Baoshan Wang

Wuhan University, Wuhan, Hubei, China

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Publications (66)124.12 Total impact

  • Hui Hu, Hua Hou, Zhen He, Baoshan Wang
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    ABSTRACT: The anionic mechanisms for the elementary dimerization reaction of monosilicic acid in basic aqueous solution have been characterized comprehensively using various ab initio methods. Many new insights into the silicate oligomerization reaction, which is fundamentally important in sol-gel chemistry, zeolite synthesis, and cement hydration, are presented in this work. Conformational dependence of the dimerization reaction is proposed in view of hundreds of conformations with various inter- and intramolecular hydrogen bonding patterns along the reaction routes. An alternative water cleavage route from the five-coordinated silicon intermediate is revealed. The detour involves a six-center cyclic transition state, which is more preferable energetically than the well-known four-center water removal step. By including explicit water molecules, the activation barrier of the four-center water cleavage path can be reduced considerably to be even lower than the first barrier of the Si-O bond formation. In contrast, the six-center detour is less affected by the additional water molecules due to the unfavorable geometric distortion. The new understanding of the dimerization mechanism could have considerable impact on the initial stages of silica nucleation.
    Physical Chemistry Chemical Physics 08/2013; · 3.83 Impact Factor
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    ABSTRACT: The epoxy spacers in SF6 Gas Insulated Switchgear (GIS) are vulnerable to discharge. Once the surface of the epoxy spacers is deteriorated under discharge, insulation break down may occur subsequently. From a number of experiments carried out on 110 kV GIS, a new gas CS2 was detected when creeping discharges occur on the epoxy spacer surface. In order to verify the correlation between CS2 and the degradation of epoxy spacers, the quantum chemistry analysis was used to investigate the mechanism of CS2 development. Based on the results, the relation between CS2 and spacer insulation degradation was determined.
    IEEE Transactions on Dielectrics and Electrical Insulation 01/2013; 20(6):2152-2157. · 1.36 Impact Factor
  • Yongyan Zhou, Hui Hu, Li Li, Hua Hou, Baoshan Wang
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    ABSTRACT: Electronic structures, vibrational properties, and dissociation energies of the elusive HO3(X2A″) radical have been calculated using various benchmark ab initio methods, including multireference RS2, MRCI+Q, MR-AQCC, NEVPT2, and the explicitly correlated RCCSD(T)-F12, RS2-F12, and MRCI-F12. The RS2 results strongly depend on the semiempirical level shifts applied to modify the zeroth-order Hamiltonian and the basis sets. The sizes of active spaces are crucial to the MRCI+Q data. The calculated dissociation energy (De) of HO3 into OH + O2 ranges from 4.6 to 6.2 kcal/mol. Theoretical intermolecular vibrational frequencies are in excellent agreement with the experimental measurements. The zero-point energy correction to De is estimated to be 2.6 kcal/mol. The formation of HO3 from OH(X2Π) and O2(X3Σg-) is determined to be a barrierless process. Temperature and pressure dependent kinetics for the association reaction are calculated variationally using the Master equations. It is revealed that the rate constants exhibit steep negative temperature dependence and typical non-Arrhenius behavior. The experimental low-temperature rate constants have been well reproduced theoretically.
    Computational and Theoretical Chemistry. 01/2013; 1026:24–30.
  • Hui Hu, Hua Hou, Baoshan Wang
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    ABSTRACT: TIP4P/2005 force-field-based classical molecular dynamics simulations were employed to investigate the microscopic mechanism for the ice growth from supercooled water when the external electric (0–109 V/m) and magnetic fields (0–10 T) are applied simultaneously. Using the direct coexistence ice/water interface, the anisotropic effect of electric and magnetic fields on the basal, primary prismatic, and the secondary prismatic planes of ice Ih has been calculated. It was revealed for the first time that the solvation shells of supercooled water could be affected by the cooperative electric and magnetic fields. Meanwhile, the self-diffusion coefficient is lowered, and the shear viscosity increases considerably. The critical electric and magnetic fields to accelerate ice growth on the prismatic plane are fairly low (ca. 106 V/m and 0.01 T). In contrast, the basal plane is hardly affected unless the fields increase to the order 109 V/m and 10 T. Rotational dynamics of water molecules might play an important role in ice growth with the applied external fields. Density functional theory with the triple numerical all-electron basis set was used to reveal the electronic structures of the basal and primary prismatic planes of ice Ih with respect to the anisotropic effect of ice growth.
    The Journal of Physical Chemistry C. 09/2012; 116(37):19773–19780.
  • Jingyu Sun, Rongshun Wang, Baoshan Wang
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    ABSTRACT: The mechanism and kinetics of the reaction of acrylonitrile (CH(2)=CHCN) with hydroxyl (OH) has been investigated theoretically. This reaction is revealed to be one of the most significant loss processes of acrylonitrile. BHandHLYP and M05-2X methods are employed to obtain initial geometries. The reaction mechanism conforms that OH addition to C[double bond, length as m-dash]C double bond or C atom of -CN group to form the chemically activated adducts, 1-IM1(HOCH(2)=CHCN), 2-IM1(CH(2)=HOCHCN), and 3-IM1(CH(2)=CHCOHN) via low barriers, and direct hydrogen abstraction paths may also occur. Temperature- and pressure-dependent rate constants have been evaluated using the Rice-Ramsperger-Kassel-Marcus theory. The calculated rate constants are in good agreement with the experimental data. At atmospheric pressure with N(2) as bath gas, 1-IM1(OHCH(2)=CHCN) formed by collisional stabilization is the major product in the temperature range of 200-1200 K. The production of CH(2)CCN and CHCHCN via hydrogen abstractions becomes dominant at high temperatures (1200-3000 K).
    Physical Chemistry Chemical Physics 08/2011; 13(37):16585-95. · 3.83 Impact Factor
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    ABSTRACT: The microscopic reaction mechanism for the water adsorption/dissociation processes on the α-Al2O3(0001) surface was calculated using density functional theory with the all-electron triple numerical polarized basis sets. Both unit-cell and 2 × 2 supercell slab models were employed to investigate the coverage-dependent hydroxylation of the surface. Geometries of the molecular adsorbed intermediates, transition states, and the hydroxylated products were fully optimized, and the energetic reaction routes were clarified. The hydroxylation occurs predominantly via the low-barrier 1,4-hydrogen migration path, and the 1,2-dissociation path is competitive. The 1,2-hydroxylated surface is more preferable thermodynamically in the consideration of reaction exothermicity. It was found that the in-plane hydrogen atoms can roam between the surface oxygen atoms, resulting in isomerization between the 1,2- and 1,4-hydroxylated products. Calculations for the multiple layer adsorption confirm that the hydroxylated surface is relatively inert to further hydroxylation by water. Further added water molecules prefer to form multilayered hexagonal ice-like arrangements through a hydrogen-bonding network. The electric field might not play a significant role in either surface reconstruction or the hydroxylation process until it exceeds 108 V/m. The present theoretical work is useful to gain some new insights on the ice accumulation of high-voltage power lines under high humidity and supercooled environment.
    The Journal of Physical Chemistry C. 06/2011; 115(27).
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    ABSTRACT: Scorpion toxins are invaluable tools for ion channel research and are potential drugs for human channelopathies. However, it is still an open task to determine the molecular basis underlying the diverse interactions between toxin peptides and ion channels. The inhibitory peptide Maurotoxin (MTX) recognized the distantly related IK(Ca) and Kv1.2 channel with approximately the same potency and using the same functional residues, their differential binding mechanism remain elusive. In this study, we applied computational methods to explore the differential binding modes of MTX to Kv1.2 and IK(Ca) channels, which would help to understand the diversity of channel-toxin interactions and accelerate the toxin-based drug design. A reasonably stable MTX-IK(Ca) complex was obtained by combining various computational methods and by in-depth comparison with the previous model of the MTX-Kv1.2 complex. Similarly, MTX adopted the β-sheet structure as the interacting surface for binding both channels, with Lys23 occluding the pore. In contrast, the other critical residues Lys27, Lys30, and Tyr32 of MTX adopted distinct interactions when associating with the IK(Ca) channel. In addition, the residues Gln229, Ala230, Ala233, and Thr234 on the IK(Ca) channel turret formed polar and non-polar interactions with MTX, whereas the turret of Kv1.2 was almost not involved in recognizing MTX. In all, the pairs of interacting residues on MTX and the IK(Ca) channel of the bound complex indicated that electrostatic and Van der Waal interactions contributed equally to the formation of a stable MTX-IK(Ca) complex, in contrast to the MTX-Kv1.2 binding that is dominantly mediated by electrostatic forces. Despite sharing similar pharmacological profiles toward both IK(Ca) and Kv1.2 channels, MTX adopted totally diverging modes in the two association processes. All the molecular information unveiled here could not only offer a better understanding about the structural differences between the IK(Ca) and Kv1.2 channels, but also provide novel structural clues that will help in the designing of more selective molecular probes to discriminate between these two channels.
    BMC Structural Biology 01/2011; 11:3. · 2.10 Impact Factor
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    ABSTRACT: Kinetics of OH formation for the reaction of C2H5CO radicals with O2 have been studied using the low-pressure discharge flow technique coupled with resonance fluorescence monitoring of OH radicals at room temperature in He buffer gas. The OH yields are close to unity at the lowest pressures studied, but decrease rapidly with increasing pressure. The experimental OH yields are reproduced well using multichannel variational RRKM theory.
    Chemical Physics Letters 01/2010; 495(4):179-181. · 2.15 Impact Factor
  • Jicun Li, Hua Hou, Baoshan Wang
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    ABSTRACT: Ab intitio molecular dynamics simulation of the electronic structure of the aqueous superoxide anion (O2(-)) has been carried out using the Car-Parrinello density functional theory at 298 and 310 K. The modeling system consists of one O2(-) solvated in 31 water molecules. On the basis of our 40 ps production run, the novel mechanism and the nature of the hydration of the superoxide anion in a relatively big aqueous environment have been revealed by using various radial distribution functions. The averaged coordinated water number was estimated to be 4.5. The calculated microscopic configurations of the first solvation shell are in good agreement with the experimental results. The vibrational frequency of the solvated O2(-) anion was red-shifted significantly in comparison with that of the free radical anion in the gas phase. The diffusion coefficient of O2(-) was estimated to be about 8 x 10(-5) cm2/s at 298 K. Comparisons with the previous force-field-based classical molecular dynamics simulations have been made, and the differences were discussed.
    The Journal of Physical Chemistry A 03/2009; 113(5):800-4. · 2.77 Impact Factor
  • Xinli Song, Jicun Li, Hua Hou, Baoshan Wang
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    ABSTRACT: [1,2,3,4]Tetrazino-[5,6-e]-[1,2,3,4]tetrazine-[1,3,5,7]tetraoxide (TTTO, C2N8O4) was suggested to be a possible candidate of high energy density materials (HEDM). The most stable conformation of TTTO is a planar structure with C2h symmetry. Using various high-level ab initio methods including Gaussian-n, Complete Basis Set, Full Coupled Cluster, and W1U models of chemistry together with density functional theory based models, the enthalpies of formation of TTTO at 0 K and standard state were calculated precisely. Moreover, the rovibrational and nuclear magnetic resonance properties were predicted as well. The solid state TTTO was studied using the crystal packing models with the Dreiding force-filed and the plane-wave periodic local-density approximation density functional theory. Three stable polymorphous cells of TTTO have been found with either P212121 or P21/C symmetry. The high heat of formation (>200 kcal/mol), the high density (>2.0 g/cm3), the planar nonpolar electronic structure, and the perfect oxygen balance lead TTTO be a very promising HEDM with exceptional performance. This work provides the first theoretical support for further experimental synthesis and testing.
    Journal of Computational Chemistry 12/2008; 30(12):1816-20. · 3.84 Impact Factor
  • Jicun Li, Xinli Song, Zhe Peng, Hua Hou, Baoshan Wang
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    ABSTRACT: The reaction of triplet methylene with methanol is a key process in alcohol combustion but surprisingly this reaction has never been studied. The reaction mechanism is investigated by using various high-level ab initio methods, including the complete basis set extrapolation (CBS-QB3 and CBS-APNO), the latest Gaussian-n composite method (G4), and the Weizmann-1 method (W1U). A total of five product channels and six transition states are found. The dominant mechanism is direct hydrogen abstraction, and the major product channel is CH(3) + CH(3)O, involving a weak prereactive complex and a 7.4 kcal/mol barrier. The other hydrogen abstraction channel, CH(3) + CH(2)OH, is less important even though it is more exothermic and involves a similar barrier height. The rate coefficients are predicted in the temperature range 200-3000 K. The tunneling effect and the hindered internal rotational freedoms play a key role in the reaction. Moreover, the reaction shows significant kinetic isotope effect.
    The Journal of Physical Chemistry A 12/2008; 112(48):12492-7. · 2.77 Impact Factor
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    ABSTRACT: We discuss in this article, the applicability of hybrid techniques [especially the our-own N-layered integrated molecular orbital and molecular mechanics (ONIOM) method] to weak chemical interactions in large systems, such as the interaction of cyclin-dependant kinases, CDK4, and CDK2, with a specific ligand (2PU) showing selectivity for CDK4. Our results show that the energies from the ONIOM calculations perfectly match our former molecular dynamics results, both for determining the amino acids which have strongest interactions with the ligand and for explaining the selectivity of 2PU towards CDK4, as compared with CDK2. We show that the ONIOM method is a good candidate for studying such interactions in large systems, even though there are still some technical and theoretical problems to solve. The calculation details will be presented together with the methodology we devised for using the ONIOM approach in such a context. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009
    International Journal of Quantum Chemistry 11/2008; 109(5):1148 - 1157. · 1.17 Impact Factor
  • Yizhen Tang, Rongshun Wang, Baoshan Wang
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    ABSTRACT: Mechanisms and kinetics of the NCCO + O2 reaction have been investigated using the extrapolated full coupled cluster theory with the complete basis set limit (FCC/CBS) and multichannel RRKM theory. Energetically, the most favorable reaction route involves the barrierless addition of the oxygen atom to one of the carbon atoms of NCCO and the subsequent isomerization-decomposition via the four-center intermediate and transition state, leading to the final products NCO and CO2. At 298 K, the calculated overall rate constant is strongly pressure-dependent, which is in good agreement with the available experimental values. It is predicted that the high-pressure limit rate constants exhibit negative temperature dependence below 350 K. The dominant products are NCO and CO2 at low pressures (ca. <10 Torr) and the NCCO(O2) radical at higher pressures, respectively.
    The Journal of Physical Chemistry A 06/2008; 112(23):5295-9. · 2.77 Impact Factor
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    ABSTRACT: Cyclin-dependent kinases (CDKs) are essential in cell cycle and important targets in the development of new anticancer strategies. Much effort has been devoted to discover and study inhibitors of CDKs, especially those which display selectivity towards specific CDKs. Understanding and predicting selectivity would be of high value to drug design, but this seems difficult due to the many factors involved, especially the sequence similarity in the CDK family. This paper is focused on a computational study of an inhibitor which shows good selectivity for CDK4 relative to CDK2. Using molecular dynamics and free-energy calculations, the main protein residues interacting with the ligand are identified, the conformational and dynamical changes are established, the role of H bonds is examined and the binding free energies are obtained for both complexes. Differences in binding mode are discussed and related to selectivity. (c) 2007 Elsevier B.V. All rights reserved.
    JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM. 01/2008; 849(1-3):62-75.
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    ABSTRACT: Direct anodic oxidation of 1,2-methylenedioxybenzene (MDOB) and 1,2-ethylenedioxybenzene (EDOB), analogues of 3,4-alkylenedioxythiophene and 3,4-alkylenedioxypyrrole, led to the formation of polyacetylene derivatives, poly(1,2-methylenedioxybenzene) (PMDOB) and poly(1,2-ethylenedioxybenzene) (PEDOB), on a platinum sheet in pure boron trifluoride diethyl etherate (BFEE). IR, 1H NMR, 13C NMR and quantum chemistry calculations confirmed that the polymerization occurred at C(4) and C(5) position on the benzene ring of the monomer, making the main backbone of PMDOB and PEDOB similar to polyacetylene. Both dedoped PMDOB and PEDOB in DMSO solution showed good fluorescence properties with quantum yields of 0.13 and 0.27, emitting blue and green light under excitation of 365 nm, respectively. PMDOB showed electrochromic properties from grass green (doped) to light nacarat (dedoped). PEDOB changed it from bottle green (doped) to nacarat (dedoped). Doped PMDOB and PEDOB own electrical conductivities of 0.1 S cm−1 and 0.17 S cm−1, respectively.
    European Polymer Journal 01/2008; 44(1):171-188. · 2.56 Impact Factor
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    ABSTRACT: The multichannel reaction of the C(2)Cl(3) radical with O(2) has been studied thoroughly by step-scan time-resolved Fourier transform infrared emission spectroscopy. Vibrationally excited products of Cl(2)CO, CO, and CO(2) are observed and three major reaction channels forming respectively ClCO + Cl(2)CO, CO + CCl(3)O, and CO(2) + CCl(3) are identified. The vibrational state distribution of the product CO is derived from the spectral fitting, and the nascent average vibrational energy of CO is determined to be 59.9 kJ/mol. A surprisal analysis is applied to evaluate the vibrational energy disposal, which reveals that the experimentally measured CO vibrational energy is much more than that predicted by statistical model. Combining previous ab initio calculation results, the nonstatistical dynamics and mechanism are characterized to be barrierless addition-elimination via short-lived reaction intermediates including the peroxy intermediate C(2)Cl(3)OO* and a crucial three-member-ring COO intermediate.
    The Journal of Physical Chemistry A 10/2007; 111(38):9606-12. · 2.77 Impact Factor
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    Hua Hou, Baoshan Wang
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    ABSTRACT: The reaction of propionyl radical with oxygen has been studied using the full coupled cluster theory with the complete basis set. This is the first time to gain a conclusive insight into the reaction mechanism and kinetics for this important reaction in detail. The reaction takes place via a chemical activation mechanism. The barrierless association of propionyl with oxygen produces the propionylperoxy radical, which decomposes to form the hydroxyl radical and the three-center alpha-lactone predominantly or the four-center beta-propiolactone. The oxidation of propionyl radical to carbon monoxide or carbon dioxide is not straightforward rather via the secondary decomposition of alpha-lactone and beta-propiolactone. Kinetically, the overall rate constant is almost pressure independent and it approaches the high-pressure limit around tens of torr of helium. At temperatures below 600 K, the rate constant shows negative temperature dependence. The experimental yields of the hydroxyl radical can be well reproduced, with the average energy transferred per collision -DeltaE=20-25 cm(-1) at 213 and 295 K (helium bath gas). At low pressures, together with the hydroxy radical, alpha-lactone is the major product, while beta-propiolactone only accounts for about one-fifth of alpha-lactone. At the high-pressure limit, the production of the propionylperoxy radical is dominant together with a fraction of the isomers. The infrared spectroscopy or the mass spectroscopy techniques are suggested to be employed in the future experimental study of the C2H5CO+O2 reaction.
    The Journal of Chemical Physics 09/2007; 127(5):054306. · 3.12 Impact Factor
  • Hua Hou, Yuzhen Li, Baoshan Wang
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    ABSTRACT: Mechanisms and kinetics of the reaction of atomic oxygen with acetone have been investigated using ab initio quantum chemistry methods and transition state theory. The structures of the stationary points along the possible reaction pathways were obtained using the second-order Møller-Plesset theory and the coupled-cluster theory with single and double excitations with the triple-zeta quality basis sets. The energetics of the reaction pathways were calculated at the reduced second-order Gaussian-3 level and the extrapolated full coupled-cluster/complete basis set limit. The rate coefficients were calculated in the temperature range 200-3000 K, with the detailed consideration of the hindered internal rotation and the tunneling effect using Eckart and the semiclassical WKB approximations. It is shown that the predominant mechanism is the direct hydrogen abstraction producing hydroxyl and acetonyl radicals. Although the nucleophilic OC addition/elimination channel leading to CH3 and CO2 involves comparable barrier with the direct hydrogen abstraction channel, kinetically it cannot play any role in the overall reaction. It is predicted that the rate coefficients show positive temperature dependence in the range 200-3000 K and strong non-Arrhenius behavior. The tunneling effect plays a significant role. Moreover, the reaction has strong kinetic isotope effect. The calculated results are in good agreement with the available experimental data. The present rigorous theoretical work is helpful for the understanding of the characteristics of the reaction of atomic oxygen with acetone.
    The Journal of Physical Chemistry A 01/2007; 110(49):13163-71. · 2.77 Impact Factor
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    ABSTRACT: Eight exothermic product channels of the reaction of chlorinated vinyl radical (C2Cl3) with molecular oxygen (O2) have been investigated using ab initio quantum chemistry methods. The energetics of the reaction pathways were calculated at the second-order Moller-Plesset Gaussian-3 level of theory (G3MP2) using the B3LYP/6-311G(d) optimized geometries. It has been shown that the C2Cl3 + O2 reaction takes place via a barrierless addition to form the chlorinated vinylperoxy radical complex, which can decompose or isomerize to various products via the complicated mechanisms. Two major reaction routes were revealed, i.e., the three-member-ring reaction mechanism leading to ClCO + CCl2O, CO + CCl3O, CO2 + CCl3, Cl + (ClCO)2, etc., and the OO bond cleavage mechanism leading to O(3P) + C2Cl3O. The other mechanisms are shown to be unimportant. The results are validated by the calculations using the restricted coupled cluster theory [RCCSD(T)] with the complete basis set extrapolation. Variational transition state theory was employed to calculate the individual and total rate coefficients as a function of temperature and pressure (helium). The theoretical rate coefficients are in good agreement with the available experimental data. It was found that the total rate coefficients show strong negative temperature dependence in the range 200-2000 K. At room temperature (297 K), the total rate coefficients are shown to be nearly pressure independent over a wide range of helium pressures (1-10(9) Torr). The deactivation of the initial adduct, C2Cl3O2, is only significant at pressures higher than 1000 Torr. The three-member-ring reaction mechanism is always predominant over the OO bond cleavage.
    The Journal of Physical Chemistry A 09/2006; 110(34):10336-44. · 2.77 Impact Factor
  • Xinli Song, Jicun Li, Hua Hou, Baoshan Wang
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    ABSTRACT: Potential energy surface for the reaction OH+CO-->H+CO2 has been calculated using the complete active space self-consistent-field and multireference configuration interaction methods with the correlation consistent triple-, quadruple-, and quintuple-zeta basis sets. A specific- reaction-parameters density functional theory has been suggested, in which the B3LYP functional is reoptimized to give the highly accurate potential energy surface with less computational efforts.
    The Journal of Chemical Physics 09/2006; 125(9):094301. · 3.12 Impact Factor

Publication Stats

233 Citations
124.12 Total Impact Points

Institutions

  • 2005–2013
    • Wuhan University
      • • College of Chemistry and Molecular Sciences
      • • State Key Laboratory of Virology
      Wuhan, Hubei, China
  • 2008–2011
    • Northeast Normal University
      • Department of Chemistry
      Hsin-ching, Jilin Sheng, China
  • 2007
    • Northeast Institute of Geography and Agroecology
      • Institute of Chemistry
      Beijing, Beijing Shi, China
  • 2003
    • Argonne National Laboratory
      Lemont, Illinois, United States
  • 2000
    • University of Jinan (Jinan, China)
      Chi-nan-shih, Shandong Sheng, China
  • 1998–2000
    • Shandong University
      • Department of Chemistry
      Jinan, Shandong Sheng, China