The frontier orbitals HOMO and LUMO of the fullerene C_(60) has been given in a system of 60 motion-coordinates, of which each origin is at each C atom of fullerene C_(60) and each z-axis is in the direction perpendic...The frontier orbitals HOMO and LUMO of the fullerene C_(60) has been given in a system of 60 motion-coordinates, of which each origin is at each C atom of fullerene C_(60) and each z-axis is in the direction perpendicular to C_(60)'S spherical surface. In this motion-coordinate system the HOMO and LUMO of fullerene C_(60) obviously display characteristics of spherical n-molecular orbitals π_n. The Fenske-Hall quantum-chemical method is used in calculation for the electronic structure of the fullerene C_(60).展开更多
We performed density functional theory (DFT) calculations for ribonucleotides and active triphosphate metabolites of candidate drugs against Coronavirus disease 2019 (Covid-19). Frontier orbitals (highest occupied mol...We performed density functional theory (DFT) calculations for ribonucleotides and active triphosphate metabolites of candidate drugs against Coronavirus disease 2019 (Covid-19). Frontier orbitals (highest occupied molecular orbital and lowest unoccupied molecular</span><span style="font-family:""> </span><span style="font-family:""><span style="font-family:Verdana;">orbital) at optimized structure of each molecule were obtained. T-705RTP (active triphosphate metabolite of favipiravir) and cytidine triphosphate (CTP) have similar shapes of frontier orbitals. We also obtained similar shapes of frontier orbitals among dihydroxy GS-441524 triphosphate (GS-441524 is an active triphosphate metabolite of remdesivir) and adenosine triphosphate (ATP). From a theoretical </span><span style="font-family:Verdana;">viewpoint, we suggest T-705RTP is a CTP analogue and dihydroxy GS-441524</span><span style="font-family:Verdana;"> triphosphate is an</span></span><span style="font-family:""> </span><span style="font-family:Verdana;">ATP analogue.展开更多
The current work probes the influence of an electric field on the reactions of side-chain active groups(-CH3,-COOH,and-OH)of coal interacting with hydroxyl radical(•OH).The level M062X/6-311+G(d,p)of DFT was employed ...The current work probes the influence of an electric field on the reactions of side-chain active groups(-CH3,-COOH,and-OH)of coal interacting with hydroxyl radical(•OH).The level M062X/6-311+G(d,p)of DFT was employed to obtain the optimized molecular models and the corresponding thermodynamic parameters for the entire elementary reactions under varying electric field intensities of 0-0.02 a.u.Additionally,the bond dissociation energy,reaction energy barrier,front molecular orbital,and electrostatic potentials of the optimized molecular models were calculated based on the frontier orbital and quantum chemistry theories.Results suggest that both the intensity and direction of the electric field pose various effects on the stability of the chemical bond,and a greater electric field intensity would increase the influence on the bond dissociation energy.Moreover,a smaller angle between the bond involved in the reactions and the electric field direction decreases the reaction energy barrier while increasing the occurrence possibility of reactions.Additionally,the electric field impacts the reaction rate of elementary reactions by affecting the electrostatic interaction among reactant molecules,thus affecting the front molecular orbital and changing the reactants’reactivity.This work provides theoretical guidance for developing technologies for mitigating coal combustion-derived environmental pollutants.展开更多
Single-atom catalysts(SACs),first proposed by Zhang and his colleagues in 2011[1],have now become one of the most active frontiers in catalysis due to their great potential in chemical industry,energy storage and conv...Single-atom catalysts(SACs),first proposed by Zhang and his colleagues in 2011[1],have now become one of the most active frontiers in catalysis due to their great potential in chemical industry,energy storage and conversion,as well as emission control[2,3].The activity of the SAC tends to be correlated with the charge state of the central M1atoms.However,this correlation does not always work.展开更多
2,3-disulfanylbutanedioic acid（DMSA） was found to be a selective depressant in the flotation separation of coppermolybdenum sulfides.The flotation results suggest that a low dosage of DMSA has a strong depression ef...2,3-disulfanylbutanedioic acid（DMSA） was found to be a selective depressant in the flotation separation of coppermolybdenum sulfides.The flotation results suggest that a low dosage of DMSA has a strong depression effect on chalcopyrite in the p H range between 4 and 12.At p H 6,the recoveries of molybdenum are up to 85%,75%,and 80% while those of chalcopyrite are 15%,5%,and 20% respectively when flotation tests are carried out with single minerals,mixed minerals and molybdenum-bearing copper concentrates.Adsorption isotherms measurement indicates that DMSA adsorbs more strongly on chalcopyrite than on molybdenite.The frontier orbital calculation reveals that the two S atoms of DMSA molecule are active centers for the adsorption of the DMSA molecule on chalcopyrite surface.Fermi level calculation shows that chalcopyrite can obtain electrons from the DMSA molecule while molybdenite cannot.展开更多
2, 9, 16, 23-tetracarboxy zinc phthalocyanine （ZnTCPc） is synthesized and characterized by physicochemical and theoretical methods and it is used as a photosensitizer in dye-sensitized solar cells （DSSC）. The exci...2, 9, 16, 23-tetracarboxy zinc phthalocyanine （ZnTCPc） is synthesized and characterized by physicochemical and theoretical methods and it is used as a photosensitizer in dye-sensitized solar cells （DSSC）. The excited lifetime, band gap and frontier orbital distribution of ZnTCPc are investigated by fluorescence spectra, cyclic voltammetry and quantum calculation. The results show that the excited lifetime and band gap are 0. 1 ns and 1.81 eV, respectively. Moreover, it is found that the highest occupied molecular orbital （HOMO） location is not shared by both the zinc metal and the isoindoline ligands, and the lowest unoccupied molecular orbital（LUMO） location does not strengthen the interaction coupling between ZnTCPc and TiO：. As a result, the ZnTCPc-DSSC gains a short-circuit current density of 0. 147 mA/cm2, an open-circuit photovoltage of 277 mV, a fill factor of 0. 51 and an overall conversion efficiency of 0. 021%.展开更多
Ten kinds of organic depressants were used to investigate the depressing performance on marmatite and pyrite.Flotation results show that the organic compounds only with single group of hydroxyl(-OH),carboxyl(-COOH) or...Ten kinds of organic depressants were used to investigate the depressing performance on marmatite and pyrite.Flotation results show that the organic compounds only with single group of hydroxyl(-OH),carboxyl(-COOH) or amino(-NH2) in molecule are ineffective in depressing marmatite,jamesonite and pyrite.The combinations of these functional groups still cannot enhance the depressing ability of organic depressant.The thioglycollic acid containing reductive functional group(-SH) has a good depressing performance for marmatite and pyrite.The presence of benzene ring in molecule can enhance the depressing performance.The functional group electronegativity,hydrophilic-hydrophobic indexes and frontier orbital of organic depressants were calculated,and the criterion for the depressing effect of organic depressants to sulphide minerals was proposed.展开更多
The band structure, density of states, Mulliken populations, and frontier orbital of spodumene crystal were calculated using the first-principles method based on the density functional theory（DFT） and further analyz...The band structure, density of states, Mulliken populations, and frontier orbital of spodumene crystal were calculated using the first-principles method based on the density functional theory（DFT） and further analyzed in detail. The calculation results reveal that the O in spodumene is the most active and easily links with H＋in the water, but the active Li is very low, so it is better to add activator to increase the concentrate grade and recovery rate of spodumene in the flotation process. Si–O bonds in spodumene crystal are mainly covalent, since the covalency of Al–O bonds is stronger than that of Li–O bonds,and minerals dissociate along the weakest Li–O bonds. In addition, the study of the frontier orbital indicates that both O and Si atoms have large contribution to the frontier orbital in the spodumene crystal. Oleate and dodecylamine are used as the collectors of spodumene. The results contribute to the understanding of crystal structures of spodumene, and can be used in guiding related practical applications.展开更多
There are often many chemicals coexisting in aquatic ecosystems, and few information on the joint toxicity of a mixture of organic pollutants is available at present. The 48-h toxicity of substituted phenols and anili...There are often many chemicals coexisting in aquatic ecosystems, and few information on the joint toxicity of a mixture of organic pollutants is available at present. The 48-h toxicity of substituted phenols and anilines and their binary mixtures to Scenedesmus obliquus was determined by the algae inhibition test. The median effective inhibition concentration EC50 values for single compounds and EC50mix values for coexistent compounds were obtained. The n-octanol/water partition coefficient （logPmlx） and the frontier orbital energy gap （AEmlx） for mixtures were calculated. The following two-descriptor quantitative structure-activity relationships （QSARs） models were developed to predict single toxicity and joint toxicity respectively： log（1/ECs0） = 0.445logP - 0.801AE ＋ 9.501 （r2 = 0.876） and log （1/EC50mix） = 0.338logPmix- 0.492AEmix ＋ 6.928 （r^2 = 0.831）. The two equations were found to fit well. In addition, the model derived from the structural parameters of single components in binary mixtures log（1/EC50mix） = 0.2221ogP - 0.277AE ＋ 5.250 （r^2 = 0.879） can be used successfully to predict the toxicity of a mixture.展开更多
Objective To measure the toxicity of phenol, aniline, and their derivatives to algae and to assess, model, and predict the toxicity using quantitative structure-activity relationship （QSAR） method. Methods Oxygen pr...Objective To measure the toxicity of phenol, aniline, and their derivatives to algae and to assess, model, and predict the toxicity using quantitative structure-activity relationship （QSAR） method. Methods Oxygen production was used as the response endpoint for assessing the toxic effects of chemicals on algal photosynthesis. The energy of the lowest unoccupied molecular orbital （ELUMO） and the energy of the highest occupied molecular orbital （EHOMO） were obtained from the ChemOffice 2004 program using the quantum chemical method MOPAC, and the frontier orbital energy gap （△E） was obtained. Results The compounds exhibited a reasonably wide range of algal toxicity. The most toxic compound was α-naphthol, whereas the least toxic one was aniline. A two-descriptor model was derived from the algal toxicity and structural parameters： logl/EC50=0.2681ogKow-1.006△E＋11.769 （n=20, r^2=0.946）. This model was stable and satisfactory for predicting toxicity. Conclusion Phenol, aniline, and their derivatives are polar narcotics. Their toxicity is greater than estimated by hydrophobicity only, and addition of the frontier orbital energy gap AE can significantly improve the prediction of logKow-dependent models.展开更多
The title compound, 1-（naphthalene-2-yl）-2-（1H-pyrazol-1-yl）ethanone O-butyl oxime, I, was synthesized. The crystal and molecular structures of I were determined by IR, 1H-NMR, mass spectrum, elemental analysis an...The title compound, 1-（naphthalene-2-yl）-2-（1H-pyrazol-1-yl）ethanone O-butyl oxime, I, was synthesized. The crystal and molecular structures of I were determined by IR, 1H-NMR, mass spectrum, elemental analysis and X-ray single crystal diffraction. Molecular geometry from X-ray experiment of I in the ground state was compared using the Density Functional Theory （DFT） with B3LYP/6-311G（d,p） basis set. In addition, DFT calculation, molecular electrostatic potentials （MEP） and frontier molecular orbitals of I were performed at the B3LYP/6-311G（d,p） level of the theory.展开更多
The electronic structures of QHS and DQHS were completely optimized and calculated by B3LYP density functional theory at the 6-31g* level. The relationship between electronic structure parameters and antimalarial acti...The electronic structures of QHS and DQHS were completely optimized and calculated by B3LYP density functional theory at the 6-31g* level. The relationship between electronic structure parameters and antimalarial activity was discussed. There exists significant difference in frontier orbitals of QHS and DQHS. Their net charges and bond orders were also compared respectively. The results of calculation prove theoretically that the endoperoxy bridge is the essential of antimalarial activity. The difference of antimalarial activity between QHS and DQHS was reasonably explained based on their electronic structures.展开更多
Based on the generalized gradient approximation （GGA）, Perdew-Wang-91 （PW91） combined with a periodic slab model has been applied to study the catalytic activity of chlorine evolution on TinRumO2 （1 1 0） surface...Based on the generalized gradient approximation （GGA）, Perdew-Wang-91 （PW91） combined with a periodic slab model has been applied to study the catalytic activity of chlorine evolution on TinRumO2 （1 1 0） surface. Metal oxide model TinRumO2 has been established with pure TiO2 and Ru02 on the basis set of Double Numerical plus polarization （DNP）, in which the proportion of n：m was 3：1, 1 ：l, or 1：3. Analysis on the reaction activity in the electrochemical reaction and the electrochemical desorption reaction was based on Frontier molecular orbital theory. The results show that the TinRumO2 with a ratio of Ti：Ru at 3：1 is best facilitates the electrochemical reaction and electrochemical desorption reaction to produce M-Clads intermediate and precipitate C12. In addition, the adsorption energy of Cl on the surface of Ti3RU102 possesses the minimum value of 2.514 eV, and thus electrochemical desorption reaction could occur most easily.展开更多
The frontier orbital energies of montmorillonite molecule and[Me(H_(2)O)_(6)]^(2+)(Me=Cu^(2+),Zn^(2+),Co^(2+)and Ni^(2+))were calculated by INDO method.Results showed that the chemical interaction between montmorillon...The frontier orbital energies of montmorillonite molecule and[Me(H_(2)O)_(6)]^(2+)(Me=Cu^(2+),Zn^(2+),Co^(2+)and Ni^(2+))were calculated by INDO method.Results showed that the chemical interaction between montmorillonite molecule and[Cu(H_(2)O)_(6)]^(2+)or[Zn(H_(2)O)_(6)]^(2+)was possible.The experimental results of powder X-ray diffraction and isothermal adsorption supported the above-mentioned calculation results.展开更多
Sulfur-containing polymer(SCP)is considered as an outstanding cathode material for lithium-sulfur batteries.However,undesirable soluble polysulfides may shuttle in electrolyte,concluding long-chain Li_(2)S_(n)(n>4)...Sulfur-containing polymer(SCP)is considered as an outstanding cathode material for lithium-sulfur batteries.However,undesirable soluble polysulfides may shuttle in electrolyte,concluding long-chain Li_(2)S_(n)(n>4)and short-chain Li2Sn(n≤4),as well as the sluggish conversion kinetics are yet to be solved to enhance the performance of lithium-sulfur batteries.Here Se-doped sulfurized polyaniline with adjusted sulfur-chain-S_(x)-(x≤6)contribute to ensure the absence of long-chain polysulfides,and the skeleton with quinoid imine can endow strongly adsorption towards short-chain polysulfides by the reversible transition between deprotonated/protonated imine(-NH^(+)=and-N=),which offer double insurance against suppressing“shuttle effect”.Furthermore,Se atoms are doped into sulfurized polysulfides to accelerate the redox conversion and take a frontier orbital theory-oriented view into catalytic mechanism.Se-doped sulfurized polyaniline as active materials for lithium-organosulfur batteries delivers good electrochemical performance,including high rate,reversible specific capacity(680 mA h g^(-1)at 0.1 A g^(-1)),and lower capacity decay rate only of 0.15%with near 100%coulomb efficiency during long-term cycle.This work provides a valuable guiding ideology and promising solution for the chemistry-oriented structure design and practical application for lithium-organosulfur batteries.展开更多
In the crystal engineering area,it is important to clearly demonstrating the relationship of structure and certain functionality.Herein,we present the study of the relationship of structure with phosphorescent nature ...In the crystal engineering area,it is important to clearly demonstrating the relationship of structure and certain functionality.Herein,we present the study of the relationship of structure with phosphorescent nature for two new room temperature phosphorescence(RTP) coordination polymers(CPs).[Pb(FDA)(H_(2)O)](1) and [NH_(3)(CH_(3))NH_(2)(CH_(3))_(2)][Pb_(4)(FDA)_(5)](2),where H_(2) FDA is 2,5-furandicarboxylic acid,have been synthesized by solvothermal method using different solvents and Pb^(2+) sources and characterized by microanalysis,powderX-ray diffraction(PXRD),thermogravimetric(TG),IR and UV-vis spectra.The Pb^(2+)ions adopt bicapped triangle prism coordination sphere in 1 and 2,which are connected together via FDA^(2-) ligands into bilayer structure in 1 while pillared-layer framework in 2.The FDA^(2-) ligands show different bridging modes in 1 and 2,leading to distinct coordination interactions between Pb^(2+) ion and FDA^(2-) ligand in both CPs.Both 1 and 2 emit ligand-centered RTP due to the heavy atom of Pb^(2+) ion,with a lifetime and quantum yield of 0.62 ms and 14.9% in 1 versus 1.69 ms and 15.7% in 2.The emission peak shows significant redshift(79 nm) in 2 regarding 1,which arises from their distinction of coordination interactions between Pb^(2+) ion and FDA^(2-) ligand in both CPs.展开更多
The molecular geometries, frontier molecular orbital properties, and absorption and emission properties of three 4-phenoxy-1,8-naphthalimide derivatives, namely 4-phenoxy-N-（2-hydroxyethyl）-1,8-naphthalimide（1）,4-...The molecular geometries, frontier molecular orbital properties, and absorption and emission properties of three 4-phenoxy-1,8-naphthalimide derivatives, namely 4-phenoxy-N-（2-hydroxyethyl）-1,8-naphthalimide（1）,4-（2-tert-butylphenoxy）-N-（2-hydroxyethyl）-1,8-naphthalimide（2）, and 4-[2,4-di（tert-butyl）]phenoxy-N-（2-hydroxyethyl）-1,8-naphthalimide（3）, are investigated by density functional theory（DFT） and time-dependent density functional theory（TD-DFT） calculations in conjunction with polarizable continuum models（PCMs）. Four functionals and ten basis sets are employed for 1 to calculate the electron transition energies, which were compared with the experimental observations. Our results reveal that the B3LYP/6-311＋G（d,p） method is the best choice to reproduce the experimental spectra. Moreover, the effects of substituents on the molecular geometries, electronic structures, absorption and emission spectra are also studied at the B3LYP/6-311＋G（d,p） level. We find that the gap between the highest occupied molecular orbital（HOMO） and the lowest unoccupied molecular orbital（LUMO） decreases with increasing the number of tert-butyl substituents onto the phenoxy groups, suggesting red-shift of the absorption and emission bands. This is related to the increase of conjugation from 1 to 2 and 3. Our calculations are in good agreement with the experimental results.展开更多
Excess electrons are not only an important source of radiation damage,but also participate in the repair process of radiation damage such as cyclobutane pyrimidine dimer(CPD).Using ab initio molecular dynamics(AIMD)si...Excess electrons are not only an important source of radiation damage,but also participate in the repair process of radiation damage such as cyclobutane pyrimidine dimer(CPD).Using ab initio molecular dynamics(AIMD)simulations,we reproduce the single excess electron stepwise catalytic CPD dissociation process in detail with an emphasis on the energy levels and molecular structure details associated with excess electrons.On the basis of the AIMD simulations on the CPD aqueous solution with two vertically added excess electrons,we exclude the early-proposed[2+2]-like concerted synchronous dissociation mechanism,and analyze the difference between the symmetry of the actual reaction and the symmetry of the frontier molecular orbitals which deeply impact the mechanism.Importantly,we propose a new model of the stepwise electron-catalyzed dissociation mechanism that conforms to the reality.This work not only provides dynamics insights into the excess electron catalyzed dissociation mechanism,but also reveals different roles of two excess electrons in two bond-cleavage steps(promoting versus inhibiting).展开更多
The title compound, 4-hexyl-1-（4-nitrophenyl）-1-H-1,2,3-triazole （CI4HIsN402）, was synthesized using one-pot strategy via click reaction and the structure was characterized mainly by single-crystal X-ray diffracti...The title compound, 4-hexyl-1-（4-nitrophenyl）-1-H-1,2,3-triazole （CI4HIsN402）, was synthesized using one-pot strategy via click reaction and the structure was characterized mainly by single-crystal X-ray diffraction, NMR, FT-IR and MS. C14H18N4O2 was crystallized from an EtOH/EtOAc solution in triclinic system, space group PI, with a = 5.3679（3）, b = 7.5499（5）, c = 17.5534（11） A, a = 92.360（4）, β = 90.359（4）, γ = 98.864（4）°, V （A3） = 702.24（8）, Z = 2, crystal size （mm） = 0.42 × 0.26 × 0.18, Rint = 0.096. Packing diagram indicates that there is dimeric interaction between two units via N（3）...H（6）. The crystal structure of the title compound （1） is stabifized by intermolecular interactions. In addition, X-ray analys!s also reveals C-H…π and π-π interactions in the molecule. Theoretical investigations were performed by using Gaussian 09 software at the B3LYP/6, 31G （d,p）level of density,finctional theory （DFT）.to compare the theoretical results with the experimental and to probe structural properties. The molecular electrostatic potential （MEP） mapped over the entire stabilized geometry of the molecule indicated their chemical reactivities. Furthermore, frontier molecular orbital （electronic properties） was computed at the same level of DFT as used. forenergy minima structure.展开更多
The 1,3-dipolar cycloaddition reactions of various substituted ynamines with hydrazoic acid were theoretically investigated with the high-accuracy CBS-QB3 method. Two regioisomers, 4-amine, and 5-amine substituted add...The 1,3-dipolar cycloaddition reactions of various substituted ynamines with hydrazoic acid were theoretically investigated with the high-accuracy CBS-QB3 method. Two regioisomers, 4-amine, and 5-amine substituted adducts, were obtained, with the former as the preferred yield. This regioselectivity is rationalized by the frontier molecular orbital theory. The reactivity and synchronicity are enhanced with the increase of the electron-withdrawing character of the substitute on ynamine fragment. The calculations also show that the effect of solvent increases the activation energy, and the reaction becomes even harder in polar solvent.展开更多
文摘The frontier orbitals HOMO and LUMO of the fullerene C_(60) has been given in a system of 60 motion-coordinates, of which each origin is at each C atom of fullerene C_(60) and each z-axis is in the direction perpendicular to C_(60)'S spherical surface. In this motion-coordinate system the HOMO and LUMO of fullerene C_(60) obviously display characteristics of spherical n-molecular orbitals π_n. The Fenske-Hall quantum-chemical method is used in calculation for the electronic structure of the fullerene C_(60).
文摘We performed density functional theory (DFT) calculations for ribonucleotides and active triphosphate metabolites of candidate drugs against Coronavirus disease 2019 (Covid-19). Frontier orbitals (highest occupied molecular orbital and lowest unoccupied molecular</span><span style="font-family:""> </span><span style="font-family:""><span style="font-family:Verdana;">orbital) at optimized structure of each molecule were obtained. T-705RTP (active triphosphate metabolite of favipiravir) and cytidine triphosphate (CTP) have similar shapes of frontier orbitals. We also obtained similar shapes of frontier orbitals among dihydroxy GS-441524 triphosphate (GS-441524 is an active triphosphate metabolite of remdesivir) and adenosine triphosphate (ATP). From a theoretical </span><span style="font-family:Verdana;">viewpoint, we suggest T-705RTP is a CTP analogue and dihydroxy GS-441524</span><span style="font-family:Verdana;"> triphosphate is an</span></span><span style="font-family:""> </span><span style="font-family:Verdana;">ATP analogue.
基金supported by the National Natural Science Foundation of China(Grant no.52104181)the China Postdoctoral Science Foundation(Grant nos.2021M700565 and 2022T150772).
文摘The current work probes the influence of an electric field on the reactions of side-chain active groups(-CH3,-COOH,and-OH)of coal interacting with hydroxyl radical(•OH).The level M062X/6-311+G(d,p)of DFT was employed to obtain the optimized molecular models and the corresponding thermodynamic parameters for the entire elementary reactions under varying electric field intensities of 0-0.02 a.u.Additionally,the bond dissociation energy,reaction energy barrier,front molecular orbital,and electrostatic potentials of the optimized molecular models were calculated based on the frontier orbital and quantum chemistry theories.Results suggest that both the intensity and direction of the electric field pose various effects on the stability of the chemical bond,and a greater electric field intensity would increase the influence on the bond dissociation energy.Moreover,a smaller angle between the bond involved in the reactions and the electric field direction decreases the reaction energy barrier while increasing the occurrence possibility of reactions.Additionally,the electric field impacts the reaction rate of elementary reactions by affecting the electrostatic interaction among reactant molecules,thus affecting the front molecular orbital and changing the reactants’reactivity.This work provides theoretical guidance for developing technologies for mitigating coal combustion-derived environmental pollutants.
文摘Single-atom catalysts(SACs),first proposed by Zhang and his colleagues in 2011[1],have now become one of the most active frontiers in catalysis due to their great potential in chemical industry,energy storage and conversion,as well as emission control[2,3].The activity of the SAC tends to be correlated with the charge state of the central M1atoms.However,this correlation does not always work.
基金Project(2012BAB01B03)supported by the National Key Technology Support Program of China
文摘2,3-disulfanylbutanedioic acid（DMSA） was found to be a selective depressant in the flotation separation of coppermolybdenum sulfides.The flotation results suggest that a low dosage of DMSA has a strong depression effect on chalcopyrite in the p H range between 4 and 12.At p H 6,the recoveries of molybdenum are up to 85%,75%,and 80% while those of chalcopyrite are 15%,5%,and 20% respectively when flotation tests are carried out with single minerals,mixed minerals and molybdenum-bearing copper concentrates.Adsorption isotherms measurement indicates that DMSA adsorbs more strongly on chalcopyrite than on molybdenite.The frontier orbital calculation reveals that the two S atoms of DMSA molecule are active centers for the adsorption of the DMSA molecule on chalcopyrite surface.Fermi level calculation shows that chalcopyrite can obtain electrons from the DMSA molecule while molybdenite cannot.
基金The National Natural Science Foundation of China(No.21173042)the National Basic Research Program of China(973 Program)(No.2007CB936300)+3 种基金the Natural Science Foundation of Jiangsu Province(No.BK201123694)Foundation of Jiangsu Key Laboratory of Environmental Material and Environmental Engineering(No.JHCG201012)Foundation of Key Laboratory of Novel Thin Film Solar Cells of Chinese Academy of Sciences(No.KF200902)Science and Technology Founda-tion of Southeast University(No.KJ2010429)
文摘2, 9, 16, 23-tetracarboxy zinc phthalocyanine （ZnTCPc） is synthesized and characterized by physicochemical and theoretical methods and it is used as a photosensitizer in dye-sensitized solar cells （DSSC）. The excited lifetime, band gap and frontier orbital distribution of ZnTCPc are investigated by fluorescence spectra, cyclic voltammetry and quantum calculation. The results show that the excited lifetime and band gap are 0. 1 ns and 1.81 eV, respectively. Moreover, it is found that the highest occupied molecular orbital （HOMO） location is not shared by both the zinc metal and the isoindoline ligands, and the lowest unoccupied molecular orbital（LUMO） location does not strengthen the interaction coupling between ZnTCPc and TiO：. As a result, the ZnTCPc-DSSC gains a short-circuit current density of 0. 147 mA/cm2, an open-circuit photovoltage of 277 mV, a fill factor of 0. 51 and an overall conversion efficiency of 0. 021%.
基金Project(50864001) supported by the National Natural Science Foundation of ChinaProject(0991082) supported by Guangxi Natural Science Foundation, China
文摘Ten kinds of organic depressants were used to investigate the depressing performance on marmatite and pyrite.Flotation results show that the organic compounds only with single group of hydroxyl(-OH),carboxyl(-COOH) or amino(-NH2) in molecule are ineffective in depressing marmatite,jamesonite and pyrite.The combinations of these functional groups still cannot enhance the depressing ability of organic depressant.The thioglycollic acid containing reductive functional group(-SH) has a good depressing performance for marmatite and pyrite.The presence of benzene ring in molecule can enhance the depressing performance.The functional group electronegativity,hydrophilic-hydrophobic indexes and frontier orbital of organic depressants were calculated,and the criterion for the depressing effect of organic depressants to sulphide minerals was proposed.
基金financially supported by the National Natural Science Foundation of China (No. 51104070)the Special Funds for Postgraduate Student Innovation Program of Jiangxi University of Science and Technology (No. YC2012-X07)the Special Funds for Postgraduate Student Innovation Program of Jiangxi province (No. YC2013-S183)
文摘The band structure, density of states, Mulliken populations, and frontier orbital of spodumene crystal were calculated using the first-principles method based on the density functional theory（DFT） and further analyzed in detail. The calculation results reveal that the O in spodumene is the most active and easily links with H＋in the water, but the active Li is very low, so it is better to add activator to increase the concentrate grade and recovery rate of spodumene in the flotation process. Si–O bonds in spodumene crystal are mainly covalent, since the covalency of Al–O bonds is stronger than that of Li–O bonds,and minerals dissociate along the weakest Li–O bonds. In addition, the study of the frontier orbital indicates that both O and Si atoms have large contribution to the frontier orbital in the spodumene crystal. Oleate and dodecylamine are used as the collectors of spodumene. The results contribute to the understanding of crystal structures of spodumene, and can be used in guiding related practical applications.
文摘There are often many chemicals coexisting in aquatic ecosystems, and few information on the joint toxicity of a mixture of organic pollutants is available at present. The 48-h toxicity of substituted phenols and anilines and their binary mixtures to Scenedesmus obliquus was determined by the algae inhibition test. The median effective inhibition concentration EC50 values for single compounds and EC50mix values for coexistent compounds were obtained. The n-octanol/water partition coefficient （logPmlx） and the frontier orbital energy gap （AEmlx） for mixtures were calculated. The following two-descriptor quantitative structure-activity relationships （QSARs） models were developed to predict single toxicity and joint toxicity respectively： log（1/ECs0） = 0.445logP - 0.801AE ＋ 9.501 （r2 = 0.876） and log （1/EC50mix） = 0.338logPmix- 0.492AEmix ＋ 6.928 （r^2 = 0.831）. The two equations were found to fit well. In addition, the model derived from the structural parameters of single components in binary mixtures log（1/EC50mix） = 0.2221ogP - 0.277AE ＋ 5.250 （r^2 = 0.879） can be used successfully to predict the toxicity of a mixture.
基金This work was supported by the Program for New Century Excellent Talents in University (No. 05-0481)National "973" Great Foundation Research Items of China (No. 2002CB412303)
文摘Objective To measure the toxicity of phenol, aniline, and their derivatives to algae and to assess, model, and predict the toxicity using quantitative structure-activity relationship （QSAR） method. Methods Oxygen production was used as the response endpoint for assessing the toxic effects of chemicals on algal photosynthesis. The energy of the lowest unoccupied molecular orbital （ELUMO） and the energy of the highest occupied molecular orbital （EHOMO） were obtained from the ChemOffice 2004 program using the quantum chemical method MOPAC, and the frontier orbital energy gap （△E） was obtained. Results The compounds exhibited a reasonably wide range of algal toxicity. The most toxic compound was α-naphthol, whereas the least toxic one was aniline. A two-descriptor model was derived from the algal toxicity and structural parameters： logl/EC50=0.2681ogKow-1.006△E＋11.769 （n=20, r^2=0.946）. This model was stable and satisfactory for predicting toxicity. Conclusion Phenol, aniline, and their derivatives are polar narcotics. Their toxicity is greater than estimated by hydrophobicity only, and addition of the frontier orbital energy gap AE can significantly improve the prediction of logKow-dependent models.
基金the Faculty of Arts and Sciences, Ondokuz Mayιs University, Turkey, for the use of the Stoe IPDSII diffractometer (purchased under grant No. F279 of the University Research Fund)
文摘The title compound, 1-（naphthalene-2-yl）-2-（1H-pyrazol-1-yl）ethanone O-butyl oxime, I, was synthesized. The crystal and molecular structures of I were determined by IR, 1H-NMR, mass spectrum, elemental analysis and X-ray single crystal diffraction. Molecular geometry from X-ray experiment of I in the ground state was compared using the Density Functional Theory （DFT） with B3LYP/6-311G（d,p） basis set. In addition, DFT calculation, molecular electrostatic potentials （MEP） and frontier molecular orbitals of I were performed at the B3LYP/6-311G（d,p） level of the theory.
文摘The electronic structures of QHS and DQHS were completely optimized and calculated by B3LYP density functional theory at the 6-31g* level. The relationship between electronic structure parameters and antimalarial activity was discussed. There exists significant difference in frontier orbitals of QHS and DQHS. Their net charges and bond orders were also compared respectively. The results of calculation prove theoretically that the endoperoxy bridge is the essential of antimalarial activity. The difference of antimalarial activity between QHS and DQHS was reasonably explained based on their electronic structures.
基金the Natural Science Foundation of China(No. 51072239)the Fundamental Research Funds for the Central Universities(No.CQDXWL-2012-032) for financial support
文摘Based on the generalized gradient approximation （GGA）, Perdew-Wang-91 （PW91） combined with a periodic slab model has been applied to study the catalytic activity of chlorine evolution on TinRumO2 （1 1 0） surface. Metal oxide model TinRumO2 has been established with pure TiO2 and Ru02 on the basis set of Double Numerical plus polarization （DNP）, in which the proportion of n：m was 3：1, 1 ：l, or 1：3. Analysis on the reaction activity in the electrochemical reaction and the electrochemical desorption reaction was based on Frontier molecular orbital theory. The results show that the TinRumO2 with a ratio of Ti：Ru at 3：1 is best facilitates the electrochemical reaction and electrochemical desorption reaction to produce M-Clads intermediate and precipitate C12. In addition, the adsorption energy of Cl on the surface of Ti3RU102 possesses the minimum value of 2.514 eV, and thus electrochemical desorption reaction could occur most easily.
文摘The frontier orbital energies of montmorillonite molecule and[Me(H_(2)O)_(6)]^(2+)(Me=Cu^(2+),Zn^(2+),Co^(2+)and Ni^(2+))were calculated by INDO method.Results showed that the chemical interaction between montmorillonite molecule and[Cu(H_(2)O)_(6)]^(2+)or[Zn(H_(2)O)_(6)]^(2+)was possible.The experimental results of powder X-ray diffraction and isothermal adsorption supported the above-mentioned calculation results.
基金partly supported by the National Natural Science Foundation of China(51763014 and 52073133)the Key Talent Project Foundation of Gansu Province+3 种基金Joint fund between Shenyang National Laboratory for Materials Science and State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals(18LHPY002)the Incubation Program of Excellent Doctoral Dissertation-Lanzhou University of Technologyexcellent doctoral Program of Gansu Province(22JR5RA240)the Program for Hongliu Distinguished Young Scholars in Lanzhou University of Technology。
文摘Sulfur-containing polymer(SCP)is considered as an outstanding cathode material for lithium-sulfur batteries.However,undesirable soluble polysulfides may shuttle in electrolyte,concluding long-chain Li_(2)S_(n)(n>4)and short-chain Li2Sn(n≤4),as well as the sluggish conversion kinetics are yet to be solved to enhance the performance of lithium-sulfur batteries.Here Se-doped sulfurized polyaniline with adjusted sulfur-chain-S_(x)-(x≤6)contribute to ensure the absence of long-chain polysulfides,and the skeleton with quinoid imine can endow strongly adsorption towards short-chain polysulfides by the reversible transition between deprotonated/protonated imine(-NH^(+)=and-N=),which offer double insurance against suppressing“shuttle effect”.Furthermore,Se atoms are doped into sulfurized polysulfides to accelerate the redox conversion and take a frontier orbital theory-oriented view into catalytic mechanism.Se-doped sulfurized polyaniline as active materials for lithium-organosulfur batteries delivers good electrochemical performance,including high rate,reversible specific capacity(680 mA h g^(-1)at 0.1 A g^(-1)),and lower capacity decay rate only of 0.15%with near 100%coulomb efficiency during long-term cycle.This work provides a valuable guiding ideology and promising solution for the chemistry-oriented structure design and practical application for lithium-organosulfur batteries.
基金the National Natural Science Foundation of China (No.21901116)。
文摘In the crystal engineering area,it is important to clearly demonstrating the relationship of structure and certain functionality.Herein,we present the study of the relationship of structure with phosphorescent nature for two new room temperature phosphorescence(RTP) coordination polymers(CPs).[Pb(FDA)(H_(2)O)](1) and [NH_(3)(CH_(3))NH_(2)(CH_(3))_(2)][Pb_(4)(FDA)_(5)](2),where H_(2) FDA is 2,5-furandicarboxylic acid,have been synthesized by solvothermal method using different solvents and Pb^(2+) sources and characterized by microanalysis,powderX-ray diffraction(PXRD),thermogravimetric(TG),IR and UV-vis spectra.The Pb^(2+)ions adopt bicapped triangle prism coordination sphere in 1 and 2,which are connected together via FDA^(2-) ligands into bilayer structure in 1 while pillared-layer framework in 2.The FDA^(2-) ligands show different bridging modes in 1 and 2,leading to distinct coordination interactions between Pb^(2+) ion and FDA^(2-) ligand in both CPs.Both 1 and 2 emit ligand-centered RTP due to the heavy atom of Pb^(2+) ion,with a lifetime and quantum yield of 0.62 ms and 14.9% in 1 versus 1.69 ms and 15.7% in 2.The emission peak shows significant redshift(79 nm) in 2 regarding 1,which arises from their distinction of coordination interactions between Pb^(2+) ion and FDA^(2-) ligand in both CPs.
基金supported by the Scientific Research Fund of Hubei Provincial Education Department(No.Q20122909)the Open Fund of Key Laboratory of Biologic Resources Protection and Utilization of Hubei Province(No.PKLHB1314)the First-class Discipline of Forestry in Hubei Minzu University
文摘The molecular geometries, frontier molecular orbital properties, and absorption and emission properties of three 4-phenoxy-1,8-naphthalimide derivatives, namely 4-phenoxy-N-（2-hydroxyethyl）-1,8-naphthalimide（1）,4-（2-tert-butylphenoxy）-N-（2-hydroxyethyl）-1,8-naphthalimide（2）, and 4-[2,4-di（tert-butyl）]phenoxy-N-（2-hydroxyethyl）-1,8-naphthalimide（3）, are investigated by density functional theory（DFT） and time-dependent density functional theory（TD-DFT） calculations in conjunction with polarizable continuum models（PCMs）. Four functionals and ten basis sets are employed for 1 to calculate the electron transition energies, which were compared with the experimental observations. Our results reveal that the B3LYP/6-311＋G（d,p） method is the best choice to reproduce the experimental spectra. Moreover, the effects of substituents on the molecular geometries, electronic structures, absorption and emission spectra are also studied at the B3LYP/6-311＋G（d,p） level. We find that the gap between the highest occupied molecular orbital（HOMO） and the lowest unoccupied molecular orbital（LUMO） decreases with increasing the number of tert-butyl substituents onto the phenoxy groups, suggesting red-shift of the absorption and emission bands. This is related to the increase of conjugation from 1 to 2 and 3. Our calculations are in good agreement with the experimental results.
基金supported by the National Natural Science Foundation of China(No.21873056,No.21773137,and No.21573128)。
文摘Excess electrons are not only an important source of radiation damage,but also participate in the repair process of radiation damage such as cyclobutane pyrimidine dimer(CPD).Using ab initio molecular dynamics(AIMD)simulations,we reproduce the single excess electron stepwise catalytic CPD dissociation process in detail with an emphasis on the energy levels and molecular structure details associated with excess electrons.On the basis of the AIMD simulations on the CPD aqueous solution with two vertically added excess electrons,we exclude the early-proposed[2+2]-like concerted synchronous dissociation mechanism,and analyze the difference between the symmetry of the actual reaction and the symmetry of the frontier molecular orbitals which deeply impact the mechanism.Importantly,we propose a new model of the stepwise electron-catalyzed dissociation mechanism that conforms to the reality.This work not only provides dynamics insights into the excess electron catalyzed dissociation mechanism,but also reveals different roles of two excess electrons in two bond-cleavage steps(promoting versus inhibiting).
基金supported by the Higher Education Commision(HEC)Govt.of Pakistan
文摘The title compound, 4-hexyl-1-（4-nitrophenyl）-1-H-1,2,3-triazole （CI4HIsN402）, was synthesized using one-pot strategy via click reaction and the structure was characterized mainly by single-crystal X-ray diffraction, NMR, FT-IR and MS. C14H18N4O2 was crystallized from an EtOH/EtOAc solution in triclinic system, space group PI, with a = 5.3679（3）, b = 7.5499（5）, c = 17.5534（11） A, a = 92.360（4）, β = 90.359（4）, γ = 98.864（4）°, V （A3） = 702.24（8）, Z = 2, crystal size （mm） = 0.42 × 0.26 × 0.18, Rint = 0.096. Packing diagram indicates that there is dimeric interaction between two units via N（3）...H（6）. The crystal structure of the title compound （1） is stabifized by intermolecular interactions. In addition, X-ray analys!s also reveals C-H…π and π-π interactions in the molecule. Theoretical investigations were performed by using Gaussian 09 software at the B3LYP/6, 31G （d,p）level of density,finctional theory （DFT）.to compare the theoretical results with the experimental and to probe structural properties. The molecular electrostatic potential （MEP） mapped over the entire stabilized geometry of the molecule indicated their chemical reactivities. Furthermore, frontier molecular orbital （electronic properties） was computed at the same level of DFT as used. forenergy minima structure.
基金Ⅴ. ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China （No.20833008）.
文摘The 1,3-dipolar cycloaddition reactions of various substituted ynamines with hydrazoic acid were theoretically investigated with the high-accuracy CBS-QB3 method. Two regioisomers, 4-amine, and 5-amine substituted adducts, were obtained, with the former as the preferred yield. This regioselectivity is rationalized by the frontier molecular orbital theory. The reactivity and synchronicity are enhanced with the increase of the electron-withdrawing character of the substitute on ynamine fragment. The calculations also show that the effect of solvent increases the activation energy, and the reaction becomes even harder in polar solvent.
