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1.
The transport of Pb2+ through a sensory gel, a polymerized crystalline colloidal array hydrogel with immobilized benzo-18-crown-6, is important for understanding and optimizing the sensor. Square wave voltammetry at a Hg/Au electrode reveals many parameters. The partition coefficient for Pb2+ into a control gel (no crown ether), K(p), is 1.00 +/- 0.018 (errors reported are SEM). The porosity, epsilon, of the gel is 0.90 +/- 0.01. Log K(c) for complexation in the gel is 2.75 +/- 0.014. Log K(c) in aqueous solution for Pb2+ with the ligand 4-acryloylamidobenzo-18-crown-6 is 3.01 +/- 0.010 with dissociation rate k(d) = (8.34 +/- 0.45) x 10(2) s(-1) and association rate k(f) = (8.79 +/- 0.025) x 10(7) M(-1) s(-1). The partition coefficient of the ligand 4-acryloylamidobenzo-18-crown-6 into the control gel, K(p,L) is 2.07 +/- 0.15. The diffusion coefficient of Pb2+ in the control gel is 6.72 x 10(-6) +/- 0.12 cm(2)/s. For the sensor gel, but not control gel, diffusion coefficients are location dependent. The range of diffusion coefficients for Pb2+ in the probed locations was found to be (6.11-12.60) x 10(-7) cm(2)/s for 0.91 mM Pb2+ and (2.84-9.39) x 10(-7) cm(2)/s for 0.35 mM Pb2+. Lead binding in the sensor gel is slightly less avid than in solution. This is attributed, in part, to the demonstrated affinity of the ligand 4-acryloylamidobenzo-18-crown-6 to the gel. Diffusion coefficients determined for the sensor gel were found to be location dependent. This is attributed to heterogeneities in the crown concentration in the gel. Analysis of diffusion coefficients and rate constants show that diffusion and not chemical relaxation will limit the time response of the material. 相似文献
2.
A synthesized bis(dibenzoylmethanato)Co(II) complex (Co(DBM)(2)), has been used as a ionophore for the preparation of a new perchlorate ion-selective electrode. The electrode exhibits a Nernstian response over the perchlorate concentration range of 8.0x10(-7)-1.0x10(-1)M with a slope of 60.3+/-0.5 mV per decade of concentration. The limit of detection as determined from the intersection of the extrapolated linear segments of the calibration plot is 5.6x10(-7)M. The electrode shows good selectivity towards perchlorate with respect to many common anions. The response time of the sensor is very fast (< or = 5s), and can be used for at least 2 months in the pH range of 2.0-9.0. The electrode was used to determine perchlorate in water and human urine. The interaction of the ionophore with perchlorate ions was demonstrated by UV-vis spectroscopy. 相似文献
3.
An electrode modified with immobilized whole cells of Desulfovibrio vulgaris (Hildenborough) produces an S-shaped voltammogram with both cathodic- and anodic-catalytic-limiting currents in a methyl viologen-containing buffer saturated with H2. Methyl viologen penetrates into the bacterial cells to serve as an electron carrier in the reversible reaction of hydrogenase in the cells and functions as an electron-transfer mediator between the bacterial cells and the electrode, thus producing the catalytic currents for the evolution and consumption of H2. An equation for the catalytic current that takes into account the reversible hydrogenase reaction explains well the shape of the voltammogram. The potential at null current on the voltammogram agrees with the potential determined by potentiometry with the same electrode, which is equal to the redox potential of the H+/H2 couple in the solution--the standard potential of a hydrogen electrode at the pH of the solution. When D. vulgaris cells are suspended in an argon-saturated buffer containing methyl viologen, the suspension produces a catalytic current at a bare glassy carbon electrode for the evolution of H2. Analysis of the current by a theory for a catalytic current for a unidirectional nonlinear enzyme catalysis allows us to determine the kinetic parameters of the reaction between methyl viologen and hydrogenase in intact D. vulgaris cells. Thus we obtain the apparent Michaelis constant for methyl viologen cation radical, K'MV.+ = 0.16 mM, and the apparent catalytic constant (that is, the turnover number per D. vulgaris cell), zkcat,H+ = 1.2 x 10(7) s-1, for the H2 evolution reaction at pH 5.5 and at 25 degrees C, z being the number of hydrogenases contained in a D. vulgaris cell. The bimolecular reaction rate constant, kcat,H+/K'MV.+, of the reaction between methyl viologen cation radical and oxidized hydrogenase in intact D. vulgaris cells is estimated as 4.2 x 10(7) M-1 s-1. Similarly, the bimolecular reaction rate constant, kcat,H2/K'MV2+, of the reaction between methyl viologen and reduced hydrogenase is estimated to be 1.2 x 10(7) M-1 s-1 at pH 9.5 and 25 degrees C. Both rate constants are large enough for the reactions to be diffusion-limited processes. 相似文献
4.
Determination of kinetic and thermodynamic protein binding constants using interferometry from a porous Si Fabry-Perot layer is presented. A protein A capture probe is adsorbed within the pores of an oxidized porous Si matrix, and binding of immunoglobulin G (IgG) antibodies derived from different species is investigated. The relative protein A/IgG binding affinity is human > rabbit > goat, in agreement with literature values. The equilibrium binding constant (Ka) for human IgG binding to surface-immobilized protein A is determined to be (3.0 +/- 0.5) x 107 M-1 using an equilibrium Langmuir model. Kinetic rate constants are calculated to be kd = (2.1 +/- 0.2) x 10-4 s-1 and ka = (1.2 +/- 0.4) x 104 M-1 s-1 using nonlinear least-squares analysis, yielding an equilibrium binding constant of Ka = (5.5 +/- 1.5) x 107 M-1. Both steady-state and time-dependent measurements yield equilibrium binding constants that are consistent with literature values. Kinetic rate constants determined through nonlinear least-squares analysis are also in agreement with protein A/IgG binding on a surface. Dosing with a high concentration of analyte leads to deviations from ideal binding behavior, interpreted in terms of restricted analyte diffusion within the porous SiO2 matrix. It is shown that the diffusion limitations can be minimized if the kinetic measurements are performed at low analyte concentrations or under conditions in which the protein A capture probe is not saturated with analyte. Potential limitations of the use of porous SiO2 interferometers for quantitative determination of protein binding constants are discussed. 相似文献
5.
Perchlorate and nitrate were reduced simultaneously in fixed biofilm reactors. Reduction of 1000 microg L(-1) perchlorate decreased slightly with the addition of 10-16 mg L(-1) NO(3)-N when excess acetate was supplied while denitrification was complete. When influent acetate was reduced by 50% to well below the stoichiometric requirement, perchlorate reduction decreased by 70% while denitrification decreased by only 20%, suggesting that competition for electrons by nitrate was a factor in inhibition. Reduction of nitrate was favored over perchlorate, even though reactor biofilm had been enriched under perchlorate-reducing conditions for 10 months. When excess acetate was restored, perchlorate and nitrate returned to initial levels. The average most probable numbers of perchlorate- and nitrate-reducing bacteria during excess substrate operation were not significantly different and ranged between 2.0 x 10(5) and 7.9 x 10(5)cells cm(-2) media surface area. The effect of nitrate on chloride generation by suspensions of perchlorate-reducing populations was studied using a chloride ion probe. The rate of reduction of 2mM perchlorate decreased by 30% in the presence of 2mM nitrate when excess acetate was added. When acetate was limited, perchlorate reduction decreased by 70% in the presence of equi-molar nitrate. 相似文献
6.
In this work, an antimony film electrode (SbFE) is reported for the first time as a possible alternative for electrochemical stripping analysis of trace heavy metals. The SbFE was prepared in situ on a glassy carbon substrate electrode and employed in combination with either anodic stripping voltammetry or stripping chronopotentiometry in nondeaerated solutions of 0.01 M hydrochloric acid (pH 2). Several key operational parameters influencing the electroanalytical response of SbFE were examined and optimized, such as deposition potential, deposition time, and composition of the measurement solution. The SbFE exhibited well-defined and separated stripping signals for both model metal ions, Cd(II) and Pb(II), surrounded with low background contribution and a relatively large negative potential range. The electrode revealed good linear behavior in the examined concentration range from 20 to 140 microg L-1 for both test metal ions, with a limit of detection (3sigma) of 0.7 microg L-1 for Cd(II) and 0.9 microg L-1 for Pb(II) obtained after a 120 s deposition step, and good reproducibility, with a relative standard deviation (RSD) of +/-3.6% for Cd(II) and +/-6.2% for Pb(II) (60 microg L-1, n = 12). When comparing the SbFE with the commonly used mercury film electrode and recently introduced bismuth film electrode, the newly proposed electrode offers a remarkable performance in more acidic solutions (pH < or = 2), which can be advantageous in electrochemical analysis of trace heavy metals, hence contributing to the wider applicability of electrochemical stripping techniques in connection with "mercury-free" electrodes. 相似文献
7.
In this work, the organic compound 2-mercaptobenzimidazole was covalently bound on the surface of a glassy carbon rod, via silanization, yielding a material capable of selectively complexing Hg(2+) ions. This material was applied as an electrode for voltammetric determination of mercury(II) following its nonelectrolytic preconcentration. After exchanging the medium, the voltammetric measurements were carried out by anodic stripping in the differential pulse mode (pulse amplitude, 50 mV; scan rate, 1.25 mV s(-)(1)) using 10(-)(2) mol L(-)(1) NaSCN solution as supporting electrolyte. An anodic stripping peak was obtained at 0.06 V (vs SCE) by scanning the potential from -0.3 to +0.3 V. After a 5 min preconcentration period in a pH 4.0 Hg(2+) solution, this electrode shows increasing voltammetric response in the range 0.1-2.2 μg mL(-)(1), with a relative standard deviation of 5% and a practical detection limit of 0.1 μg mL(-)(1) (5.0 × 10(-)(7) mol dm(-)(3)). Compared with the conventional stripping approach, this chemically modified glassy carbon electrode procedure presented good discrimination against interference from Cu(II) in up to 10-fold molar excess. 相似文献
8.
Expanded space grid digital simulation of second-order, two-electron homogeneous electrocatalysis was extended to slow scan voltammetry at hemispherical microelectrodes. Predictions of the simulations are examined for reversible and quasireversible heterogeneous charge transfer of catalyst for a range of homogeneous catalytic rate constants (k1) and electrode radii. Working curves of catalytic efficiency vs long k1 were generated assuming reacting species with equal diffusion coefficients. As electrode radii in the less than 10-microns range decrease, progressively larger homogeneous catalytic rates are needed to yield analytically significant amplification of limiting currents. Simulations using hemispherical radii of (2/pi)rd can be used to predict catalytic efficiencies for microdisk electrodes with radii rd. Simulated working curves were used to estimate a log k1 of 3.88 +/- 0.55 (M-1 s-1) for electron transfer from the anion radical of 9,10-diphenylanthracene to 4,4'-dibromobiphenyl from steady-state catalytic efficiencies obtained at carbon microdisk electrodes. This value was in good agreement with 3.90 +/- 0.16 M-1 s-1 found previously by cyclic voltammetry. 相似文献
9.
Single-run capillary electrophoretic determination of inorganic nitrogen species in rainwater 总被引:2,自引:0,他引:2
A capillary electrophoretic (CE) method for the simultaneous determination of nitrate, nitrite, and ammonium ions has been developed. Direct (NO3-, NO2-) and indirect (NH4+) UV detection at 214 nm in conjunction with electromigration sampling from both ends of the capillary was used. The optimized separations were carried out in 10 mmol/L imidazole sulfate, 2 mmol/L 18-crown-6, and 0.02 mmol/L tetradecyltrimethylammonium hydroxide electrolyte (pH 4.0). The method permits excellent separation of three nitrogen species in only 4 min. A 1 x 10(-4) mol/L KBr solution was used as an internal standard to limit possible electrokinetic injection biases. Experimental results showed that the use of an anionic internal standard for cationic analytes and vice versa gives only slightly better precision than analysis with no internal standard. Using Br- internal standard for NO3- and NO2- ions and K+ for NH4+, peak area RSD values decrease significantly. The proposed system was applied to the speciation of inorganic nitrogen ions in rainwater samples. The recovery tests established for external calibration and standard addition techniques using one or two internal standards were within the range 100 +/- 10%. The CE results agree with those obtained by spectrophotometric methods. 相似文献
10.
A new kind of solid substrate, a glassy carbon (GC) electrode, was selected to support lipid layer membranes. On the surface of the GC electrode, we made layers of didodecyldimethylammonium bromide (a synthetic lipid). From electrochemical impedance experiments, we demonstrated that the lipid layers on the GC electrode were bilayer lipid membranes. We studied the ion channel behavior of the supported bilayer lipid membrane. In the presence of perchlorate anions as the stimulus and ruthenium(II) complex cations as the marker ions, the lipid membrane channel was open and exhibited distinct channel current. The channel was in a closed state in the absence of perchlorate anions. 相似文献
11.
Kavallieratos K Danby A Van Berkel GJ Kelly MA Sachleben RA Moyer BA Bowman-James K 《Analytical chemistry》2000,72(21):5258-5264
A systematic study of a dual-host system exhibiting pairwise anion/cation separations has been performed for CsNO3 extraction. Tripodal triamides 1-4 and 9 derived from condensation of hexanoic (for 1), octanoic (for 2), decanoic (for 3), lauric (for 4), and p-tert-butylbenzoic (for 9) acid with tris(2-aminoethyl)amine (tren) were used together with tetrabenzo-24-crown-8, a well-known Cs+ cation receptor. By using 5 mM crown ether in the organic phase and 10 mM CsNO3 with 0.1 mM HNO3 in the aqueous phase, tripods 1, 2, and 9 enhance CsNO3 extraction by factors of 2.4, 1.7, and 4.4, respectively (for 50 mM amide concentration), while the corresponding monoamide controls 5-8 derived from n-propylamine (5, 6) or N,N'-dimethylethylenediamine (7, 8) and hexanoic (5, 7) or octanoic (6, 8) acid derivatives gave no significant enhancement under the same conditions. This behavior may be ascribed to nitrate complexation by the triamides, which lowers the overall thermodynamic barrier for the salt transfer to the organic phase. The nitrate binding was confirmed by 1H NMR titration of receptor solutions, using tetrabutylammonium nitrate. Association constants for the formation of the anion-nitrate complexes were found to vary between 33 and 52 M-1 for the more soluble triamides. The synergistic effects for CsNO3 extraction are in reasonable agreement with the values predicted theoretically from the measured association constants. Electrospray ionization mass spectrometry confirmed the predominant formation of 1:1 tripod-nitrate complexes. Monoamide controls gave no evidence of anion complexation. 相似文献
12.
Sorption of traces of Cd(II) ions onto beach sand is investigated as a function of nature and concentration of electrolyte (10(-4) to 10(-2)M nitric, hydrochloric and perchloric acids, pH 2-10 buffers and deionized water), shaking time 5-40min, shaking speed 50-200strokes/min, dosage of sand (50-1000mg/15cm(3)), concentration of sorbate (1.04x10(-6) to 1.9x10(-4)M) and temperature (293-323K). Maximum sorption of Cd(II) ions (approximately 66%) is achieved from deionized water using 300mg/15cm(3) sand in 20min. The data are successfully tested by Langmuir, Freundlich and Dubinin-Redushkevich (D-R) sorption isotherms. The values for characteristic Langmuir constants Q=13.31+/-0.20micromol/g and of b=(6.56+/-0.53)x10(3)dm(3)/mol, Freundlich constants A=2.23+/-1.16mmol/g and 1/n=0.70+/-0.05 of (D-R) constants beta=-0.005068+/-0.000328kJ(2)/mol(2), X(m)=46.91+/-11.91micromol/g and energy E=9.92+/-0.32kJ/mol have been estimated. Kinetics of sorption has been studied by applying Morris-Weber, Richenberg and Lagergren equations. The sorption follows first order rate equation resulting 0.182+/-0.004min(-1) The thermodynamic parameters DeltaH=32.09+/-2.92kJ/mol, DeltaS=111.0+/-9.5J/molK and DeltaG=-1.68+/-0.02kJ/mol are evaluated. The influence of common ions on the sorption of Cd(II) ions is also examined. Some common ions reduce the sorption while most of the ions have very little effect. It can be concluded that beach sand may be used as an alternative for the expensive synthetic sorbents. 相似文献
13.
Loetanantawong B Suracheep C Somasundrum M Surareungchai W 《Analytical chemistry》2004,76(8):2266-2272
Mixed-valent films of ruthenium oxide-ruthenium cyanide were electrodeposited onto glassy carbon and characterized for the electrocatalytic oxidation of tetracycline. The currents produced by tetracycline were higher than from previously reported electrode modifications or pretreatments. In H(2)SO(4) pH 1.0 + 0.5 M K(2)SO(4), the second-order rate constant for the reaction between tetracycline and the Ru(III/IV) couple of ruthenium oxide was 3 x 10(5) +/- 1 x 10(5) mol(-1) cm(3) s(-1), and the rate of charge diffusion through the films was 4.5 x 10(-7) +/- 3.5 x 10(-7) cm(2) s(-1). Reaction was localized at the film-solution interface. When used as detectors in liquid chromatography (in H(3)PO(4) pH 2.5 + 0.1 M KH(2)PO(4) + 20% CH(3)CN, E = 1.10 V vs SCE), the electrodes gave limits of detection (>3 S/N) of 0.1 ppm for tetracycline and oxytetracycline and 0.5 ppm for doxycycline and chlorotetracycline. These limits were suitable for FDA and Codex Alimentarius guidelines for tetracyclines in food. Recoveries of the four tetracyclines from sea and freshwater shrimp were in the range 73-111%, which was higher or similar to the previously reported recoveries from shrimp. 相似文献
14.
Kinetics of nitrate reduction by zero-valent iron at elevated temperatures was studied through batch and column experiments. It was hypothesized that under increased solution temperatures, the zero-valent iron may accelerate the reduction of nitrate by overcoming the activation energy barrier to nitrate reduction. The results of the batch experiment showed the synergistic effects of elevated temperature (75 degrees C) and a buffered condition (pH 7.4 with 0.1 M HEPES) to enhance the rate of nitrate reduction by zero-valent iron from 0.072+/-0.006 h(-1) ((0.35+/-0.03) x 10(-4) L m(-2) h(-1)) at room temperature to 1.39+/-0.23 h(-1) ((1.03+/-0.07) x 10(-3) L m(-2) h(-1)). Complete nitrate removal was obtained in a Fe(0) column after 30 min under both buffered and unbuffered conditions at 75 degrees C. These results indicate that a temperature increase could overcome the energy barrier. We suggest that an iron reduction process at moderately elevated temperature (50-75 degrees C) may be a suitable method for removing nitrate from industrial discharges. 相似文献
15.
Maghasi AT Conklin SD Shtoyko T Piruska A Richardson JN Seliskar CJ Heineman WR 《Analytical chemistry》2004,76(5):1458-1465
Detection of lead and mercury by attenuated total internal reflectance spectroscopy coupled to stripping voltammetry is demonstrated. Changes in attenuation of light passing through an indium tin oxide optically transparent electrode (ITO-OTE) accompany the electrodeposition and stripping of lead and mercury on the electrode surface. The change in absorbance during stripping of electrodeposited metal constitutes the analytical response that enables detection over a range of 2.5 x 10(-7)-5 x 10(-5) and 5 x 10(-8)-5 x 10(-5) M for mercury and lead, respectively. The spectroelectrochemical responses of mercury and lead on the ITO surface are characterized and optimized with respect to solution conditions, the potential excitation signals used for deposition and stripping, and wavelength for detection. The deposited metals were examined by environmental scanning electron miscroscopy, and the electrodeposition pattern of lead and mercury was found to influence the optical response. 相似文献
16.
Two redox-active crown ethers, (1,1'- bi-2-naphthyl)-23-crown-6 incorporating 9,10-anthraquinone (BNAQ) and 1,4-benzoquinone (BNBQ), were synthesized and employed in the selective binding of NH(4)(+) over K(+). Their applications to NH(4)(+) detection were studied by cyclic voltammetry and amperometry in aqueous media. The results showed that the magnitude of the quinone redox peak decreased linearly as the concentration of NH(4)(+) increased, indicating the formation of BNAQ-NH(4)(+) and BNBQ-NH(4)(+) complexes. Formation constants of BNAQ-NH(4)(+) and BNBQ-NH(4)(+) complexes were determined to be 4.3 x 10(3) and 4.0 x 10(3) M(-1), respectively, which were 2 orders of the magnitude greater than those of BNAQ-K(+) and BNBQ-K(+) complexes. The (1)H NMR titration method carried out in DMSO-d(6) showed that both complexes possessed 1:1 stoichiometry, and association constants were determined to be 648 +/- 35 and 600 +/- 47 M(-1) for BNAQ-NH(4)(+) and BNBQ-NH(4)(+), respectively. Interference effects from other alkali and alkaline earth metal ions in the analysis of NH(4)(+) were also investigated. The BNAQ-modified sensor showed a linear response from 1.0 microM to 1.0 mM for NH(4)(+), and the detection limit was determined to be 0.9 +/- 0.03 microM. 相似文献
17.
18.
The L3 isoform of alpha-fetoprotein (AFP) is a specific marker for hepatocellular carcinoma. The separation and quantitation of L3 isoform from the L1 isoform is facilitated by Lens culinaris agglutin (LCA) affinity of the L3 isoform. The affinity-based separation is characterized by nonequilibrium conditions since electrophoresis perturbs the species concentrations away from equilibrium. The design of such separations requires careful consideration of the interplay between the reaction, diffusion, and separation time scales. We performed experiments to investigate the effect of separation parameters such as LCA concentration and CE voltage on the L1-L3 separation dynamics. We also describe a comprehensive mathematical model to predict electropherograms for affinity-based separations. The model includes the effects of molecular diffusion, electromigration, nonequilibrium reaction, and detection process. Together, the results demonstrate a process by which to optimize the affinity-based separations of AFP isoforms. We also obtained the kinetic rate constants for LCA affinity (kon=1.6x10(3) mol(-1) s(-1) L, koff=1x10(-3) s(-1)) by comparing the model predictions with experimental data. This study provides insight into the physics of affinity-based separations and can be extended to describe and optimize other nonequilibrium CE systems. 相似文献
19.
Cyclic voltammetry of a mixture containing 0.2 mM Na2IrCl6, 0.1 mM PdCl2, 0.2 M K2SO4, and 0.1 M HCl between 1.2 and -0.3 V vs Ag/AgCl for five cycles at 50 mV s-1 yields a stable film on a glassy carbon electrode. The reduction of hydrogen peroxide in 0.1 M KCl is diffusion controlled at that modified electrode. Calibration curves obtained at a 100 mV s-1 scan rate are linear in the range 0.2-1.8 mM H2O2. The slope, 28 microA L mmol-1, is independent of film thickness. Since dissolved oxygen is reduced at about the same potential as H2O2, -0.3 V, at the modified electrode, it will act as an interferent in solutions that are not deaerated; however, the currents are additive. A second limitation of the described procedure is that with the KCl electrolyte the immobilized film must be reoxidized prior to each measurement. Preliminary data are described which suggest that this problem is alleviated by switching to a basic supporting electrolyte. 相似文献
20.
High-efficiency liquid chromatographic separation utilizing long monolithic silica capillary columns
Miyamoto K Hara T Kobayashi H Morisaka H Tokuda D Horie K Koduki K Makino S Núñez O Yang C Kawabe T Ikegami T Takubo H Ishihama Y Tanaka N 《Analytical chemistry》2008,80(22):8741-8750
Long monolithic silica-C18 capillary columns of 100 microm i.d. were prepared, and the efficiency was examined using reversed-phase HPLC under a pressure of up to 47 MPa. At linear velocities of 1-2 mm/s, 100,000-500,000 theoretical plates could be generated with a single column (90-440 cm in length) using an acetonitrile-water (80/20) mobile phase with a column dead time (t0) of 5-40 min. It was possible to prepare columns with a minimum plate height of 8.5 +/- 0.5 microm and permeability of (1.45 +/- 0.09) x 10(-13) m(2). The chromatographic performance of a long octadecylsilylated monolithic silica capillary column was demonstrated by the high-efficiency separations of aromatic hydrocarbons, benzene derivatives, and a protein digest. The efficiency for a peptide was maintained for an injection of up to 0.5-2 ng. When three 100 microm i.d. columns were connected to form a 1130-1240 cm column system, 1,000,000 theoretical plates were generated for aromatic hydrocarbons with retention factors of up to 2.4 with a t0 of 150 min. The fact that very high efficiencies were obtained for the retained solutes suggests the practical utility of these long monolithic silica capillary columns. 相似文献