scholarly journals Titration of chelating fibrous sorbent in the presence of complex-forming divalent cations

Author(s):  
V. S. Soldatov ◽  
T. A. Korshunova ◽  
E. G. Kosandrovich ◽  
P. V. Nesteronok

Titration curves of H-forms of the fibrous chelating sorbent with iminodiacetic groups based on industrial polyacrylonitrile fiber Nitron with potassium hydroxide in 1M KCl solution in the presence of Ni2+, Co2+, Cu2+ and Ca2+ chlorides were obtained. The method used made it possible to simultaneously measure the pH of the solution and the concentration of the divalent cation at each point of the titration curve. From these data, the dependences of their sorption values on the pH of the equilibrium solution were calculated. The curves of direct and back titration practically coincided in all cases. As the pH changed during titration, precipitation was observed at pH values of precipitation of the corresponding hydroxides. In this case, the increase in pH was suspended or greatly slowed down by adding alkali to the titration cell. The formation of a precipitate occurred mainly in a solution for Co2+ and Ni2+ (pH 8), when the ion exchanger was saturated with a metal ion. In the case of Cu2+ (precipitate formation pH 4), Cu2+ sorption occurs at both lower and higher pH due to ionization of carboxyl groups and partial dissolution of the precipitate. In all cases, the maximum sorption of Ni2+, Co2+, Cu2+, Ca2+ corresponded to the formation of sorption complexes of the R–N(CH2COO-)2Me2+ type.

1979 ◽  
Vol 41 (02) ◽  
pp. 296-308
Author(s):  
Daniel J Schaefer ◽  
Mary E Scott ◽  
Don A Gabriel ◽  
Jean L Gerth ◽  
David L Aronson ◽  
...  

SummaryVariation of pH strongly affects the fluorescence intensity of human prothrombin fragment-1 in a manner suggesting contributions from a number of protropic equilibria including groups with apparent pKa values near 3.0. These results suggest a structural role for pKa 1 of γ-carboxyglutamic acid moieties. Added calcium ions (9 mM calcium chloride) quench the fluorescence titration curve.uniformly above pH 4. Below pH 4, however, the titration curve in the presence of calcium ions suggests that calcium-ion-dependent processes leading to fluorescence quenching are pH-dependent. Upon back titration of human fragment-1, from pH 9, hysteresis is observed.Human prothrombin fragment-2 fluorescence titration curves are relatively broad at low pH suggesting the titration of normal carboxyl groups. The titration curves of fragment-2 are not affected by the presence of calcium ions, and hysteresis occurs upon back titration from low pH values. Circular dichroism (CD) Cotton effects appear at 232 nm and 280 nm and a trough appears at 203 nm in the CD spectrum of human prothrombin fragment-2. The Cotton effects in the region from 230 nm to 300 nm are sensitive to pH, ellipticity values at 232 nm increasing from approximately 300 at pH 2.5 to 1300 (degree-cm/decimole) at neutral pH and finally become negative at high pH values. In contrast to fragment-1, at neutral pH the fragment-2 Cotton effect at 232 nm is insensitive to the presence of 8 mM calcium chloride.


Author(s):  
V. S. Soldatov ◽  
L. N. Shachenkova ◽  
E. G. Kasandrovich ◽  
P. V. Nesteronok

Curves of potentiometric titration of fully protonized fibrous ion exchangers with potassium hydroxide against the background of 1 M KCl in the presence of chlorides of Ni2+, Со2+, Сu2+ and Ca2+ were obtained. The ion exchangers were synthesized by modifying of industrial polyacrylonitrile fiber with diethylenetriamine and triethylenetetraamine and predominantly contained functional groups R-CO-NH- (CH2CH2NH)nH (n = 2 or 3) and a small amount of carboxyl groups. The sorption of Ni2+, Со2+, Сu2+ и Ca2+by ion exchangers was calculated from the data obtained depending on the pH of the medium. It was found that the investigated ion exchangers with high selectivity sorb heavy metal ions in a wide range of acidity of solutions (pH 2–9) due to the formation of metal-polymer complexes with polyamine functional groups. The maximum sorption capacity is 1.5–2.7 and 4–5 meq/g for ion exchangers with n = 2 and 3, respectively.


1969 ◽  
Vol 47 (8) ◽  
pp. 1269-1273 ◽  
Author(s):  
A. L. Beauchamp ◽  
J. Israeli ◽  
H. Saulnier

Cu(II), Ni(II), Co(II), and Zn(II) nitrilotriacetates (MeX−) react with histamine nitrate (LH+) to form a protonated mixed complex MeXLH where the metal appears to be bound only to the tertiary imidazolic nitrogen of histaminium ion. At higher pH values the proton dissociates to yield a mixed complex ion MeXL− in which both the imidazolic nitrogen and the terminal amino group are coordinated. The formation constants of these species were calculated from the potentiometric titration curves.


1981 ◽  
Vol 34 (2) ◽  
pp. 365 ◽  
Author(s):  
H Stunzi

The reactions of isatin-5-sulfonate anion (si-) which cause a hysteresis in pH titrations were studied by pH-metric and n.m.r, spectroscopic methods. Rapid alkalimetric titrations [I 0.15 M (KNO3),37�] gave the pKa value corresponding to the addition of OH- to si- [pKa(ring) 9.55]. The slow ring opening to the sulfonatoisatate dianion (sia2-) led to a drift of the pH values towards an equilibrium buffer region. Its pKa, value [pKa(eq) 3.44] corresponds to the reaction si-+H2O ↔ sia 2-+H+ Rapid back-titration gave the pKa value of the ring-opened species Hsia- [pKa(open) c. 1.3]. The rate law for the ring opening d[sia]/dt=k2 [siOH](OH)+k1*[si] was obtained from the rate of change of pH. N-Methylisatin-5-sulfonate behaves analogously.


2005 ◽  
Vol 70 (9) ◽  
pp. 1341-1356 ◽  
Author(s):  
Saima Q. Memon ◽  
Muhammad I. Bhanger ◽  
Muhammad Y. Khuhawar

A simple and reliable method has been developed using styrene-divinylbenzene-based polymeric material containing 1-nitroso-2-naphthol as chelating agent, to concentrate ultratrace amounts of Ni(II) and Cu(II) ions in aqueous samples. Sorption of both the ions on the new synthetic resin under static and dynamic conditions has been investigated. The sorption has been optimized with respect to pH, shaking and contact time of two phases. Maximum sorption has been achieved from solution of pH 5-8 after 8 min of agitation. Total saturation capacities were 516 ± 2 and 316 ± 2.5 μmol g-1 for Ni(II) and Cu(II) ions, respectively. The lowest concentration for quantitative recovery (98 ± 1%) is 1.33 and 5 ppb with the preconcentration factor of 750 and 200 for Ni(II) and Cu(II), respectively. Monitoring of the influence of diverse ions on the sorption of metal ions has revealed that phosphate, hydrogencarbonate and citrate reduce the sorption to some extent. Under optimum conditions the sorption data followed Langmuir, Freundlich, and Dubinin-Radushkevich isotherms. The kinetics and thermodynamics of sorption are studied in detail. The sorption procedure is utilized to preconcentrate these ions prior to their determination in tea, human hair, and tap water samples by atomic absorption spectrometry using direct and standard addition methods.


1970 ◽  
Vol 73 (5) ◽  
pp. 874-878 ◽  
Author(s):  
Takao YOTSUYANAGI ◽  
Katsumi GOTO ◽  
Masaichi NAGAYAMA
Keyword(s):  
Low Ph ◽  

1993 ◽  
Vol 330 ◽  
Author(s):  
John Kasianowicz ◽  
Barbara Walker ◽  
Musti Krishnasastry ◽  
Hagan Bayley

ABSTRACTWe are adapting proteins that form pores in lipid bilayers for use as components of biosensors. Specifically, we have produced genetically engineered variants of the α hemolysin (αHL) fromStaphylococcusaureus with properties that are sensitive to low concentrations of divalent cations. For example, the pore-forming activity of one mutant (αHL-H5: residues 130–134 inclusive replaced with histidine) is inhibited by Zn2+at concentrations as low as 1 μM, as judged by the reduction in its ability to lyse rabbit red blood cells and to increase the conductance of planar lipid bilayer membranes. When αHL-H5 is added to the aqueous phase bathing one side of a planar membrane, the subsequent addition of 100 μM Zn2+to either side blocks the pores that form. This result suggests that at least part of the mutated region lines the channel lumen. Ca2+and Mg2+do not block the channel and therefore the H5 mutation confers a degree of analyte specificity to the αHL pore. The results suggest that genetically engineered pores have great promise for the rapid and sensitive detection of metal cations and we discuss the merits and potential limitations for their use in this application. Specifically, we examine the issues of selectivity, sensitivity, response time, dynamic range and longevity. Some of these properties are interdependent. For example, the goals of high sensitivity and rapid response time can be in conflict.


2001 ◽  
Vol 204 (6) ◽  
pp. 1053-1061 ◽  
Author(s):  
A. Sacher ◽  
A. Cohen ◽  
N. Nelson

Transition metals are essential for many metabolic processes, and their homeostasis is crucial for life. Metal-ion transporters play a major role in maintaining the correct concentrations of the various metal ions in living cells. Little is known about the transport mechanism of metal ions by eukaryotic cells. Some insight has been gained from studies of the mammalian transporter DCT1 and the yeast transporter Smf1p by following the uptake of various metal ions and from electrophysiological experiments using Xenopus laevis oocytes injected with RNA copies (c-RNA) of the genes for these transporters. Both transporters catalyze the proton-dependent uptake of divalent cations accompanied by a ‘slippage’ phenomenon of different monovalent cations unique to each transporter. Here, we further characterize the transport activity of DCT1 and Smf1p, their substrate specificity and their transport properties. We observed that Zn(2+) is not transported through the membrane of Xenopus laevis oocytes by either transporter, even though it inhibits the transport of the other metal ions and enables protons to ‘slip’ through the DCT1 transporter. A special construct (Smf1p-s) was made to enhance Smf1p activity in oocytes to enable electrophysiological studies of Smf1p-s-expressing cells. 54Mn(2+) uptake by Smf1p-s was measured at various holding potentials. In the absence of Na(+) and at pH 5.5, metal-ion uptake was not affected by changes in negative holding potentials. Elevating the pH of the medium to 6.5 caused metal-ion uptake to be influenced by the holding potential: ion uptake increased when the potential was lowered. Na(+) inhibited metal-ion uptake in accordance with the elevation of the holding potential. A novel clutch mechanism of ion slippage that operates via continuously variable stoichiometry between the driving-force pathway (H(+)) and the transport pathway (divalent metal ions) is proposed. The possible physiological advantages of proton slippage through DCT1 and of Na(+) slippage through Smf1p are discussed.


1972 ◽  
Vol 43 (4) ◽  
pp. 553-559 ◽  
Author(s):  
C. T. Kappagoda ◽  
J. B. Stoker ◽  
H. M. Snow ◽  
R. J. Linden

1. Simultaneous CO2 titration curves of arterial and mixed venous blood were determined in both dog and man in vivo. 2. The slopes of the CO2 titration curves of mixed venous blood were significantly less than those of the corresponding arterial curves. 3. The non-respiratory pH values of the CO2 titration curves of mixed venous blood were significantly greater than those of the corresponding arterial curves. 4. The theoretical explanations of these differences have been discussed.


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