This scale-up study demonstrated the feasibility of an ionic liquid(IL)pretreatment process at 40 kg scale,using the IL 1-ethyl-3-methylimidazolium acetate([C2C1Im][OAc])as the solvent.The pretreatment was followed by...This scale-up study demonstrated the feasibility of an ionic liquid(IL)pretreatment process at 40 kg scale,using the IL 1-ethyl-3-methylimidazolium acetate([C2C1Im][OAc])as the solvent.The pretreatment was followed by enzymatic hydrolysis through which the process efficiency for biomass conversion to monomeric sugars was determined.The results show that 43 wt%of switchgrass was dissolved in IL after 2 h of pretreatment at 160℃ with 15 wt%solid loading.A 120 h enzymatic hydrolysis of the pretreated switchgrass results in 96%glucan and 98%xylan conversion.[C2C1Im][OAc]pretreatment has been successfully scaled up to 40 kg with improved sugar titers and yields relative to bench scale(6 kg).The mass flow of the overall process was established and the major scale-up challenges of the process were identified.展开更多
AIM:To study the mechanism of 5-fluorouracil(5-FU)resistance in colon cancer cells and to develop strategies for overcoming such resistance by combination treatment.METHODS:We established and characterized a 5-FU resi...AIM:To study the mechanism of 5-fluorouracil(5-FU)resistance in colon cancer cells and to develop strategies for overcoming such resistance by combination treatment.METHODS:We established and characterized a 5-FU resistance(5-FU-R)cell line derived from continuous exposure(25μmol/L)to 5-FU for 20 wk in 5-FU sensitive HCT-116 cells.The proliferation and expression of different representative apoptosis and anti-apoptosis markers in 5-FU sensitive and 5-FU resistance cells were measured by the MTT assay and by Western blotting,respectively,after treatment with Resveratrol(Res)and/or 1,3-Bis(2-chloroethyl)-1-nitrosourea(BCNU).Apoptosis and cell cycle arrest was measured by 4',6'-diamidino-2-phenylindole hydrochloride staining and fluorescence-activated cell sorting analysis,respectively.The extent of DNA damage was measured by the Comet assay.We measured the visible changes in the DNA damage/repair cascade by Western blotting.RESULTS:The widely used chemotherapeutic agents BCNU and Res decreased the growth of 5-FU sensitive HCT-116 cells in a dose dependent manner.Combined application of BCNU and Res caused more apoptosis in5-FU sensitive cells in comparison to individual treatment.In addition,the combined application of BCNU and Res caused a significant decrease of major DNA base excision repair components in 5-FU sensitive cells.We established a 5-FU resistance cell line(5-FU-R)from 5-FU-sensitive HCT-116(mismatch repair deficient)cells that was not resistant to other chemotherapeutic agents(e.g.,BCNU,Res)except 5-FU.The 5-FU resistance of 5-FU-R cells was assessed by exposure to increasing concentrations of 5-FU followed by the MTT assay.There was no significant cell death noted in5-FU-R cells in comparison to 5-FU sensitive cells after5-FU treatment.This resistant cell line overexpressed anti-apoptotic[e.g.,AKT,nuclear factorκB,FLICE-like inhibitory protein),DNA repair(e.g.,DNA polymerase beta(POL-β),DNA polymerase eta(POLH),protein Flap endonuclease 1(FEN1),DNA damage-binding protein 2(DDB2)]and 5-FU-resistance proteins(thymidylate synthase)but under expressed pro-apoptotic proteins(e.g.,DAB2,CK1)in comparison to the parental cells.Increased genotoxicity and apoptosis were observed in resistant cells after combined application of BCNU and Res in comparison to untreated or parental cells.BCNU increased the sensitivity to Res of 5-FU resistant cells compared with parental cells.Fifty percent cell death were noted in parental cells when 18μmol/L of Res was associated with fixed concentration(20μmol/L)of BCNU,but a much lower concentration of Res(8μmol/L)was needed to achieve the same effect in 5-FU resistant cells.Interestingly,increased levels of adenomatous polyposis coli and decreased levels POL-β,POLH,FEN1 and DDB2 were noted after the same combined treatment in resistant cells.CONCLUSION:BCNU combined with Res exerts a synergistic effect that may prove useful for the treatment of colon cancer and to overcome drug resistance.展开更多
The Hartree-Fock method has been employed to investigate the electronic structures of EMIM^+(1-ethyl-3-methyl-imidazolium^+), CuCl2^-, Cu2Cl3^-, CuCl3^2-, EMIM+^-CuCl2^-, EMIM^+-Cu2Cl3^-, and EMIM^+-CuCl3^2- pa...The Hartree-Fock method has been employed to investigate the electronic structures of EMIM^+(1-ethyl-3-methyl-imidazolium^+), CuCl2^-, Cu2Cl3^-, CuCl3^2-, EMIM+^-CuCl2^-, EMIM^+-Cu2Cl3^-, and EMIM^+-CuCl3^2- pairs. Full optimization and frequency analyses of EMIM^+, CuCl2^-, Cu2Cl3^-, CuC13^-, eight initial EMIM^+-CuCl2^-, six EMIM^+-Cu2Cl3^-, and four EMIM^+-CuCl3^2- geometries have been carried out using Gaussian-94 soft-package at 6-31+G(d,p) basis set level for hydrogen, carbon, nitrogen, chlorine atoms and Hay-Wadt effective core potential for copper atom. The electronic structures of lowest energy of EMIM^+-CuCl2^-, EMIM+-Cu2Cl3^-, EMIM^+-CuCl3^2-, single EMIM^+, CuCl2^-, Cu2Cl3^-, and CuCl3^2- have been comparatively studied. The calculated results showed that EMIM^+-CuCl2^- pair conformer of lowest energy was five ring parallel to Cl-Cu-Cl with 3.2A distance, EMIM^+-CuCl3^2- pair conformer of lowest energy was five ring parallel to CuCl3^2-plane with 3.4A distance, and the optimized EMIM^+-Cu2Cl3^- pair conformer of lowest energy was five ring perpendicular to Cl-Cu-Cl-Cu-Cl plane with 3.0A distance between the terminal Cl atoms and the 5-ring of EMIM^+. The cohesion between cations and anions is brought about by C-H. C1 hydrogen bonds that are reinforced by charge assistance. The frequency analyses suggested that all stationary points are minimum because of no appearing of imaginary frequency. The assigned frequencies were in agreement with the experimental report. The low energy of interaction because of the bulkyasymmetry of EMIM+ and the charge dispersion of cation and anion leads to the low melting point of the ionic liquids, EMIM^+-CuCl2^-, EMIM^+-Cu2Cl3^-, and EMIM^+-CuCl3^2-. The interaction energy of EMIM^+-CuCl2^-, EMIM^+-Cu2Cl3^-, and EMIM^+-CuCl3^2- is 309.0 kJ/mol, 316.8 kJ/mol, and 320.2 kJ/mol, respectively. The relationship of interaction energy via distance between cations and anions was also investigated by single point energy scan.展开更多
The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H1...The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H15N2O3)3(H2O)]DMFH2O. The coordi- nation sphere about each copper ion in the complex consists of two oxygen atoms from hydroxylpyridinone moiety of one ligand and one oxygen and one nitrogen atoms from salicyladehyde Schiff-base moiety of another ligand arranged in a slightly distorted square planar geometry. Among the three copper ions, one (Cu(2)) is coordinated by the other oxygen atom of water molecule on the fifth coordinate position to form a distorted square pyramid geometry. The crystal is of monoclinic, space group P21/c with a = 12.9202(5), b = 27.197(1), c = 17.0116(7) ? b = 100.588(1), V = 5875.9(4) 3, Z = 4, C63H57N7O12Cu3, Mr = 1294.78, Dc = 1.464 g/cm3, m = 1.146 mm-1, F(000) = 2668, R = 0.0784 and wR = 0.1546 for 6926 observed reflections with I > 2s(I). The differences of coordinate bond lengths are observed between anhydrous and hydrous units: in the former unit, the average bond lengths are 1.978 ?for CuN (azomethine), 1.883 ?for CuO (phenolic) in Schiff-base moiety, 1.959 ?for CuO (keto), and 1.919 ?for CuO (hydroxy) in hydroxypyridinone moiety; while those in the latter are longer with the following corresponding values: 1.985(5), 1.908(5), 1.993(5) and 1.919(4) ? respectively. The Cu(2)O (water) bond length is 2.375(6) ?展开更多
Producing 2-ethyl-1-hexyl thioglycolate(ETE)via esterification reaction with thioglycolic acid(TGA)aqueous solution as raw material by reactive-separation coupling technology is a promising process intensification met...Producing 2-ethyl-1-hexyl thioglycolate(ETE)via esterification reaction with thioglycolic acid(TGA)aqueous solution as raw material by reactive-separation coupling technology is a promising process intensification method.To choose suitable reactive-separation coupling strategy,the kinetic studies of the esterification of TGA with 2-ethyl-1-hexanol(EHL)were carried out in a batch system.The commercial ion exchange resin was employed as an eco-friendly catalyst.The effects of temperature,catalyst concentration and molar ratio were determined.It was interesting to observe that the equilibrium conversion of TGA increased with the increase of catalyst mass fraction due to the adsorption of product water onto resin surface.The activity-based pseudo-homogeneous(PH),Eley-Rideal(ER)and Langmuir-Hinshelwood-Ho ugen-Watson(LHHW)models were used to fit the kinetics data of the resin-catalyzed reaction.The models of ER and LHHW performed better than the PH model.The kinetics of the TGA-self-catalyzed reaction was also determined.An activity-based homogeneous kinetics model could well describe this self-catalyzed reaction.These results would be meaningful to the selection and design of an appropriate reactionseparation strategy for the production of ETE,to realize the process intensification.展开更多
This paper reports the ab initio and Density Functional Theory (DFT) studies on the structure of the ionic liquid 1-ethyl-3-methylimidazolium hexafluorophosphate ([EMIM]+[PF6]-). Hartree-Fock (HF) and DFT(B3LYP) metho...This paper reports the ab initio and Density Functional Theory (DFT) studies on the structure of the ionic liquid 1-ethyl-3-methylimidazolium hexafluorophosphate ([EMIM]+[PF6]-). Hartree-Fock (HF) and DFT(B3LYP) methods are respectively used to obtain the stable structure of the gas phase ion pair at the 6-311++G(d, p) basis set level. The theoretical IR spectra of [EMIM]+[PF6]- were obtained from the calculated vibrational frequencies and intensities. The changes of atomic charge population have been investigated using Natural Bond Orbital (NBO) analysis. The computational results show that there may exist hydrogen bonds between the cation and the anion. After ZPE and BSSE corrections, the interaction energy between the cation and the anion is –314.44 kJ?mol-1.展开更多
3-(1-Ethyl-1H-indole-3-carbonyl)aminopropionic acid has been synthesized by alkylation of 3-(1H-indole-3-carbonyl)aminopropionic acid methyl ester with bromoethane,follo-wed by saponifying and acidating,in 89.0% y...3-(1-Ethyl-1H-indole-3-carbonyl)aminopropionic acid has been synthesized by alkylation of 3-(1H-indole-3-carbonyl)aminopropionic acid methyl ester with bromoethane,follo-wed by saponifying and acidating,in 89.0% yield.Its crystal structure was gotten and determined by X-ray diffraction method.The crystal is of orthorhombic,space group P212121 with a = 8.9490(12),b = 11.1010(15),c = 13.0475(18) ,V = 1296.2(3) 3,Z = 4,Dc = 1.334 g/cm3,λ = 0.71073 ,μ(MoKα) = 0.095 mm-1,Mr = 260.29 and F(000) = 552.The structure was refined to R = 0.0306 and wR = 0.1445 for 2612 observed reflections with I 2σ(I).In the crystal structure,molecules are linked to each other through hydrogen bonds of N(2)-H(2)···O(1) and O(3)-H(3)···O(1),generating a three-dimensional network.展开更多
The density functional theory (DFT) has been employed to investigate the electronic structures ofEMIM^+(1-ethyl-3-methylimidazolium+), CuCl2^-, Cu2Cl3^- and EMIM^+-CuCl2^-, EMIM^+-Cu2Cl3^- pairs. Full optimiza...The density functional theory (DFT) has been employed to investigate the electronic structures ofEMIM^+(1-ethyl-3-methylimidazolium+), CuCl2^-, Cu2Cl3^- and EMIM^+-CuCl2^-, EMIM^+-Cu2Cl3^- pairs. Full optimization and frequency analyses of EMIM^+, CuCl2^-, Cu2Cl3^-, eight initial EMIM^+-CuCl2^-, and six initial EMIM^+-Cu2Cl3^- geometries have been carried out using Gaussian-94 software-package at 6-3 I+G (d, p) basis set level for hydrogen, carbon, nitrogen, chlorine atoms and the Hay-Wadt effective core potential for copper atoms. The electronic structures of the lowest energy of EMIM^+-CuCl2^-, EMIM^+-Cu2Cl3^- pairs, single EMIM^+, CuCl2^-, and Cu2Cl3^- have been comparatively studied. The calculated results showed that the optimized EMIM^+-CuCl2^- pair conformer of the lowest energy was five ring moiety parallel to CuCl2^- plane with a distance of around 3.5,A, while EMIM^+-Cu2Cl3^- pair conformer of the lowest energy was five ring moiety of EMIM^+ perpendicular to Cu2Cl3^- plane with a distance of around 3.0 ,A between terminal chlorine atoms and 5-ring plane of EMIM^+. The cohesion between cation and anion is electrostatic interaction and C-H---Cl hydrogen bonds are reinforced by charge assistance. The frequency analyses suggested that all stationary points are minimum points because of absence of imaginary frequency. The low energy of interaction caused by bulky asymmetry of EMIM^+, and charge dispersion of cation and anion give rise to low melting point of ionic liquids EMIM^+-CuCl2^-, and EMIM^+-Cu2Cl3^- . The interaction energy caused by the distance between cations and anions was investigated by single point energy scan.展开更多
The Hartree-Fock method has been employed to investigate the electronic structures of EMIM+(1- ethyl-3-methylimidazolium+), AlCl4^-, and EMIM+-AlCl4^-. Full optimization and frequency analyses of EMIM+, AlCl4^-,...The Hartree-Fock method has been employed to investigate the electronic structures of EMIM+(1- ethyl-3-methylimidazolium+), AlCl4^-, and EMIM+-AlCl4^-. Full optimization and frequency analyses of EMIM+, AlCl4^-, ten initial EMIM+-AlCl4^- geometries have been carried out using the Gaussian-94 soft-package at 6- 31+G(d,p) basis set level for hydrogen, carbon, nitrogen, chlorine, and aluminum atoms. The electronic structures of the lowest energy of EMIM+-AlCl4^-pairs, single EMIM^+, and AlCl4^- have been comparatively studied. The calculated results showed that the optimized EMIM^+-AlCl4^-pair conformer of lowest energy was AlCl4^-outside the five-ring plane between methyl group and ethyl group with a H6--C122 distance of 2.7 A. The frequency analyses suggested that all stationary points were minimum points because of no imaginary frequency appearing, and the assigned frequencies were in agreement with experimental report. The interaction energy between EMIM^+ and AlCl4^-was 776.2 kJ/mol.展开更多
In this study, we used a mixture of organic liquid propane-1,3-diol and ionic liquid 1-ethyl-3-methylimidazolium chloride([emim]Cl) as the entrainer to separate tert-butyl alcohol(TBA) + water. We measured the isobari...In this study, we used a mixture of organic liquid propane-1,3-diol and ionic liquid 1-ethyl-3-methylimidazolium chloride([emim]Cl) as the entrainer to separate tert-butyl alcohol(TBA) + water. We measured the isobaric vapor–liquid equilibrium(VLE) for the quaternary system TBA + water + propane-1,3-diol + [emim]Cl at 101.3 kPa, and found the VLE data to be well correlated with the nonrandom two-liquid model. These results show that the mixed solvent of propane-1,3-diol + [emim]Cl can increase the relative volatility of TBA to water and break the azeotropic point. We found no notable synergetic effect between them, and observed that the liquid mixed solvent of propane-1,3-diol and [emim]Cl had lower viscosity than [emim]Cl, which makes it a promising entrainer for separating the TBA + water azeotrope in industrial applications.展开更多
Tumor necrosis factor-alpha (TNF-α) is a potent inflammatory cytokine and its exaggerated production has been implicated in acute, chronic and autoimmune inflammatory diseases. Proteinaceous and non-proteinaceous ant...Tumor necrosis factor-alpha (TNF-α) is a potent inflammatory cytokine and its exaggerated production has been implicated in acute, chronic and autoimmune inflammatory diseases. Proteinaceous and non-proteinaceous anti-TNF-α agents have been developed to reduce its circulating levels either by neutralizing, binding or inhibiting the de novo synthesis with the aim of achieving desirable therapeutic effects. In the present study, we compared the effects of a protein-based anti-TNF-α drug, etanercept, and a non-protein-based anti-TNF-α small molecule, 5-ethyl-1-phenyl-2-(1H) pyridone (5-EPP), on the LPS-stimulated secretion of TNF-α in the medium and TNF-α associated with the THP-1 cells in vitro. Both drugs had marked concentration-dependent inhibitory effects on the LPS-stimulated secretion of TNF-α. However, their effects on the LPS-stimulated cell-associated TNF-α were diametrically opposed to each other. For instance, etanercept further increased the level by up to 12-fold, whereas 5-EPP inhibited the level in a dose dependent manner. In addition, 5-EPP caused a significant reduction in the elevated level of cell associated TNF-α caused by LPS + etanercept. The differences in the levels of cell-associated TNF-α as reported in the present study may partly explain the adverse effects of some protein-based anti-TNF-α drugs including etanercept as opposed to a non-protein-based anti-TNF-α drug such as pirfenidone, a structural analogue of 5-EPP, for treatment of some TNF-α mediated diseases. It was concluded from the findings of this study that drugs which elevate the levels of cell associated-TNF-α will potentially have more adverse events even after reducing the secreted levels of TNF-α than the drugs which reduce both the secreted and cell-associated TNF-α levels.展开更多
Phthalates have been used in a wide variety of consumer goods. Their versatility as plasticizers has translated into worldwide use in a vast array of consumer products. These compounds can leach into matrices, such as...Phthalates have been used in a wide variety of consumer goods. Their versatility as plasticizers has translated into worldwide use in a vast array of consumer products. These compounds can leach into matrices, such as food and liquids that can be routed for human exposure. One of the most used phthalates is Diethylhexyl phthalate (DEHP). Diethylhexyl phthalate and its metabolite 2-ethyl-1-hexanol (2-EH) have demonstrated biological effects which merit further evaluation. In this work, we expand on our previous work with DEHP and screen the 2-EH metabolite for different cell death endpoints such as growth inhibition, apoptosis, autophagy, caspase activation, DNA fragmentation, and cell cycle arrest using fluorophores and the NC3000 instrument. Significant results (p 0.05) revealed higher toxicity for the 2-EH metabolite when compared to DEHP. Also, 2-EH presented apoptosis induction with characteristic hallmarks, such as loss of mitochondrial membrane potential, caspase activation, DNA fragmentation and cell cycle arrest at the S phase. In addition, the presence of autophagosome was detected through L3CB protein staining. We conclude that 2-EH presents differences in cell death endpoints that interestingly differ from the DEHP parent compound. Further studies are needed to establish the molecular pathways responsible for the observed effects.展开更多
This study aims at investigating the impact of ionic liquid extraction on lignin structure by studying the mechanism of lignin depolymerization in 1-ethyl-3-methylimidazolium acetate EMIM[OAc]) and comparing it with t...This study aims at investigating the impact of ionic liquid extraction on lignin structure by studying the mechanism of lignin depolymerization in 1-ethyl-3-methylimidazolium acetate EMIM[OAc]) and comparing it with that of organosolv and milled wood methods. Ionic liquid mediated lignin (ILL) using EMIM[OAc]), ethanol organosolv lignin (EOL) and milled wood lignin (MWL) were isolated from Typha capensis (TC) and subjected to several analytical characterizations. Experimental data shows that ILL exhibited a relatively lower degree of condensation, lower aromatic C-C structures and a higher aliphatic OH with values of 0.42/Ar, 1.94/Ar and 1.33/Ar moieties compared with EOL values of 0.92/Ar, 2.22/Ar and 0.51/Ar moieties respectively. The ILL was depolymerized under mild conditions giving relatively higher β-aryl ether linkages content, higher molecular mass, and exhibited closer structures and reactivity to native lignin than EOL. These insights on TC lignin depolymerization in EMIM[OAc]) acetate may contribute to better value-addition of lignocellulosic biomass.展开更多
Objective: To establish a reformative detection system which has sound ability of providing information on molecular mutagenesis spectrum and the specificity of detection system of repackaged λ phage. Methods: LacZ g...Objective: To establish a reformative detection system which has sound ability of providing information on molecular mutagenesis spectrum and the specificity of detection system of repackaged λ phage. Methods: LacZ gene, as mutational target gene and reporter gene, was applied into the detection system. The λ gt11 DNA treated with ENU (1-ethyl-1-nitrosourea) and 9-AA (9-aminoacridine) was repackaged in vitro. The packaged λ phage was then grown in E. coli Y1090 on a selective plate containing X-gel and IPTG. The survival and mutation frequencies were determined by counting the clear-plaque and blue-plaque, and the molecular mutation mechanism was studied by extracting and sequencing the LacZ gene of mutants. Results: The survival of repackaged λ phages treated with 9-AA and ENU apparently decreased in consistent dose-dependence. The mutation frequency of clear-plaque mutants showed a linear dose-related increase. The predominant mutations induced by 9-AA were ± 1 frameshift mutation, and 9-AA induced - 1 frameshift was much more effective than induced +1 frameshift. 9-AA also induced substitutions with transversions more common. ENU-induced mutations were chiefly occurred at G: C sites. Substitutions induced by ENU were mainly G: C→A: T, G: C→C: G and A: T→T: A transversion. Conclusion: Mutation detection system of λgt11 DNA containing LacZ gene is proven better than that of λDNA without LacZ gene. The combination of survival, mutant frequency and sequence spectrum can not only increase the sensitivity and specificity of the new method, but also provide a better understanding of the molecular mechanism of mutation for ultimate extrapolation to risk assessment.展开更多
The relative chemical shifts (△δ) △δwere put forward to investigate the microscopic structure of 1-ethyl-3-methyl-imidazolium tetrafluoroborate (EmimBF4) during the dilution process with water.The concentration-de...The relative chemical shifts (△δ) △δwere put forward to investigate the microscopic structure of 1-ethyl-3-methyl-imidazolium tetrafluoroborate (EmimBF4) during the dilution process with water.The concentration-dependent △δ(C2)H-(C4)H,△δ(C2)H-(C5)H and △δ(C4)H-(C5)H were analyzed.The results reveal that the variations of the microscopic structures of three aromatic protons are inconsistent.The strength of the H-bond between water and three aromatic protons follows the order:(C2)H···O 】 (C4)H···O 】 (C5)H···O.The concentration-dependent △δ(C6)H-(C7)H and △δ(C6)H-(C8)H indicate the formation of the H-bonds of (Calkyl)H···O is impossible,and more water is located around (C6)H than around (C7)H or (C8)H.The concentration-dependent △δ(C2)H-(C4)H and △δ(C2)H-(C5)H both increase rapidly when xwater 】 0.9 or so,suggesting the ionic pairs of EmimBF4 are dissociated rapidly.The turning points of concentration-dependent △δ(C2)H-(C4)H and △δ(C2)H-(C5)H indicate that some physical properties of the EmimBF4/water mixtures also change at the corresponding concentration point.The microscopic structures of EmimBF4 in water could be clearly detected by the relative chemical shifts.展开更多
The anodic behavior of neodymium in acidic AlCl3-1-ethyl-3-methyl-imidazolium chloride (AIC13-EMIC) ionic liquid was investigated by conducting linear sweep voltammeter and chonopotentiometry. The viscosity of Nd di...The anodic behavior of neodymium in acidic AlCl3-1-ethyl-3-methyl-imidazolium chloride (AIC13-EMIC) ionic liquid was investigated by conducting linear sweep voltammeter and chonopotentiometry. The viscosity of Nd dissolved ionic liquid and the surface morphologies of Nd were characterized using an Ostwald viscometer and a scanning electron microscope, respectively. The chemical composition of Nd surface was indentified by Raman spectra. The results showed that dissolution of Nd under anodic polarization occurred after the breakdown of oxide films. A viscous layer formed at the interface of Nd/ionic liquid during the galvanostatic process of 5 and 20 mA/cm^2. The formation of viscous layer was attributed to the accumulation of Nd dissolved AlCl3-EMIC ionic liquid, which had high viscosity. The oxide films could be removed thoroughly and the surface of Nd was homogeneous without etching pits, when viscous layer formed in the anodic process. Otherwise, the surface showed a pitting morphology.展开更多
The WO_3/C composite was successfully prepared by calcination of a mixture of WO_3 and g-C_3N_4 at 520 ℃. The as-synthesized samples were analyzed by X-ray diffraction(XRD), electronic differential system(EDS), scann...The WO_3/C composite was successfully prepared by calcination of a mixture of WO_3 and g-C_3N_4 at 520 ℃. The as-synthesized samples were analyzed by X-ray diffraction(XRD), electronic differential system(EDS), scanning electron microscopy(SEM), infrared spectrometry(IR) and the Brunner-Emmet-Teller(BET) techniques. The WO_3/C composite, in comparison with the WO_3 and C_3N_4, features smaller particle size, bigger surface area and higher desulphurization performance. The influence of the reaction temperature, the catalyst dosage, the reaction time, the oxidant dosage, the sulfide type and the extractant dose on desulfurization reaction was studied. The results showed that the WO_3/C composite revealed a higher desulfurization activity than the WO_3. The desulfurization rate could reach up to 95.8% under optimal conditions covering a catalyst dosage of 0.02 g, a H_2O_2 amount of 0.2 mL, a 1-ethyl-3-methylimidazolium ethyl sulfate(EMIES) amount of 1.0 mL, a reaction temperature of 70 ℃ and a reaction time of 180 min. After five recycles, the desulfurization activity of catalyst did not significantly decline.展开更多
Ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate, 1E-3MI-TFB) and HP-β- CD as modifier was added to the buffer to separate hyperoside, luteolin and chlorogenic acid. Experiments explored the effect of co...Ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate, 1E-3MI-TFB) and HP-β- CD as modifier was added to the buffer to separate hyperoside, luteolin and chlorogenic acid. Experiments explored the effect of concentration of 1E-3MI-TFB and HP-β-CD on separation. The results indicated that 1.0 mmol/L HP-β-CD and 1%0 (v/v) 1E-3MI-TFB added to the buffer simultaneously could achieve a good compromise of resolution and analysis time. Capillary experiments and UV spectra indicated that there was interaction between 1E-3MI-TFB and analytes.展开更多
基金the funding support from The Bioenergy Technologies Office (BETO) within the US DOE’s Office of Energy Efficiency and Renewable Energythe funding support from the American Recovery and Reinvestment Actsupported by the US DOE’s Office of Science, Biological and Environmental Research program through contract DE-AC02-05CH11231 between Lawrence Berkeley National Laboratory and the U.S. Department of Energy
文摘This scale-up study demonstrated the feasibility of an ionic liquid(IL)pretreatment process at 40 kg scale,using the IL 1-ethyl-3-methylimidazolium acetate([C2C1Im][OAc])as the solvent.The pretreatment was followed by enzymatic hydrolysis through which the process efficiency for biomass conversion to monomeric sugars was determined.The results show that 43 wt%of switchgrass was dissolved in IL after 2 h of pretreatment at 160℃ with 15 wt%solid loading.A 120 h enzymatic hydrolysis of the pretreated switchgrass results in 96%glucan and 98%xylan conversion.[C2C1Im][OAc]pretreatment has been successfully scaled up to 40 kg with improved sugar titers and yields relative to bench scale(6 kg).The mass flow of the overall process was established and the major scale-up challenges of the process were identified.
基金Supported by Indian Council of Medical Research and Department of Biotechnology,Government of India
文摘AIM:To study the mechanism of 5-fluorouracil(5-FU)resistance in colon cancer cells and to develop strategies for overcoming such resistance by combination treatment.METHODS:We established and characterized a 5-FU resistance(5-FU-R)cell line derived from continuous exposure(25μmol/L)to 5-FU for 20 wk in 5-FU sensitive HCT-116 cells.The proliferation and expression of different representative apoptosis and anti-apoptosis markers in 5-FU sensitive and 5-FU resistance cells were measured by the MTT assay and by Western blotting,respectively,after treatment with Resveratrol(Res)and/or 1,3-Bis(2-chloroethyl)-1-nitrosourea(BCNU).Apoptosis and cell cycle arrest was measured by 4',6'-diamidino-2-phenylindole hydrochloride staining and fluorescence-activated cell sorting analysis,respectively.The extent of DNA damage was measured by the Comet assay.We measured the visible changes in the DNA damage/repair cascade by Western blotting.RESULTS:The widely used chemotherapeutic agents BCNU and Res decreased the growth of 5-FU sensitive HCT-116 cells in a dose dependent manner.Combined application of BCNU and Res caused more apoptosis in5-FU sensitive cells in comparison to individual treatment.In addition,the combined application of BCNU and Res caused a significant decrease of major DNA base excision repair components in 5-FU sensitive cells.We established a 5-FU resistance cell line(5-FU-R)from 5-FU-sensitive HCT-116(mismatch repair deficient)cells that was not resistant to other chemotherapeutic agents(e.g.,BCNU,Res)except 5-FU.The 5-FU resistance of 5-FU-R cells was assessed by exposure to increasing concentrations of 5-FU followed by the MTT assay.There was no significant cell death noted in5-FU-R cells in comparison to 5-FU sensitive cells after5-FU treatment.This resistant cell line overexpressed anti-apoptotic[e.g.,AKT,nuclear factorκB,FLICE-like inhibitory protein),DNA repair(e.g.,DNA polymerase beta(POL-β),DNA polymerase eta(POLH),protein Flap endonuclease 1(FEN1),DNA damage-binding protein 2(DDB2)]and 5-FU-resistance proteins(thymidylate synthase)but under expressed pro-apoptotic proteins(e.g.,DAB2,CK1)in comparison to the parental cells.Increased genotoxicity and apoptosis were observed in resistant cells after combined application of BCNU and Res in comparison to untreated or parental cells.BCNU increased the sensitivity to Res of 5-FU resistant cells compared with parental cells.Fifty percent cell death were noted in parental cells when 18μmol/L of Res was associated with fixed concentration(20μmol/L)of BCNU,but a much lower concentration of Res(8μmol/L)was needed to achieve the same effect in 5-FU resistant cells.Interestingly,increased levels of adenomatous polyposis coli and decreased levels POL-β,POLH,FEN1 and DDB2 were noted after the same combined treatment in resistant cells.CONCLUSION:BCNU combined with Res exerts a synergistic effect that may prove useful for the treatment of colon cancer and to overcome drug resistance.
文摘The Hartree-Fock method has been employed to investigate the electronic structures of EMIM^+(1-ethyl-3-methyl-imidazolium^+), CuCl2^-, Cu2Cl3^-, CuCl3^2-, EMIM+^-CuCl2^-, EMIM^+-Cu2Cl3^-, and EMIM^+-CuCl3^2- pairs. Full optimization and frequency analyses of EMIM^+, CuCl2^-, Cu2Cl3^-, CuC13^-, eight initial EMIM^+-CuCl2^-, six EMIM^+-Cu2Cl3^-, and four EMIM^+-CuCl3^2- geometries have been carried out using Gaussian-94 soft-package at 6-31+G(d,p) basis set level for hydrogen, carbon, nitrogen, chlorine atoms and Hay-Wadt effective core potential for copper atom. The electronic structures of lowest energy of EMIM^+-CuCl2^-, EMIM+-Cu2Cl3^-, EMIM^+-CuCl3^2-, single EMIM^+, CuCl2^-, Cu2Cl3^-, and CuCl3^2- have been comparatively studied. The calculated results showed that EMIM^+-CuCl2^- pair conformer of lowest energy was five ring parallel to Cl-Cu-Cl with 3.2A distance, EMIM^+-CuCl3^2- pair conformer of lowest energy was five ring parallel to CuCl3^2-plane with 3.4A distance, and the optimized EMIM^+-Cu2Cl3^- pair conformer of lowest energy was five ring perpendicular to Cl-Cu-Cl-Cu-Cl plane with 3.0A distance between the terminal Cl atoms and the 5-ring of EMIM^+. The cohesion between cations and anions is brought about by C-H. C1 hydrogen bonds that are reinforced by charge assistance. The frequency analyses suggested that all stationary points are minimum because of no appearing of imaginary frequency. The assigned frequencies were in agreement with the experimental report. The low energy of interaction because of the bulkyasymmetry of EMIM+ and the charge dispersion of cation and anion leads to the low melting point of the ionic liquids, EMIM^+-CuCl2^-, EMIM^+-Cu2Cl3^-, and EMIM^+-CuCl3^2-. The interaction energy of EMIM^+-CuCl2^-, EMIM^+-Cu2Cl3^-, and EMIM^+-CuCl3^2- is 309.0 kJ/mol, 316.8 kJ/mol, and 320.2 kJ/mol, respectively. The relationship of interaction energy via distance between cations and anions was also investigated by single point energy scan.
基金This work was supported by the foundation of Natural Science Research of Jiangsu Education Department (02KJB150007)
文摘The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H15N2O3)3(H2O)]DMFH2O. The coordi- nation sphere about each copper ion in the complex consists of two oxygen atoms from hydroxylpyridinone moiety of one ligand and one oxygen and one nitrogen atoms from salicyladehyde Schiff-base moiety of another ligand arranged in a slightly distorted square planar geometry. Among the three copper ions, one (Cu(2)) is coordinated by the other oxygen atom of water molecule on the fifth coordinate position to form a distorted square pyramid geometry. The crystal is of monoclinic, space group P21/c with a = 12.9202(5), b = 27.197(1), c = 17.0116(7) ? b = 100.588(1), V = 5875.9(4) 3, Z = 4, C63H57N7O12Cu3, Mr = 1294.78, Dc = 1.464 g/cm3, m = 1.146 mm-1, F(000) = 2668, R = 0.0784 and wR = 0.1546 for 6926 observed reflections with I > 2s(I). The differences of coordinate bond lengths are observed between anhydrous and hydrous units: in the former unit, the average bond lengths are 1.978 ?for CuN (azomethine), 1.883 ?for CuO (phenolic) in Schiff-base moiety, 1.959 ?for CuO (keto), and 1.919 ?for CuO (hydroxy) in hydroxypyridinone moiety; while those in the latter are longer with the following corresponding values: 1.985(5), 1.908(5), 1.993(5) and 1.919(4) ? respectively. The Cu(2)O (water) bond length is 2.375(6) ?
基金the financial support for this work from the National Natural Science Foundation of China(No.21706034)the Guiding Project of Fujian Province(No.2018H0016)+1 种基金the Open Foundation of State Key Laboratory of Chemical Engineering(No.SKL-ChE-18B02)the Integration of Industry,Education and Research of Fujian Province(No.2018Y4008).
文摘Producing 2-ethyl-1-hexyl thioglycolate(ETE)via esterification reaction with thioglycolic acid(TGA)aqueous solution as raw material by reactive-separation coupling technology is a promising process intensification method.To choose suitable reactive-separation coupling strategy,the kinetic studies of the esterification of TGA with 2-ethyl-1-hexanol(EHL)were carried out in a batch system.The commercial ion exchange resin was employed as an eco-friendly catalyst.The effects of temperature,catalyst concentration and molar ratio were determined.It was interesting to observe that the equilibrium conversion of TGA increased with the increase of catalyst mass fraction due to the adsorption of product water onto resin surface.The activity-based pseudo-homogeneous(PH),Eley-Rideal(ER)and Langmuir-Hinshelwood-Ho ugen-Watson(LHHW)models were used to fit the kinetics data of the resin-catalyzed reaction.The models of ER and LHHW performed better than the PH model.The kinetics of the TGA-self-catalyzed reaction was also determined.An activity-based homogeneous kinetics model could well describe this self-catalyzed reaction.These results would be meaningful to the selection and design of an appropriate reactionseparation strategy for the production of ETE,to realize the process intensification.
基金This work was supported by the National Natural Science Key Foundation of China (20490209) and Young Teacher Foundation of Beijing University of Chemical Technology (QN0308)
文摘This paper reports the ab initio and Density Functional Theory (DFT) studies on the structure of the ionic liquid 1-ethyl-3-methylimidazolium hexafluorophosphate ([EMIM]+[PF6]-). Hartree-Fock (HF) and DFT(B3LYP) methods are respectively used to obtain the stable structure of the gas phase ion pair at the 6-311++G(d, p) basis set level. The theoretical IR spectra of [EMIM]+[PF6]- were obtained from the calculated vibrational frequencies and intensities. The changes of atomic charge population have been investigated using Natural Bond Orbital (NBO) analysis. The computational results show that there may exist hydrogen bonds between the cation and the anion. After ZPE and BSSE corrections, the interaction energy between the cation and the anion is –314.44 kJ?mol-1.
基金supported by the Natural Science Foundation of Guangdong Province (No.06300581)
文摘3-(1-Ethyl-1H-indole-3-carbonyl)aminopropionic acid has been synthesized by alkylation of 3-(1H-indole-3-carbonyl)aminopropionic acid methyl ester with bromoethane,follo-wed by saponifying and acidating,in 89.0% yield.Its crystal structure was gotten and determined by X-ray diffraction method.The crystal is of orthorhombic,space group P212121 with a = 8.9490(12),b = 11.1010(15),c = 13.0475(18) ,V = 1296.2(3) 3,Z = 4,Dc = 1.334 g/cm3,λ = 0.71073 ,μ(MoKα) = 0.095 mm-1,Mr = 260.29 and F(000) = 552.The structure was refined to R = 0.0306 and wR = 0.1445 for 2612 observed reflections with I 2σ(I).In the crystal structure,molecules are linked to each other through hydrogen bonds of N(2)-H(2)···O(1) and O(3)-H(3)···O(1),generating a three-dimensional network.
文摘The density functional theory (DFT) has been employed to investigate the electronic structures ofEMIM^+(1-ethyl-3-methylimidazolium+), CuCl2^-, Cu2Cl3^- and EMIM^+-CuCl2^-, EMIM^+-Cu2Cl3^- pairs. Full optimization and frequency analyses of EMIM^+, CuCl2^-, Cu2Cl3^-, eight initial EMIM^+-CuCl2^-, and six initial EMIM^+-Cu2Cl3^- geometries have been carried out using Gaussian-94 software-package at 6-3 I+G (d, p) basis set level for hydrogen, carbon, nitrogen, chlorine atoms and the Hay-Wadt effective core potential for copper atoms. The electronic structures of the lowest energy of EMIM^+-CuCl2^-, EMIM^+-Cu2Cl3^- pairs, single EMIM^+, CuCl2^-, and Cu2Cl3^- have been comparatively studied. The calculated results showed that the optimized EMIM^+-CuCl2^- pair conformer of the lowest energy was five ring moiety parallel to CuCl2^- plane with a distance of around 3.5,A, while EMIM^+-Cu2Cl3^- pair conformer of the lowest energy was five ring moiety of EMIM^+ perpendicular to Cu2Cl3^- plane with a distance of around 3.0 ,A between terminal chlorine atoms and 5-ring plane of EMIM^+. The cohesion between cation and anion is electrostatic interaction and C-H---Cl hydrogen bonds are reinforced by charge assistance. The frequency analyses suggested that all stationary points are minimum points because of absence of imaginary frequency. The low energy of interaction caused by bulky asymmetry of EMIM^+, and charge dispersion of cation and anion give rise to low melting point of ionic liquids EMIM^+-CuCl2^-, and EMIM^+-Cu2Cl3^- . The interaction energy caused by the distance between cations and anions was investigated by single point energy scan.
文摘The Hartree-Fock method has been employed to investigate the electronic structures of EMIM+(1- ethyl-3-methylimidazolium+), AlCl4^-, and EMIM+-AlCl4^-. Full optimization and frequency analyses of EMIM+, AlCl4^-, ten initial EMIM+-AlCl4^- geometries have been carried out using the Gaussian-94 soft-package at 6- 31+G(d,p) basis set level for hydrogen, carbon, nitrogen, chlorine, and aluminum atoms. The electronic structures of the lowest energy of EMIM+-AlCl4^-pairs, single EMIM^+, and AlCl4^- have been comparatively studied. The calculated results showed that the optimized EMIM^+-AlCl4^-pair conformer of lowest energy was AlCl4^-outside the five-ring plane between methyl group and ethyl group with a H6--C122 distance of 2.7 A. The frequency analyses suggested that all stationary points were minimum points because of no imaginary frequency appearing, and the assigned frequencies were in agreement with experimental report. The interaction energy between EMIM^+ and AlCl4^-was 776.2 kJ/mol.
基金supported by the Innovation Fund of Tianjin University (No. 2010XJ-0022)
文摘In this study, we used a mixture of organic liquid propane-1,3-diol and ionic liquid 1-ethyl-3-methylimidazolium chloride([emim]Cl) as the entrainer to separate tert-butyl alcohol(TBA) + water. We measured the isobaric vapor–liquid equilibrium(VLE) for the quaternary system TBA + water + propane-1,3-diol + [emim]Cl at 101.3 kPa, and found the VLE data to be well correlated with the nonrandom two-liquid model. These results show that the mixed solvent of propane-1,3-diol + [emim]Cl can increase the relative volatility of TBA to water and break the azeotropic point. We found no notable synergetic effect between them, and observed that the liquid mixed solvent of propane-1,3-diol and [emim]Cl had lower viscosity than [emim]Cl, which makes it a promising entrainer for separating the TBA + water azeotrope in industrial applications.
文摘Tumor necrosis factor-alpha (TNF-α) is a potent inflammatory cytokine and its exaggerated production has been implicated in acute, chronic and autoimmune inflammatory diseases. Proteinaceous and non-proteinaceous anti-TNF-α agents have been developed to reduce its circulating levels either by neutralizing, binding or inhibiting the de novo synthesis with the aim of achieving desirable therapeutic effects. In the present study, we compared the effects of a protein-based anti-TNF-α drug, etanercept, and a non-protein-based anti-TNF-α small molecule, 5-ethyl-1-phenyl-2-(1H) pyridone (5-EPP), on the LPS-stimulated secretion of TNF-α in the medium and TNF-α associated with the THP-1 cells in vitro. Both drugs had marked concentration-dependent inhibitory effects on the LPS-stimulated secretion of TNF-α. However, their effects on the LPS-stimulated cell-associated TNF-α were diametrically opposed to each other. For instance, etanercept further increased the level by up to 12-fold, whereas 5-EPP inhibited the level in a dose dependent manner. In addition, 5-EPP caused a significant reduction in the elevated level of cell associated TNF-α caused by LPS + etanercept. The differences in the levels of cell-associated TNF-α as reported in the present study may partly explain the adverse effects of some protein-based anti-TNF-α drugs including etanercept as opposed to a non-protein-based anti-TNF-α drug such as pirfenidone, a structural analogue of 5-EPP, for treatment of some TNF-α mediated diseases. It was concluded from the findings of this study that drugs which elevate the levels of cell associated-TNF-α will potentially have more adverse events even after reducing the secreted levels of TNF-α than the drugs which reduce both the secreted and cell-associated TNF-α levels.
文摘Phthalates have been used in a wide variety of consumer goods. Their versatility as plasticizers has translated into worldwide use in a vast array of consumer products. These compounds can leach into matrices, such as food and liquids that can be routed for human exposure. One of the most used phthalates is Diethylhexyl phthalate (DEHP). Diethylhexyl phthalate and its metabolite 2-ethyl-1-hexanol (2-EH) have demonstrated biological effects which merit further evaluation. In this work, we expand on our previous work with DEHP and screen the 2-EH metabolite for different cell death endpoints such as growth inhibition, apoptosis, autophagy, caspase activation, DNA fragmentation, and cell cycle arrest using fluorophores and the NC3000 instrument. Significant results (p 0.05) revealed higher toxicity for the 2-EH metabolite when compared to DEHP. Also, 2-EH presented apoptosis induction with characteristic hallmarks, such as loss of mitochondrial membrane potential, caspase activation, DNA fragmentation and cell cycle arrest at the S phase. In addition, the presence of autophagosome was detected through L3CB protein staining. We conclude that 2-EH presents differences in cell death endpoints that interestingly differ from the DEHP parent compound. Further studies are needed to establish the molecular pathways responsible for the observed effects.
文摘This study aims at investigating the impact of ionic liquid extraction on lignin structure by studying the mechanism of lignin depolymerization in 1-ethyl-3-methylimidazolium acetate EMIM[OAc]) and comparing it with that of organosolv and milled wood methods. Ionic liquid mediated lignin (ILL) using EMIM[OAc]), ethanol organosolv lignin (EOL) and milled wood lignin (MWL) were isolated from Typha capensis (TC) and subjected to several analytical characterizations. Experimental data shows that ILL exhibited a relatively lower degree of condensation, lower aromatic C-C structures and a higher aliphatic OH with values of 0.42/Ar, 1.94/Ar and 1.33/Ar moieties compared with EOL values of 0.92/Ar, 2.22/Ar and 0.51/Ar moieties respectively. The ILL was depolymerized under mild conditions giving relatively higher β-aryl ether linkages content, higher molecular mass, and exhibited closer structures and reactivity to native lignin than EOL. These insights on TC lignin depolymerization in EMIM[OAc]) acetate may contribute to better value-addition of lignocellulosic biomass.
基金National Science Foundation of China (NS-FC:No: 3880680 No: 39670643)
文摘Objective: To establish a reformative detection system which has sound ability of providing information on molecular mutagenesis spectrum and the specificity of detection system of repackaged λ phage. Methods: LacZ gene, as mutational target gene and reporter gene, was applied into the detection system. The λ gt11 DNA treated with ENU (1-ethyl-1-nitrosourea) and 9-AA (9-aminoacridine) was repackaged in vitro. The packaged λ phage was then grown in E. coli Y1090 on a selective plate containing X-gel and IPTG. The survival and mutation frequencies were determined by counting the clear-plaque and blue-plaque, and the molecular mutation mechanism was studied by extracting and sequencing the LacZ gene of mutants. Results: The survival of repackaged λ phages treated with 9-AA and ENU apparently decreased in consistent dose-dependence. The mutation frequency of clear-plaque mutants showed a linear dose-related increase. The predominant mutations induced by 9-AA were ± 1 frameshift mutation, and 9-AA induced - 1 frameshift was much more effective than induced +1 frameshift. 9-AA also induced substitutions with transversions more common. ENU-induced mutations were chiefly occurred at G: C sites. Substitutions induced by ENU were mainly G: C→A: T, G: C→C: G and A: T→T: A transversion. Conclusion: Mutation detection system of λgt11 DNA containing LacZ gene is proven better than that of λDNA without LacZ gene. The combination of survival, mutant frequency and sequence spectrum can not only increase the sensitivity and specificity of the new method, but also provide a better understanding of the molecular mechanism of mutation for ultimate extrapolation to risk assessment.
基金the National Natural Science Foundation of China (20773109 & 20704035)the Natural Science Foundation of Zhejiang Province (Y4090453)
文摘The relative chemical shifts (△δ) △δwere put forward to investigate the microscopic structure of 1-ethyl-3-methyl-imidazolium tetrafluoroborate (EmimBF4) during the dilution process with water.The concentration-dependent △δ(C2)H-(C4)H,△δ(C2)H-(C5)H and △δ(C4)H-(C5)H were analyzed.The results reveal that the variations of the microscopic structures of three aromatic protons are inconsistent.The strength of the H-bond between water and three aromatic protons follows the order:(C2)H···O 】 (C4)H···O 】 (C5)H···O.The concentration-dependent △δ(C6)H-(C7)H and △δ(C6)H-(C8)H indicate the formation of the H-bonds of (Calkyl)H···O is impossible,and more water is located around (C6)H than around (C7)H or (C8)H.The concentration-dependent △δ(C2)H-(C4)H and △δ(C2)H-(C5)H both increase rapidly when xwater 】 0.9 or so,suggesting the ionic pairs of EmimBF4 are dissociated rapidly.The turning points of concentration-dependent △δ(C2)H-(C4)H and △δ(C2)H-(C5)H indicate that some physical properties of the EmimBF4/water mixtures also change at the corresponding concentration point.The microscopic structures of EmimBF4 in water could be clearly detected by the relative chemical shifts.
基金Project supported by the National Natural Science Foundation of China(51271166)
文摘The anodic behavior of neodymium in acidic AlCl3-1-ethyl-3-methyl-imidazolium chloride (AIC13-EMIC) ionic liquid was investigated by conducting linear sweep voltammeter and chonopotentiometry. The viscosity of Nd dissolved ionic liquid and the surface morphologies of Nd were characterized using an Ostwald viscometer and a scanning electron microscope, respectively. The chemical composition of Nd surface was indentified by Raman spectra. The results showed that dissolution of Nd under anodic polarization occurred after the breakdown of oxide films. A viscous layer formed at the interface of Nd/ionic liquid during the galvanostatic process of 5 and 20 mA/cm^2. The formation of viscous layer was attributed to the accumulation of Nd dissolved AlCl3-EMIC ionic liquid, which had high viscosity. The oxide films could be removed thoroughly and the surface of Nd was homogeneous without etching pits, when viscous layer formed in the anodic process. Otherwise, the surface showed a pitting morphology.
基金the financial support of the Natural Science Foundation of China (Project No. 21003069)the Liaoning Province Doctoral Fund (Project No.201501105)
文摘The WO_3/C composite was successfully prepared by calcination of a mixture of WO_3 and g-C_3N_4 at 520 ℃. The as-synthesized samples were analyzed by X-ray diffraction(XRD), electronic differential system(EDS), scanning electron microscopy(SEM), infrared spectrometry(IR) and the Brunner-Emmet-Teller(BET) techniques. The WO_3/C composite, in comparison with the WO_3 and C_3N_4, features smaller particle size, bigger surface area and higher desulphurization performance. The influence of the reaction temperature, the catalyst dosage, the reaction time, the oxidant dosage, the sulfide type and the extractant dose on desulfurization reaction was studied. The results showed that the WO_3/C composite revealed a higher desulfurization activity than the WO_3. The desulfurization rate could reach up to 95.8% under optimal conditions covering a catalyst dosage of 0.02 g, a H_2O_2 amount of 0.2 mL, a 1-ethyl-3-methylimidazolium ethyl sulfate(EMIES) amount of 1.0 mL, a reaction temperature of 70 ℃ and a reaction time of 180 min. After five recycles, the desulfurization activity of catalyst did not significantly decline.
基金the National Natural Science Foundation of China (No. 20175025, 29875027, 20235010).
文摘Ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate, 1E-3MI-TFB) and HP-β- CD as modifier was added to the buffer to separate hyperoside, luteolin and chlorogenic acid. Experiments explored the effect of concentration of 1E-3MI-TFB and HP-β-CD on separation. The results indicated that 1.0 mmol/L HP-β-CD and 1%0 (v/v) 1E-3MI-TFB added to the buffer simultaneously could achieve a good compromise of resolution and analysis time. Capillary experiments and UV spectra indicated that there was interaction between 1E-3MI-TFB and analytes.
基金Supported by The State Key Program of Fundam ental Research( G19980 613 0 8) ,National Natural Science Foundationof China( Nos.2 99710 0 5 ,2 0 0 2 3 0 0 5 ,2 0 0 710 0 4) ,and Scientific Research Foundation for the Returned Overseas ChineseScholars( S