Equilibria of the Simultaneously Existing Multiple Species in the Copper(II)–L-Histidine System

1973 ◽  
Vol 51 (21) ◽  
pp. 3549-3554 ◽  
Author(s):  
Theo P. A. Kruck ◽  
Bibudhendra Sarkar

The complete species distribution and the stability constants of the complex species in the Cu(II)–L-histidine system have been worked out for the pH range 2–11. The method of "analytical potentiometry" has been applied successfully to this system having excess ligand with respect to Cu(II) ion. The equilibria of three systems of Cu(II) (M) and L-histidine (H3A) in molar ratios of 1:2, 1:4, and 1:8 were investigated by this technique in 0.15 M NaCl at 25°. The following species were detected in this system: MHA, MA, MH2A2, MHA2, MA2, MH−1A2, MH−1A, and M2H−2A2. Statistical analysis on the numerical results has been performed and is given as standard deviation together with the individual values for the stability constants.

1973 ◽  
Vol 51 (21) ◽  
pp. 3555-3562 ◽  
Author(s):  
Theo P. A. Kruck ◽  
Bibudhendra Sarkar

The equilibria involved in the ternary systems Cu(II)–A–B′ and Cu(II)–A–B″ (A = L-histidine, B′ = L-serine, B″ = L-glutamine) have been investigated by potentiometry in aqueous solution (0.15 M NaCl, 25°). In the ternary system Cu(II)–A–B′, three mixed complexes (MHAB′, MAB′, and MH−1AB′) were detected in addition to the binary complex species (MHA, MA, MH2A2, MHA2, MA2, MH−1A2, MB′, MB′2). The results observed in the Cu(II)–A–B″ system were quite similar to the system Cu(II)–A–B′ except that it did not show the presence of the species MH−1AB″. The stability constants were refined with a general least squares treatment. In the case of an equimolecular mixture of the constituents, a maximum of about 75% of Cu(II) is present as MAB′ at pH 5.5–9 and about 60% of Cu(II) as MAB″ at pH 5–10 when the concentration of each constituent is set equal to 10−2 M. A theoretical analysis and derivations of the expected stability constants of the complexes are presented on the basis of successive formation constants of the individual complexes carrying identical ligands. In each case an enhancement of the stability was observed with the ternary coordination complexes. Attempts have been made to explain the enhanced stability of the ternary coordination complexes.


1973 ◽  
Vol 51 (21) ◽  
pp. 3563-3571 ◽  
Author(s):  
Theo P. A. Kruck ◽  
Bibudhendra Sarkar

The presence of simultaneously existing multiple species were taken into account in interpreting the structures of the complex species in the Cu(II)–L-histidine system. A refined proton displacement technique was utilized for structure elucidation of the species in solution. The absorbance and the molar extinction of the individual species were computed from the total absorbance and the species distribution over the pH range studied. The i.r. spectra of L-histidine and Cu(II)–L-histidine in D2O were obtained as a function of pD. They were interpreted in view of the species detected in a given pH range. The results of the species distribution as a function of pH, proton displacement, visible spectra of the individual species, and infrared data, were all combined to make structural interpretations. The following modes of metal coordination were proposed for the major species in the Cu(II)–L-histidine system: MHA, O(carboxyl) and N(imidazole); MH2A2, O(carboxyl) and N(amino) in both L-histidines; MA, O(carboxyl), N(imidazole), and N(amino); MHA2O(carboxyl), N(imidazole), and N(amino) in one L-histidine and O(carboxyl) and N(amino) in the other; MA2, O(carboxyl). N(imidazole), and N(amino) in both L-histidines, or O(carboxyl), N(imidazole), and N(amino) in one L-histidine and N(amino) and N(imidazole) in the other or an equilibrium mixture of both structures.


1981 ◽  
Vol 199 (3) ◽  
pp. 649-656 ◽  
Author(s):  
S J Lau ◽  
B Sarkar

The interaction between Cu(II) and the growth-modulating tripeptide glycyl-L-histidyl-L-lysine in the presence and absence of L-histidine was investigated by potentiometric titration and visible-absorption spectrophotometry at 25 degrees C in 0.15 M-NaCl. Analyses of the results in the pH range 3.5--10.6 indicated the presence of multiple species in solution in the binary system and extensive amounts of the ternary complexes in the ternary system. The species distribution and the stability constants, as well as the visible-absorption spectra of the species, were evaluated. The combined results were used to propose the structure of some of the complexes. The influence of the epsilon-amino group of the peptide in the enhancement of the stability constants was reflected prominently when compared with those complexes formed by either glycyl-L-histidine or glycyl-L-histidylglycine. The results obtained from the equilibrium-dialysis experiments showed that this tripeptide was able to compete with albumin for Cu(II) at pH 7.5 and 6 degrees C. At equimolar concentrations of albumin and the peptide, about 42% of the Cu(II) was bound to the peptide. At the physiologically relevant concentrations of Cu(II), albumin, L-histidine and this peptide, about 6% of the Cu(II) was associated with the low-molecular-weight components. This distribution could be due to the binary as well as the ternary complexes. The possible physiological role of these complexes in the transportation of Cu(II) from blood to tissues is discussed.


1968 ◽  
Vol 21 (3) ◽  
pp. 641 ◽  
Author(s):  
RS Saxena ◽  
KC Gupta ◽  
ML Mittal

Potentiometric and conductometric studies of the nickel-thiomalic acid system, in aqueous medium of 0. lM KNO3, reveal the formation of two complexes; one light violet 1 : 1 predominating at pH 6.5-7.5 and another deep violet 1 : 2 in the pH range 8.5-10.0. The stability constants of the complexes formed have been determined by applying Calvin and Melchior's extension of Bjerrum's method at three different temperatures and were further refined by using alternative methods. The logK values (final) for 1 : 1 and 1 : 2 complexes at 20, 25, and 30� have been found to be 7.86, 7.87, 7.96, and 6.24, 6.31, 6.39 respectively. The values of the overall changes in ΔG, ΔH, and ΔS accompanying the reaction have also been evaluated at 25� and found to be -19.31 kcal/mole, -8.77 kcal/mole, and +35.36 cal/deg respectively.


2018 ◽  
Vol 11 (7) ◽  
pp. 4059-4072 ◽  
Author(s):  
Sergio Fabián León-Luis ◽  
Alberto Redondas ◽  
Virgilio Carreño ◽  
Javier López-Solano ◽  
Alberto Berjón ◽  
...  

Abstract. Total ozone column measurements can be made using Brewer spectrophotometers, which are calibrated periodically in intercomparison campaigns with respect to a reference instrument. In 2003, the Regional Brewer Calibration Centre for Europe (RBCC-E) was established at the Izaña Atmospheric Research Center (Canary Islands, Spain), and since 2011 the RBCC-E has transferred its calibration based on the Langley method using travelling standard(s) that are wholly and independently calibrated at Izaña. This work is focused on reporting the consistency of the measurements of the RBCC-E triad (Brewer instruments #157, #183 and #185) made at the Izaña Atmospheric Observatory during the period 2005–2016. In order to study the long-term precision of the RBCC-E triad, it must be taken into account that each Brewer takes a large number of measurements every day and, hence, it becomes necessary to calculate a representative value of all of them. This value was calculated from two different methods previously used to study the long-term behaviour of the world reference triad (Toronto triad) and Arosa triad. Applying their procedures to the data from the RBCC-E triad allows the comparison of the three instruments. In daily averages, applying the procedure used for the world reference triad, the RBCC-E triad presents a relative standard deviation equal to σ = 0.41 %, which is calculated as the mean of the individual values for each Brewer (σ157 = 0.362 %, σ183 = 0.453 % and σ185 = 0.428 %). Alternatively, using the procedure used to analyse the Arosa triad, the RBCC-E presents a relative standard deviation of about σ = 0.5 %. In monthly averages, the method used for the data from the world reference triad gives a relative standard deviation mean equal to σ = 0.3 % (σ157 = 0.33 %, σ183 = 0.34 % and σ185 = 0.23 %). However, the procedure of the Arosa triad gives monthly values of σ = 0.5 %. In this work, two ozone data sets are analysed: the first includes all the ozone measurements available, while the second only includes the simultaneous measurements of all three instruments. Furthermore, this paper also describes the Langley method used to determine the extraterrestrial constant (ETC) for the RBCC-E triad, the necessary first step toward accurate ozone calculation. Finally, the short-term or intraday consistency is also studied to identify the effect of the solar zenith angle on the precision of the RBCC-E triad.


1977 ◽  
Vol 55 (14) ◽  
pp. 2613-2619 ◽  
Author(s):  
M. S. El-Ezaby ◽  
M. A. El-Dessouky ◽  
N. M. Shuaib

The interactions of Ni(II) and Co(II) with 2-pyridinecarboxaldehyde have been investigated in aqueous solutions at μ = 0.10 M (KNO3) at 30 °C. The stability constants of different complex equilibria have been determined using potentiometric methods. Spectrophotometric methods were also used in the case of the nickel(II) – 2-pyridinecarboxaldehyde system. It was concluded that nickel(II) and cobalt(II), analogous to copper(II), enhance hyrdation of 2-pyridinecarboxaldehyde prior to deprotonation of one of the geminal hydroxy groups. Complex species of 1:1 as well as 1:2 metal ion to ligand composition exist under the experimental conditions used.


2019 ◽  
Vol 2019 ◽  
pp. 1-7
Author(s):  
Felix Maurer ◽  
Martin Geiger ◽  
Thomas Volk ◽  
Daniel I. Sessler ◽  
Sascha Kreuer ◽  
...  

The anesthetic propofol and other exhaled organic compounds can be sampled in Tenax sorbent tubes and analyzed by gas chromatography coupled with mass spectrometry. The aim of this study was to evaluate the stability of propofol in Tenax sorbent tubes during overseas shipping. This is relevant for international pharmacokinetic studies on propofol in exhaled air. Tenax sorbent tube propofol samples with concentrations between 10 and 100 ng were prepared by liquid injection and with a calibration gas generator. For each preparation method, one reference set was analyzed immediately after preparation, a second set was stored at room temperature, and a third one was stored refrigerated. The fourth set was sent from Germany by airmail to USA and back. The shipped set of tubes was analyzed when it returned after 55 days elapsed. Then, the room temperature samples and the refrigerated stored samples were also analyzed. To evaluate the stability of propofol in the stored and shipped tubes, we calculated the recovery rates of each sample set. The mean recovery in the stored samples was 101.2% for the liquid preparation and 134.6% for the gaseous preparation at 4°C. At 22°C, the recovery was 96.1% for liquid preparation and 92.1% for gaseous preparation, whereas the shipped samples had a recovery of 85.3% and 111.3%. Thus, the deviation of the shipped samples is within a range of 15%, which is analytically acceptable. However, the individual values show significantly larger deviations of up to -32.1% (liquid) and 30.9% (gaseous). We conclude that storage of propofol on Tenax tubes at room temperature for 55 days is possible to obtain acceptable results. However, it appears that due to severe temperature and pressure variations air shipment of propofol samples in Tenax tubes without cooling shows severe deviations from the initial concentration. Although it was not tested in this study, we assume that refrigerated transport might be necessary to obtain comparable results as in the stored samples.


2001 ◽  
Vol 89 (6) ◽  
Author(s):  
K. Vercammen ◽  
M.A. Glaus ◽  
Luc R. Van Loon

The complexation of Th(IV) and Eu(III) by α-isosaccharinic acid (ISA) has been studied in the pH range from 10.7 to 13.3 by batch sorption experiments, and the influence of Ca on the complexation was investigated. Sixteen data sets – each determined at variable ISA concentrations – are used to determine the stoichiometry of the complexation reactions and the stability constants. Based on best-fit analysis of the sorption data, it is postulated that 1:1 Th:ISA complexes are formed in the absence of Ca according to the complexation reaction: Th+ISA↔(ThISA)


1984 ◽  
Vol 49 (1) ◽  
pp. 39-44 ◽  
Author(s):  
Emanuel Makrlík ◽  
Jaroslava Hálová ◽  
Miroslav Kyrš

The stability constants for the ML+ complex species, where M+ is an alkali metal cation and L is dibenzo-18-crown-6, in nitrobenzene saturated with water were calculated by employing published equilibrium data. The stability is found to increase in the cation order Li+ < Cs+ < Rb+ < K+ < Na+. For the NaL+, KL+, RbL+, and CsL+ complex cations the individual extraction constants in the water-nitrobenzene system were determined; their values increase in the series Na+ < K+ < Rb+ < Cs+.


2016 ◽  
Vol 81 (6) ◽  
pp. 661-672
Author(s):  
Zaklina Todorovic ◽  
Ljubinka Rajakovic ◽  
Antonije Onjia

Interpretive retention modeling was utilized to optimize the isocratic ion chromatographic (IC) separation of the nine anions (formate, fluoride, chloride, nitrite, bromide, nitrate, phosphate, sulfate, oxalate). The carbonate-bicarbonate eluent was used and separation was done on a Dionex AS14 ion-exchange column. The influence of combined effects of two mobile phase factors, the total eluent concentration (2 - 6 mM) and the carbonate/bicaronate ratio from 1:9 to 9:1 (which corespondent to pH range 9.35 - 11.27), on the IC separation was studied. The multiple species analyte/eluent model that takes into account ion-exchange equilibria of the eluent and sample anions was used. In order to estimate the parameters in the model, a non-linear fitting of the retention data, obtained at two-factor three-level experimental design, was applied. To find the optimal conditions in the experimental design, the normalized resolution product as a chromatographic objective function was employed. This criterion includes both the individual peak resolution and the total analysis time. A good agreement between experimental and simulated chromatograms was obtained.


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