Zhao Gao

Northeast Institute of Geography and Agroecology, Peping, Beijing, China

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Publications (14)46.53 Total impact

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    ABSTRACT: The current responses of a generation/collection (G/C) system based on dual micropipettes are simulated by the boundary element (BE) method, from which the collection efficiencies for various pipettes with different geometries are calculated. The influence of the shape of a dual micropipette on the collection efficiency, such as curvature and symmetry of the pipette, as well as the thickness of glassy band between generator and collector, is presented and discussed in detail. Moreover, the simulation results have been tested using the experiments of potassium and sodium ions transfers facilitated by dibenzo-18-crown-6 (DB18C6) at the water/1,2-dichloroethane (W/DCE) interface. These results demonstrate that the BE method is an efficient and useful approach for the simulation of collection efficiency of symmetric geometries of dual micropipettes operating in the G/C mode under transport conditions of diffusion control. However, there are still some problems for the cases of asymmetric dual micropipettes, which show rather large differences between the values of simulated and experimental ones. This work also indicates that such an ionic G/C technique should have advantages in applications when the dual pipettes have symmetric geometries.
    Science China-Chemistry 01/2011; 54(8):1311-1318. · 1.33 Impact Factor
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    ABSTRACT: Facilitated ion transfer (FIT) and simple ion transfer (IT) reactions at the water|1,2-dichloroethane (W|DCE) interface with media of low ionic strength are investigated by employing micro- and nano-pipettes. The model systems chosen for the FIT and IT are K+ transfer facilitated by dibenzo-18-crown-6 (DB18C6) and tetramethylammonium (TMA+), respectively. For the FIT reaction at micro- and submicro-liquid|liquid interfaces, when the supporting electrolyte concentrations in the organic phase are at micromolar levels, its voltammetric waves are analyzed by the theory for one-electron oxidation of uncharged species in organic solution with little added supporting electrolyte on solid ultramicroelectrodes (UMEs) proposed by Oldham [K.B. Oldham, J. Electroanal. Chem. 250 (1988) 1]. Its chronoamperograms are strongly affected by the externally applied potentials, which is consistent with the theory proposed by Stojek and co-workers [A. Jaworski, M. Donten, Z. Stojek, Anal. Chim. Acta 305 (1995) 106, A. Jaworski, M. Donten, Z. Stojek, J. Electroanal. Chem. 407 (1996) 75, W. Hyk, M. Palys, Z. Stojek, J. Electroanal. Chem. 415 (1996) 13, W. Hyk, Z. Stojek, J. Electroanal. Chem. 422 (1997) 179] for reactions at solid UMEs with different concentrations of supporting electrolyte. In addition, the FIT reaction can exhibit well-defined steady-state waves at the nano-liquid|liquid interface when no supporting electrolyte is added to the organic phase. For the TMA+ transfer reaction from the aqueous phase to DCE (or from DCE to the aqueous phase), the magnitude of its steady-state limiting current depends on the concentration of supporting electrolyte in the same phase, and the shape and position of its transfer waves are influenced by the supporting electrolyte concentrations in the adjacent phase. We can observe clearly the migration effect on the transfer reaction of charged species.
    Journal of Electroanalytical Chemistry - J ELECTROANAL CHEM. 01/2005; 579(1):89-102.
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    ABSTRACT: The kinetics of facilitated ion-transfer (FIT) reactions at high driving force across the water/1,2-dichloroethane (W/DCE) interface is investigated by scanning electrochemical microscopy (SECM). The transfers of lithium and sodium ions facilitated by dibenzo-18-crown-6 (DB18C6) across the polarized W/DCE interface are chosen as model systems because they have the largest potential range that can be controlled externally. By selecting the appropriate ratios of the reactant concentrations (Kr = cM+/cDB18C6) and using nanopipets as the SECM tips, we obtained a series of rate constants (kf) at various driving forces (   − Es,   is the formal potential of facilitated ion transfer and Es is the potential applied externally at the substrate interface) based on a three-electrode system. The FIT rate constants kf are found to be dependent upon the driving force. When the driving force is low, the dependence of ln kf on the driving force is linear with a transfer coefficient of about 0.3. It follows the classical Butler−Volmer theory and then reaches a maximum before it decreases again when we further increase the driving forces. This indicates that there exists an inverted region, and these behaviors have been explained by Marcus theory.
    Journal of Physical Chemistry B - J PHYS CHEM B. 02/2004; 108(10).
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    ABSTRACT: Investigation of a heterogeneous electron-transfer (ET) reaction at the water/1,2-dichloroethane interface employing a double-barrel micropipet technique is reported. The chosen system was the reaction between Fe(CN)63- in the aqueous phase (W) and ferrocene in 1,2-dichloroethane (DCE). According to the generation and the collection currents as well as collection efficiency, the ET-ion-transfer (IT) coupling process at such an interface and competing reactions with the organic supporting electrolyte in the organic phase can be studied. In addition, this technique has been found to be an efficient method to distinguish and measure the charge-transfer coupling reaction between two ions (IT-IT) processes occurring simultaneously at a liquid/liquid interface. On this basis, the formal Gibbs energies of transfer of some ions across the W/DCE interface, such as NO3-, NO2-, Cl-, COO-, TBA+, TPAs+, Cs+, Rb+, K+, Na+, and Li+, for which their direct transfers are usually difficult to obtain because of the IT-IT coupling processes, were quantitatively evaluated.
    Analytical Chemistry 01/2004; 75(23):6593-601. · 5.70 Impact Factor
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    ABSTRACT: Failitated ion transfer reactions of 20 amino acids with dibenzo-18-crown-6 (DB18C6) at the water/1,2-dichloroethane (W/DCE) interfaces supported at the tips of micro- and nano-pipets were investigated systematically using cyclic voltammetry. It was found that there were only 10 amino acids, that is, Leu, Val, lle, Phe, Trp, Met, Ala, Gly, Cys, Gln (in brief), whose protonated forms as cations can give well-defined facilitated ion transfer voltammograms within the potential window, and the reaction pathway was proven to be consistent with the transfer by interfacial complexation/dissociation (TIC/TID) mechanisms. The association constants of DB 18C6 with different amino acids in the DCE (β°), and the kinetic parameters of reaction were evaluated based on the steady-state voltammetry of micro- or nano-pipets, respectively. The experimental results demonstrated that the selectivity of complexation of protonated amino acid by DB18C6 compared with that of alkali metal cations was low, which can be attributed to the vicinal effect arising from steric hindrance introduced by their side group and the steric bulk effect by lipophilic stabilization. Moreover, the association constants and the standard rate constants for different amino acids showed good correlations with their hydrophobicity (π), except Gly and Met, which inferred that the selectivity of such heterogeneous complex reaction for different amino acids with DB18C6, was not only affected by discrimination in binding these ions to the crown ether macro-cycle, but also significantly modified by the ion transfer Gibbs energy which was closely related to the structure of the transferred ions, protonated amino acids.
    Science in China Series B Chemistry 12/2003; 47(1):24-33. · 1.20 Impact Factor
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    ABSTRACT: The electrochemical behavior of pyridine distribution at the water/1,2-dichloroethane interface with variable phase volume ratios (r = Vo/Vw) was investigated by cyclic voltammetry. The system was composed of an aqueous droplet supported on a Ag/AgCl disk electrode covered with an organic solution or an organic droplet supported on a Ag/AgTPBCl disk electrode covered with an aqueous solution. In this way, a conventional three-electrode potentiostat can be used to study an ionizable compound transfer process at a liquid/liquid interface with a wide range of phase volume ratios (from 0.0004 to 1 and from 1 to 2500). Using this special cell we designed, only very small volumes of both phase were needed for r equal to unity, which is very useful for the investigation of the distribution of ionizable species at a biphasic system when the available amount of species is limited. The ionic partition diagrams were obtained for different phase volume ratios.
    Analytical Chemistry 09/2003; 75(16):4341-5. · 5.70 Impact Factor
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    ABSTRACT: Scanning electrochemical microscopy was used to probe the influence of a driving force on the heterogeneous electron transfer (ET) processes at the externally polarized water/1,2-dichloroethane interface. Being a part of the driving force, the Galvani potential difference at the interface, Deltaowphi, can be quantitatively controlled in a wide range, allowing the precise measurements of the rate constants of the ET reactions. Two opposite systems were chosen in this work. One was 5,10,15,20-tetraphenyl 21H,23H-porphyrin zinc (ZnPor, O)/Fe(CN)64- (W), and the other was TCNQ (O)/Fe(CN)63- (W). For both systems studied, the relations between the rate constant and the Deltaowphi were of parabolic shape; that is, the rate constants increased initially with the Deltaowphi until reaching a maximum and then decreased steadily as the Deltaowphi increased further. This is in accordance with the prediction of the Marcus theory. To our knowledge, this is the first report that the Marcus inverted region can be observed electrochemically at an unmodified liquid/liquid interface with only one redox couple at each phase. The effect of the concentrations of the organic supporting electrolyte has also been discussed in detail.
    Journal of the American Chemical Society 09/2003; 125(32):9600-1. · 10.68 Impact Factor
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    ABSTRACT: The study of interfacial electron transfer (ET) reaction between ferricinium (Fc+) producedin situ in 1,2-dichloroethane (DCE) and ferrocyanide in ice matrix under low temperatures by the scanning electrochemical microscopy (SECM) is reported. Tetrabutylammonium (TBA+) is used as the common ion (potential-determining ion) in both phases to control the interfacial potential difference. The potential drop across the liquid/liquid interface can be quantitatively adjusted by changing the ratio of concentrations of TBA+ between the two phases. The apparent heterogeneous rate constants for Fc+ reduction by Fe(CN)64− at the interface under different temperatures have been obtained by a best-fit analysis, where the experimental approach curves are fitted to the theoretical simulated curves. A sharp change has been observed for heterogeneous rate constants around the freezing point of the aqueous phase, which reflects the phase transition process. Keywordsice/1,2-dichloroethane interface-electron transfer-scanning electrochemical microscopy
    Chinese Science Bulletin 01/2003; 48(1):39-43. · 1.37 Impact Factor
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    ABSTRACT: Scanning electrochemical microscopy (SECM) is employed to investigate the effect of solution viscosity on the rate constants of electron transfer (ET) reaction between potassium ferricyanide in water and 7,7,8,8-tetracyanoquinodimethane (TCNQ) in 1,2-dichloroethane. Either tetrabutylammonium (TBA+) or ClO4− is chosen as the common ion in both phases to control the interfacial potential drop. The rate constant of heterogeneous ET reaction between TCNQ and ferrocyanide produced in-situ, k12, is evaluated by SECM and is inversely proportional to the viscosity of the aqueous solution and directly proportional to the diffusion coefficient of K4Fe(CN)6 in water when the concentration of TCNQ in the DCE phase is in excess. The k12 dependence on viscosity is explained in terms of the longitudinal relaxation time of the solution. The rate constant of the heterogeneous ET reaction between TCNQ− and ferricyanide, k21, is also obtained by SECM and these results cannot be explained by the same manner.
    Electrochimica Acta 01/2003; 48(23):3447-3453. · 4.09 Impact Factor
  • Analytical Chemistry - ANAL CHEM. 01/2003; 75(16):4341-4345.
  • Angewandte Chemie International Edition 10/2002; 41(18):3445-8. · 11.34 Impact Factor
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    ABSTRACT: A droplet of aqueous solution containing a certain molar ratio of redox couple is first attached onto a platinum electrode surface, then the resulting drop electrode is immersed into the organic solution containing very hydrophobic electrolyte. Combined with reference and counter electrodes, a classical three-electrode system has been constructed. Ion transfer (IT) and electron transfer (ET) are investigated systematically using three-electrode voltammetry. Potassium ion transfer and electron transfer between potassium ferricyanide in the aqueous phase and ferrocene in nitrobenzene are observed with potassium ferricyanide/potassium ferrocyanide as the redox couple. Meanwhile, the transfer reactions of lithium, sodium, potassium, proton and ammonium ions are obtained with ferric sulfate/ferrous sulfate as the redox couple. The formal transfer potentials and the standard Gibbs transfer energy of these ions are evaluated and consistent with the results obtained by a four-electrode system and other methods.
    Science in China Series B Chemistry 01/2002; 45(5):494-502. · 1.20 Impact Factor
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    ABSTRACT: A study of potassium ion transfer across a water∣1,2-dichloroethane (W∣DCE) interface facilitated by dibenzo-18-crown-6 (DB18C6) with various phase volume ratio systems is presented. The key point was that a droplet of aqueous solution containing a redox couple, Fe(CN)63−/Fe(CN)64−, with equal molar ratio, was first attached to a platinum electrode surface, and the resulting droplet electrode was then immersed into the organic solution containing a hydrophobic electrolyte to construct a platinum electrode/aqueous phase/organic phase system. The interfacial potential of the W∣DCE within the series could be externally controlled because the specific compositions in the aqueous droplet make the Pt electrode function like a reference electrode as long as the concentration ratio of Fe(CN)63−/Fe(CN)64− remains constant. In this way, a conventional three-electrode potentiostat can be used to study the ion transfer process at a liquid∣liquid (L∣L) interface facilitated by an ionophore with variable phase volume ratio (r=Vo/Vw). The effect of r on ion transfer and facilitated ion transfer was studied in detail experimentally. We also demonstrated that as low as 5×10−8 M DB18C6 could be determined using this method due to the effect of the high phase volume ratio.
    Journal of Electroanalytical Chemistry 01/2002; 526(1):85-91. · 2.58 Impact Factor
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    ABSTRACT: The electrochemical behavior of ionizable drugs (Amitriptyline, Diphenhydramine and Trihexyphenedyl) at the water/1,2-dichloroethane interface with the phase volume ratio (r = V o/Vw) equal to 1 are investigated by cyclic voltammetry. The system is composed of an aqueous droplet supported at an Ag/AgCl disk electrode and it was covered with an organic solution. In this manner, a conventional three-electrode potentiostat can be used to study the ionizable drugs transfer process at a liquid/liquid interface. Physicochemical parameters such as the formal transfer potential, the Gibbs energy of transfer and the standard partition coefficients of the ionized forms of these drugs can be evaluated from cyclic voltammograms obtained. The obtained results have been summarized in ionic partition diagrams, which are a useful tool for predicting and interpreting the transfer mechanisms of ionizable drugs at the liquid/liquid interfaces and biological membranes. Keywordswater/1,2-dichloroethane interface-ionizable drug transfer-three-electrode system-phase volume ratio-ionic partition diagram
    Chinese Science Bulletin 48(12):1234-1239. · 1.37 Impact Factor