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In vitro study on fluoxetine adsorption onto charcoal using potentiometry.

This in vitro investigation was performed to study the adsorption rate constant as well as the adsorption characteristics of fluoxetine (F) to activated charcoal and its commercial formulation Carbomix powder in simulated gastric (pH 1.2) fluid environment. Ion-selective electrode (ISE) potentiometry, based on the selective, direct and continuous monitoring of F with an F-ISE constructed in our laboratory was used. The method used in the kinetic experiments consists of the rapid addition of a slurry containing the charcoal into the drug solution under stirring and continuous recording of the F-ISE potential until the establishment of equilibrium. The free ionized drug concentration at appropriate time intervals was calculated from the recorded adsorption curve and the apparent adsorption rate constant was estimated assuming pseudo first order kinetics. Within run R.S.D. of the estimates ranged from 0.24 to 11.5%, while between run R.S.D. (n=3-4) ranged from 0.90 to 13.8%. A linear relationship was found between the apparent adsorption rate constants and the amount of charcoal used with slopes (+/-S.D.) for activated charcoal and Carbomix equal to 1.14(+/-0.21) and 0.146(+/-0.009) s(-1)g(-1), respectively. Successive additions of microvolumes of F solution were made into a charcoal slurry with measurement of the F-ISE potential at equilibrium. The maximum adsorption capacity values (+/-S.D.) of activated charcoal and Carbomix were 254.8+/-1.8 and 405+/-41 mg/g, respectively while the affinity constant values (+/-S.D.) were 45.6+/-2.2 and 55.5+/-2.9 l/g, respectively. The adsorption of F to charcoals was rapid and for amounts of charcoal 10 times greater than the amount of the drug, 95% of F was adsorbed within the first 5 min. Relative to the toxic and lethal doses in cases of F intoxications, both types of charcoals tested adsorbed effectively F at gastric pH. Carbomix can be considered as appropriate charcoal formulation for medical treatment in cases of F poisoning.

Adsorption↗

Circular dichroism and potentiometry of FAD, heme and Mo-pterin prosthetic groups of assimilatory nitrate reductase.

Oxidation-reduction midpoint potentials for flavin, heme, and molybdenum-pterin prosthetic groups of assimilatory nitrate reductase (NR) from Chlorella vulgaris were measured at room temperature by using CD and EPR potentiometry. The CD changes accompanying reduction of each prosthetic group were determined by using enzyme fragments containing either FAD or heme and molybdenum prosthetic groups, obtained by limited proteolysis, and by poising the enzyme at various redox potentials in the presence of dye mediators. Limited proteolysis did not appear to alter the environment of the prosthetic groups, as judged by their CD spectra. Also, CD potentiometric titration of FAD in intact NR (Em' = -272 mV, n = 2) gave a similar value (Em' = -286 mV) to the FAD of the flavin-containing proteolytic domain, determined by visible spectroscopy. Less than 1% of the flavin semiquinone was detected by EPR spectroscopy, indicating that Em' (FAD/FAD.-) may be more than 200 mV lower than Em' (FAD.-/FADH-). Reduction of heme resulted in splitting of both Soret and alpha CD bands into couplets. The heme Em' was -162 mV (n = 1) determined by both CD and visible spectroscopy. Reduction of Mo-pterin was followed by CD at 333 nm, and Mo(V) was monitored by room temperature EPR spectroscopy. Most of the change in the Mo-pterin CD spectrum was due to the Mo(VI)/Mo(V) transition. The Em' values determined for Mo(VI)/Mo(V) were +26 mV by CD and +16 mV by EPR, whereas Mo(V)/Mo(IV) values were -40 mV by CD and -26 mV by EPR.(ABSTRACT TRUNCATED AT 250 WORDS)

Circular Dichroism↗

Potentiometry at trace levels in confined samples: ion-selective electrodes with subfemtomole detection limits.

We explore here for the first time the direct potentiometric detectability of calcium, lead, and silver ions in amounts on the order of 300 attomoles at 100 picomolar concentrations without any preconcentration, analyte recycling, or electrocatalytic signal enhancement. The results presented here place zero-current potentiometry among the most sensitive electrochemical methods available.

Calcium↗

Determination of selenium in nuts by cathodic stripping potentiometry (CSP).

The aim of this work was to determine the selenium content in nut samples by cathodic stripping potentiometry. Dry-powdered nuts were digested by HNO(3) and dissolved with concentrated hydrochloric acid. To avoid the interference of natural oxygen, the potentiometric determination of selenium was carried out in an electrolyte solution consisting of 2 M CaCl(2) and 4 M HCl. The analysis was executed applying an electrolysis potential of -150 mV for 60 s and a constant current of -30 microA. Under these conditions, detection limits lower than 1.0 ng g(-)(1) were obtained for selenium analysis in nuts. The relative standard deviation of these measurements (expressed as rsd %) ranged from 0.44 to 0.88% while recoveries ranged from 90.2 to 95.3%. The results obtained with the proposed method were compared with those obtained via hydride vapor generation atomic absorption spectroscopy, a common method for determining selenium. The results of the two methods agreed within 5% for almond, hazelnut, and pistachio samples. The mean concentrations of selenium determined in Sicilian samples of almond, hazelnut, and pistachio were 531 +/- 1, 865 +/- 1, and 893 +/- 4 microg/kg, respectively.

Corylus↗

Determination of selenium content in different types of seed oils by cathodic stripping potentiometry (CSP).

Seed oils are consumed worldwide; moreover, they are used in the alimentary, cosmetic, pharmaceutical, and chemical industries. Due to their diffusion, it is interesting to investigate the presence of important micronutrients such as selenium in seed oils. The aim of this work was to develop a rapid, precise, and sensitive cathodic stripping potentiometry (CSP) method to determine the concentration of selenium in different types of seed oils. Selenium was extracted from the oily matrix by concentrated hydrochloric acid treatment at 90 degrees C. The analysis was executed by applying an electrolysis potential of -150 mV for 60 s and a constant current of -30 microA. Under these conditions, detection limits of <0.5 ng g(-1) were obtained. The method reproducibility (expressed as total RSD %) spanned from 0.2 to 0.8%. Recoveries ranged from 92.1 to 97.5%, providing evidence that selenium quantification remained unaffected by the extraction procedure described. The results obtained with the proposed method were compared with those obtained via graphite furnace atomic absorption spectroscopy (GFAAS), a common method for determining selenium. The results of the two methods agreed within 93.5-107.7%. The mean amounts of selenium found were 313.0 +/- 2.0, 458.3 +/- 1.3, 224.6 +/- 0.9, 99.5 +/- 0.8, 332.2 +/- 0.5, 144.0 +/- 0.7, and 295.5 +/- 1.2 ng g(-1), respectively, in peanut, soybean, sunflower, rice, corn, grapestone, and seed oils.

Plant Oils↗

Ionophore properties of monensin derivatives studied on human erythrocytes by 23Na NMR and K+ and H+ potentiometry: relationship with antimicrobial and antimalarial activities.

Eight derivatives of monensin with a modified C25-C26 moiety were synthesized. Their ionophore properties were studied on human erythrocytes by measuring Na+ influx with 23Na NMR and concomitant K+ and H+ efflux by potentiometry. Modification of OH-26 led to inversion of selectivity of transport in favor of K+/Na+ in comparison with monensin. This selectivity disappeared by suppression of the C26-OH moiety. Finally the ionophore ability was lost if the head-to-tail chelation of the monensin skeleton was prevented by blocking the terminal OH-25 and -26 functions. All the compounds were inactive on Gram-negative bacteria and fungi. MIC measured on Bacillus cereus showed that derivatives with increased K+/Na+ selectivity were clearly the most active against Bacillus growth. Most of the compounds showed potential antimalarial properties in the nanomolar range when tested in vitro against Plasmodium falciparum. The IC50S measured were correlated with the whole Na+ and K+ transport efficiency rather than with the ionic selectivity. In both cases determination of initial fluxes of transport for both cations (Na+ and K+) was necessary to investigate the relationship between biological and ionophore properties.

Adult↗

NMR spectra and potentiometry studies of aluminum(III) binding with coenzyme NAD+ in acidic aqueous solutions.

Complexation and conformational studies of coenzyme NAD+ with aluminum were conducted in acidic aqueous solutions (pH 2-5) by means of potentiometry as well as multinuclear (1H, 13C, 31P, 27Al) and two-dimensional (1H, 1H-NOESY) NMR spectroscopy. These led to the following results: (1) Al could coordinate with NAD+ through the following binding sites: N7' of adenine and pyrophosphate free oxygen (O(A)1, O(N)1,O(A)2) to form various mononuclear 1:1 (AlLH23+, AlLH2+) and 2:1 (AlL2-) species, and dinuclear 2:2 (Al2L22+) species. (2) The conformations of NAD+ and Al-NAD+ depended on the solvents and different species in the complexes. The results suggest the occurrence of an Al-linked complexation, which causes structural changes at the primary recognition sites and secondary conformational alterations for coenzymes. This finding will help us to understand role of Al in biological enzyme reaction systems.

Aluminum↗

The effect of polyethylene glycol on the charcoal adsorption of chlorpromazine studied by ion selective electrode potentiometry.

BACKGROUND: This investigation was undertaken to study: a) the adsorption characteristics of chlorpromazine to activated charcoal and its formulations Carbomix powder and Ultracarbon tablets at gastric pH; b) the effect on chlorpromazine adsorption of polyethylene glycol and its combination with electrolyte lavage solution; c) the effect of the order of addition of polyethylene glycol-electrolyte lavage solution. METHOD: Ion selective electrode potentiometry, based on the selective, direct and continuous response of a chlorpromazine-ion selective electrode to the concentration of the free drug, was used. Successive additions of microvolumes of a chlorpromazine solution were made into a charcoal slurry in acidic medium of pH 1.2 with measurement of the chlorpromazine-ion selective electrode potential at equilibrium. RESULTS: The maximum adsorption capacity values of activated charcoal, Carbomix and Ultracarbon, were 297, 563, and 382 mg/g respectively, while the affinity constant values were 40.2, 70.4, and 40.5 L/g, respectively. The adsorption of chlorpromazine to each of the Ultracarbon and Carbomix components was compared to the total adsorption of the formulations. The addition of polyethylene glycol-electrolyte lavage solution causes a slight desorption of chlorpromazine from activated charcoal at gastric pH, more pronounced when polyethylene glycol-electrolyte lavage solution follows the addition of activated charcoal, suggesting the possibility of a nonspecific binding of chlorpromazine to polyethylene glycol. The amount of chlorpromazine absorbed to Carbomix and Ultracarbon was not significantly affected at gastric pH by the presence of polyethylene glycol or polyethylene glycol-electrolyte lavage solution added either concurrently or sequentially to these formulations.

Adsorption↗

Effects of residual liquid junction potential in direct potentiometry of potassium.

To further the accurate direct potentiometry of plasma electrolyte concentrations, we investigated the effects of solution composition on the residual liquid junction potential (RLJP) during measurement of K+. Assuming that the binding constant between K+ and proteins or bicarbonate is no greater than with Na+, we calculate that the amount of bound K+ can be neglected. A significant RLJP exists between simple solutions containing Na+, K+, and Cl- ions and solutions containing Na+, K+, Cl-, and HCO3- ions. Replacing Cl- with HCO3- leads to an increase in the RLJP, which in turn contributes to a negative error in K+ analysis. A small decrease in RLJP is observed as the ionic strength is increased. The Henderson equation gives a reasonable estimate of the magnitude of the observed RLJP, even though the liquid junction does not meet the conditions under which the equation is rigorously applicable. Errors attributed to RLJP may be substantially minimized by using a calibrator solution that contains an anion with mobility similar to that of HCO3-.

Bicarbonates↗

Potentiometry of Na+ in undiluted serum and urine with use of an improved neutral carrier-based solvent polymeric membrane electrode.

We present an improved Na+-selective liquid membrane electrode for measurement of Na+ concentrations in both undiluted serum and urine. The values for urinary Na+ obtained with the ion-selective electrode agree well with those obtained with the flame photometer. The correlation gives a standard residual deviation of +/- 2.7 mmol/L over the Na+ range of 25-280 mmol/L. In serum, this direct potentiometry yields Na+ concentrations 5.4% (SD 1.1%) higher than those obtained by atomic spectrometry and a standard residual deviation of +/- 1.1 mmol/L. Correction of these values for the volumes of protein and lipid leads to potentiometric values 1.2% (SD 0.7%) lower than those by flame photometry (residual standard deviation: +/- 1.0 mmol/L). Other factors that possibly contribute to this discrepancy are discussed.

Electrodes↗

Novel potentiometry immunoassay with amplified sensitivity for diphtheria antigen based on Nafion, colloidal Ag and polyvinyl butyral as matrixes.

A novel potentiometry immunoassay with amplified sensitivity has been developed for the detection of diphtheria antigen (Diph) via immobilizing diphtheria antibody (anti-Diph) on a platinum electrode based on Nafion, colloidal Ag (Ag), and polyvinyl butyral (PVB) as matrixes in this study. The modified procedure was further characterized by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The influence and factors influencing the performance of resulting immunosensor were studied in detail. The resulting immunosensor exhibited sigmoid curve with log Diph concentrations, high sensitivity (51.4 mV/decade), wide linear range from 8 to 800 ng ml(-1) with a detection limit of 1.5 ng ml(-1), rapid potentiometric response (<3 min) and long-term stability (>6 months). Analytical results of clinical samples show that the developed immunoassay is comparable with the enzyme-linked immunosorbent assays (ELISAs) method, implying a promising alternative approach for detecting diphtheria antigen in the clinical diagnosis.

Antigens↗

Synthesis, Potentiometry, and NMR Studies of Two New 1,7-Disubstituted Tetraazacyclododecanes and Their Complexes Formed with Lanthanide, Alkaline Earth Metal, Mn(2+), and Zn(2+) Ions.

Two new 1,7-disubstituted-1,4,7,10-tetraazacyclododecane ligands, DO2P and DO2PME, and their complexes with Mg(2+), Ca(2+), Sr(2+), Mn(2+), Zn(2+) and Ln(3+) were prepared and characterized by pH potentiometry. The pH titration data showed that DO2P and DO2PME both form 1:1 M:L complexes with all divalent and trivalent metal ions. Protonated complexes did not appear to form with the bis(phosphonate ester) ligand, DO2PME, but were evident for all of the metal ion-DO2P complexes. The alkaline earth metal ion-DO2P complexes formed both ML and MHL complexes while the lanthanide ion (Ln(3+)), Zn(2+), and Mn(2+) complexes of DO2P formed ML, MHL, and MH(2)L species. Zn(2+) formed the most stable complex with both ligands. The stability (beta(101)) of the LnDO2PME(+) complexes increased by about 2 orders of magnitude along the lanthanide series (La(3+) to Lu(3+)) while the stability of the LnDO2P(-) complexes over this same series increased by over 3 orders of magnitude. The bis(phosphonate) ligand, DO2P, and some of its complexes formed with Ln(3+) ions were further examined by NMR spectroscopy. (1)H and (31)P spectra of DO2P collected as a function of pH provided evidence that the first two protonations on the ligand take place largely at the tertiary nitrogens. The similarity of the (31)P chemical shifts of EuDO2P(-) and EuDOTP(5)(-) indicate that DO2P forms an "in-cage" complex with Eu(3+) using all four macrocyclic ring nitrogens and the two phosphonate sidearms as ligands. (17)O NMR shifts of the water signal indicated that the DyDO2P(-) complex has two inner-sphere coordinated water molecules. In the presence of excess of DO2P, a 1:2 metal:ligand, LnDO2P(HDO2P)(4)(-), complex forms with the second ligand interacting only weakly with the coordination sites left vacant by the first DO2P. Both water proton relaxivity data for GdDO2P(-) and (31)P NMR spectra of EuDO2P(-) provide evidence for formation of an "out-of-cage" LnH(2)DO2P(+) complex at low pH values (<6.5) in which the two phosphonate groups of DO2P are only involved in bonding with the lanthanide cation.

Journal Article↗

Perspectives of carbon paste electrodes in stripping potentiometry.

The testing of various types of carbon paste electrodes (CPEs) for their use in stripping potentiometry was carried out by means of specially proposed procedures and by using various model analyte systems. CPEs containing three different pasting liquids (paraffin oil, silicone oil, tricresyl phosphate) were tested as supports for mercury- and gold films, and as substrates for electrolytic, adsorptive, ion-pair forming, and extractive accumulation. Test measurements in organic solvent-containing media and studies of some irreversible electrochemical reactions were performed as well. Individual examples to be studied allowed one to formulate and outline some perspectives of CPEs in potentiometric stripping analysis and related constant current stripping analysis.

Journal Article↗

Biospeciation, by potentiometry and computer simulation, of Sm-EDTMP, a bone tumor palliative agent.

153Sm-EDTMP (ethylenediaminetetra(methylenephosphonic) acid) is of considerable interest as a bone therapeutic radiopharmaceutical but its properties in solution are not yet well characterized. The protonation constants of EDTMP and the formation constants of the complexes of Sm-EDTMP have accordingly been measured potentiometrically by glass electrode titrations at 25 degrees C in 0.15 M NaCl. Six protonation constants (log beta 011 = 9.638, log beta 012 = 17.330, log beta 013 = 23.597, 10g beta 014 = 28.636, log beta 015 = 31.501, log beta 016 = 32.624) and the formation constants of the [Sm(EDTMP)H-1]6-(log beta 11-1 = 4.865), [SmEDTMP]5-(log beta 110 = 12.018), [Sm(EDTMP)H]4- (log beta 111 = 17.892) and [Sm(EDTMP)H2]3- (log beta 112 = 23.437) complexes were determined. Computer simulations indicate that the [SmEDTMP]5- and the hydroxy [Sm(EDTMP)H-1]6- species are the major Sm(III) complexes formed in blood plasma, which explains the high degree of localization in the kidney and urine observed in biodistribution studies. Calcium ions are probably the major competitor for EDTMP in blood plasma. As the presence of secondary skeletal metastases results in a high rate of bone turnover, it is possible that the high concentration of calcium at these sites encourages localization of 153Sm-EDTMP.

Bone Neoplasms↗

Simple and rapid determination of iodide in table salt by stripping potentiometry at a carbon-paste electrode.

A simple and rapid procedure, utilising constant-current stripping analysis (CCSA) at a carbon-paste electrode containing tricresyl phosphate as a pasting liquid (TCP-CPE), has been developed for the determination of iodide in table salt. Because of a synergistic accumulation mechanism based on ion-pairing and extraction of iodide in combination with electrolytic pretreatment of the TCP-CPE, the method is selective for iodide and enables direct determination of iodide in samples of table salt containing anti-caking agents such as K(4)[Fe(CN)(6)] (food additive "E 536") or MgO. The iodide content (calculated as KI) can be determined in a concentration range of 2 to 100 mg kg(-1) salt, with a detection limit (S/N=3) of 1 mg kg(-1), and a recovery from 90 to 115%. The proposed method has been used to determine iodide in several types of artificially iodised table salt and in one sample of natural sea salt. The results obtained agreed well with those obtained by use of three independent reference methods (titration, spectrophotometry, and ICP-MS) used to validate the CCSA method, indicating that the developed method is applicable as a routine procedure for rapid testing in salt production process control and in the analysis of marketed table salts.

Carbon↗

Measurement of oxidation-reduction midpoint potentials by room temperature electron paramagnetic resonance potentiometry.

A room temperature electron paramagnetic resonance potentiometric cell has been developed for the measurement of oxidation-reduction midpoint potentials of enzymes containing paramagnetic centers. Based upon an aqueous flat cell designed for use with the Varian TM high sensitivity cavity, the apparatus combines a high degree of anaerobiosis with low volume requirements. The cell is simple in design, easily constructed, and can be adapted for use with most spectrometer cavities. Tests of the cell using xanthine oxidase, in 50 mM Bicine buffer, pH 7.7, yielded midpoint potentials of -345 and -371 mV for the Mo(VI)/Mo(V) and Mo(V)/Mo(IV) couples compared with values of -373 and -377 mV obtained by electron paramagnetic resonance analysis of frozen potentiometric samples. These values indicate that shifts, of the order of 20-40 mV, may occur upon freezing poised samples. For the Mo center of xanthine oxidase, these shifts in potential are more pronounced for the Mo(VI)/Mo(V) couple and result in a destabilization of the Mo(V) intermediate during freezing.

Animals↗