Activated carbons calcined at 400˚C and 600˚C (AC-400 and AC-600), prepared using palm nuts, collected in the town of Franceville in Gabon, were used to study the dynamic adsorption of MnO<sub>4</sub>-<...Activated carbons calcined at 400˚C and 600˚C (AC-400 and AC-600), prepared using palm nuts, collected in the town of Franceville in Gabon, were used to study the dynamic adsorption of MnO<sub>4</sub>-</sup> ions in acidic media on fixed bed column and on the kinetic modeling of experimental data of breakthrough curves of MnO<sub>4</sub>-</sup> ions obtained. Results on the adsorption of MnO<sub>4</sub>-</sup> ions in fixed-bed dynamics obtained on AC-400 and AC-600 adsorbents beds indicated that the AC-400 bed appears to be the most efficient in removing MnO<sub>4</sub>-</sup> ions in acidic media. Indeed, the adsorbed amounts, the adsorbed capacities at saturation and the elimination percentage of MnO<sub>4</sub>-</sup> ions obtained with AC-400 (31.24 mg;52.06 mg·g<sup>-1</sup> and 41.65% respectively) were higher compared to those obtained with AC-600 (9.87 mg;16.45 mg·g<sup>-1</sup> and 17.79% respectively). The breakthrough curves kinetic modeling revealed that the Thomas model and the pseudo-first-order kinetic model were the most suitable models to describe the adsorption of MnO<sub>4</sub>-</sup> ions on adsorbents studied in our experimental conditions. The results of the intraparticle diffusion model showed that intraparticle diffusion was involved in the adsorption mechanism of MnO<sub>4</sub>-</sup> ions on investigated adsorbents and was not the limiting step and the only process controlling MnO<sub>4</sub>-</sup> ions adsorption. In contrast to AC-400, the intraparticle diffusion on AC-600 bed plays an important role in the adsorption mechanism of MnO<sub>4</sub>-</sup> ions.展开更多
ABSTRACT Four novel 1D lanthanide coordination polymers with formula [Ln(3,4-pybz)3(HzO)2. H2O]n (Ln = 1 Sm; 2 Eu; 3 Tb; 4 Dy, 3,4-Hpybz = 3-(pyridin-4-yl)benzoic acid) have been synthesized by hydrothermal re...ABSTRACT Four novel 1D lanthanide coordination polymers with formula [Ln(3,4-pybz)3(HzO)2. H2O]n (Ln = 1 Sm; 2 Eu; 3 Tb; 4 Dy, 3,4-Hpybz = 3-(pyridin-4-yl)benzoic acid) have been synthesized by hydrothermal reactions of lanthanide oxide and 3-(pyridine-4-yl) benzoic acid. Single-crystal X-ray diffraction shows that the four compounds are isostructural. They all crystallize in a monoelinic system, space group P1^-. They have a doubly carboxylate-bridged infinite-chain structure with alternating Ln-(carboxylate)2-Ln linkages and one chelating carboxylate group on each metal center. The Ln ion also combines to two water molecules to form an eight-coordinate square antiprismatic geometry. The pyridine nitrogen atoms of the ligand do not coordinate to the metal centers but direct the formation of a 3D network through hydrogen bonding with coordinated water molecules. The photoluminescent properties of 2 and 3 have been also studied.展开更多
A new Cu(Ⅱ) coordination polymer, [Cu(L1)(L2)](1), was synthesized under hydrothermal conditions(H_2L1 = 4-(carboxymethoxy)benzoic acid, L2 = 2-(4-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline). Crystallograph...A new Cu(Ⅱ) coordination polymer, [Cu(L1)(L2)](1), was synthesized under hydrothermal conditions(H_2L1 = 4-(carboxymethoxy)benzoic acid, L2 = 2-(4-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline). Crystallographic data for 1: triclinic, space group P1 with a = 9.750(5), b = 10.148(5), c = 12.869(5) ?, α = 104.904(5), β = 102.133(5), γ = 95.219(5)°, V = 1188.7(10) ?~3, Z = 2, C_(28)H_(17)FN_4O_5Cu, Mr = 572.01, D_c = 1.598 g/cm^3, F(000) = 582, μ(MoKa) = 0.977 mm^(-1), R = 0.0474 and w R = 0.1144. The TGA behaviors and luminescence of 1 have been studied in detail. The L1 dianions link neighboring Cu(Ⅱ) atoms in a bis-chelating mode, yielding a one-dimensional chain structure along the b axis. The L2 ligands are attached on one side of the chain through chelating the Cu(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a layer structure. Additionally, the N–H???O hydrogen bonds further stabilize the structure of 1.展开更多
A new ID coordination polymer, [Cda(L1)2(L2)2].H2O (1, H2L1 = 4-(carboxy- methoxy)benzoic acid and L2 = 2-(4-fluorophenyl)-I H-imidazo[4,5-f][1,10]phenanthroline), has been hydrothermally synthesized and cha...A new ID coordination polymer, [Cda(L1)2(L2)2].H2O (1, H2L1 = 4-(carboxy- methoxy)benzoic acid and L2 = 2-(4-fluorophenyl)-I H-imidazo[4,5-f][1,10]phenanthroline), has been hydrothermally synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 9.985(5), b = 10.768(5), c = 12.512(5) A, a = 68.959(5), β = 80.354(5), γ = 79.663(5)°, V= 1227.4(10) A3, Z = 1, C56H36Cd2F2N8O11, Mr = 1259.73, Dc = 1.704 g/cm3, F(000) = 630, μ(MoKa) = 0.949 mm-1, R = 0.0261 and wR = 0.0655. The L1 anions link the neighboring Cd(II) atoms to form a 1D double chain structure. The L2 ligands are alternately located on both sides of the double chains. More interestingly, the lateral L2 ligands from adjacent double chains are paired to furnish strong π-π interactions, yielding a 2D supramolecular layer. N-H...O, O-H...N and O-H...O hydrogen bonds further stabilize the structure of 1. The luminescent property of 1 was studied in solid state at room temperature.展开更多
The dehydration of 2-(4'-ethylbenzoyl) benzoic acid (BE acid) to 2-ethylanthraquinone (2-EAQ) was investigated over solid acid catalysts. The results showed that H-beta zeolite catalyst modified by dilute HNO3 ...The dehydration of 2-(4'-ethylbenzoyl) benzoic acid (BE acid) to 2-ethylanthraquinone (2-EAQ) was investigated over solid acid catalysts. The results showed that H-beta zeolite catalyst modified by dilute HNO3 solution exhibited an excellent performance. In our study, the conversion of BE acid can reach 96.7%, and the selectivity to 2-EAQ is up to 99.6%.展开更多
A new Cu(Ⅱ) complex [Cu(4-cba)(1,10-phen)(H2O)2](NO3) (4-Hcba = 4-cyanobenzoic acid) has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characteriz...A new Cu(Ⅱ) complex [Cu(4-cba)(1,10-phen)(H2O)2](NO3) (4-Hcba = 4-cyanobenzoic acid) has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data: C20H16CuN4O7, Mr= 487.91, triclinic, space group PI, a = 7.8420(2), b = 9.1070(2), c = 15.1140(6) A, a = 76.889(9), β = 81.332(11), γ = 74.844( 11)°, V = 1009.89(5) A^3, Z = 2, Dc = 1.605 g/cm^3, F(000) = 498, μ = 1.134 mm^-1, the final R = 0.0379 and wR = 0.0865 for 2977 observed reflections with 1 〉 2σ(Ⅰ). The Cu(Ⅱ) atom is coordinated by two terminal water molecules, one chelating 1,10-phen molecule and one monodentate 4-cba ligand to form a slightly distorted square pyramid. The title complex molecules are connected through hydrogen bonds and π-π stacking interactions to generate a 2D layered network. The thermogravimetric analysis of the title complex has also been discussed.展开更多
Two Pb^Ⅱ coordination polymers [Pb(oba)(2,2′-bipy)]·1.5H2O(1) and [Pb(oba)(phen)](2)(H2oba = 2,4-oxybis(benzoic acid), 2,2′-bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline) were synthesized...Two Pb^Ⅱ coordination polymers [Pb(oba)(2,2′-bipy)]·1.5H2O(1) and [Pb(oba)(phen)](2)(H2oba = 2,4-oxybis(benzoic acid), 2,2′-bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline) were synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction, thermogravimetric analyses, IR spectroscopy and elemental analysis. Structures of compounds 1 and 2 are similar. Compounds 1 and 2 show 1D wavy chains, which are further connected through aromatic π-π stacking interactions to expand into 2D wavelike networks. The crystal structure of 2,4-oxybis(benzoic acid) ligand(3) was obtained, and its full geometry optimization was carried out by using DFT methods at the B3LYP/6-31G(d) level. The calculated data show that the bond distances and bond angles were very close to the experimental data. The values of the frontier orbital energies indicate that this configuration is stable. Moreover, the solid-state fluorescence properties of 1-3 have also been investigated.展开更多
A complex [Cd2Na2(BOABA)2(H2O)8]·H2O(1) was synthesized by using 2,4-bisoxyacetate-benzoic acid(H3BOABA) and Cd(OH)2. It was characterized by elemental analysis, IR spectra, and single-crystal X-ray dif...A complex [Cd2Na2(BOABA)2(H2O)8]·H2O(1) was synthesized by using 2,4-bisoxyacetate-benzoic acid(H3BOABA) and Cd(OH)2. It was characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. Complex 1 shows a two-dimensional 3-connected rigid plane. The interactions between the ligand and its complex with DNA were studied by Et Br fluorescence probe. Photoluminescent studies indicate that the complex may be excellent candidates for potential photoactive materials.展开更多
Urokinase-type plasminogen activator (uPA) is a trypsin-like serine protease and plays a key role in several biological processes, including tissue remodeling, cell migration, and matrix degradation. The inhibitors ...Urokinase-type plasminogen activator (uPA) is a trypsin-like serine protease and plays a key role in several biological processes, including tissue remodeling, cell migration, and matrix degradation. The inhibitors of uPA have been shown to prevent the spread of metastasis and tumor growth, and accordingly uPA is widely recognized as a target for the treatment of cancer. In this work, we report the crystal structures of the complexes of uPA with its inhibitors: 4- (aminomethyl)-benzoic acid (AMBA) and 4-(aminomethyl-phenyl)-methanol (AMPM), both at a resolution of 2.35 А. The inhibitory constants of these two inhibitors were measured by a chromogenic competitive assay, and it was found that AMBA is a better inhibitor for uPA (Ki = 2.68 mM) than AMPM (Ki = 13.99 mM). The structural study shows that the binding mode of inhibitor AMBA on uPA is similar to that of AMPM on uPA, both docked into the active site S1 pocket of uPA. Structural details of these complexes are provided to explain the difference of inhibitory constants.展开更多
Two Co(Ⅱ) coordination polymers, namely [Co(L)Cl]n(1) and [Co(L)(CH3 COO)]n(2), {HL = 3,5-di(4 H-1,2,4-triazole-4-yl)benzoic acid}, were synthesized under hydrothermal conditions. Compound 1 crystallize...Two Co(Ⅱ) coordination polymers, namely [Co(L)Cl]n(1) and [Co(L)(CH3 COO)]n(2), {HL = 3,5-di(4 H-1,2,4-triazole-4-yl)benzoic acid}, were synthesized under hydrothermal conditions. Compound 1 crystallizes in orthorhombic system, space group Pmma with a = 7.032(5), b = 11.555(8), c = 8.185(5) A, V = 665.1(7) А3, Z = 2, Dc = 1.746 g/cm3, F(000) = 350, Mr = 349.61, μ = 1.504 mm(-1), the final R = 0.0568 and w R = 0.1739 for 2312 observed reflections with I 2σ(I). Compound 2 crystallizes in orthorhombic system, space group Pmma with a = 7.7505(17), b = 11.391(3), c = 8.0298(18) A, V = 708.9(3) A3, Z = 2, Dc = 1.748 g/cm3, F(000) = 378, Mr = 373.20, μ = 1.245 mm-1, the final R = 0.0350 and w R = 0.0873 for 5239 observed reflections with I 2σ(I). Single-crystal X-ray analyses revealed that complexes 1 and 2 exhibit similar 2 D layer structures with uncoordinated carboxyl as dangling arms. The neighboring layers are further connected by these arms, leading to interest 2 D → 3 D polythreading frameworks. Moreover, the magnetic susceptibility study indicates compound 1 exhibits antiferromagnetic behavior.展开更多
A photorheologically reversible micelle composed of polymerizable cationic surfactant n-cetyl dimethylallyl am- monium chloride (CDAAC) and trans-4-phenylazo benzoic acid (trans-ACA) was prepared. The effects of m...A photorheologically reversible micelle composed of polymerizable cationic surfactant n-cetyl dimethylallyl am- monium chloride (CDAAC) and trans-4-phenylazo benzoic acid (trans-ACA) was prepared. The effects of molar ratio of CDAAC/trans-ACA, time of UV and visible light irradiation and temperature on the rheological properties of micellar system were investigated. The results show that before UV irradiation the system with an optimum CDAAC/trans-ACA molar ratio of 1.4 forms viscoelastic micelles at 45 ℃. After 365 nm UV irradiation, the viscos- ities of micelle systems with different concentrations at fixed molar ratio of 1.4 are decreased by 85%-95%. The CDAAC/trans-ACA (14 mmol. L- 1/10 mmol. L- 1 ) micelle system exhibits shear thinning property and its viscos- ity is decreased obviously with the increases of UV irradiation time less than I h. The rheological process during LIV irradiation for CDAAC/trans-ACA (14 mmol- L- 1/10 mmol. L 1) micelle proves that viscosity, elastic modulus G' and viscous modulus G" will reduce quickly with the UV light. Furthermore, the micelle system after 1 h UV- irradiation is able to revert to its initial high viscosity with 460 nm visible light irradiation for 4 h, and the micelle can be cycled between low and high viscosity states by repetitive UV and visible light irradiations. The LIV-Vis spectra of CDAAC/trans-ACA micelle indicate that its photosensitive theological properties are related closely to photoisomerization of trans-ACA to c/s-ACA.展开更多
Two inorganic-organic coordination polymers, [Cd(TBA)2]·3H2O (1) and [Cu(TBA)2]·2H2O (2) have been synthesized by reaction of the metal ions of Cd(II) and Cu(II) with the ligand HTBA [HTBA = 4- (1H-1, 2, 4-t...Two inorganic-organic coordination polymers, [Cd(TBA)2]·3H2O (1) and [Cu(TBA)2]·2H2O (2) have been synthesized by reaction of the metal ions of Cd(II) and Cu(II) with the ligand HTBA [HTBA = 4- (1H-1, 2, 4-triazol-1-yl)benzoic acid] under solvothermal condition. The compounds were characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, X-ray powder diffraction (XRPD), and thermo gravimetric analysis (TGA). The structural analyses reveal the two independent polymers exhibit different structures. Complex 1 exhibits a 3D framework with 1D channels, and complex 2 shows a 2-fold interpenetrating 3D diamond net.展开更多
The title compound 2-[(4-methoxy-6-methylthio-2-pyrimidinyl)aminocarbonyl- aminosulfonyl]benzoic acid methyl ester (C15H16N4O6S2, Mr = 412.44) was obtained by the reaction of (4-methoxy-6-methylthio-2-pyrimidinyl)amin...The title compound 2-[(4-methoxy-6-methylthio-2-pyrimidinyl)aminocarbonyl- aminosulfonyl]benzoic acid methyl ester (C15H16N4O6S2, Mr = 412.44) was obtained by the reaction of (4-methoxy-6-methylthio-2-pyrimidinyl)amine with 2-methoxylcarbonylbenzene-sulfonylisocya- nate. The crystal is of monoclinic, space group P21/c with a =11.169(3), b = 9.508(3), c = 17.690(5) ? b = 91.593(5), Z = 4, V = 1877.9(10) 3, Dc = 1.459 g/cm3, F(000) = 856, m(MoKa) = 0.324 mm-1, R = 0.0690 and wR = 0.1368 for 3301 observed reflections (I > 2s(I)). The N(1)H…N(3) and N(2)H…O(4) hydrogen bonds can be observed. In the molecule the phenyl plane(I), pyrimi- din-2-yl-urea bridge plane(Ⅱ) and ester plane(Ⅲ) form three conjugated systems.展开更多
Two new isomorphous metal-organic coordination polymers, [Zn(dhmdb)(2,2'- bpy)]n 1 and [Zn(dhmdb)(1,10-phen)]n 2, have been obtained under hydrothermal reactions from 4,4'-(dihydroxymethylene)dibenzoic ac...Two new isomorphous metal-organic coordination polymers, [Zn(dhmdb)(2,2'- bpy)]n 1 and [Zn(dhmdb)(1,10-phen)]n 2, have been obtained under hydrothermal reactions from 4,4'-(dihydroxymethylene)dibenzoic acid (H2dhmdb), Zn(NO3)2·6H2O and 2,2'-pyridine or 1,10- phenanthroline, respectively. Compounds 1 and 2 have been characterized by FT-IR spectroscopy, thermal analysis and single-crystal X-ray diffraction. The zigzag chains of 1 and 2 are linked into three-dimensional supramolecular networks by both O–H…O hydrogen bonds and π…π stacking interactions. Crystal data for 1: ZnC25H18N2O6, Mr = 507.78, orthorhombic, space group Pbca, a = 14.031(3), b = 10.826(2), c = 27.343(6), V = 4153.5(14)3, Z = 8, Dc = 1.624 g/cm3, F(000) = 2080, μ = 1.231 mm-1, R = 0.0699 and wR = 0.1829. Crystal data for 2: ZnC27H18N2O6, Mr = 531.80, orthorhombic, space group Pbca, a = 13.796(3), b = 10.809(2), c = 28.612(6), V = 4266.8(15)3, Z = 8, Dc = 1.656 g/cm3, F(000) = 2176, μ = 1.203 mm-1, R = 0.0454 and wR = 0.1399.展开更多
A novel interpenetrating structure [(HMA^+)(FB^- )] ·2H2O of melamine(MA) with 4-fluoro-benzoic acid (HFB) was synthesized. It crystallized in the monoclinic system with space group P21/c. The complex ha...A novel interpenetrating structure [(HMA^+)(FB^- )] ·2H2O of melamine(MA) with 4-fluoro-benzoic acid (HFB) was synthesized. It crystallized in the monoclinic system with space group P21/c. The complex has a interpenetrating 2D structure with hydrogen-bonded grid networks. Carboxylic acid to melamine proton transfer occurs in the complex. The adjacent HMA^+ cations related by an inverse center form cationic [HMA^+]∞ ribbons via a pair of N-H…N hydrogen bonds. Adjacent FB-anions are paired by C-H…F hydrogen bonds to form dimers, which are connected to [HMA^+]∞ ribbons through N-H…O interactions. The supramolecular features in the complex are guided by control of strong N-H…N, N-H…O and O-H…O hydrogen bonds, as well as highly directional weak C-H…F interactions and aromatic π-π stacking interactions.展开更多
BACKGROUND Disorders of primary bile acid synthesis may be life-threatening if undiagnosed,or not treated with primary bile acid replacement therapy. To date, there are few reports on the management and follow-up of p...BACKGROUND Disorders of primary bile acid synthesis may be life-threatening if undiagnosed,or not treated with primary bile acid replacement therapy. To date, there are few reports on the management and follow-up of patients with Δ4-3-oxosteroid 5β-reductase(AKR1 D1) deficiency. We hypothesized that a retrospective analysis of the responses to oral bile acid replacement therapy with chenodeoxycholic acid(CDCA) in patients with this bile acid synthesis disorder will increase our understanding of the disease progression and permit evaluation of this treatment regimen as an alternative to the Food and Drug Administration(FDA) approved drug cholic acid, which is currently unavailable in China.AIM To evaluate the therapeutic responses of patients with AKR1 D1 deficiency to oral bile acid therapy, specifically CDCA.METHODS Twelve patients with AKR1 D1 deficiency, confirmed by fast atom bombardment ionization-mass spectrometry analysis of urine and by gene sequencing for mutations in AKR1 D1, were treated with differing doses of CDCA or ursodeoxycholic acid(UDCA). The clinical and biochemical responses to therapy were monitored over a period ranging 0.5-6.4 years. Dose adjustment, to optimize the therapeutic dose, was based on changes in serum biochemistry parameters,notably liver function tests, and suppression of the urinary levels of atypical hepatotoxic 3-oxo-Δ4-bile acids measured by mass spectrometry.RESULTS Physical examination, serum biochemistry parameters, and sonographic findings improved in all 12 patients during bile acid therapy, except one who underwent liver transplantation. Urine bile acid analysis confirmed a significant reduction in atypical hepatotoxic 3-oxo-Δ4 bile acids concomitant with clinical and biochemical improvements in those patients treated with CDCA. UDCA was ineffective in down-regulating endogenous bile acid synthesis as evidenced from the inability to suppress the urinary excretion of atypical 3-oxo-Δ4-bile acids. The dose of CDCA required for optimal clinical and biochemical responses varied from 5.5-10 mg/kg per day among patients based on maximum suppression of the atypical bile acids and improvement in serum biochemistry parameters, and careful titration of the dose was necessary to avoid side effects from CDCA.CONCLUSION The primary bile acid CDCA is effective in treating AKR1 D1 deficiency but the therapeutic dose requires individualized optimization. UDCA is not recommended for long-term management.展开更多
AIM To determine the effects of ω-3 fatty acids(ω-3FA) on the toll-like receptor 4(TLR4)/nuclear factor κB p56(NF-κBp56) signal pathway in the lungs of rats with severe acute pancreatitis(SAP).METHODS A total of 5...AIM To determine the effects of ω-3 fatty acids(ω-3FA) on the toll-like receptor 4(TLR4)/nuclear factor κB p56(NF-κBp56) signal pathway in the lungs of rats with severe acute pancreatitis(SAP).METHODS A total of 56 Sprague-Dawley rats were randomly divided into 4 groups: control group, SAP-saline group, SAP-soybean oil group and SAP-ω-3FA group. SAP was induced by the retrograde infusion of sodium taurocholate into the pancreatic duct. The expression of TLR4 and NF-κBp56 in the lungs was evaluated by immunohistochemistry and Western blot analysis. The levels of inflammatory cytokines interleukin-6 and tumor necrosis factor-alpha in the lungs were measured by enzyme-linked immunosorbent assay. RESULTS The expression of TLR4 and NF-κBp56 in lungs and of inflammatory cytokines in serum significantly increased in the SAP group compared with the control group(P < 0.05), but was significantly decreased in the ω-3FA group compared with the soybean oil group at 12 and 24 h(P < 0.05).CONCLUSION During the initial stage of SAP, ω-3FA can efficiently lower the inflammatory response and reduce lung injury by triggering the TLR4/NF-κBp56 signal pathway.展开更多
Six new transition metal complexes, [Zn(HBTC)(PYTPY)]n·n PYTPY(1), [Cu(HBTC)(PYTPY)]n·n PYTPY(2), [Co(HBTC)(PYTPY)]n·n DMF(3), [Mn(HBTC)(PYTPY)]n·n DMF(4), [Cd(HBTC)(PYTP...Six new transition metal complexes, [Zn(HBTC)(PYTPY)]n·n PYTPY(1), [Cu(HBTC)(PYTPY)]n·n PYTPY(2), [Co(HBTC)(PYTPY)]n·n DMF(3), [Mn(HBTC)(PYTPY)]n·n DMF(4), [Cd(HBTC)(PYTPY)(H2O)]n·2nH2O(5), and [Co(HBTC)(PYTPY)(H2O)2](6),(H3BTC = 1,3,5-benzenetricarboxylic acid, PYTPY = 4'-(4-pyridyl)-2,2':6',2''-terpyridine, DMF = N,N?-dimethylformamide), have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complexes 1~5 all feature one-dimensional chain structures, and complex 6 exhibits a zero-dimensional structure. Complexes 1~5 present three-dimensional(3D) supramolecular frameworks via π-π stacking interactions, whenas 6 has also a 3D supramolecular structure assembled by hydrogen bonding. Meanwhile, complexes 1 ~ 6 exhibit the thermal stabilities and photoluminescent properties.展开更多
文摘Activated carbons calcined at 400˚C and 600˚C (AC-400 and AC-600), prepared using palm nuts, collected in the town of Franceville in Gabon, were used to study the dynamic adsorption of MnO<sub>4</sub>-</sup> ions in acidic media on fixed bed column and on the kinetic modeling of experimental data of breakthrough curves of MnO<sub>4</sub>-</sup> ions obtained. Results on the adsorption of MnO<sub>4</sub>-</sup> ions in fixed-bed dynamics obtained on AC-400 and AC-600 adsorbents beds indicated that the AC-400 bed appears to be the most efficient in removing MnO<sub>4</sub>-</sup> ions in acidic media. Indeed, the adsorbed amounts, the adsorbed capacities at saturation and the elimination percentage of MnO<sub>4</sub>-</sup> ions obtained with AC-400 (31.24 mg;52.06 mg·g<sup>-1</sup> and 41.65% respectively) were higher compared to those obtained with AC-600 (9.87 mg;16.45 mg·g<sup>-1</sup> and 17.79% respectively). The breakthrough curves kinetic modeling revealed that the Thomas model and the pseudo-first-order kinetic model were the most suitable models to describe the adsorption of MnO<sub>4</sub>-</sup> ions on adsorbents studied in our experimental conditions. The results of the intraparticle diffusion model showed that intraparticle diffusion was involved in the adsorption mechanism of MnO<sub>4</sub>-</sup> ions on investigated adsorbents and was not the limiting step and the only process controlling MnO<sub>4</sub>-</sup> ions adsorption. In contrast to AC-400, the intraparticle diffusion on AC-600 bed plays an important role in the adsorption mechanism of MnO<sub>4</sub>-</sup> ions.
基金Supported by NSFC 20973174 and MOST project (2006DFA43020 and 2007CB815307)
文摘ABSTRACT Four novel 1D lanthanide coordination polymers with formula [Ln(3,4-pybz)3(HzO)2. H2O]n (Ln = 1 Sm; 2 Eu; 3 Tb; 4 Dy, 3,4-Hpybz = 3-(pyridin-4-yl)benzoic acid) have been synthesized by hydrothermal reactions of lanthanide oxide and 3-(pyridine-4-yl) benzoic acid. Single-crystal X-ray diffraction shows that the four compounds are isostructural. They all crystallize in a monoelinic system, space group P1^-. They have a doubly carboxylate-bridged infinite-chain structure with alternating Ln-(carboxylate)2-Ln linkages and one chelating carboxylate group on each metal center. The Ln ion also combines to two water molecules to form an eight-coordinate square antiprismatic geometry. The pyridine nitrogen atoms of the ligand do not coordinate to the metal centers but direct the formation of a 3D network through hydrogen bonding with coordinated water molecules. The photoluminescent properties of 2 and 3 have been also studied.
基金Supported by the National Natural Science Foundation of China(No.21607051)Institute Foundation of Siping City(No.2017057)the Science and Technology Research Projects of the Education Committee of Jilin Province(No.JJKH20180779KJ)
文摘A new Cu(Ⅱ) coordination polymer, [Cu(L1)(L2)](1), was synthesized under hydrothermal conditions(H_2L1 = 4-(carboxymethoxy)benzoic acid, L2 = 2-(4-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline). Crystallographic data for 1: triclinic, space group P1 with a = 9.750(5), b = 10.148(5), c = 12.869(5) ?, α = 104.904(5), β = 102.133(5), γ = 95.219(5)°, V = 1188.7(10) ?~3, Z = 2, C_(28)H_(17)FN_4O_5Cu, Mr = 572.01, D_c = 1.598 g/cm^3, F(000) = 582, μ(MoKa) = 0.977 mm^(-1), R = 0.0474 and w R = 0.1144. The TGA behaviors and luminescence of 1 have been studied in detail. The L1 dianions link neighboring Cu(Ⅱ) atoms in a bis-chelating mode, yielding a one-dimensional chain structure along the b axis. The L2 ligands are attached on one side of the chain through chelating the Cu(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a layer structure. Additionally, the N–H???O hydrogen bonds further stabilize the structure of 1.
基金Supported by Jilin Province Science and Technology Development projects (No. 201105085)
文摘A new ID coordination polymer, [Cda(L1)2(L2)2].H2O (1, H2L1 = 4-(carboxy- methoxy)benzoic acid and L2 = 2-(4-fluorophenyl)-I H-imidazo[4,5-f][1,10]phenanthroline), has been hydrothermally synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 9.985(5), b = 10.768(5), c = 12.512(5) A, a = 68.959(5), β = 80.354(5), γ = 79.663(5)°, V= 1227.4(10) A3, Z = 1, C56H36Cd2F2N8O11, Mr = 1259.73, Dc = 1.704 g/cm3, F(000) = 630, μ(MoKa) = 0.949 mm-1, R = 0.0261 and wR = 0.0655. The L1 anions link the neighboring Cd(II) atoms to form a 1D double chain structure. The L2 ligands are alternately located on both sides of the double chains. More interestingly, the lateral L2 ligands from adjacent double chains are paired to furnish strong π-π interactions, yielding a 2D supramolecular layer. N-H...O, O-H...N and O-H...O hydrogen bonds further stabilize the structure of 1. The luminescent property of 1 was studied in solid state at room temperature.
文摘The dehydration of 2-(4'-ethylbenzoyl) benzoic acid (BE acid) to 2-ethylanthraquinone (2-EAQ) was investigated over solid acid catalysts. The results showed that H-beta zeolite catalyst modified by dilute HNO3 solution exhibited an excellent performance. In our study, the conversion of BE acid can reach 96.7%, and the selectivity to 2-EAQ is up to 99.6%.
基金This work was supported by the NSF for Distinguished Young Scientist of China (20425104) and the NSF of Fujian Province (A0420002, 2005I017)
文摘A new Cu(Ⅱ) complex [Cu(4-cba)(1,10-phen)(H2O)2](NO3) (4-Hcba = 4-cyanobenzoic acid) has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data: C20H16CuN4O7, Mr= 487.91, triclinic, space group PI, a = 7.8420(2), b = 9.1070(2), c = 15.1140(6) A, a = 76.889(9), β = 81.332(11), γ = 74.844( 11)°, V = 1009.89(5) A^3, Z = 2, Dc = 1.605 g/cm^3, F(000) = 498, μ = 1.134 mm^-1, the final R = 0.0379 and wR = 0.0865 for 2977 observed reflections with 1 〉 2σ(Ⅰ). The Cu(Ⅱ) atom is coordinated by two terminal water molecules, one chelating 1,10-phen molecule and one monodentate 4-cba ligand to form a slightly distorted square pyramid. The title complex molecules are connected through hydrogen bonds and π-π stacking interactions to generate a 2D layered network. The thermogravimetric analysis of the title complex has also been discussed.
基金supported by the Natural Scientific Research and Overall innovation plan major project of Shaanxi Provincial Education Office of China(No.2012KTCL03-16)the National Natural Science Foundation of China(No.21373178)+2 种基金the Natural Scientific Research Foundation of Shaanxi Provincial Education Office(No.2013Jk0668)the National College Students'innovation and entrepreneurship training program(201310719002)the special fund of Yan’an University(No.YDZ2013-10)
文摘Two Pb^Ⅱ coordination polymers [Pb(oba)(2,2′-bipy)]·1.5H2O(1) and [Pb(oba)(phen)](2)(H2oba = 2,4-oxybis(benzoic acid), 2,2′-bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline) were synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction, thermogravimetric analyses, IR spectroscopy and elemental analysis. Structures of compounds 1 and 2 are similar. Compounds 1 and 2 show 1D wavy chains, which are further connected through aromatic π-π stacking interactions to expand into 2D wavelike networks. The crystal structure of 2,4-oxybis(benzoic acid) ligand(3) was obtained, and its full geometry optimization was carried out by using DFT methods at the B3LYP/6-31G(d) level. The calculated data show that the bond distances and bond angles were very close to the experimental data. The values of the frontier orbital energies indicate that this configuration is stable. Moreover, the solid-state fluorescence properties of 1-3 have also been investigated.
基金supported by the Natural Science Project of Zhejiang Province(LY12B01003)
文摘A complex [Cd2Na2(BOABA)2(H2O)8]·H2O(1) was synthesized by using 2,4-bisoxyacetate-benzoic acid(H3BOABA) and Cd(OH)2. It was characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. Complex 1 shows a two-dimensional 3-connected rigid plane. The interactions between the ligand and its complex with DNA were studied by Et Br fluorescence probe. Photoluminescent studies indicate that the complex may be excellent candidates for potential photoactive materials.
基金Supported by the National Natural Science Foundation of China (30430190, 30625011)973 (2007CB914304)Young Talent Programme of Fujian Province (2007F3119)
文摘Urokinase-type plasminogen activator (uPA) is a trypsin-like serine protease and plays a key role in several biological processes, including tissue remodeling, cell migration, and matrix degradation. The inhibitors of uPA have been shown to prevent the spread of metastasis and tumor growth, and accordingly uPA is widely recognized as a target for the treatment of cancer. In this work, we report the crystal structures of the complexes of uPA with its inhibitors: 4- (aminomethyl)-benzoic acid (AMBA) and 4-(aminomethyl-phenyl)-methanol (AMPM), both at a resolution of 2.35 А. The inhibitory constants of these two inhibitors were measured by a chromogenic competitive assay, and it was found that AMBA is a better inhibitor for uPA (Ki = 2.68 mM) than AMPM (Ki = 13.99 mM). The structural study shows that the binding mode of inhibitor AMBA on uPA is similar to that of AMPM on uPA, both docked into the active site S1 pocket of uPA. Structural details of these complexes are provided to explain the difference of inhibitory constants.
基金supported by the National Natural Science Foundation of China(21372112)
文摘Two Co(Ⅱ) coordination polymers, namely [Co(L)Cl]n(1) and [Co(L)(CH3 COO)]n(2), {HL = 3,5-di(4 H-1,2,4-triazole-4-yl)benzoic acid}, were synthesized under hydrothermal conditions. Compound 1 crystallizes in orthorhombic system, space group Pmma with a = 7.032(5), b = 11.555(8), c = 8.185(5) A, V = 665.1(7) А3, Z = 2, Dc = 1.746 g/cm3, F(000) = 350, Mr = 349.61, μ = 1.504 mm(-1), the final R = 0.0568 and w R = 0.1739 for 2312 observed reflections with I 2σ(I). Compound 2 crystallizes in orthorhombic system, space group Pmma with a = 7.7505(17), b = 11.391(3), c = 8.0298(18) A, V = 708.9(3) A3, Z = 2, Dc = 1.748 g/cm3, F(000) = 378, Mr = 373.20, μ = 1.245 mm-1, the final R = 0.0350 and w R = 0.0873 for 5239 observed reflections with I 2σ(I). Single-crystal X-ray analyses revealed that complexes 1 and 2 exhibit similar 2 D layer structures with uncoordinated carboxyl as dangling arms. The neighboring layers are further connected by these arms, leading to interest 2 D → 3 D polythreading frameworks. Moreover, the magnetic susceptibility study indicates compound 1 exhibits antiferromagnetic behavior.
基金Supported by the National Natural Science Foundation of China(21273072)
文摘A photorheologically reversible micelle composed of polymerizable cationic surfactant n-cetyl dimethylallyl am- monium chloride (CDAAC) and trans-4-phenylazo benzoic acid (trans-ACA) was prepared. The effects of molar ratio of CDAAC/trans-ACA, time of UV and visible light irradiation and temperature on the rheological properties of micellar system were investigated. The results show that before UV irradiation the system with an optimum CDAAC/trans-ACA molar ratio of 1.4 forms viscoelastic micelles at 45 ℃. After 365 nm UV irradiation, the viscos- ities of micelle systems with different concentrations at fixed molar ratio of 1.4 are decreased by 85%-95%. The CDAAC/trans-ACA (14 mmol. L- 1/10 mmol. L- 1 ) micelle system exhibits shear thinning property and its viscos- ity is decreased obviously with the increases of UV irradiation time less than I h. The rheological process during LIV irradiation for CDAAC/trans-ACA (14 mmol- L- 1/10 mmol. L 1) micelle proves that viscosity, elastic modulus G' and viscous modulus G" will reduce quickly with the UV light. Furthermore, the micelle system after 1 h UV- irradiation is able to revert to its initial high viscosity with 460 nm visible light irradiation for 4 h, and the micelle can be cycled between low and high viscosity states by repetitive UV and visible light irradiations. The LIV-Vis spectra of CDAAC/trans-ACA micelle indicate that its photosensitive theological properties are related closely to photoisomerization of trans-ACA to c/s-ACA.
文摘Two inorganic-organic coordination polymers, [Cd(TBA)2]·3H2O (1) and [Cu(TBA)2]·2H2O (2) have been synthesized by reaction of the metal ions of Cd(II) and Cu(II) with the ligand HTBA [HTBA = 4- (1H-1, 2, 4-triazol-1-yl)benzoic acid] under solvothermal condition. The compounds were characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, X-ray powder diffraction (XRPD), and thermo gravimetric analysis (TGA). The structural analyses reveal the two independent polymers exhibit different structures. Complex 1 exhibits a 3D framework with 1D channels, and complex 2 shows a 2-fold interpenetrating 3D diamond net.
基金The project was supported by the National Natural Science Foundation of China (20372021) and Natural Science Foundation of Hunan Province (03JJY3018)
文摘The title compound 2-[(4-methoxy-6-methylthio-2-pyrimidinyl)aminocarbonyl- aminosulfonyl]benzoic acid methyl ester (C15H16N4O6S2, Mr = 412.44) was obtained by the reaction of (4-methoxy-6-methylthio-2-pyrimidinyl)amine with 2-methoxylcarbonylbenzene-sulfonylisocya- nate. The crystal is of monoclinic, space group P21/c with a =11.169(3), b = 9.508(3), c = 17.690(5) ? b = 91.593(5), Z = 4, V = 1877.9(10) 3, Dc = 1.459 g/cm3, F(000) = 856, m(MoKa) = 0.324 mm-1, R = 0.0690 and wR = 0.1368 for 3301 observed reflections (I > 2s(I)). The N(1)H…N(3) and N(2)H…O(4) hydrogen bonds can be observed. In the molecule the phenyl plane(I), pyrimi- din-2-yl-urea bridge plane(Ⅱ) and ester plane(Ⅲ) form three conjugated systems.
基金supported by the National Natural Science Foundation of China(21071087,91122012)the Open Foundation of State Key Laboratory of Structural Chemistry(20090057)the K.C.Wong Magna Fund in Ningbo University
文摘Two new isomorphous metal-organic coordination polymers, [Zn(dhmdb)(2,2'- bpy)]n 1 and [Zn(dhmdb)(1,10-phen)]n 2, have been obtained under hydrothermal reactions from 4,4'-(dihydroxymethylene)dibenzoic acid (H2dhmdb), Zn(NO3)2·6H2O and 2,2'-pyridine or 1,10- phenanthroline, respectively. Compounds 1 and 2 have been characterized by FT-IR spectroscopy, thermal analysis and single-crystal X-ray diffraction. The zigzag chains of 1 and 2 are linked into three-dimensional supramolecular networks by both O–H…O hydrogen bonds and π…π stacking interactions. Crystal data for 1: ZnC25H18N2O6, Mr = 507.78, orthorhombic, space group Pbca, a = 14.031(3), b = 10.826(2), c = 27.343(6), V = 4153.5(14)3, Z = 8, Dc = 1.624 g/cm3, F(000) = 2080, μ = 1.231 mm-1, R = 0.0699 and wR = 0.1829. Crystal data for 2: ZnC27H18N2O6, Mr = 531.80, orthorhombic, space group Pbca, a = 13.796(3), b = 10.809(2), c = 28.612(6), V = 4266.8(15)3, Z = 8, Dc = 1.656 g/cm3, F(000) = 2176, μ = 1.203 mm-1, R = 0.0454 and wR = 0.1399.
基金Supported by the National Natural Science Foundation of China(No.20972178)a Grant for Key Research Items in Na-tural Science of Guangdong Higher Education Institutions of China(No.06Z027)
文摘A novel interpenetrating structure [(HMA^+)(FB^- )] ·2H2O of melamine(MA) with 4-fluoro-benzoic acid (HFB) was synthesized. It crystallized in the monoclinic system with space group P21/c. The complex has a interpenetrating 2D structure with hydrogen-bonded grid networks. Carboxylic acid to melamine proton transfer occurs in the complex. The adjacent HMA^+ cations related by an inverse center form cationic [HMA^+]∞ ribbons via a pair of N-H…N hydrogen bonds. Adjacent FB-anions are paired by C-H…F hydrogen bonds to form dimers, which are connected to [HMA^+]∞ ribbons through N-H…O interactions. The supramolecular features in the complex are guided by control of strong N-H…N, N-H…O and O-H…O hydrogen bonds, as well as highly directional weak C-H…F interactions and aromatic π-π stacking interactions.
基金Supported by the National Natural Science Foundation of China,No.81570468 and No.81741056Jinshan Science and Technology Commission,No.2014-3-07
文摘BACKGROUND Disorders of primary bile acid synthesis may be life-threatening if undiagnosed,or not treated with primary bile acid replacement therapy. To date, there are few reports on the management and follow-up of patients with Δ4-3-oxosteroid 5β-reductase(AKR1 D1) deficiency. We hypothesized that a retrospective analysis of the responses to oral bile acid replacement therapy with chenodeoxycholic acid(CDCA) in patients with this bile acid synthesis disorder will increase our understanding of the disease progression and permit evaluation of this treatment regimen as an alternative to the Food and Drug Administration(FDA) approved drug cholic acid, which is currently unavailable in China.AIM To evaluate the therapeutic responses of patients with AKR1 D1 deficiency to oral bile acid therapy, specifically CDCA.METHODS Twelve patients with AKR1 D1 deficiency, confirmed by fast atom bombardment ionization-mass spectrometry analysis of urine and by gene sequencing for mutations in AKR1 D1, were treated with differing doses of CDCA or ursodeoxycholic acid(UDCA). The clinical and biochemical responses to therapy were monitored over a period ranging 0.5-6.4 years. Dose adjustment, to optimize the therapeutic dose, was based on changes in serum biochemistry parameters,notably liver function tests, and suppression of the urinary levels of atypical hepatotoxic 3-oxo-Δ4-bile acids measured by mass spectrometry.RESULTS Physical examination, serum biochemistry parameters, and sonographic findings improved in all 12 patients during bile acid therapy, except one who underwent liver transplantation. Urine bile acid analysis confirmed a significant reduction in atypical hepatotoxic 3-oxo-Δ4 bile acids concomitant with clinical and biochemical improvements in those patients treated with CDCA. UDCA was ineffective in down-regulating endogenous bile acid synthesis as evidenced from the inability to suppress the urinary excretion of atypical 3-oxo-Δ4-bile acids. The dose of CDCA required for optimal clinical and biochemical responses varied from 5.5-10 mg/kg per day among patients based on maximum suppression of the atypical bile acids and improvement in serum biochemistry parameters, and careful titration of the dose was necessary to avoid side effects from CDCA.CONCLUSION The primary bile acid CDCA is effective in treating AKR1 D1 deficiency but the therapeutic dose requires individualized optimization. UDCA is not recommended for long-term management.
基金Supported by Jinling Hospital Research Fund,No.2013064
文摘AIM To determine the effects of ω-3 fatty acids(ω-3FA) on the toll-like receptor 4(TLR4)/nuclear factor κB p56(NF-κBp56) signal pathway in the lungs of rats with severe acute pancreatitis(SAP).METHODS A total of 56 Sprague-Dawley rats were randomly divided into 4 groups: control group, SAP-saline group, SAP-soybean oil group and SAP-ω-3FA group. SAP was induced by the retrograde infusion of sodium taurocholate into the pancreatic duct. The expression of TLR4 and NF-κBp56 in the lungs was evaluated by immunohistochemistry and Western blot analysis. The levels of inflammatory cytokines interleukin-6 and tumor necrosis factor-alpha in the lungs were measured by enzyme-linked immunosorbent assay. RESULTS The expression of TLR4 and NF-κBp56 in lungs and of inflammatory cytokines in serum significantly increased in the SAP group compared with the control group(P < 0.05), but was significantly decreased in the ω-3FA group compared with the soybean oil group at 12 and 24 h(P < 0.05).CONCLUSION During the initial stage of SAP, ω-3FA can efficiently lower the inflammatory response and reduce lung injury by triggering the TLR4/NF-κBp56 signal pathway.
基金Supported by the National Natural Science Foundation of China(No.21576112)Natural Science Foundation of Jilin Province(20150623024TC-19,20170520147JH)the Science and Technology Development Plan of Siping City(2015049)
文摘Six new transition metal complexes, [Zn(HBTC)(PYTPY)]n·n PYTPY(1), [Cu(HBTC)(PYTPY)]n·n PYTPY(2), [Co(HBTC)(PYTPY)]n·n DMF(3), [Mn(HBTC)(PYTPY)]n·n DMF(4), [Cd(HBTC)(PYTPY)(H2O)]n·2nH2O(5), and [Co(HBTC)(PYTPY)(H2O)2](6),(H3BTC = 1,3,5-benzenetricarboxylic acid, PYTPY = 4'-(4-pyridyl)-2,2':6',2''-terpyridine, DMF = N,N?-dimethylformamide), have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complexes 1~5 all feature one-dimensional chain structures, and complex 6 exhibits a zero-dimensional structure. Complexes 1~5 present three-dimensional(3D) supramolecular frameworks via π-π stacking interactions, whenas 6 has also a 3D supramolecular structure assembled by hydrogen bonding. Meanwhile, complexes 1 ~ 6 exhibit the thermal stabilities and photoluminescent properties.