Under solvothermal conditions,six new coordination polymers(CPs)[Mn(L)(phen)(H_(2)O)]_(n)(1),[Co(L)(phen)(H_(2)O)]_(n)(2),[Cu(L)(phen)(H_(2)O)]_(n)(3),[Zn_(2)(L)_(2)(phen)2(H_(2)O)]_(n)(4),[Zn(L)(phen)]_(n)(5),and[Cd(...Under solvothermal conditions,six new coordination polymers(CPs)[Mn(L)(phen)(H_(2)O)]_(n)(1),[Co(L)(phen)(H_(2)O)]_(n)(2),[Cu(L)(phen)(H_(2)O)]_(n)(3),[Zn_(2)(L)_(2)(phen)2(H_(2)O)]_(n)(4),[Zn(L)(phen)]_(n)(5),and[Cd(L)(phen)2]_(n)(6)were synthesized by reactions of dicarboxylate ligand 2,2'-(1,2-phenylenebis(methylene))bis(sulfanediyl)dinobutyric acid(H_(2)L)and 1,10-phenanthroline(phen)with the corresponding metal salts.Complexes 1-6 have been structurally characterized by single-crystal X-ray diffraction analyses,elemental analysis,IR,thermogravimetric analysis,and powder X-ray diffraction.The structures of 1-6 are 1D chains,which are further connected by hydrogen bonding interac-tions to form 3D supramolecular structures.Among them,1 and 2 are isomorphic with L2-of syn-conformation,while L2-shows anti-conformation in 3-6.In addition,the solid-state photoluminescence property of 4-6 was investigated.展开更多
Three coordination polymers[Mn(epda)(2,2'⁃bipy)(H_(2)O)](1),[Mn(epda)(phen)](2),and[Co_(2)(epda)2(bpe)2(H_(2)O)_(4)]·5H_(2)O(3)(H2epda=5⁃ethyl⁃pyridine⁃2,3⁃dicarboxylic acid,2,2'⁃bipy=2,2'⁃bipyridine,...Three coordination polymers[Mn(epda)(2,2'⁃bipy)(H_(2)O)](1),[Mn(epda)(phen)](2),and[Co_(2)(epda)2(bpe)2(H_(2)O)_(4)]·5H_(2)O(3)(H2epda=5⁃ethyl⁃pyridine⁃2,3⁃dicarboxylic acid,2,2'⁃bipy=2,2'⁃bipyridine,phen=phenanthroline,bpe=1,2⁃bis(4⁃pyridyl)ethylene)were synthesized by solvothermal reactions and characterized by single⁃crystal X⁃ray diffraction,thermogravimetric analyses,IR spectroscopy and elemental analysis.1 displays a 1D chain struc⁃ture,and these chains are joined by O-H…O hydrogen bonding andπ⁃πstacking interactions to generate a 2D layer structure.2 displays a 2D layer structure,and adjacent layers are generated 3D architecture throughπ⁃πstacking interactions.3 displays a 1D chain structure,and adjacent chains are generated double layer structure through O-H…O hydrogen bonding.The fluorescent properties of 1 and 3 indicate that they can potentially be used as a luminescent sensor.1 was highly selective and sensitive towards o⁃nitrophenol through different detection mechanisms,however,3 was highly selective and sensitive towards 2,4,6⁃trinitrophenol.In addition,the magnetic behavior of 2 has also been investigated.CCDC:2172533,1,2355773,2,2355774,3.展开更多
A high_CO 2_requiring mutant of Synechococcus sp. PCC7942 has been isolated after chemical mutagenesis of ethyl methane sulphonate (EMS). It was able to grow at 4% CO 2, but not under ambient CO 2. The initial s...A high_CO 2_requiring mutant of Synechococcus sp. PCC7942 has been isolated after chemical mutagenesis of ethyl methane sulphonate (EMS). It was able to grow at 4% CO 2, but not under ambient CO 2. The initial screening of the mutant showed that the genetic reversion rate was about 10 -7 and death occurred 2-3 days after being transferred from 4% CO 2 to the ambient air. Its photosynthetic dependence on external dissolved inorganic carbon was higher than that of the wild type cells, but its carbonic anhydrase activity was comparatively low. In the ultrastructural level, various types of aberrant carboxysomes appeared in the mutant cells: rod_shaped carboxysomes, irregular carboxysomes and the “empty_inclusion carboxysomes" with increasing number of glycogen granules surrounding the thylakoids. All these alterations indicated that the mutant was defective in utilizing the external CO 2. The induction of carboxysomes by lower levels of CO 2 and the biogenesis of carboxysomes are herein discussed.展开更多
The carboxyl terminal of sodium oleate has a stronger polarity than that of oleic acid;this terminal is more likely to be dipole polarized and ionically conductive in a microwave field.Sodium oleate was used as the mo...The carboxyl terminal of sodium oleate has a stronger polarity than that of oleic acid;this terminal is more likely to be dipole polarized and ionically conductive in a microwave field.Sodium oleate was used as the model compound to study the decarboxylation of oleic acid leading to hydrocarbon formation via microwave-assisted pyrolysis technology.The pyrolysis gas,liquid,and solid products were precisely analyzed to deduce the mechanism for decarboxylation of sodium oleate.Microwave energy was able to selectively heat the carboxyl terminal of sodium oleate.During decarboxylation,the double bond in the long hydrocarbon chain formed a p-πconjugated system with the carbanion intermediate.The resulting p-πconjugated system was more stable and beneficial to the pyrolysis reaction(decarboxylation,terminal allylation,isomerization,and aromatization).The physical properties of pyrolysis liquid were generally similar to those of diesel fuel,thereby demonstrating the possible use of microwaves for controlling the decarboxylation of sodium oleate in order to manufacture renewable hydrocarbon fuels.展开更多
A Mn(II) picolilato complex Mn(2-C5H4NCOO)2(H2O)2?/2CH3CN 1 has been synthesized. Crystal of 1 is of monoclinic, space group C2/c with a = 25.6613(3), b = 8.6357(2), c = 16.8286(2) ? b = 122.835(1), V = 3133.47(9) ?, ...A Mn(II) picolilato complex Mn(2-C5H4NCOO)2(H2O)2?/2CH3CN 1 has been synthesized. Crystal of 1 is of monoclinic, space group C2/c with a = 25.6613(3), b = 8.6357(2), c = 16.8286(2) ? b = 122.835(1), V = 3133.47(9) ?, Mr=355.7, Dc = 1.508 g/cm3, F(000) = 1456, m = 0.874 cm1 and Z = 8. The final refinement gave R = 0.0362 and wR = 0.1096 for 2264 reflections (I > 2s(I)). The Mn(II) atom possesses distorted octahedral coordination geometry and the structural parameters around the Mn ion are close to those of other Mn analogues. Extensive hydrogen bonding interactions between carboxylate and H2O were observed making one-dimensional chains of the Mn monomers.展开更多
To research techniques for removing the water blocking effect caused by hydraulic applications in coal seams,the use of surfactants is proposed,based on the mechanics of the water blocking effect.Centrifugal experimen...To research techniques for removing the water blocking effect caused by hydraulic applications in coal seams,the use of surfactants is proposed,based on the mechanics of the water blocking effect.Centrifugal experiments were used to validate the effects of using surfactants;the results show that after dealing with vacuum saturation with water,the volume of micropores decreases,which results in a larger average pore size,and the volume of transitional pores,mesopores,macropores and total pores increases.Based on the distribution of pore size,the operation mode of ‘‘water infusion after gas extraction,then continuing gas extraction" is recommended to improve the volume of coal mine gas drainage.When the reflectance of vitrinite in coal samples is less than 1,using the surfactants Fast T,1631,APG,BS can mitigate the damage caused by the water blocking effect.But when the reflectance of vitrinite is larger than 1.4,the damage caused by the water blocking effect can be increased.When the surfactant CMC is used in hydraulic applications,the capillary forces of coal samples are almost negative,which means the capillary force is in the same direction as the gas extraction.The direction of capillary forces benefits the gas flow.So,using CMC can play an active role in removing the water blocking effect.Centrifugal experiments confirm that using CMC can effectively remove the water blocking effect,which has a beneficial effect on improving the gas drainage volume.展开更多
In this study we used l-allyl-3-methyl imidazole formate ([Amim][COOH]) as ionic liquid to pre-treat the cellulose and determined the rate of polymerization and enzymatic hydrolysis. The results showed that pretreat...In this study we used l-allyl-3-methyl imidazole formate ([Amim][COOH]) as ionic liquid to pre-treat the cellulose and determined the rate of polymerization and enzymatic hydrolysis. The results showed that pretreatment with ([Amim][COOH]) significantly decreased the cellulose polymerization. As the pretreatment temperature went up, the enzymatic hydrolysis rate was first increased and then decreased The maximal enzymatic hydrolysis rate was achieved when the pretreatment temperature was 90 ℃. Under the ultrasonic condition, the initial rate of enzmatic hydrolysis for the ionic liquid-treated cellulose was up to 11.10 gL-1h-1, which was 33% increase compared to the untreated cellulose. Scanning Electronic Microscopy (SEM) and Fourier Transform Infrared-Raman Spectroscop (FT-IR) analysis showed that ionic liquidtreated cellulose started to depolymerize. In addition, the cr3'stallinity of the cellulose was significantly decreased after pretreatment with ionic liquid.展开更多
Orthogonal-test-design method has been used to determine the optimal formula by phase behavior and interfacial tension studies, respectively. The effect of each component of two alkaline/surfactant/polymer flooding sy...Orthogonal-test-design method has been used to determine the optimal formula by phase behavior and interfacial tension studies, respectively. The effect of each component of two alkaline/surfactant/polymer flooding systems on interfacial tension is discussed, in which a low-price natural mixed carboxylate (SDC) is used as the major surfactant. The results indicate that the optimal composition is SDC (0.5%), alkaline NaHCO3/Na2CO3 with mass ratio of 1 (1.0%), and hydrolyzed polyacrylamide(0.1%). In the coreflood experiment, their oil recovery is increased by about 25.2% and 26.8% original oil in place, respectively.展开更多
Engineering the surface microenvironment by tuning the binary interactions between a supported metal with a secondary metal oxide(MO_(x))or support has been a common method for improving the catalytic performance of s...Engineering the surface microenvironment by tuning the binary interactions between a supported metal with a secondary metal oxide(MO_(x))or support has been a common method for improving the catalytic performance of supported metal catalysts.However,few studies have investigated the ternary interactions among the metal,MO_(x),and support.Here,we report for the first time the formation of metal-MO_(x)-support interaction(MMSI)in reducible TiO_(2)-supported PtReO_(x) catalysts,affording 87% yield and 100% ee in the tandem hydrogenation of an aqueous chiral cyclohexane-1,2-dicarboxylic acid into the corresponding diol;the catalytic activity is eight times higher than that obtained with non-reducible support counterparts in the same reaction via traditional batch synthesis with multiple steps and unfriendly reagents.Detailed experimental and computational studies suggest that the TiO_(2) crystalline phase-dependent density of the oxygen vacancies induces different Pt-ReO_(x)-TiO_(2) interactions,which dominate the electron transfer therein and tune the adsorption strength of the carbonyl moiety of the substrate/intermediate,thus promoting the hydrogenation activity and selectivity.In addition,the strong MMSI endows the optimal rutile TiO_(2) supported PtReO_(x) catalyst with an outstanding lifetime of 400 h in a fixed-bed reactor under acidic aqueous conditions and ensures efficient applications in the selective hydrogenation of aliphatic dicarboxylic acids and functional carboxylic acids.This work provides a promising strategy for the development of efficient and stable supported catalysts for the selective hydrogenation of diverse C-O and C=O bonds.展开更多
A new kind of hydrophobic ionic liquids [1-alkyl-3-(1-carboxylpropyl)im][PF6] has been synthesized, and their extraction.properties for Y(III) in the nitric acid medium was also investigated. The effects of extrac...A new kind of hydrophobic ionic liquids [1-alkyl-3-(1-carboxylpropyl)im][PF6] has been synthesized, and their extraction.properties for Y(III) in the nitric acid medium was also investigated. The effects of extractant concentration, equilibrium pH of aqueous phase, salt concentration, temperature etc. were discussed. The results show that this kind of Task-Specific Ionic Liquid (TSIL) needs to be saponified before being used for the Y(III) extraction, and the extraction is-acid dependent,-and the extraction efficiency increases with the aqueous phase acldity decreasing. Furthermore, the loaded organic phase is easy to be stripped; more than 95% Y(III) could be stripped from the loaded organic phase when the stripping acidity is higher than 0.07 mol-L-1. The slope analysis technique is used to investigate the extraction mechanism, and a possible cation-exchange extraction mechanism is proposed in the oresent extraction system.展开更多
Binary and ternary complexes of Cd(II) involving pyrazine 2,3-dicarboxylic acid (pzdca) and various biologically relevant ligands containing different functional groups are investigated at 25 ℃, I = 0.10 M (NaNO...Binary and ternary complexes of Cd(II) involving pyrazine 2,3-dicarboxylic acid (pzdca) and various biologically relevant ligands containing different functional groups are investigated at 25 ℃, I = 0.10 M (NaNO3) and in 20% (v/v) ethanol-water media. The ligands (L) used are amino acids, dicarboxylic acids and peptides. The results showed the formation of Cd (pzdca) (L) complexes with amino acids and dicarboxylic acids. Peptides form both Cd (pzdca) (L) complexes and the corresponding deprotonated amide species Cd (pzdca) (LH-1). The relative stabilities of ternary complexes are compared with those of the corresponding binary complexes in terms of AlogK values. The concentration distribution of the complexes in solution was evaluated.展开更多
Phenazine antibiotics phenazine-l-carboxylic acid (PCA) and l-hydroxyphenazine (1-OH-PHZ) were purified from culture broth and mycelia ofStreptomyces griseoluteus P510, Both PCA and 1 -OH-PHZ exhibit strong antifu...Phenazine antibiotics phenazine-l-carboxylic acid (PCA) and l-hydroxyphenazine (1-OH-PHZ) were purified from culture broth and mycelia ofStreptomyces griseoluteus P510, Both PCA and 1 -OH-PHZ exhibit strong antifun- gal activity against six plant pathogens, especially Fusarium oxysporium, with minimal inhibition concentrations less than I and 2/ag, ml- 1 for PCA and 1-OH-PHZ, respectively, The presence of PCA and 1 -OH-PHZ indicates that S. griseoluteus PSlO can be used as a potential source of pesticides,展开更多
The chaotic characteristics of bubbles rising with accompanying coalescences in pseudoplastic aqueous carboxymethylcellulose sodium(CMC)solution were studied by means of smoothed pseudo Wigner-Ville distribution and W...The chaotic characteristics of bubbles rising with accompanying coalescences in pseudoplastic aqueous carboxymethylcellulose sodium(CMC)solution were studied by means of smoothed pseudo Wigner-Ville distribution and Wigner-Hough distribution.The temporal signal of bubble passage was measured utilizing a photoconductive data acquisition system.As bubble coalescence occurred,the smoothed pseudo Wigner-Ville distribution of the signal revealed that the signal could be divided into low-frequency and high-frequency ranges and the transition range according to the distribution feature of frequency domain,which reflected eddy motion of fluid,high frequency fluctuations of fluid velocity and other random components measured in the signal,and bubbles rising accompanied with coalescences,respectively.However,bubble coalescence occurred in the lower position and the frequency range of bubbles motion became wide under higher gas flowrate,while the frequency range of bubbles motion became narrow when the CMC concentration increased.The typical dynamics of bubbles motion,such as periodicity,bifurcation and chaos,could be easily found in terms of the Wigner-Hough distribution.展开更多
A new crystalline form of carboxypeptidase A (CPA) complexes withan inactivator was obtained by the method of hanging drop vapor diffusion. The inacti-’vator, 2-benzyl-3-iodo-propanoic acid (BIPA ), binds covalently ...A new crystalline form of carboxypeptidase A (CPA) complexes withan inactivator was obtained by the method of hanging drop vapor diffusion. The inacti-’vator, 2-benzyl-3-iodo-propanoic acid (BIPA ), binds covalently to an active siteresidue Glu-27O of CPA. The complex was crystallized in space group P212121 with a= 48. 8 A, b=66. 9 A, c= 96. 0 A. The complex structure was determined by molecu-lar replacement using the native CPA crystal structure as the search model. The finalcrystallographic residual is 0. 152. Except for the modification of Glu-270, the inactiva-tor exhibits normal binding mode compared with other ligand complexes of CPA. Inthe final different electron density maps (2Fo-Fc, Fo-Fc), the density of the iodo ioncould not be found while the conserved molecule remains coordinated to Zn2+ as in thenative CPA. Comparisons of complex of CPA-BIPA with the native CPA and theCPA/D-Phe complex are presented. The mechanism of inactivation of CPA was dis-cussed.展开更多
Objective Glutamic acid decarboxylase 2(GAD65) is a gamma-aminobutyric acid(GABA) synthetase.This study aimed to construct a recombinant lentivirus-rGAD65(rLV-rGAD65) vector containing the cDNA of rat GAD65(rGA...Objective Glutamic acid decarboxylase 2(GAD65) is a gamma-aminobutyric acid(GABA) synthetase.This study aimed to construct a recombinant lentivirus-rGAD65(rLV-rGAD65) vector containing the cDNA of rat GAD65(rGAD65) and assess its functional activity in vitro and in vivo.Methods cDNA of rGAD65 was amplified by RT-PCR and subcloned into the LV vector,forming the rLV-GFP-rGAD65 plasmid.The recombinant lentivirus particles(rLVrGAD65) were packaged by the LV Helper-Free System and the titer was measured.Primary rat lung fibroblasts were transfected with rLV-rGAD65.The expression of rGAD65 in fibroblasts was detected by immunocytochemistry and western blot and the level of GABA in the medium was assessed by high-performance liquid chromatograph(HPLC).In vivo,rLV-rGAD65 was injected into the subthalamic nucleus(STN) of Sprague-Dawley rats using stereotaxic methods,and rGAD65 protein levels in the STN were assessed by immunohistochemistry and Western blot,while the GABA concentration in the substantia nigra pars reticulata(SNr) was assayed by HPLC.Results The sequence of rGAD65 cDNA was in accord with that in GenBank.The amino-acid sequence of rGAD65 had no mutations and the titer of rLVrGAD65 reached 6.8 × 108/mL.The efficiency of infection of fibroblasts was 80%,and the concentration of GABA in the medium was(48.14 ± 9.35) nmol/L.In vivo,rGAD65 expression was detected in the STN,and the concentration of GABA in the SNr increased from(5.95 ± 1.09) to(12.44 ± 3.79) nmol/g tissue.Conclusion The recombinant LVGFP-rGAD65 vector was successfully constructed.rLV-rGAD65-infected primary fibroblasts in vitro and the expressed rGAD65 catalyzed the formation of GABA from glutamic acid.In vivo,the concentration of GABA in the SNr was increased after rLV-rGAD65 injection into the STN.展开更多
General application of "greener methods" to the synthesis of monodisperse colloidal nanocrystals introduces impurities, including metal carboxylate precursors, non-volatile solvents, free ligands, and non-nanocrysta...General application of "greener methods" to the synthesis of monodisperse colloidal nanocrystals introduces impurities, including metal carboxylate precursors, non-volatile solvents, free ligands, and non-nanocrystalline side products. These impurities seriously diminish the solution processability and potential applications of colloidal nanocrystals. A protocol was established for evaluating purification schemes. The results revealed that commonly applied purification schemes and their variants do not exhibit a high level of performance and may degrade the ligand surface coverage. A new scheme involving chloroformacetonitrile precipitation quantitatively removed all impurities from colloidal solutions of CdSe and CdS nanocrystals coated with a variety of carboxylate ligands. The new scheme was benign to the surface structure of nanocrystaMigands complexes and resulted in each nanocrystal bearing a close-packed monolayer of carboxylate ligands.展开更多
文摘Under solvothermal conditions,six new coordination polymers(CPs)[Mn(L)(phen)(H_(2)O)]_(n)(1),[Co(L)(phen)(H_(2)O)]_(n)(2),[Cu(L)(phen)(H_(2)O)]_(n)(3),[Zn_(2)(L)_(2)(phen)2(H_(2)O)]_(n)(4),[Zn(L)(phen)]_(n)(5),and[Cd(L)(phen)2]_(n)(6)were synthesized by reactions of dicarboxylate ligand 2,2'-(1,2-phenylenebis(methylene))bis(sulfanediyl)dinobutyric acid(H_(2)L)and 1,10-phenanthroline(phen)with the corresponding metal salts.Complexes 1-6 have been structurally characterized by single-crystal X-ray diffraction analyses,elemental analysis,IR,thermogravimetric analysis,and powder X-ray diffraction.The structures of 1-6 are 1D chains,which are further connected by hydrogen bonding interac-tions to form 3D supramolecular structures.Among them,1 and 2 are isomorphic with L2-of syn-conformation,while L2-shows anti-conformation in 3-6.In addition,the solid-state photoluminescence property of 4-6 was investigated.
文摘Three coordination polymers[Mn(epda)(2,2'⁃bipy)(H_(2)O)](1),[Mn(epda)(phen)](2),and[Co_(2)(epda)2(bpe)2(H_(2)O)_(4)]·5H_(2)O(3)(H2epda=5⁃ethyl⁃pyridine⁃2,3⁃dicarboxylic acid,2,2'⁃bipy=2,2'⁃bipyridine,phen=phenanthroline,bpe=1,2⁃bis(4⁃pyridyl)ethylene)were synthesized by solvothermal reactions and characterized by single⁃crystal X⁃ray diffraction,thermogravimetric analyses,IR spectroscopy and elemental analysis.1 displays a 1D chain struc⁃ture,and these chains are joined by O-H…O hydrogen bonding andπ⁃πstacking interactions to generate a 2D layer structure.2 displays a 2D layer structure,and adjacent layers are generated 3D architecture throughπ⁃πstacking interactions.3 displays a 1D chain structure,and adjacent chains are generated double layer structure through O-H…O hydrogen bonding.The fluorescent properties of 1 and 3 indicate that they can potentially be used as a luminescent sensor.1 was highly selective and sensitive towards o⁃nitrophenol through different detection mechanisms,however,3 was highly selective and sensitive towards 2,4,6⁃trinitrophenol.In addition,the magnetic behavior of 2 has also been investigated.CCDC:2172533,1,2355773,2,2355774,3.
文摘A high_CO 2_requiring mutant of Synechococcus sp. PCC7942 has been isolated after chemical mutagenesis of ethyl methane sulphonate (EMS). It was able to grow at 4% CO 2, but not under ambient CO 2. The initial screening of the mutant showed that the genetic reversion rate was about 10 -7 and death occurred 2-3 days after being transferred from 4% CO 2 to the ambient air. Its photosynthetic dependence on external dissolved inorganic carbon was higher than that of the wild type cells, but its carbonic anhydrase activity was comparatively low. In the ultrastructural level, various types of aberrant carboxysomes appeared in the mutant cells: rod_shaped carboxysomes, irregular carboxysomes and the “empty_inclusion carboxysomes" with increasing number of glycogen granules surrounding the thylakoids. All these alterations indicated that the mutant was defective in utilizing the external CO 2. The induction of carboxysomes by lower levels of CO 2 and the biogenesis of carboxysomes are herein discussed.
基金the National Natural Science Foundation of China(No.21266022)the National High Technology Research and Development Program 863(2012AA101800-03+4 种基金2012AA02120562012AA021704)the International Cooperation of Jiangxi Province(No.20101208)the International Science & Technology Cooperation Program of China(No.2010DFB63750)the Natural Science Foundation of Jiangxi Province(No.2008GZH0047)
文摘The carboxyl terminal of sodium oleate has a stronger polarity than that of oleic acid;this terminal is more likely to be dipole polarized and ionically conductive in a microwave field.Sodium oleate was used as the model compound to study the decarboxylation of oleic acid leading to hydrocarbon formation via microwave-assisted pyrolysis technology.The pyrolysis gas,liquid,and solid products were precisely analyzed to deduce the mechanism for decarboxylation of sodium oleate.Microwave energy was able to selectively heat the carboxyl terminal of sodium oleate.During decarboxylation,the double bond in the long hydrocarbon chain formed a p-πconjugated system with the carbanion intermediate.The resulting p-πconjugated system was more stable and beneficial to the pyrolysis reaction(decarboxylation,terminal allylation,isomerization,and aromatization).The physical properties of pyrolysis liquid were generally similar to those of diesel fuel,thereby demonstrating the possible use of microwaves for controlling the decarboxylation of sodium oleate in order to manufacture renewable hydrocarbon fuels.
基金This work was supported by the State Key Basic Research and Development Plan (G1998010100) NNSFC (No. 29733090 and 29973047)
文摘A Mn(II) picolilato complex Mn(2-C5H4NCOO)2(H2O)2?/2CH3CN 1 has been synthesized. Crystal of 1 is of monoclinic, space group C2/c with a = 25.6613(3), b = 8.6357(2), c = 16.8286(2) ? b = 122.835(1), V = 3133.47(9) ?, Mr=355.7, Dc = 1.508 g/cm3, F(000) = 1456, m = 0.874 cm1 and Z = 8. The final refinement gave R = 0.0362 and wR = 0.1096 for 2264 reflections (I > 2s(I)). The Mn(II) atom possesses distorted octahedral coordination geometry and the structural parameters around the Mn ion are close to those of other Mn analogues. Extensive hydrogen bonding interactions between carboxylate and H2O were observed making one-dimensional chains of the Mn monomers.
基金financially supported by the National Natural Science Foundation of China (No.51504084)the Education Department of Fujian Province (No.JA15493)
文摘To research techniques for removing the water blocking effect caused by hydraulic applications in coal seams,the use of surfactants is proposed,based on the mechanics of the water blocking effect.Centrifugal experiments were used to validate the effects of using surfactants;the results show that after dealing with vacuum saturation with water,the volume of micropores decreases,which results in a larger average pore size,and the volume of transitional pores,mesopores,macropores and total pores increases.Based on the distribution of pore size,the operation mode of ‘‘water infusion after gas extraction,then continuing gas extraction" is recommended to improve the volume of coal mine gas drainage.When the reflectance of vitrinite in coal samples is less than 1,using the surfactants Fast T,1631,APG,BS can mitigate the damage caused by the water blocking effect.But when the reflectance of vitrinite is larger than 1.4,the damage caused by the water blocking effect can be increased.When the surfactant CMC is used in hydraulic applications,the capillary forces of coal samples are almost negative,which means the capillary force is in the same direction as the gas extraction.The direction of capillary forces benefits the gas flow.So,using CMC can play an active role in removing the water blocking effect.Centrifugal experiments confirm that using CMC can effectively remove the water blocking effect,which has a beneficial effect on improving the gas drainage volume.
文摘In this study we used l-allyl-3-methyl imidazole formate ([Amim][COOH]) as ionic liquid to pre-treat the cellulose and determined the rate of polymerization and enzymatic hydrolysis. The results showed that pretreatment with ([Amim][COOH]) significantly decreased the cellulose polymerization. As the pretreatment temperature went up, the enzymatic hydrolysis rate was first increased and then decreased The maximal enzymatic hydrolysis rate was achieved when the pretreatment temperature was 90 ℃. Under the ultrasonic condition, the initial rate of enzmatic hydrolysis for the ionic liquid-treated cellulose was up to 11.10 gL-1h-1, which was 33% increase compared to the untreated cellulose. Scanning Electronic Microscopy (SEM) and Fourier Transform Infrared-Raman Spectroscop (FT-IR) analysis showed that ionic liquidtreated cellulose started to depolymerize. In addition, the cr3'stallinity of the cellulose was significantly decreased after pretreatment with ionic liquid.
文摘Orthogonal-test-design method has been used to determine the optimal formula by phase behavior and interfacial tension studies, respectively. The effect of each component of two alkaline/surfactant/polymer flooding systems on interfacial tension is discussed, in which a low-price natural mixed carboxylate (SDC) is used as the major surfactant. The results indicate that the optimal composition is SDC (0.5%), alkaline NaHCO3/Na2CO3 with mass ratio of 1 (1.0%), and hydrolyzed polyacrylamide(0.1%). In the coreflood experiment, their oil recovery is increased by about 25.2% and 26.8% original oil in place, respectively.
文摘Engineering the surface microenvironment by tuning the binary interactions between a supported metal with a secondary metal oxide(MO_(x))or support has been a common method for improving the catalytic performance of supported metal catalysts.However,few studies have investigated the ternary interactions among the metal,MO_(x),and support.Here,we report for the first time the formation of metal-MO_(x)-support interaction(MMSI)in reducible TiO_(2)-supported PtReO_(x) catalysts,affording 87% yield and 100% ee in the tandem hydrogenation of an aqueous chiral cyclohexane-1,2-dicarboxylic acid into the corresponding diol;the catalytic activity is eight times higher than that obtained with non-reducible support counterparts in the same reaction via traditional batch synthesis with multiple steps and unfriendly reagents.Detailed experimental and computational studies suggest that the TiO_(2) crystalline phase-dependent density of the oxygen vacancies induces different Pt-ReO_(x)-TiO_(2) interactions,which dominate the electron transfer therein and tune the adsorption strength of the carbonyl moiety of the substrate/intermediate,thus promoting the hydrogenation activity and selectivity.In addition,the strong MMSI endows the optimal rutile TiO_(2) supported PtReO_(x) catalyst with an outstanding lifetime of 400 h in a fixed-bed reactor under acidic aqueous conditions and ensures efficient applications in the selective hydrogenation of aliphatic dicarboxylic acids and functional carboxylic acids.This work provides a promising strategy for the development of efficient and stable supported catalysts for the selective hydrogenation of diverse C-O and C=O bonds.
基金Supported by the National Basic Research Program of China (2012CBA01202)the National Natural Science Foundation of China (51174184)
文摘A new kind of hydrophobic ionic liquids [1-alkyl-3-(1-carboxylpropyl)im][PF6] has been synthesized, and their extraction.properties for Y(III) in the nitric acid medium was also investigated. The effects of extractant concentration, equilibrium pH of aqueous phase, salt concentration, temperature etc. were discussed. The results show that this kind of Task-Specific Ionic Liquid (TSIL) needs to be saponified before being used for the Y(III) extraction, and the extraction is-acid dependent,-and the extraction efficiency increases with the aqueous phase acldity decreasing. Furthermore, the loaded organic phase is easy to be stripped; more than 95% Y(III) could be stripped from the loaded organic phase when the stripping acidity is higher than 0.07 mol-L-1. The slope analysis technique is used to investigate the extraction mechanism, and a possible cation-exchange extraction mechanism is proposed in the oresent extraction system.
文摘Binary and ternary complexes of Cd(II) involving pyrazine 2,3-dicarboxylic acid (pzdca) and various biologically relevant ligands containing different functional groups are investigated at 25 ℃, I = 0.10 M (NaNO3) and in 20% (v/v) ethanol-water media. The ligands (L) used are amino acids, dicarboxylic acids and peptides. The results showed the formation of Cd (pzdca) (L) complexes with amino acids and dicarboxylic acids. Peptides form both Cd (pzdca) (L) complexes and the corresponding deprotonated amide species Cd (pzdca) (LH-1). The relative stabilities of ternary complexes are compared with those of the corresponding binary complexes in terms of AlogK values. The concentration distribution of the complexes in solution was evaluated.
基金Supported by the National High Technology Research and Development Program of China(2012AA022107)the National Basic Research Program of China(2012CB722105)+1 种基金the National Natural Science Foundation of China(20706037)the Ph.D.Programs Foundation of Ministry of Education of China(20090073110052)
文摘Phenazine antibiotics phenazine-l-carboxylic acid (PCA) and l-hydroxyphenazine (1-OH-PHZ) were purified from culture broth and mycelia ofStreptomyces griseoluteus P510, Both PCA and 1 -OH-PHZ exhibit strong antifun- gal activity against six plant pathogens, especially Fusarium oxysporium, with minimal inhibition concentrations less than I and 2/ag, ml- 1 for PCA and 1-OH-PHZ, respectively, The presence of PCA and 1 -OH-PHZ indicates that S. griseoluteus PSlO can be used as a potential source of pesticides,
基金Supported by the National Natural Science Foundation of China (20476073), the Opening Project of State Key Laboratory of Chemical Engineering (SKL-ChE-08B03) and the Program of Introducing Talents of Discipline to Universities (B06006).
文摘The chaotic characteristics of bubbles rising with accompanying coalescences in pseudoplastic aqueous carboxymethylcellulose sodium(CMC)solution were studied by means of smoothed pseudo Wigner-Ville distribution and Wigner-Hough distribution.The temporal signal of bubble passage was measured utilizing a photoconductive data acquisition system.As bubble coalescence occurred,the smoothed pseudo Wigner-Ville distribution of the signal revealed that the signal could be divided into low-frequency and high-frequency ranges and the transition range according to the distribution feature of frequency domain,which reflected eddy motion of fluid,high frequency fluctuations of fluid velocity and other random components measured in the signal,and bubbles rising accompanied with coalescences,respectively.However,bubble coalescence occurred in the lower position and the frequency range of bubbles motion became wide under higher gas flowrate,while the frequency range of bubbles motion became narrow when the CMC concentration increased.The typical dynamics of bubbles motion,such as periodicity,bifurcation and chaos,could be easily found in terms of the Wigner-Hough distribution.
文摘A new crystalline form of carboxypeptidase A (CPA) complexes withan inactivator was obtained by the method of hanging drop vapor diffusion. The inacti-’vator, 2-benzyl-3-iodo-propanoic acid (BIPA ), binds covalently to an active siteresidue Glu-27O of CPA. The complex was crystallized in space group P212121 with a= 48. 8 A, b=66. 9 A, c= 96. 0 A. The complex structure was determined by molecu-lar replacement using the native CPA crystal structure as the search model. The finalcrystallographic residual is 0. 152. Except for the modification of Glu-270, the inactiva-tor exhibits normal binding mode compared with other ligand complexes of CPA. Inthe final different electron density maps (2Fo-Fc, Fo-Fc), the density of the iodo ioncould not be found while the conserved molecule remains coordinated to Zn2+ as in thenative CPA. Comparisons of complex of CPA-BIPA with the native CPA and theCPA/D-Phe complex are presented. The mechanism of inactivation of CPA was dis-cussed.
文摘Objective Glutamic acid decarboxylase 2(GAD65) is a gamma-aminobutyric acid(GABA) synthetase.This study aimed to construct a recombinant lentivirus-rGAD65(rLV-rGAD65) vector containing the cDNA of rat GAD65(rGAD65) and assess its functional activity in vitro and in vivo.Methods cDNA of rGAD65 was amplified by RT-PCR and subcloned into the LV vector,forming the rLV-GFP-rGAD65 plasmid.The recombinant lentivirus particles(rLVrGAD65) were packaged by the LV Helper-Free System and the titer was measured.Primary rat lung fibroblasts were transfected with rLV-rGAD65.The expression of rGAD65 in fibroblasts was detected by immunocytochemistry and western blot and the level of GABA in the medium was assessed by high-performance liquid chromatograph(HPLC).In vivo,rLV-rGAD65 was injected into the subthalamic nucleus(STN) of Sprague-Dawley rats using stereotaxic methods,and rGAD65 protein levels in the STN were assessed by immunohistochemistry and Western blot,while the GABA concentration in the substantia nigra pars reticulata(SNr) was assayed by HPLC.Results The sequence of rGAD65 cDNA was in accord with that in GenBank.The amino-acid sequence of rGAD65 had no mutations and the titer of rLVrGAD65 reached 6.8 × 108/mL.The efficiency of infection of fibroblasts was 80%,and the concentration of GABA in the medium was(48.14 ± 9.35) nmol/L.In vivo,rGAD65 expression was detected in the STN,and the concentration of GABA in the SNr increased from(5.95 ± 1.09) to(12.44 ± 3.79) nmol/g tissue.Conclusion The recombinant LVGFP-rGAD65 vector was successfully constructed.rLV-rGAD65-infected primary fibroblasts in vitro and the expressed rGAD65 catalyzed the formation of GABA from glutamic acid.In vivo,the concentration of GABA in the SNr was increased after rLV-rGAD65 injection into the STN.
基金This work was supported by the National Natural Science Foundation of China (Nos. 21233005 and 91433204) and Fundamental Research Funds for the Central Universities (No. 2014FZA3006).
文摘General application of "greener methods" to the synthesis of monodisperse colloidal nanocrystals introduces impurities, including metal carboxylate precursors, non-volatile solvents, free ligands, and non-nanocrystalline side products. These impurities seriously diminish the solution processability and potential applications of colloidal nanocrystals. A protocol was established for evaluating purification schemes. The results revealed that commonly applied purification schemes and their variants do not exhibit a high level of performance and may degrade the ligand surface coverage. A new scheme involving chloroformacetonitrile precipitation quantitatively removed all impurities from colloidal solutions of CdSe and CdS nanocrystals coated with a variety of carboxylate ligands. The new scheme was benign to the surface structure of nanocrystaMigands complexes and resulted in each nanocrystal bearing a close-packed monolayer of carboxylate ligands.