted tentacle polymer chains have potenial application in large-scale removal of Cr(VI) in aqueous solution.展开更多
This article reports on the synthesis of acrylate monomer from renewable material. Vanillin was selected to be the start material to produce new monomer called vanillin acrylate and abbreviated by (VA). It has been su...This article reports on the synthesis of acrylate monomer from renewable material. Vanillin was selected to be the start material to produce new monomer called vanillin acrylate and abbreviated by (VA). It has been successfully investigated by 1H, 13C NMR, IR and UV and all results were in logic state. The next step was to synthetize three different thermo-responsive functional copolymers by incorporation of three different molar ratios of vanillin acrylate (10, 20, 30 mol%) with N-Isopropylacrylamide via free radical polymerization by AIBN as initiator in solution. All copolymers were deduced by 1NMR and IR and all showed the presence of aldehyde group. The copolymer was used for grafting of tryptophan and β-alanine through the chemical link between amino group and the active aldehyde group by click reactions to form Schiff’s base imine compounds. Moreover, polymers were also elucidated by 1HNMR, IR and UV, Size Exclusion Chromatography (SEC) was used for the molecular weight determination, differential scanning calorimeter (DSC) for glass temperature of solid polymers, XRD for crystallinity. UV-vis Spectroscopy was used for the determination of phase separation or the lower critical solution temperature (Tc) of polymers solution not only in deionized water but in pH5 and pH11. The mount of conversation and linked amino acid was determined by UV-vis Spectroscopy.展开更多
The optical alpha-amino acids were synthesized under room temperature by alkylation of N-(diphenyl methylene) glycine t-butyl ester under polymer-supported phase transfer conditions using polymer-supported cinchonine ...The optical alpha-amino acids were synthesized under room temperature by alkylation of N-(diphenyl methylene) glycine t-butyl ester under polymer-supported phase transfer conditions using polymer-supported cinchonine (or quinine) alkaloids as chiral phase transfer catalysts and dichloromethane as solvent, followed by hydrolysis of the above intermediates introduced to the final products-optical alpha-amino acids. This is a new method for the asymmetric synthesis of alpha-amino acids. The influences of catalyst, temperature, substrates, and organic solvents on the chemical yield and optical purities of products were studied.展开更多
Reaction of FeCIz'6H20, pyridine-2,4,6-tricarboxylic acid(H3pyta) and NaOH in the hydrothermal system at 185 ℃ resulted in the formation of 1D coordination polymer[Fe(Hpyta)(H2O)2](1) based on Fe-Hpyta chain...Reaction of FeCIz'6H20, pyridine-2,4,6-tricarboxylic acid(H3pyta) and NaOH in the hydrothermal system at 185 ℃ resulted in the formation of 1D coordination polymer[Fe(Hpyta)(H2O)2](1) based on Fe-Hpyta chains. When the abpt[abpt=-4-amino-3,5-bis(4-pyridyl)-l,2,4-triazole] ligand was employed in the reaction system, a 3D supramolecular porous network (H2bpt)[Fe(pyta)(H2O)2]·4H2O(2) was obtained. The framework was constructed with negative (Fe-pyta) chains and the positive H3bpt^+ in situ, formed from the abpt reagent, to form 1D channels filled with guest water molecules via hydrogen-bonds. X-Ray diffraction crystal structure analysis shows that complex 1 crystallized in the monoclinic system, space group C2/c, a=1.1490(5) nm, b=0.9008(4) nm, c=1.0058(5) nm, B=107.254(9)°, V=0.9942(8) nm3, Z=4; and complex 2 crystallizes in the triclinic system, space group P1 with a=0.90392(11) nm, b=0.96027(11 ) nm, c=1.55540(18) nm, a=73.558(2)°,B= 86.126(2)°,r= 68.745(2)°, V=1.2059(2) nm^3 and Z=2.展开更多
A novel coordination polymer, namely [Zn2(CAPA)(DMA)(H2O)]2n·n(H2O)(1,H4CAPA = 5-(bis(4-carboxybenzyl) amino) isophthalic acid, DMA = N,N-dimethylacetamide) has been synthesized through a solvotherm...A novel coordination polymer, namely [Zn2(CAPA)(DMA)(H2O)]2n·n(H2O)(1,H4CAPA = 5-(bis(4-carboxybenzyl) amino) isophthalic acid, DMA = N,N-dimethylacetamide) has been synthesized through a solvothermal method and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectra, and thermogravimetric analyses. The crystal structure is of monoclinic, space group P21/n with a = 8.0585(5), b = 18.9733(10), c = 20.2044(14) A^°3, β = 101.144(7)°, V = 3030.9(3) ?~3, C56H54Zn4N4O21, Mr = 1378.58, Z = 2). The compound forms a three-dimensional(3D) supramolecular framework by linking adjacent layers via hydrogen bonds and π···π interactions. It is interesting that the crystal structure is much related to the flexibility and configuration of the ligand. In addition, the thermal stability and luminescence properties for the compound have also been investigated.展开更多
Mn(L-Phe)2稨2O]n (Phe=phenylalanine) with a single stranded coordination poly- mer has been synthesized by self-assembly of manganese salt and phenylalanine and characterized by X-ray single-crystal diffraction method...Mn(L-Phe)2稨2O]n (Phe=phenylalanine) with a single stranded coordination poly- mer has been synthesized by self-assembly of manganese salt and phenylalanine and characterized by X-ray single-crystal diffraction method. The complex crystallizes in the orthorhombic, space group P212121 with a = 6.0911(1), b = 10.3642(1), c = 30.4321(7) ? V = 1921.16(6) ?, Z = 4, Dc = 1.387 g/cm3, C18H22N2O5Mn, Mr = 401.32, F(000) = 836 and m(MoKa) = 0.717 mm-1. The final R = 0.0614 and wR = 0.1412 for 2291 observed reflections with I > 2s(I). The magnetic behavior study shows that there exist super-exchange antiferromagnetic interactions between the magnetic centers through the effective exchange pathway of the carboxylate group.展开更多
A new complex [Cu(L)(1,10-phen)]n (1, L = N-3-pyridine sulfonyl amino acid) has been synthesized and characterized by IR, elemental analysis and X-ray diffraction analysis, and its crystal belongs to monoclinic,...A new complex [Cu(L)(1,10-phen)]n (1, L = N-3-pyridine sulfonyl amino acid) has been synthesized and characterized by IR, elemental analysis and X-ray diffraction analysis, and its crystal belongs to monoclinic, space group P2Jc with a = 11.481 (2), b = 1 8.094(4), c = 8.5198(17) ]°, β= 102.26(3)°, V = 1729.5(6) ,/k3, Z = 4, Dc = 1.759 g/cm3, F(000) = 932, p = 1.422 mm-1, R = 0.0368 and wR = 0.0893. In 1, the Cu(ll) ion adopts a slightly distorted five-coordinated square pyramidal geometry. The L2- ligand adopts O of the carboxyl bridging adjacent Cu(Ⅱ)units to form an infinite chain structure along the c axis. Also, π-π stacking interactions between the adjacent chains expanded the 1-D structures into a 3-D supramolecular structure.展开更多
Efficient polymer supported synthesis of multi-substituted pyrimidine-4-one derivatives was described. Target products were produced from fluorenylmethoxycarbonyl(Fmoc) protected β-amino acid loaded on hydro- xymet...Efficient polymer supported synthesis of multi-substituted pyrimidine-4-one derivatives was described. Target products were produced from fluorenylmethoxycarbonyl(Fmoc) protected β-amino acid loaded on hydro- xymethyl resin through deprotection, N-alkylation, guanidine formation, and cleavage of 2,2,4,6,7-pentamethyl dihy-drobenzofuran-sulfonyl(Pbf) by trifluoracetic acid(TFA) followed with cyclization. The procedure has the advantages of easy operation, mild reaction conditions, and forming multiple substituents.展开更多
Molecularly imprinted polymers selective for L-aspartic acid (LAA) have been prepared using the carboxy-betaine polymer bearing zwitterionic centres along the backbone. LAA is well known to promote good me-tabolism, t...Molecularly imprinted polymers selective for L-aspartic acid (LAA) have been prepared using the carboxy-betaine polymer bearing zwitterionic centres along the backbone. LAA is well known to promote good me-tabolism, treat fatigue and depression along with its significance in accurate age estimation in the field of forensic science and is an important constituent of ‘aspartame’, the low calorie sweetener. In order to study the intermolecular interactions in the prepolymerization mixture between the monomer and the template (LAA)/non-template (DAA), a computational approach was developed. It was based on the binding energy of the complex between the template and functional monomer. The results demonstrate that electrostatic in-teractions primarily guide the imprinting protocol. The MIP was able to selectively and specifically take up LAA from aqueous solution, human blood serum and certain pharmaceutical samples quantitatively. Hence, a facile, specific and selective technique to detect the amino acid, LAA in the presence of various interfer-rants, in different kinds of matrices is presented.展开更多
A novel composite polymer electrolyte was prepared by blending an appropriateamount of LiClO_4 and 10 percent (mass fraction) fumed SiO_2 with the block copolymer of poly(ethylene oxide) (PEO) synthesized by poly (eth...A novel composite polymer electrolyte was prepared by blending an appropriateamount of LiClO_4 and 10 percent (mass fraction) fumed SiO_2 with the block copolymer of poly(ethylene oxide) (PEO) synthesized by poly (ethylene glycol) (PEG) 400 and CH_2C1_2 The ionicconductivity, electrochemical stability, interfacial characteristic and thermal behavior of thecomposite polymer electrolyte were studied by the measurements of AC impedance spectroscopy, linearsweep voltammetry and differential scanning calorimetry (DSC), respectively. The glass transitiontemperature acts as a function of salt concentration, which increases with the LiClO_4 content.Lewis acid-base model interaction mechanism was introduced to interpret the interactive relationbetween the filled fumed SiO_2 and the lithium salt in the composite polymer electrolyte. Over thesalt concentration range and the measured temperature, the maximum ionic conductivity of thecomposite polymer electrolyte (10^(-4.41) S/cm) appeared at EO/Li=25 (mole ratio) and 30 deg C, andthe beginning oxidative degradation potential versus Li beyond 5 V.展开更多
Ab initio calculations were performed using the Gaussian 03 software package to obtain the optimized structure, interaction energy and infrared spectrum of ionic liquids (ILs) containing a tetraalkylphosphonium cati...Ab initio calculations were performed using the Gaussian 03 software package to obtain the optimized structure, interaction energy and infrared spectrum of ionic liquids (ILs) containing a tetraalkylphosphonium cation and an amino acid anion. In order to investigate the effect of the presence of nitrogen in the cation, the tetraalkylphosphonium cation was replaced by a tetraalkylammonium cation, while amino acids were retained as anions in the ionic liquid. The amino acids studied here included glycine, alanine, serine, lysine, and glutamine. Optimized structures of several ILs in the gas phase were determined at the levels of Hartree-Fock (HF/6-3+G(d)) and 1density functional theory (B3LYP/6-3 1++G(d,p)). At high-level estimations, MP2/6-31+G(d) and MP2/6-31++G(d,p), the interaction energies between the cations and anions of the ILs were determined. In order to investigate the effect of alkyl-chain length on interaction energy, the alkyl groups were varied from methyl to ethyl and propyl in the tetraalkylphosphonium functional groups. This procedure revealed that there is a considerably stronger interaction between the alkylphosphonium cations and amino acids than between alkylammonium cations and amino acids. Vibrational spectroscopy of ILs shows that a significant -OH vibration peak occurs at 4124 cmt in serine-containing ILs, and a prominent C=O vending peak occurs at 1626 cm^-1 in amino acids.展开更多
Two new alkaline earth metal coordination polymers constructed from the deriva-tive of 1,2,4-triazole are presented herein,namely,{[Sr(AmTAZAc)2(H2O)]}(1) and {[Ba(AmTAZAc)2(H2O)]}(2)(AmTAZAc = 3-amino-1H...Two new alkaline earth metal coordination polymers constructed from the deriva-tive of 1,2,4-triazole are presented herein,namely,{[Sr(AmTAZAc)2(H2O)]}(1) and {[Ba(AmTAZAc)2(H2O)]}(2)(AmTAZAc = 3-amino-1H-1,2,4-triazole-5-carboxylate),which have been synthesized by using the layering method and structurally characterized by elemental analysis,IR,and single-crystal X-ray diffraction.Complexes 1 and 2 are isostructural,and both crystallize in the orthorhombic system,space group Fdd2.X-ray structural analysis shows that 1 or 2 has an intriguing 3-D infinite network of(318.438.510) topology based on a 2-D sheet structure of(4,4) net.The result shows that noncovalent interactions play an important role in strengthening the whole structures of the compounds.展开更多
A novel two-dimensional Mn(II) coordination polymer, [Mn3(L)R(cis-chdc)fftrans- chdc)]n (L = 2-amino-4-(1H-imidazo[4,5-J][1,10]phenanthrolin-2-yl)phenol and chdc = 1,4-cyclo- hexanedicarboxylate), has been ...A novel two-dimensional Mn(II) coordination polymer, [Mn3(L)R(cis-chdc)fftrans- chdc)]n (L = 2-amino-4-(1H-imidazo[4,5-J][1,10]phenanthrolin-2-yl)phenol and chdc = 1,4-cyclo- hexanedicarboxylate), has been hydrothermally synthesized and characterized by elemental analysis, IR, TG PL and single-crystal X-ray diffraction. Crystallographic data for this compound: monoclinic space group P2/n with a = 11.0058(13), b = 9.0179(11), c = 28.431(3) A, β = 92.850(2)°, V = 2818.3(6) A3, Z = 2, C62Hs6Mn3N10O14, Mr = 1329.99, Dc = 1.567 g/cm3, F(000) = 1370, p(MoKa) = 0.742 mm-1, R = 0.0553 and wR = 0.1421. The chdc carboxylates bridge the Mn(II) atoms to form a trinuclear Mn(lI) cluster. The cis-chdc ligands are held together by the trinuclear Mn(II) clusters to result in a chain structure. Further, the trans-chdc ligands link adjacent chains to furnish a two-dimensional network. The π-π interactions between neighboring layers link the adjacent layers into a three-dimensional supramolecular architecture. Moreover, the N-H...O and O-H...O hydrogen bonds further stabilize the 3D supramolecular architecture.展开更多
文摘The application of amino acid-based surfactant in dishwasher detergent was studied in this paper. The foam and oil-removing performance of amino acid surfactants in alkaline condition were test to discuss feasibility of amino acid-based surfactant from natural origin as the alternative to traditional nonionic surfactants from petroleum origin in dishwasher detergent. Comparative study was conducted through using various amino acid-based surfactants and nonionic surfactants respectively, together with enzymes and peroxide to formulate dishwasher detergents, and their application properties such as foam performance and detergency were also evaluated when washing different tableware in automatic dishwasher. The results showed that among all tested amino acid surfactants, glutamate surfactants showed low foaming and high oil-removing ability in alkaline condition, and excellent decontamination ability in dishwashing tests.
基金Project supported by the National Natural Science Foundation of China (No. 50578073)the Natural Science Foundation of Jiangsu Province, China (No. 2004088)the Major Projects of Environment Protection Office of Jiangsu Province, China (No. 2004001).
文摘Two novel polymers (NJ-1 and N J-2) were synthesized by chemically modified a hypercrosslinked polymer NJ-0 with dimethylamine and trimethylamine, respectively. The comparison of the adsorption properties of the three polymers toward phenol, resorcin and phloroglucin was made. The study focused on the static equilibrium adsorption behaviors and the adsorption thermodynamics. Freundlich equation was found to fit the adsorption results well. The effect of amino groups introduced onto the surface of the resin and the structure of phenolic compounds on the adsorption were also studied. The hydrogen-bonding interaction and electrostatic interaction could happen between the amino groups and the adsorbates. The adsorption impetus increased as quantity of hydroxyl groups increased, but the adsorption capacity decreased due to the drop of the matching degree of the aperture of resins and the diameter of adsorbate molecules.
基金supported by the State Key Laboratory of Structural Chemistry, NNSFC (20733003)Chinese Academy of Sciences (KJCX2-YW-M05)+1 种基金973 Program (2007CB815301, 2006CB932900)the NSF of Fujian Province (2006L2005, 2006J0014)
文摘The creation of a porous magnet is a long-sought academic goal since magnetism and porosity are hostile to one another. While long-range magnetic ordering needs spin carriers of short separation through short bridges, porosity relies on the use of extended connecting ligands. Here, we will give a survey of the cluster-based magnetic porous coordination polymers, i.e., 0-D MPCPs, according to their functional subunits: (1) nanoporous spin crossover materials with single metal nodes; (2) metal-radical approach with rigid organic radical ligands and single metal nodes; (C) PCPs with rigid organic ligands and metal oligomer nodes; (D) PCPs with metal complex linkers and polymetal cluster nodes; (E) PCPs with organo-polymetal cluster linkers and single metal nodes. The assembly from clusters can provide a reasonable route to resolve the hostility between magnetism and porosity. This assembly’s merits are obvious: the pore benefits from the big cluster according to "Scale Chemistry", and the functional framework inherits interesting physical properties from the clusters with a large ground spin S.
基金financially supported by the National Natural Science Foundation of China(No.21606100)the Natural Science Foundation of Jiangsu Province(No.BK20180850)+1 种基金the China Postdoctoral Science Foundation(Nos.2019M651740 and 2019T120397)the Young Talent Cultivate Programme of Jiangsu University。
文摘5-Hydroxymethylfurfural(5-HMF),as a key platform compound for the conversion of biomass to various biomass-derived chemicals and biofuels,has been attracted extensive attention.In this research,using Pickering high internal phase emulsions(Pickering HIPEs)as template and functional metal-organic frameworks(MOFs,UiO-66-SO;H and UiO-66-NH;)/Tween 85 as co-stabilizers to synthesis the dual acid-base bifunctional macroporous polymer catalyst by one-pot process,which has excellent catalytic activity in the cascade reaction of converting cellulose to 5-HMF.The effects of the emulsion parameters including the amount of surfactant(ranging from 0.5%to 2.0%(mass)),the internal phase volume fraction(ranging from 75%to 90%)and the acid/base Pickering particles mass ratio(ranging from 0:6 to 6:0)on the morphology and catalytic performance of solid catalyst were systematically researched.The results of catalytic experiments suggested that the connected large pore size of catalyst can effectively improve the cellulose conversion,and the synergistic effect of acid and base active sites can effectively improve the 5-HMF yield.The highest 5-HMF yield,about 40.5%,can be obtained by using polymer/MOFs composite as catalyst(Poly-P12,the pore size of(53.3±11.3)μm,the acid density of 1.99 mmol·g^(-1)and the base density of 1.13 mol·g^(-1))under the optimal reaction conditions(130℃,3 h).Herein,the polymer/MOFs composite with open-cell structure was prepared by the Pickering HIPEs templating method,which provided a favorable experimental basis and theoretical reference for achieving efficient production of high addedvalue product from abundant biomass.
基金Supported by the National Natural Science Foundation of China(Nos.20601007, 20773034)the Natural Science Foundation of Hebei Province, China (No.B2008000143)+1 种基金the Natural Science Foundation of Hebei Education Department, China(No. ZH2006002)the Doctoral Foundation of Hebei Normal University, China (No.103261)
文摘Five new coordination polymers Cu(phen)(H2O)(phth)·CH3OH(1), [Cu(2,2′-bipy)(H2O)](phth)·3.5H2O(2), Zn(phen)(phth)(H2O)·1.125H2O(3) and [M(4,4′-bipy)(H2O)2](phth)·2H2O[M=Zn(4), Mn(5)](H2phth=phthalic acid, bipy=bipyridine, phen=1,10-phenanthroline) have been synthesized from the amino acid derivatives(phthalyl-l- valine, H2L) and structurally characterized. H2L was hydrolyzed into phth2- group during the reaction, but the strucure feature was different from that of the complex directly synthesized from H2phth in the reported literature, revealing that H2L played an important role in composing the novel compounds. Compounds 1, 2 and 3 are all 1D chains, but the differences are that compound 1 is further hydrogen-bonded into 2D networks, and compound 2 is further extended into 3D supramolecular network through π-π stacking and hydrogen-bonding interactions. However, compound 3 is a 1D helix chain structure and further links into 2D networks through π-π stacking. Compounds 4 and 5 are isostructural and exhibit the same 2D layers, which are further connected by hydrogen-bonding interactions to form 3D supramolecular network. Antiferromagnetic superexchange was observed for compounds 1, 2 and 5.
基金supported by the National Natural Science of Foundation of China(No.21671094)
文摘Two N-donor ligands mediated Cd(Ⅱ) coordination polymers, namely,[Cd(L)(dmpz)2]n (1) and {[Cd(L)(atr)05(H20)](H2O)}n (2) (H2L = methyl-3-hydroxy-5-carboxy-2-thiophenecarboxylate, dmpz = 3,5-dimethylpyrazole, and atr= 4-amino-l,2,4-triazole), havebeen produced. Their structures were characterized by single-crystal X-ray diffraction analysis,elemental analyses and infrared spectra. Compound 1 possesses a one-dimensional (1D) chainstructure and is finally extended into a three-dimensional (3D) supramolecular architecturethough hydrogen bonding interactions. Compound 2 features a two-dimensional (2D) networkwith 4-connected sql topology based on dinuclear Cd(Ⅱ) clusters as nodes, which is alsoassembled into a 3D supramolecular architecture through hydrogen bonding interactions.Furthermore, compounds 1 and 2 exhibit high thermal stabilities and intense fluorescent emissionin the solid, and can be explored as potential luminescent materials.
基金Supported by the National Natural Science Foundation of China (21106162)the National Key Natural Science Foundation of China (21136009)+1 种基金the National High Technology Research and Development Program of China (2009CB219904)the State Key Laboratory of Chemical Engineering (SKL-ChE-11A04)
文摘Abstract A novel polyglycidylmethacrylate (PGMA) microspheres with high adsorption capacity of Cr(VI) was prepared by cerium(IV) initiated graft polymerization of tentacle-type polymer chains with amino group on polymer microspheres with hydroxyl groups. The micron-sized PGMA microspheres were prepared by a dispersion polym erization method and subsequently modified by ring-opening reaction to introduce functional hydroxyl groups. The polymer microspheres were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The results indicated that the polymer microspheres had an average diameter of 5 m with uniform size distribution. The free amino group content was determined to be 5.13 mmol·g^-1 for g;PGMA-NH2 microspheres by potentiometric and conductometric titration methods. The Cr(VI) adsorption results indicated that the graft polymerization of tentacle-type polymer chains on the polymer microspheres could produce adsorbents with high adsorption capacity (500 mg-g-l). The polymer microspheres with grafted tentacle polymer chains have potenial application in large-scale removal of Cr(VI) in aqueous solution.
文摘This article reports on the synthesis of acrylate monomer from renewable material. Vanillin was selected to be the start material to produce new monomer called vanillin acrylate and abbreviated by (VA). It has been successfully investigated by 1H, 13C NMR, IR and UV and all results were in logic state. The next step was to synthetize three different thermo-responsive functional copolymers by incorporation of three different molar ratios of vanillin acrylate (10, 20, 30 mol%) with N-Isopropylacrylamide via free radical polymerization by AIBN as initiator in solution. All copolymers were deduced by 1NMR and IR and all showed the presence of aldehyde group. The copolymer was used for grafting of tryptophan and β-alanine through the chemical link between amino group and the active aldehyde group by click reactions to form Schiff’s base imine compounds. Moreover, polymers were also elucidated by 1HNMR, IR and UV, Size Exclusion Chromatography (SEC) was used for the molecular weight determination, differential scanning calorimeter (DSC) for glass temperature of solid polymers, XRD for crystallinity. UV-vis Spectroscopy was used for the determination of phase separation or the lower critical solution temperature (Tc) of polymers solution not only in deionized water but in pH5 and pH11. The mount of conversation and linked amino acid was determined by UV-vis Spectroscopy.
基金Project supported by State Education Committee Initial Research Crams for Return Scholar and supported by NSFC No 29774012.
文摘The optical alpha-amino acids were synthesized under room temperature by alkylation of N-(diphenyl methylene) glycine t-butyl ester under polymer-supported phase transfer conditions using polymer-supported cinchonine (or quinine) alkaloids as chiral phase transfer catalysts and dichloromethane as solvent, followed by hydrolysis of the above intermediates introduced to the final products-optical alpha-amino acids. This is a new method for the asymmetric synthesis of alpha-amino acids. The influences of catalyst, temperature, substrates, and organic solvents on the chemical yield and optical purities of products were studied.
基金the Scientific and Technological Project of Guangdong Province, China(No.2006B36703005)
文摘Reaction of FeCIz'6H20, pyridine-2,4,6-tricarboxylic acid(H3pyta) and NaOH in the hydrothermal system at 185 ℃ resulted in the formation of 1D coordination polymer[Fe(Hpyta)(H2O)2](1) based on Fe-Hpyta chains. When the abpt[abpt=-4-amino-3,5-bis(4-pyridyl)-l,2,4-triazole] ligand was employed in the reaction system, a 3D supramolecular porous network (H2bpt)[Fe(pyta)(H2O)2]·4H2O(2) was obtained. The framework was constructed with negative (Fe-pyta) chains and the positive H3bpt^+ in situ, formed from the abpt reagent, to form 1D channels filled with guest water molecules via hydrogen-bonds. X-Ray diffraction crystal structure analysis shows that complex 1 crystallized in the monoclinic system, space group C2/c, a=1.1490(5) nm, b=0.9008(4) nm, c=1.0058(5) nm, B=107.254(9)°, V=0.9942(8) nm3, Z=4; and complex 2 crystallizes in the triclinic system, space group P1 with a=0.90392(11) nm, b=0.96027(11 ) nm, c=1.55540(18) nm, a=73.558(2)°,B= 86.126(2)°,r= 68.745(2)°, V=1.2059(2) nm^3 and Z=2.
基金supported by the “Strategic Priority Research Program” of the Chinese Academy of Sciences(XDA07070200,XDA09030102)the Science Foundation of Fujian Province(2006l2005)
文摘A novel coordination polymer, namely [Zn2(CAPA)(DMA)(H2O)]2n·n(H2O)(1,H4CAPA = 5-(bis(4-carboxybenzyl) amino) isophthalic acid, DMA = N,N-dimethylacetamide) has been synthesized through a solvothermal method and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectra, and thermogravimetric analyses. The crystal structure is of monoclinic, space group P21/n with a = 8.0585(5), b = 18.9733(10), c = 20.2044(14) A^°3, β = 101.144(7)°, V = 3030.9(3) ?~3, C56H54Zn4N4O21, Mr = 1378.58, Z = 2). The compound forms a three-dimensional(3D) supramolecular framework by linking adjacent layers via hydrogen bonds and π···π interactions. It is interesting that the crystal structure is much related to the flexibility and configuration of the ligand. In addition, the thermal stability and luminescence properties for the compound have also been investigated.
基金This work was supported by the grants of the National Natural Science Foundation of China the Chinese Academy of Sciences and Hong Kong Polytechnic University (29901005)
文摘Mn(L-Phe)2稨2O]n (Phe=phenylalanine) with a single stranded coordination poly- mer has been synthesized by self-assembly of manganese salt and phenylalanine and characterized by X-ray single-crystal diffraction method. The complex crystallizes in the orthorhombic, space group P212121 with a = 6.0911(1), b = 10.3642(1), c = 30.4321(7) ? V = 1921.16(6) ?, Z = 4, Dc = 1.387 g/cm3, C18H22N2O5Mn, Mr = 401.32, F(000) = 836 and m(MoKa) = 0.717 mm-1. The final R = 0.0614 and wR = 0.1412 for 2291 observed reflections with I > 2s(I). The magnetic behavior study shows that there exist super-exchange antiferromagnetic interactions between the magnetic centers through the effective exchange pathway of the carboxylate group.
基金supported by Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources(Guangxi Normal University),Ministry of Education of China(No.CMEMR2011-13)the Scientific research and technological development project of Guilin(No.20110330)
文摘A new complex [Cu(L)(1,10-phen)]n (1, L = N-3-pyridine sulfonyl amino acid) has been synthesized and characterized by IR, elemental analysis and X-ray diffraction analysis, and its crystal belongs to monoclinic, space group P2Jc with a = 11.481 (2), b = 1 8.094(4), c = 8.5198(17) ]°, β= 102.26(3)°, V = 1729.5(6) ,/k3, Z = 4, Dc = 1.759 g/cm3, F(000) = 932, p = 1.422 mm-1, R = 0.0368 and wR = 0.0893. In 1, the Cu(ll) ion adopts a slightly distorted five-coordinated square pyramidal geometry. The L2- ligand adopts O of the carboxyl bridging adjacent Cu(Ⅱ)units to form an infinite chain structure along the c axis. Also, π-π stacking interactions between the adjacent chains expanded the 1-D structures into a 3-D supramolecular structure.
基金Supported by the Scientific Forefront and Interdisciplinary Innovation Project of Jilin UniversityChina(No.421031531412)+1 种基金the Jilin Provincial Research Foundation for Basic Research China(No.3D109K856604)
文摘Efficient polymer supported synthesis of multi-substituted pyrimidine-4-one derivatives was described. Target products were produced from fluorenylmethoxycarbonyl(Fmoc) protected β-amino acid loaded on hydro- xymethyl resin through deprotection, N-alkylation, guanidine formation, and cleavage of 2,2,4,6,7-pentamethyl dihy-drobenzofuran-sulfonyl(Pbf) by trifluoracetic acid(TFA) followed with cyclization. The procedure has the advantages of easy operation, mild reaction conditions, and forming multiple substituents.
文摘Molecularly imprinted polymers selective for L-aspartic acid (LAA) have been prepared using the carboxy-betaine polymer bearing zwitterionic centres along the backbone. LAA is well known to promote good me-tabolism, treat fatigue and depression along with its significance in accurate age estimation in the field of forensic science and is an important constituent of ‘aspartame’, the low calorie sweetener. In order to study the intermolecular interactions in the prepolymerization mixture between the monomer and the template (LAA)/non-template (DAA), a computational approach was developed. It was based on the binding energy of the complex between the template and functional monomer. The results demonstrate that electrostatic in-teractions primarily guide the imprinting protocol. The MIP was able to selectively and specifically take up LAA from aqueous solution, human blood serum and certain pharmaceutical samples quantitatively. Hence, a facile, specific and selective technique to detect the amino acid, LAA in the presence of various interfer-rants, in different kinds of matrices is presented.
文摘A novel composite polymer electrolyte was prepared by blending an appropriateamount of LiClO_4 and 10 percent (mass fraction) fumed SiO_2 with the block copolymer of poly(ethylene oxide) (PEO) synthesized by poly (ethylene glycol) (PEG) 400 and CH_2C1_2 The ionicconductivity, electrochemical stability, interfacial characteristic and thermal behavior of thecomposite polymer electrolyte were studied by the measurements of AC impedance spectroscopy, linearsweep voltammetry and differential scanning calorimetry (DSC), respectively. The glass transitiontemperature acts as a function of salt concentration, which increases with the LiClO_4 content.Lewis acid-base model interaction mechanism was introduced to interpret the interactive relationbetween the filled fumed SiO_2 and the lithium salt in the composite polymer electrolyte. Over thesalt concentration range and the measured temperature, the maximum ionic conductivity of thecomposite polymer electrolyte (10^(-4.41) S/cm) appeared at EO/Li=25 (mole ratio) and 30 deg C, andthe beginning oxidative degradation potential versus Li beyond 5 V.
文摘Ab initio calculations were performed using the Gaussian 03 software package to obtain the optimized structure, interaction energy and infrared spectrum of ionic liquids (ILs) containing a tetraalkylphosphonium cation and an amino acid anion. In order to investigate the effect of the presence of nitrogen in the cation, the tetraalkylphosphonium cation was replaced by a tetraalkylammonium cation, while amino acids were retained as anions in the ionic liquid. The amino acids studied here included glycine, alanine, serine, lysine, and glutamine. Optimized structures of several ILs in the gas phase were determined at the levels of Hartree-Fock (HF/6-3+G(d)) and 1density functional theory (B3LYP/6-3 1++G(d,p)). At high-level estimations, MP2/6-31+G(d) and MP2/6-31++G(d,p), the interaction energies between the cations and anions of the ILs were determined. In order to investigate the effect of alkyl-chain length on interaction energy, the alkyl groups were varied from methyl to ethyl and propyl in the tetraalkylphosphonium functional groups. This procedure revealed that there is a considerably stronger interaction between the alkylphosphonium cations and amino acids than between alkylammonium cations and amino acids. Vibrational spectroscopy of ILs shows that a significant -OH vibration peak occurs at 4124 cmt in serine-containing ILs, and a prominent C=O vending peak occurs at 1626 cm^-1 in amino acids.
基金Supported by the National Natural Science Foundation of China (Nos. 20771006 and 20901004)
文摘Two new alkaline earth metal coordination polymers constructed from the deriva-tive of 1,2,4-triazole are presented herein,namely,{[Sr(AmTAZAc)2(H2O)]}(1) and {[Ba(AmTAZAc)2(H2O)]}(2)(AmTAZAc = 3-amino-1H-1,2,4-triazole-5-carboxylate),which have been synthesized by using the layering method and structurally characterized by elemental analysis,IR,and single-crystal X-ray diffraction.Complexes 1 and 2 are isostructural,and both crystallize in the orthorhombic system,space group Fdd2.X-ray structural analysis shows that 1 or 2 has an intriguing 3-D infinite network of(318.438.510) topology based on a 2-D sheet structure of(4,4) net.The result shows that noncovalent interactions play an important role in strengthening the whole structures of the compounds.
基金supported by the Education Office of Jilin Province(No.2013212)
文摘A novel two-dimensional Mn(II) coordination polymer, [Mn3(L)R(cis-chdc)fftrans- chdc)]n (L = 2-amino-4-(1H-imidazo[4,5-J][1,10]phenanthrolin-2-yl)phenol and chdc = 1,4-cyclo- hexanedicarboxylate), has been hydrothermally synthesized and characterized by elemental analysis, IR, TG PL and single-crystal X-ray diffraction. Crystallographic data for this compound: monoclinic space group P2/n with a = 11.0058(13), b = 9.0179(11), c = 28.431(3) A, β = 92.850(2)°, V = 2818.3(6) A3, Z = 2, C62Hs6Mn3N10O14, Mr = 1329.99, Dc = 1.567 g/cm3, F(000) = 1370, p(MoKa) = 0.742 mm-1, R = 0.0553 and wR = 0.1421. The chdc carboxylates bridge the Mn(II) atoms to form a trinuclear Mn(lI) cluster. The cis-chdc ligands are held together by the trinuclear Mn(II) clusters to result in a chain structure. Further, the trans-chdc ligands link adjacent chains to furnish a two-dimensional network. The π-π interactions between neighboring layers link the adjacent layers into a three-dimensional supramolecular architecture. Moreover, the N-H...O and O-H...O hydrogen bonds further stabilize the 3D supramolecular architecture.