共查询到20条相似文献,搜索用时 15 毫秒
1.
Voltammetric determination of facilitated ion transfer across the water/1,2-dichloroethane interface
The facilitated transfer characteristics of Cd2+ ion by 4-morpholinoacetophenone-4-ethyl-3-thiosemicarbazone (MAPET) across water/1,2-dicholoroethane (1,2-DCE) interface and its electrochemical properties were investigated by voltammetric measurements. Cyclic voltammetry (CV) was employed to examine the transfer in the conditions of the ligand (organic phase) in excess and the obtained transfer peaks have reversible nature at different metal concentrations and scan rates. The dependence of the obtained half-wave transfer potential on MAPET concentration showed that the equilibrium is effectively displaced towards a 1: 3 (Cd2+: ligand) stoichiometry with an association constant of logβ 3 0 = 12.96 ± 0.09 for the Cd2+ ion, corresponding to the TIC/TID mechanism. 相似文献
2.
Gulaboski R Pereira CM Cordeiro MN Bogeski I Ferreira E Ribeiro D Chirea M Silva AF 《The journal of physical chemistry. B》2005,109(25):12549-12559
The ion transfer of acetylcholine (AcH(+)) ions across the unmodified and phospholipid-modified water|1,2-dichloroethane (DCE) interface has been studied by means of square-wave and cyclic voltammetry, as well as by electrochemical impedance spectroscopy. After being transferred in the organic phase, the AcH(+) ions undergo chemical reactions with the phospholipids. The overall behavior of the experimental system studied in the presence of phospholipids has been compared with the theoretical results of an ECrev reaction. The kinetic parameters of the chemical interactions between AcH(+) and the phospholipids have been determined from the voltammetric and impedance measurements. Additional characterization of those interactions has been made by using the surface tension measurements. 相似文献
3.
Electrochemical study of a dendritic family at the water/1,2-dichloroethane interface 总被引:1,自引:0,他引:1
Calderon M Monzón LM Martinelli M Juarez AV Strumia MC Yudi LM 《Langmuir : the ACS journal of surfaces and colloids》2008,24(12):6343-6350
The transfer of six dendritric molecules, DMs, across the water/1,2-dichloroethane interface was investigated using cyclic voltammetry. From the variation of peak potential with pH, two different mechanisms of transfer were postulated depending on the nature of the molecules. Voltammetric parameters were employed to evaluate the hydrophilic/hydrophobic character and calculate the acid dissociation constant of these molecules. The results were explained taking into account the nature and multiplicity of functional surface groups. 相似文献
4.
The results of electrochemical studies on the reaction of tetrabutyl- and tetramethylammonium (TBA+ and TMA+) ion transfer from water to 1,2-dichloroethane are presented in this paper and are compared with se of the water—nitrobenzene interface. The TMA+ ion transfer has been studied by the chronopotentiometric cyclic voltammetry methods and that of the TBA+ ion by the chronopotentiometric method only.It has been found that the reactions are diffusion controlled over the current density range up to about 1O μA cm?2 and at polarization rates up to 0.15V s?1. Diffusion coefficients of the studied ions have been detemined, as well as their formal potentials with respect to an ion-selective tetrabutylammonium electrode to a partition electrode containing tetraethylammonium picrate whose potential is close to zero. In additon, kinetic parameters of the transfer reaction have been determined for the tetrabutylammonium ion from data obtained at current densities over 10 μA cm?2 (irreversible range). 相似文献
5.
CHEN Yong YUAN Yi ZHANG Meiqin LI Fei SUN Peng GAO Zhao & SHAO YuanhuaState Key Laboratory of Electroanalytical Chemistry Changchun Institute of Applied Chemistry Chinese Academy of Sciences Changchun China College of Chemistry Molecular Engineering Peking University Beijing China 《中国科学B辑(英文版)》2004,47(1)
Facilitated 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, lie, Phe, Trp, Met, Ala, Gly, Cys, Gin (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 (β0), 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 attribu 相似文献
6.
The kinetics of facilitated proton transfer by polyether 18-crown-6 across the water-1,2-dichloroethane interface has been investigated by cyclic voltammetry and ac impedance. It was found that rate apparent constant is quite similar for the several concentrations of 18-crown-6 used in the experiments, the rate constant values (k
s
) were in the range: 0.028, 0.031, 0.027, and 0. 03 cm/s for 0.1, 0.15, 0.2, and 0.25 mM of 18-crown-6.A formal transfer potential of 0
wi
0= 0.01 V was found for the facilitated proton transfer by 18-crown-6 at the water-1,2-dichloroethane interface; this value remained constant in the range of concentration considered in this work. According to the kinetic results, an interfacial reaction between the proton and the polyether 18-crown-6 is discussed in which the polyether does not transfer into the aqueous phase, in the time scale of the experiments. As a consequence, it can be concluded that the solvation and desolvation of ligand and proton play an important role in the rate-determining step.From Elektrokhimiya, Vol. 41, No. 2, 2005, pp. 206–212.Original English Text Copyright © 2005 by Velázquez-Manzanares, Amador-Hernández.This article was submitted by the authors in English.Part of this work was presented at XXV Congreso Latinoamericano de Qu#X00ED;mica in Cancun, Quintana Roo, Mexico, 2002.This revised version was published online in April 2005 with corrections to the article note and article title and cover date. 相似文献
7.
Hirohisa Nagatani Satoshi Dejima Hiroki Hotta Toru Ozeki Toshiyuki Osakai 《Analytical sciences》2004,20(11):1575-1579
The photocurrent at the polarized water/1,2-dichloroethane (DCE) interface was successfully observed in the presence of a lipophilic sensitizer, 5,10,15,20-tetraphenylporphyrinato zinc (ZnTPP), in the organic phase. The photocurrent transient responses were apparently affected by the employed organic supporting electrolyte: tetrapenthylammonium tetraphenylborate (TPnATPB) or tris(tetraoctylammonium)tungstophosphate ((TOcA)3PW12O40). The photocurrent measured in the TPnATPB system exhibited rather slow responses associated with the ion transfer of photoproducts. On the other hand, the photoinduced heterogeneous electron transfer could be observed in the use of (TOcA)3PW12O40. The photocurrent intensity in the (TOcA)3PW12O40 system exhibited an apparent pH dependence and the photoreduction of hydrogen ions probably took place at the water/DCE interface. By analyzing the real and imaginary components of the photocurrent depending on the photoexcitation frequency, we roughly estimated the phenomenological rate constants of the product separation (k(ps)) and recombination (k(rec)) processes as log(k(ps)/s(-1)) = 1.5 +/- 0.2 and log(k(rec)/s(-1)) = 1.8 +/- 0.1, respectively. 相似文献
8.
9.
Facilitated ammonium ion transfer reactions, using the crown ether dibenzo-18-crown-6, at a single microhole supported water/1,2-dichloroethane interface were used as the transducer to detect the biomolecule creatinine. The ammonium ion was produced during the enzymatic action of creatinine deiminase on creatinine. A prototype sensing device incorporating a Teflon gas permeable membrane, to exclude possible interferents, yielded a linear amperometric response to added creatinine from 20 M to 1 mM. This range is sufficient for that required for the determination of creatinine in serum. 相似文献
10.
11.
Hélder A. Santos Elisabete S. Ferreira Elisa J. Pereira Carlos M. Pereira Prof. Kyösti Kontturi Prof. Fernando Silva Prof. 《Chemphyschem》2007,8(10):1540-1547
The interaction between glucose oxidase (GOx) and phospholipid monolayers is studied at the 1,2-dichloroethane/water interface by electrochemical impedance spectroscopy. Electrochemical experiments show that the presence of GOx induces changes in the capacitance curves at both negative and positive potentials, which are successfully explained by a theoretical model based on the solution of the Poisson-Boltzmann equation. These changes are ascribed to a reduced partition coefficient of GOx and an increase of the permittivity of the lipid hydrocarbon domain. Our results show that the presence of lipid molecules enhances the adsorption of GOx molecules at the liquid/liquid interface. At low lipid concentrations, the adsorption of GOx is probably the first step preceding its penetration into the lipid monolayer. The experimental results indicate that GOx penetrates better and forms more stable monolayers for lipids with longer hydrophobic tails. At high GOx concentrations, the formation of multilayers is observed. The phenomenon described here is strongly dependent on 1) the GOx and lipid concentrations, 2) the nature of the lipid, and 3) the potential drop across the interface. 相似文献
12.
Osakai T Yoshimura T Kaneko D Nagatani H Son SH Yamagishi Y Yamada K 《Analytical and bioanalytical chemistry》2012,404(3):785-792
The previously introduced technique of potential-modulated fluorescence (PMF) spectroscopy was used to study the potential-induced fluorescence change of some different dyes at the polarized 1,2-dichloroethane (DCE)/water (W) interface. A zwitterionic dye (POLARIC 488PPS) showed a PMF response similar to that for the previously studied dye (di-4-ANEPPS) with the same ionic state, and the PMF response was likewise explained by the potential-dependent reorientation of the dye at the DCE/W interface. Though a monocationic dye (POLARIC 488PM) showed no distinct PMF signal, a dicationic dye (di-2-ANEPEQ) showed two relatively weak but detectable PMF signals at lower and higher potential. It has thus been found that the ionic state of a potential-sensitive dye strongly influences the potential-induced reorientation of the dye at the interface and consequently its PMF response. These results support the reorientation/solvatochromic mechanism proposed for "slow" dyes but do not necessarily exclude the electrochromic mechanism proposed for "fast" dyes. PMF spectroscopy would provide useful information on the design of slow dyes for the measurement of the resting potential of cell membranes. 相似文献
13.
Chronopotentiometric studies of the tetrabutylammonium ion transfer from water to 1,2-dichloroethane
Electrochemically reduced graphite in contact with tetralkylammonium ions/DMF may react with electrophiles either as a nucleophile or as a reducing reagent. The reaction at the interface or at the immediately accessible active centres of the crystal causes some modification of the structure, which is studied here. This method allows the formation of polybutylated or poly-carboxylated graphite and may lead to other modified crystals of great interest for building modified electrodes. 相似文献
14.
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. 相似文献
15.
Cui R Li Q Gross DE Meng X Li B Marquez M Yang R Sessler JL Shao Y 《Journal of the American Chemical Society》2008,130(44):14364-14365
The facilitated transfer of four hydrophilic anions, i.e., Cl-, Br-, NO2-, and CH3CO2-, at the micro-water/1,2-dichloroethane interface supported at the tip of a micropipet has been observed successfully using beta-octafluoro-meso-octamethylcalix[4]pyrrole 2 as the receptor. We have also shown for the first time that the dynamics of this process can be studied by micropipet voltammetry. The standard kinetic rate constants (kdegrees) for facilitated anion transfer at such an interface were determined to be (2.11 +/- 0.90) x 10(-2) and (0.75 +/- 0.50) x 10(-2) cm/s in the case of Cl- and CH3CO2-, respectively. These values are much smaller than those associated with the facilitated transfer of analogous alkali metal ions. This difference is thought to reflect a number of underlying factors, including the higher hydration of anions as compared to similar sized cations. Studies such as these are expected to be useful in understanding the mechanism of anion transport at soft interfaces and for the design of yet-improved anion receptors and carriers. 相似文献
16.
Nagatani H Suzuki S Fermín DJ Girault HH Nakatani K 《Analytical and bioanalytical chemistry》2006,386(3):633-638
The transfer mechanism of an amphoteric rhodamine, sulforhodamine 101 (SR101), across the polarized water/1,2-dichloroethane
(DCE) interface was investigated using cyclic voltammetry, differential voltfluorometry and potential-modulated fluorescence
(PMF) spectroscopy. The voltammetric response for the ion transfer of SR101 monoanion from water to DCE was observed as the
diffusion-controlled transfer process. An unusual voltammetric response was found at 0.15 V more negative than the formal
transfer potential of SR101−
in the cyclic voltammogram and voltfluorogram. The frequency dependence of the PMF responses confirmed the presence of the
adsorption processes at negative potentials. In addition, a further transient adsorption step was uncovered at The interfacial mechanism of SR101 is discussed by comparing the results obtained from each technique. 相似文献
17.
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. 相似文献
18.
Nagatani H Sakamoto T Torikai T Sagara T 《Langmuir : the ACS journal of surfaces and colloids》2010,26(22):17686-17694
Molecular encapsulation of water-soluble anionic fluorescent dye molecules, 8-anilino-1-naphthalenesulfonic acid (ANS), and its bimolecular derivative (bis-ANS), in the generation 3.5 polyamidoamine (G3.5 PAMAM) dendrimer was investigated in the bulk aqueous phase and at the polarized water|1,2-dichloroethane interface. ANS(-) was electrostatically incorporated in the dendrimer, and the fluorescence enhancement with a blue shift of the emission maximum was observed at pH values <6, where the interior of the dendrimer was positively charged. The fluorescence enhancement of ANS was maximized around pH 3 and then decreased under more acidic conditions. The potential dependences of the molecular encapsulation and the interfacial mechanism were studied in detail by means of potential modulated fluorescence (PMF) spectroscopy. Under acidic conditions, the dendrimer incorporated ANS(-) at the positively polarized interface as well as in the aqueous phase. ANS(-) was released from the dendrimer at the intrinsic transfer potential and independently transferred across the interface. Bis-ANS exhibited relatively strong interaction with the dendrimer over a wide pH range (1 < pH < 8), and a negative shift of the transfer potential was observed under the corresponding pH condition. The PMF analysis clearly demonstrated that the interfacial mechanism of the dendrimer involves transfer and adsorption processes depending on the pH condition and the Galvani potential difference. 相似文献
19.
Toshiyuki Osakai Junpei Sawada Hirohisa Nagatani 《Analytical and bioanalytical chemistry》2009,395(4):1055-1061
The spectrofluorometric behavior of a membrane potential-sensitive dye, 1-(3-sulfonatopropyl)-4-[β-{2-(di-N-butylamino)-6-naphthyl}vinyl]pyridinium betaine (di-4-ANEPPS), at the polarized 1,2-dichloroethane/water interface was studied
by means of potential-modulated fluorescence (PMF) spectroscopy. The results, combined with those from cyclic and alternating
current voltammetry, clearly suggested that the dye adsorbed at the interface underwent a reorientation with increasing the
interfacial potential, giving a well-developed PMF response as well as a voltammetric response. In addition to the PMF response,
another PMF response was observed by addition of dilauroyl phosphatidylcholine (DLPC). This additional response was well explained
in terms of a reorientation of di-4-ANEPPS at the interface, which would be induced by the potential-dependent desorption
of DLPC from the interface. Thus, the present study supported the reorientation/solvatochromic mechanism for the membrane
potential-sensitive dye rather than the electrochromic mechanism. 相似文献
20.
Gründer Y Ho HL Mosselmans JF Schroeder SL Dryfe RA 《Physical chemistry chemical physics : PCCP》2011,13(34):15681-15689
The deposition of gold at the interface between immiscible electrolyte solutions has been investigated using reduction of tetrachloroaurate or tetrabromoaurate in 1,2-dichloroethane, with aqueous phase hexacyanoferrate as reducing agent. In a clean environment without defects present at the interface, the Au(III) complex was reduced to the Au(I) complex, but no solid phase formation could be observed. A deposition process could only be observed through the addition of artificial nucleation sites in the form of palladium nanoparticles at the interface. This process could be associated with the reduction of the Au(I) halide complex to metallic gold, by determining the gold reduction potentials in 1,2-dichloroethane. XANES measurements indicate that tetrachloroaurate ion transfers intact into the organic phase, with the central Au atom retaining its oxidation state of +3 and the overall anion remaining charged at -1. 相似文献