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PubMed1999

New Approach for Determination of Macroscopic Binding Constants of Ligands to Macromolecules.

A new method has been developed for determining macroscopic binding constants of a few surfactants to some macromolecules. Then, the binding of ionic surfactants (cetyltrimethyl ammonium bromide, tetradecyltrimethyl ammonium bromide, and sodium tetradecyl sulfate) [STS]) to macromolecules (bovine serum albumin, human serum albumin, and polyvinyl pyrollidone was investigated. The binding constants and binding isotherms were calculated using this new method. Experimental data were obtained through a potentiometry technique. Finally, the results obtained were compared with the results obtained based on the Wyman binding potential concept. Copyright 1999 Academic Press.

Journal Article↗
PubMed2001

The Structure and Properties of TiO(2)-Cu(II)-EDTA Ternary Surface Complexes.

The formation, composition, structure, and electrochemical properties of ternary surface complexes between copper(II) and ethylenediaminetetraacetate adsorbed on TiO(2) xerogels and on thin-film TiO(2) electrodes from solutions of varying pH have been studied by potentiometry, EPR spectroscopy, and electrochemical methods. The results strongly indicate that, in contrast to other organic ligands, B-type ternary surface complexes are formed in this system. The organic ligand forms an isolating layer between the surface of the TiO(2) electrode and the redox-active copper ions. Copyright 2001 Academic Press.

Journal Article↗
PubMed2001

Apparent Binding Degree of a Counterion and Micellar Composition in Cationic and Nonionic Surfactant Mixed Solutions at CMC.

The Gibbs-Duhem equation of an ionic aggregate is obtained, considering the activity coefficient of the aggregate due to the interaction between the aggregate ion and its diffusion layer. The equation is applied to mixtures of cationic and nonionic surfactants. The critical micelle concentrations of the cationic and nonionic surfactant mixtures were measured in the presence of an inorganic salt with the same counterion. The logarithm of the CMC of the mixture gives a linear relationship versus the logarithm of the counterion concentration for a constant molar ratio of the two surfactants. The apparent binding degree of the counterion and the fraction of the nonionic surfactant in the mixed micelle were obtained from the CMC data using the Gibbs-Duhem equation. The binding degree which is obtained by the Corrin-Harkins equation is apparent. The apparent binding degree increases with the decrease in the counterion concentration. The behavior of the apparent binding degree is different from that of the real binding degree obtained by potentiometry. These facts are explained by our definition of the apparent binding degree of the counterion. Copyright 2001 Academic Press.

Journal Article↗
PubMed2002

Adsorption and association in aqueous solutions of dissymmetric gemini surfactant.

A gemini surfactant with two hydrocarbon chains differing in length and with an ethylene spacer N,N-dimethyl-N-(2-(N',N'-dimethyl-N'-dodecylammonio) ethyl) tetradecylammonium dibromide, 12-2-14, was synthesized and its physicochemical properties were studied by surface tension, conductometry, potentiometry, viscosimetry, and light scattering measurements, as well as by optical microscopy. Surface properties and thermodynamic parameters lie between those obtained for its symmetric counterparts, while association in solution exhibited peculiar properties, i.e., high polydispersity and the coexistence of three populations of differently sized aggregates.

Journal Article↗
PubMed1999

Expression and one-step purification of a fully active polyhistidine-tagged cytochrome bc1 complex from Rhodobacter sphaeroides.

The fbcB and fbcC genes encoding cytochromes b and c1 of the bc1 complex were extended with a segment to encode a polyhistidine tag linked to their C-terminal sequence allowing a one-step affinity purification of the complex. Constructions were made in vitro in a pUC-derived background using PCR amplification. The modified fbc operons were transferred to a pRK derivative plasmid, and this was used to transform the fbc- strain of Rhodobacter sphaeroides, BC17. The transformants showed normal rates of growth. Chromatophores prepared from these cells showed kinetics of turnover of the bc1 complex on flash activation which were essentially the same as those from wild-type strains, and analysis of the cytochrome complement and spectral and thermodynamic properties by redox potentiometry showed no marked difference from the wild type. Chromatophores were solubilized and mixed with Ni-NTA-Sepharose resin. A modification of the standard elution protocol in which histidine replaced imidazole increased the activity 20-fold. Imidazole modified the redox properties of heme c1, suggesting ligand displacement and inactivation when this reagent is used at high concentration. The purified enzyme contained all four subunits in an active dimeric complex. This construction provides a facile method for preparation of wild-type or mutant bc1 complex, for spectroscopy and structural studies.

Amino Acid Sequence↗
PubMed1989

Iron chelators of the pyridoxal isonicotinoyl hydrazone class. III. Formation constants with calcium(II), magnesium(II) and zinc(II).

Formation constants for the calcium(II), magnesium(II) and zinc(II) complexes of the orally effective iron chelator, pyridoxal isonicotinoyl hydrazone (PIH) and three analogues, pyridoxal benzoyl hydrazone (PBH), pyridoxal p-methoxybenzoyl hydrazone (PpMBH) and pyridoxal m-fluorobenzoyl hydrazone (PmFBH) have been determined by potentiometry at 25 degrees C and I = 0.1 M [KNO3]. The four ligands bind calcium(II) weakly and magnesium(II) only slightly more strongly, as a 1:1 complex which is formed at pH greater than 8. The chelation of zinc(II) for all the ligands studied was greater than that for calcium(II) and magnesium(II), with complexation generally becoming significant at about pH 5. Thus, chelation of zinc(II) but not calcium(II) or magnesium(II) at physiological pH, 7.4 may be expected. Calculated values of the concentration of uncomplexed metal ion indicate that the selectivity of these ligands towards Fe(III) is comparable to that of the clinically used chelator desferrioxamine.

Calcium↗
PubMed2003

Ion-selective electrodes based on metalloporphyrins for gibberellic acid determination in agricultural products.

This work describes the construction, evaluation and analytical application of electrodes selective to the gibberellate anion for the determination of gibberellic acid in agricultural products. Several types of PVC membrane electrodes without internal reference solution were prepared using the manganese(III) complex of meso-tetraphenylporphyrin (TPP) as ionophore and dibutyl phthalate (DBP), as plasticizer. The incorporation of lipophilic chemical species as additives, was also carried out aiming the evaluation of the response characteristics of the electrodes. To accomplish the analysis of commercial agricultural products a selective membrane composed of 28.0% (w/w) of PVC, 66.0% (w/w) of plasticizer and 6% (w/w) of ionophore was used, with no additive. This potentiometric unit presented a linear response between 10(-4) and 10(-1) mol L(-1) in gibberellate, a slope of about -69 mV dec(-1) and a reproducibility of about +/-1 mV day(-1). The potentiometric analysis of gibberellic acid in commercial products was carried out by direct potentiometry and the results obtained were compared with those provided by HPLC.

Crops, Agricultural↗
PubMed2003

Tangential-flow ultrafiltration: a versatile methodology for determination of complexation parameters in refractory organic matter from Brazilian water and soil samples.

In this work the copper(II) complexation parameters of aquatic organic matter, aquatic and soil humic substances from Brazilian were determined using a new versatile approach based on a single-stage tangential-flow ultrafiltration (TF-UF) technique (cut-off 1 kDa) and sensitive atomic spectrometry methods. The results regarding the copper(II) complexation capacity and conditional stability constants obtained for humic materials were compared with those obtained using direct potentiometry with a copper-ion-selective electrode. The analytical procedure based on ultrafiltration is a good alternative to determine the complexation parameters in natural organic material from aquatic and soil systems. This approach presents additional advantages such as better sensibility, applicability for multi-element capability, and its possible to be used under natural conditions when compared with the traditional ion-selective electrode.

Brazil↗
PubMed2004

Determination of acidity constants of enolisable compounds by capillary electrophoresis.

Research on the structure-activity relationships of molecules with acidic carbon atoms led us to undertake a feasibility study on the determination of their acidity constants by capillary electrophoresis (CE). The studied molecules had diverse structures and were tetronic acid, acetylacetone, diethylmalonate, Meldrum's acid, 3-methylrhodanine, nitroacetic acid ethyl ester, pyrimidine-2,4,6-trione, 3-oxo-3-phenylpropionic acid ethyl ester, 1-phenylbutan-1,3-dione, 5,5-dimethylcyclohexan-1,3-dione and homophthalic anhydride. The p Ka range explored by CE was therefore very large (from 3 to 12) and p Ka values near 12 were evaluated by mathematical extrapolations. The analyses were carried out in CZE mode using a fused silica capillary grafted (or not) with hexadimethrine. Owing to the electrophoretic behaviour of these compounds according to the pH, their acidity constants could be evaluated and appeared in perfect agreement with the literature data obtained, a few decades ago, by means of potentiometry, spectrometry or conductimetry. The p Ka of homophthalic anhydride and 3-methylrhodanine were evaluated for the first time.

Journal Article↗
PubMed2004

Determination of ion-pair formation constants of univalent metal-crown ether complex ions with anions in water using ion-selective electrodes: application of modified determination methods to several salts.

Ion-pair formation constants (mol(-1) dm3 unit), K(MX) for a univalent metal salt (MX) and K(MLX) for its ion-pair complex (ML+X-) with a crown ether (L) in water, were determined at various ionic strengths (I) and 25 degrees C by potentiometry with ion-selective electrodes for MX=NaPic, NaMnO4, NaBPh4, KPic, and KMnO4; and MLX = Na(18C6)Pic, K(18C6)Pic, and Na(18C6)BPh4, where Pic- and 18C6 denote a picrate ion and 18-crown-6 ether, respectively. Equations for analyzing I-dependence of logK(MLX) and logK(MX) were derived and fitted well to the I-dependence using a non-linear regression analysis. The equilibrium constants at I = 0 mol dm(-3), K(MLX) degrees and K(MX) degrees, were simultaneously obtained from the analysis. The experimental values of K(MLX) and K(MX) were only in agreement with the values calculated from K(MLX) degrees and K(MX) degrees , respectively, in the ranges of higher I.

Journal Article↗
PubMed2005

FIA acid-base titrations with a new flow-through pH detector.

A pH-sensitive detector for flow-through potentiometry based on a graphite/quinhydrone composite electrode was applied for flow-injection analysis (FIA) titrations. Hydrochloric acid and acetic acid were titrated by injection of samples into a sodium hydroxide carrier solution. System conditions were optimised by variation of flow rate, injection volume and titrant concentration. The parameters sampling frequency, residence time and dispersion coefficient were determined. The evaluation of peak width (time between the two inflection points on each side of the peak), peak area and slope of the raising edge of the peak lead were studied with respect to their use for calibration. Hydrochloric acid and acetic acid could be titrated down to a concentration of 2 x 10(-4) mol L(-1) using 150-microL injection volumes, which is almost ten times lower than can be achieved using colour indicators and a spectrophotometric detection.

Acetic Acid↗
PubMed2006

A new approach to flow-batch titration. A monosegmented flow titrator with coulometric reagent generation and potentiometric or biamperometric detection.

Monosegmented flow analysis (MSFA) has been used as a flow-batch system to produce a simple, robust, and mechanized titrator that enables true titrations to be performed without the use of standards. This paper also introduces the use of coulometry with monosegmented titration by proposing a versatile flow cell. Coulometric generation of the titrand is attractive for titrations performed in monosegmented systems, because the reagent can be added without increasing the volume of sample injected. Also, biamperomeric and potentiometric detection of titration end-points can increase the versatility of the monosegmented titrator. The cell integrates coulometric generation of the titrand with detection of end-point by potentiometry or biamperometry. The resulting titrator is a flow-batch system in which the liquid monosegment, constrained by the interfaces of the gaseous carrier stream, plays the role of a sample of known volume to be titrated. The system has been used for determination of ascorbic acid, by coulometric generation of I2 with biamperometric detection, and for determination of Fe(II), by coulometric generation of Ce(IV) with potentiometric detection of the end-point, both in feed supplements.

Journal Article↗
PubMed2001

Synthesis of glycosylated porphyrins as neutral ionophores for a berberine-sensitive electrode.

For preparing a berberine-sensitive electrode, 5,10,15,20-tetrakis[2-(2,3,4,6-tetraacetyl-beta-D-glucopyranosyl)-1-O- phenyl]porphyrin (T(o-glu)PPH2) was synthesized from the reaction of pyrrole with ortho-acetylglycosylated benzaldehyde by Lindsay's method. The electrode based on T(o-glu)PPH2 with an optimized membrane composition exhibits Nernstian response to berberine in the concentration range 2.4 x 10(-7)-5.0 x 10(-3) mol L-1, with a pH range from 3.9 to 10.2, and a fast response time of 30 s. The electrode shows fair selectivity towards berberine with respect to common co-existing species. T(o-glu)PPH2 shows better potentiometric response characteristics comparing to chloro[5,10,15,20-tetrakis[2-(2,3,4,6-tetraacetyl-beta-D- glucopyranosyl)-1-O-phenyl]-porphinato]-manganese (MnT(o-glu)PPCl) and better selectivity towards berberine than tetraphenylporphyrin (TPPH2). The effect of the composition of the electrode membrane has been studied and the experimental conditions optimized. The contents of berberine in pharmaceutical tablets were determined by direct potentiometry and the results agreed with values obtained by the pharmacopoeia method.

Berberine↗
PubMed2001

Interference of sulfate(VI) with poly(pyrrole) electrochemistry.

The effect of the SO4(2-) anion on both potentiometry and voltammetry with poly(pyrrole) films doped with chloride or hexacyanoferrate(II/III) ions has been studied and compared with the responses obtained in KCl solutions. Strong interference was observed when the SO4(2-) to Cl- molar ratio was 1:1000, leading to a decrease in polymer film electroactivity at higher sulfate concentrations. The effect is attributed to incorporation of the divalent anion into the polymer film structure, a hypothesis supported by analysis of the composition of the elemental film.

Journal Article↗
PubMed1996

Functional crown ether derivatives as sorbents for ligand exchange chromatography.

Two kinds of macrocyclic compounds, S-TAROH18C6 and S-TAROEt12C4 derived from tartaric acid have been synthesized. The structure and conversion of functional groups on this silica gel based resin have been confirmed by IR spectral and elemental analysis. The coordination behaviour of these materials has been investigated by means of IR, EPR, potentiometry and the modification of Langmuir isotherm equation. The metal complexes have been investigated as stationary phases for the separation of amino acid mixtures. Factors affecting the retention and the sample selectivity have been examined. S-TAROEt12C4 possesses good chromatographic characteristics and a unique selectivity in separating underivatized amino acid mixtures and can be used as well for enantiomeric separations.

Journal Article↗
PubMed1998

An efficient procedure for studying pectin structure which combines limited depolymerization and 13C NMR.

A protocol for partial thermally-induced depolymerization of differently methoxylated pectin samples is described. The resulting macromolecules have been fully characterized with various complementary techniques, such as size exclusion chromatography (SEC), potentiometry, viscometry and 13C NMR. Optimum conditions afford samples at 50-80% yield with weight-average molecular weights in the 4 to 20 kDa range. The major fraction of these polysaccharides adopts the random-coil conformation and such samples are suitable for 13C NMR structural studies at room temperature. The methoxyl distributions of two apple pectin samples with a degree of esterification (DE) between 54 and 74% and a citrus pectin (DE, 72%) were shown to be random in nature, whereas that of a lightly methoxylated apple pectin (DE 39%) was partially blockwise. The carbon relaxation parameters of the depolymerized pectins attain asymptotic values for Mw > 4 kDa. The Mw values estimated from intrinsic viscosity data with the Mark-Houwink relationship reported for native pectins are in good agreement with those obtained by either end-group analysis (NMR) or SEC. Thus, all the physicochemical data indicate that the secondary structure of the isolated chains of depolymerized pectin is closely related to that of the parent polymers. Finally, pectinmethylesterase activity towards the depolymerized pectins was similar to that of the untreated samples.

Carbon Isotopes↗
PubMed2004

153Sm and 166Ho complexes with tetraaza macrocycles containing pyridine and methylcarboxylate or methylphosphonate pendant arms.

A set of tetraaza macrocycles containing pyridine and methylcarboxylate (ac(3)py14) or methylphosphonate (MeP(2)py14 and P(3)py14) pendant arms were prepared and their stability constants with La(3+), Sm(3+), Gd(3+) and Ho(3+) determined by potentiometry at 25 degrees C and 0.10 M ionic strength in NMe(4)NO(3). The metal:ligand ratio for (153)Sm and (166)Ho and for ac(3)py14, MeP(2)py14 and P(3)py14, as well as the pH of the reaction mixtures, were optimized to achieve a chelation efficiency higher than 98%. These radiocomplexes are hydrophilic and have a significant plasmatic protein binding. In vitro stability was studied in physiological solutions and in human serum. All complexes are stable in saline and PBS, but 20% of radiochemical impurities were detected after 24 h of incubation in serum. Biodistribution studies in mice indicated a slow rate of clearance from blood and muscle, a high and rapid liver uptake and a very slow rate of total radioactivity excretion. Some bone uptake was observed for complexes with MeP(2)py14 and P(3)py14, which was enhanced with time and the number of methylphosphonate groups. This biological profile supports the in vitro instability found in serum and is consistent with the thermodynamic stability constants found for these complexes.

Blood Proteins↗
PubMed2006

Complexation of oxoanions and cationic metals by the biscatecholate siderophore azotochelin.

Azotochelin is a biscatecholate siderophore produced by the nitrogen-fixing soil bacterium Azotobacter vinelandii. The complexation properties of azotochelin with a series of oxoanions [Mo(VI), W(VI) and V(V)] and divalent cations [Cu(II), Zn(II), Co(II) and Mn(II)] were investigated by potentiometry, UV-vis and X-ray spectroscopy. Azotochelin forms a strong 1:1 complex with molybdate (log K=7.6+/-0.4) and with tungstate and vanadate; the stability of the complexes increases in the order Mo<V<W (log KappMo=7.3+/-0.4; log KappV=8.8+/-0.4 and log KappW=9.0+/-0.4 at pH 6.6). The Mo atom in the 1:1 Mo-azotochelin complex is bound to two oxo groups in a cis position and to the two catecholate groups of azotochelin, resulting in a slightly distorted octahedral configuration. Below pH 5, azotochelin appears to form polynuclear complexes with Mo in addition to the 1:1 complex. Azotochelin also forms strong complexes with divalent metals. Of the metals studied, Cu(II) binds most strongly to azotochelin (log betaCuLH2-=-12.9+/-0.1), followed by Zn(II) log betaZnL3-=-24.1+/-0.14, log betaZnLH2-=-17.83+/-0.09), Mn(II) (log betaMnL3-=-29, log betaMnLH2-=-18.6+/-0.8, log betaMnLH2-=-11.5+/-0.7) and Co(II) (log betaCoLH2-=-23.0+/-0.3, log betaCoLH2-=-13.5+/-0.2). Since very few organic ligands are known to bind strongly to oxoanions (and particularly molybdate) at circumneutral pH, the unusual properties of azotochelin may be used for the separation and concentration of oxoanions in the laboratory and in the field. In addition, azotochelin may prove useful for the investigation of the biogeochemistry of Mo, W and V in aquatic and terrestrial systems.

Anions↗