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 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
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 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
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
The title complex [Zn2(hfipbb)2(2,2′-bpy)2], 1 has been hydrothermally synthesized from Zn(NO3)2·6H2O, 4,4′-(hexafluoroisopropylidene)bis(benzoic acid) and 2,2′-bipyridine. Singlecrystal X-ray analys...The title complex [Zn2(hfipbb)2(2,2′-bpy)2], 1 has been hydrothermally synthesized from Zn(NO3)2·6H2O, 4,4′-(hexafluoroisopropylidene)bis(benzoic acid) and 2,2′-bipyridine. Singlecrystal X-ray analysis reveals that 1 presents a one-dimensional coordination polymer with pseudo-helical chain structure. Two Zn(Ⅱ) atoms in an unsymmetrical unit of 1 adopt distorted octahedral and square-pyramidal coordination geometries, respectively. The packing of parallel chains gives a three-dimensional supramolecular network supported by π-π stacking interactions. Crystal data: C54H32F12N4O8Zn2, Mr = 1223.58, monoclinic, space group P2 1/c, a = 27.557(6), b = 16.751(3), c = 11.350(2) A, β= 99.21(3)°, V= 5171.5(18) A^3, Z= 4, Dc = 1.572 g/cm^3, F(000) = 2464, μ= 1.030 mm^-1, the final R = 0.0552 and wR = 0.1070 for 6631 observed reflections (I〉 2σ(I)).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
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
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
Recent studies have shown that chlorogenic acid(CGA),which is present in coffee,has protective effects on the nervous system.However,its role in neonatal hypoxic-ischemic brain injury remains unclear.In this study,we ...Recent studies have shown that chlorogenic acid(CGA),which is present in coffee,has protective effects on the nervous system.However,its role in neonatal hypoxic-ischemic brain injury remains unclear.In this study,we established a newborn mouse model of hypoxic-ischemic brain injury using a modified Rice-Vannucci method and performed intraperitoneal injection of CGA.We found that CGA intervention effectively reduced the volume of cerebral infarct,alleviated cerebral edema,restored brain tissue structure after injury,and promoted axon growth in injured brain tissue.Moreover,CGA pretreatment alleviated oxygen-glucose deprivation damage of primary neurons and promoted neuron survival.In addition,changes in ferroptosis-related proteins caused by hypoxic-ischemic brain injury were partially reversed by CGA.Furthermore,CGA intervention upregulated the expression of the key ferroptosis factor glutathione peroxidase 4 and its upstream glutamate/cystine antiporter related factors SLC7A11 and SLC3A2.In summary,our findings reveal that CGA alleviates hypoxic-ischemic brain injury in neonatal mice by reducing ferroptosis,providing new ideas for the treatment of neonatal hypoxic-ischemic brain injury.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
In this work, we synthesized a new Cd(Ⅱ) coordination polymer, [Cd(L)(cmb)H;O]· H;O(1), by using mixed 2-(carboxymethoxy)benzoic acid(H2 cmb) and typical chelating N-donor ligands 2-(2-fluoro-6-fluoro...In this work, we synthesized a new Cd(Ⅱ) coordination polymer, [Cd(L)(cmb)H;O]· H;O(1), by using mixed 2-(carboxymethoxy)benzoic acid(H2 cmb) and typical chelating N-donor ligands 2-(2-fluoro-6-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline ligand(L). 1 crystallizes in monoclinic, space group P21/c with a = 17.6150(8), b = 9.7811(4), c = 18.1603(8) ?, β = 118.9150(10)o, V = 2738.9(2) ?;, Z = 4, C28 H20 CdF2 N4 O7, Mr = 674.88, Dc = 1.637 g/cm3, F(000) = 1352, μ(Mo Ka) = 0.865 mm–1, R = 0.0643 and w R = 0.1976. In 1, the cmb2– anions link neighboring Cd(Ⅱ) atoms in a bis-chelating mode, yielding a one-dimensional chain structure along the b axis. The L ligands are attached on one side of the chain through chelating the Cd(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions to generate a one-dimensional double-chain structure. Furthermore, the one-dimensional double-chains are stacked by C–H???π interactions between the carbon atom of L ligand and the benzene ring of cmb2–ligand to give a layer structure. Moreover, the solid state luminescent property of 1 was also investigated at room temperature.展开更多
A new energetic complex, Ni(3,4'-Hbpt)2(Hoba)2(H20)2 (3,4'-Hbpt = 3-(3-pyridyl)- 5-(4'-pyridyl)-l-H-l,2,4-triazole and H2oba = 4,4'-oxybis(benzoic acid)), has been synthesized by hydrothermal reactio...A new energetic complex, Ni(3,4'-Hbpt)2(Hoba)2(H20)2 (3,4'-Hbpt = 3-(3-pyridyl)- 5-(4'-pyridyl)-l-H-l,2,4-triazole and H2oba = 4,4'-oxybis(benzoic acid)), has been synthesized by hydrothermal reaction and characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, thermogravimetric analyses and X-ray powder diffraction. Single-crystal X-ray diffraction analysis indicates that the complex belongs to the monoclinic system, space group P2j/c with a = 10.2357(9), b = 24.594(2), c = 10.4225(9)/k, β = 114.0110(10)°, V = 2396.7(4) A3, Dc = 1.460 g/cm3,μ = 0.482 mm-1, Mr = 1053.63, F(000) = 1088, Z = 2, the final R = 0.0358 and wR = 0.0973 with I 〉 2σ(I). Both 3,4'-Hbpt and H2oba ligands adopt monodentate modes linking one Ni(II) ion to form a 0D motif. Furthermore, the 0D motifs are linked into a 3D supramolecular architecture with hydrogen bonds. In addition, the catalytic performance for thermal decomposition of the efficacy of ammonium perchlorate (AP) is explored by differential scanning calorimetry (DSC), which indicates that the complex is a good candidate for a promoter of the thermal decomposition of ammonium perchlorate.展开更多
R2(4hydroxyphenoxy)propionic acid(RHPPA)is a key intermediate for the synthesis of classic herbicides with high selectivity against grassy weed.The main route for RHPPA biosynthesis is to hydroxylate the substrate R2p...R2(4hydroxyphenoxy)propionic acid(RHPPA)is a key intermediate for the synthesis of classic herbicides with high selectivity against grassy weed.The main route for RHPPA biosynthesis is to hydroxylate the substrate R2phenoxypropionic acid(RPPA)at C4 position with microbes.In order to provide sufficient RPPA for the industrial production of RHPPA,an effective RPPA synthesis method was established and optimized in this work.The synthesis process mainly consisted of two steps:(1)synthesis of S2chloropropionic acid from Lalanine via diazotization and chlorination reactions;and(2)synthesis of RPPA from S2chloropropionic acid and phenol via etherification reaction.The optimal reaction conditions were as follows:HCl:NaNO_(2):KI:LAla=2.0:1.2:0.7:1.0(in molar),125℃reflux for 1.5 h,with KI as catalyst,and KI:S2chloropropionic acid:phenol=0.075:1.2:1.0(in molar).Under these conditions,an improved molar conversion rate(74.9%,calculated in phenol)was achieved.After extraction using anionic exchange resin Amberlite IRA400(CI),RPPA product with a purity of 95.08%was obtained.The purified RPPA was identified and evaluated in the application of the biotransformative production of RHPPA.The results indicated that the synthesized RPPA supported the RHPPA biosynthesis with a comparable yield as that of the standard RPPA.The RPPA synthesis method provided herein exhibited the advantages of low price and easy availability of raw materials,less toxicity of reagents,simple manipulations,and low equipment/instrument requirements.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
Two new metal-organic complexes [Cd2(1,4-BDC)(4-pytyp)(H2O)4]·(1,4-BDC)(1) and [Cu2(1,4-BDC)(4-pytyp)2(H2O)2]·(1,4-BDC)·8H2O(2)(4-pytyp = 4'-(4''-pyridyl)-2,2':6',2''-terp...Two new metal-organic complexes [Cd2(1,4-BDC)(4-pytyp)(H2O)4]·(1,4-BDC)(1) and [Cu2(1,4-BDC)(4-pytyp)2(H2O)2]·(1,4-BDC)·8H2O(2)(4-pytyp = 4'-(4''-pyridyl)-2,2':6',2''-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.展开更多
The reaction of 3-nitro-4-chlorobenzenesulfinic acid and ethylene oxide to obtain 2-nitro-4-(β-hydroxyethylsulfonyl)chlorobenzene had been studied. Except hydroxyethylation on the sulfur atom of 3-nitro-4-chloroben...The reaction of 3-nitro-4-chlorobenzenesulfinic acid and ethylene oxide to obtain 2-nitro-4-(β-hydroxyethylsulfonyl)chlorobenzene had been studied. Except hydroxyethylation on the sulfur atom of 3-nitro-4-chlorobenzenesulfinic acid to form the target product, 2-nitro-4-(β- hydroxyethylsulfonyl)chlorobenzene, there presented three kinds of side reactions: 1. Condensation and elimination of HCI to form biphenyl sulfone derivatives; 2. Addition to give bisulfonyl ethane derivative via vinyl sulfone; and 3. Hydroxylethylation on O-atom to produce hydroxylethylsulfinate due to the tautomerism of sulfinic acid.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 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.
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.
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Supported by the National Natural Science Foundation of China (20701022)Natural Science Foundation of Zhejiang Province (Y4080435)+1 种基金Natural Science Foundation of Ningbo Municipal (2007A610024, 2008A610045)Open Foundation of Ningbo Municipal Key Laboratory (2007A22003)
文摘The title complex [Zn2(hfipbb)2(2,2′-bpy)2], 1 has been hydrothermally synthesized from Zn(NO3)2·6H2O, 4,4′-(hexafluoroisopropylidene)bis(benzoic acid) and 2,2′-bipyridine. Singlecrystal X-ray analysis reveals that 1 presents a one-dimensional coordination polymer with pseudo-helical chain structure. Two Zn(Ⅱ) atoms in an unsymmetrical unit of 1 adopt distorted octahedral and square-pyramidal coordination geometries, respectively. The packing of parallel chains gives a three-dimensional supramolecular network supported by π-π stacking interactions. Crystal data: C54H32F12N4O8Zn2, Mr = 1223.58, monoclinic, space group P2 1/c, a = 27.557(6), b = 16.751(3), c = 11.350(2) A, β= 99.21(3)°, V= 5171.5(18) A^3, Z= 4, Dc = 1.572 g/cm^3, F(000) = 2464, μ= 1.030 mm^-1, the final R = 0.0552 and wR = 0.1070 for 6631 observed reflections (I〉 2σ(I)).
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.
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supported by the National Natural Science Foundation of China,No.81971425the Natural Science Foundation of Zhejiang Province,No.LY20H040002(both to XQF).
文摘Recent studies have shown that chlorogenic acid(CGA),which is present in coffee,has protective effects on the nervous system.However,its role in neonatal hypoxic-ischemic brain injury remains unclear.In this study,we established a newborn mouse model of hypoxic-ischemic brain injury using a modified Rice-Vannucci method and performed intraperitoneal injection of CGA.We found that CGA intervention effectively reduced the volume of cerebral infarct,alleviated cerebral edema,restored brain tissue structure after injury,and promoted axon growth in injured brain tissue.Moreover,CGA pretreatment alleviated oxygen-glucose deprivation damage of primary neurons and promoted neuron survival.In addition,changes in ferroptosis-related proteins caused by hypoxic-ischemic brain injury were partially reversed by CGA.Furthermore,CGA intervention upregulated the expression of the key ferroptosis factor glutathione peroxidase 4 and its upstream glutamate/cystine antiporter related factors SLC7A11 and SLC3A2.In summary,our findings reveal that CGA alleviates hypoxic-ischemic brain injury in neonatal mice by reducing ferroptosis,providing new ideas for the treatment of neonatal hypoxic-ischemic brain injury.
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.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In this work, we synthesized a new Cd(Ⅱ) coordination polymer, [Cd(L)(cmb)H;O]· H;O(1), by using mixed 2-(carboxymethoxy)benzoic acid(H2 cmb) and typical chelating N-donor ligands 2-(2-fluoro-6-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline ligand(L). 1 crystallizes in monoclinic, space group P21/c with a = 17.6150(8), b = 9.7811(4), c = 18.1603(8) ?, β = 118.9150(10)o, V = 2738.9(2) ?;, Z = 4, C28 H20 CdF2 N4 O7, Mr = 674.88, Dc = 1.637 g/cm3, F(000) = 1352, μ(Mo Ka) = 0.865 mm–1, R = 0.0643 and w R = 0.1976. In 1, the cmb2– anions link neighboring Cd(Ⅱ) atoms in a bis-chelating mode, yielding a one-dimensional chain structure along the b axis. The L ligands are attached on one side of the chain through chelating the Cd(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions to generate a one-dimensional double-chain structure. Furthermore, the one-dimensional double-chains are stacked by C–H???π interactions between the carbon atom of L ligand and the benzene ring of cmb2–ligand to give a layer structure. Moreover, the solid state luminescent property of 1 was also investigated at room temperature.
基金Supported by the National Natural Science Foundation of China(No.21263019)
文摘A new energetic complex, Ni(3,4'-Hbpt)2(Hoba)2(H20)2 (3,4'-Hbpt = 3-(3-pyridyl)- 5-(4'-pyridyl)-l-H-l,2,4-triazole and H2oba = 4,4'-oxybis(benzoic acid)), has been synthesized by hydrothermal reaction and characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, thermogravimetric analyses and X-ray powder diffraction. Single-crystal X-ray diffraction analysis indicates that the complex belongs to the monoclinic system, space group P2j/c with a = 10.2357(9), b = 24.594(2), c = 10.4225(9)/k, β = 114.0110(10)°, V = 2396.7(4) A3, Dc = 1.460 g/cm3,μ = 0.482 mm-1, Mr = 1053.63, F(000) = 1088, Z = 2, the final R = 0.0358 and wR = 0.0973 with I 〉 2σ(I). Both 3,4'-Hbpt and H2oba ligands adopt monodentate modes linking one Ni(II) ion to form a 0D motif. Furthermore, the 0D motifs are linked into a 3D supramolecular architecture with hydrogen bonds. In addition, the catalytic performance for thermal decomposition of the efficacy of ammonium perchlorate (AP) is explored by differential scanning calorimetry (DSC), which indicates that the complex is a good candidate for a promoter of the thermal decomposition of ammonium perchlorate.
文摘R2(4hydroxyphenoxy)propionic acid(RHPPA)is a key intermediate for the synthesis of classic herbicides with high selectivity against grassy weed.The main route for RHPPA biosynthesis is to hydroxylate the substrate R2phenoxypropionic acid(RPPA)at C4 position with microbes.In order to provide sufficient RPPA for the industrial production of RHPPA,an effective RPPA synthesis method was established and optimized in this work.The synthesis process mainly consisted of two steps:(1)synthesis of S2chloropropionic acid from Lalanine via diazotization and chlorination reactions;and(2)synthesis of RPPA from S2chloropropionic acid and phenol via etherification reaction.The optimal reaction conditions were as follows:HCl:NaNO_(2):KI:LAla=2.0:1.2:0.7:1.0(in molar),125℃reflux for 1.5 h,with KI as catalyst,and KI:S2chloropropionic acid:phenol=0.075:1.2:1.0(in molar).Under these conditions,an improved molar conversion rate(74.9%,calculated in phenol)was achieved.After extraction using anionic exchange resin Amberlite IRA400(CI),RPPA product with a purity of 95.08%was obtained.The purified RPPA was identified and evaluated in the application of the biotransformative production of RHPPA.The results indicated that the synthesized RPPA supported the RHPPA biosynthesis with a comparable yield as that of the standard RPPA.The RPPA synthesis method provided herein exhibited the advantages of low price and easy availability of raw materials,less toxicity of reagents,simple manipulations,and low equipment/instrument requirements.
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.
基金Supported by the Program for New Century Excellent Talents in University(NCET-10-0176)the Natural Science Foundation of Jilin Province(No.20130521019JH)the fund of Jilin Provincial Education Department of China(No.2014154)
文摘Two new metal-organic complexes [Cd2(1,4-BDC)(4-pytyp)(H2O)4]·(1,4-BDC)(1) and [Cu2(1,4-BDC)(4-pytyp)2(H2O)2]·(1,4-BDC)·8H2O(2)(4-pytyp = 4'-(4''-pyridyl)-2,2':6',2''-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.
文摘The reaction of 3-nitro-4-chlorobenzenesulfinic acid and ethylene oxide to obtain 2-nitro-4-(β-hydroxyethylsulfonyl)chlorobenzene had been studied. Except hydroxyethylation on the sulfur atom of 3-nitro-4-chlorobenzenesulfinic acid to form the target product, 2-nitro-4-(β- hydroxyethylsulfonyl)chlorobenzene, there presented three kinds of side reactions: 1. Condensation and elimination of HCI to form biphenyl sulfone derivatives; 2. Addition to give bisulfonyl ethane derivative via vinyl sulfone; and 3. Hydroxylethylation on O-atom to produce hydroxylethylsulfinate due to the tautomerism of sulfinic acid.