Determination Of Stability Constants Research Articles

Three cobalt(II) porphyrins ligated with pyridyl-containing nanocarbon/gold(III) porphyrin for solar cells: Synthesis and characterization

Three new donor–acceptor systems, synthesized by axial coordination of 1-N-methyl-2-(pyridin-4-yl)-3,4-fullero[60]pyrrolidine (PyC60)/2,5-di-(pyridin-2-yl)-3,4-fullero[70]pyrrolidine (Py2C70) and meso-tetra(4-pyridyl)porphyrinato)gold(III) chloride (ClAuP) with (meso-tetra(4-octyloxyphenyl)porphyrinato)cobalt(II) (CoP) were observed. In order to optimize the reaction conditions, the formation mechanism and composition of the complexes dependent on the structure of axial molecular ligand were explored. The triad, (PyC60)2CoP/(Py2C70)2CoP, and dyad, (ClAuP)CoP, were formed respectively in the two-stage and one-stage process. The confirmation of their chemical structure and determination of stability constants was performed using the UV–vis, IR, 1H NMR, MS (MALDI-TOF) spectrometry and chemical thermodynamics/kinetics, respectively. Photoelectrochemical studies of the porphyrin-fullerene/porphyrin-porphyrin systems were carried out compared with corresponding precursors by the amperometry methods. The high values of the photocurrent density and incident photon energy conversion to current (IPCE365nm) of the titanium electrode modified by (PyC60)2CoP/(Py2C70)2CoP/(ClAuP)CoP were demonstrated, which points to good perspectives in the application of the coordination complexes synthesized as a photoactive molecular material for solar cells.

Phytochelatins as a Dynamic System for Cd(II) Buffering from the Micro- to Femtomolar Range.

Phytochelatins (PCs) are short Cys-rich peptides with repeating γ-Glu-Cys motifs found in plants, algae, certain fungi, and worms. Their biosynthesis has been found to be induced by heavy metals—both biogenic and toxic. Among all metal inducers, Cd(II) has been the most explored from a biological and chemical point of view. Although Cd(II)-induced PC biosynthesis has been widely examined, still little is known about the structure of Cd(II) complexes and their thermodynamic stability. Here, we systematically investigated glutathione (GSH) and PC2–PC6 systems, with regard to their complex stoichiometries and spectroscopic and thermodynamic properties. We paid special attention to the determination of stability constants using several complementary techniques. All peptides form CdL complexes, but CdL2 was found for GSH, PC2, and partially for PC3. Moreover, binuclear species CdxLy were identified for the series PC3–PC6 in an excess of Cd(II). Potentiometric and competition spectroscopic studies showed that the affinity of Cd(II) complexes increases from GSH to PC4 almost linearly from micromolar (log K7.4GSH = 5.93) to the femtomolar range (log K7.4PC4 = 13.39) and additional chain elongation does not increase the stability significantly. Data show that PCs form an efficient system which buffers free Cd(II) ions in the pico- to femtomolar range under cellular conditions, avoiding significant interference with Zn(II) complexes. Our study confirms that the favorable entropy change is the factor governing the elevation of phytochelatins’ stability and illuminates the importance of the chelate effect in shifting the free Gibbs energy.

Spectrophotometric Determination of the Overall Stability Constants of Complexes of Calcium(Ii) Ions with Glycine, L-Methionine, and L-Tryptophan Using Multiple Linear Regression

Spectrophotometric Determination of the Overall Stability Constants of Complexes of Calcium(Ii) Ions with Glycine, L-Methionine, and L-Tryptophan Using Multiple Linear Regression

Uranyl oxalate species in high ionic strength environments: stability constants for aqueous and solid uranyl oxalate complexes

Abstract Uranyl ion, UO2 2+, and its aqueous complexes with organic and inorganic ligands can be the dominant species for uranium transport on the Earth surface or in a nuclear waste disposal system if an oxidizing condition is present. As an important biodegradation product, oxalate, C2O4 2−, is ubiquitous in natural environments and is known for its ability to complex with the uranyl ion. Oxalate can also form solid phases with uranyl ion in certain environments thus limiting uranium migration. Therefore, the determination of stability constants for aqueous and solid uranyl oxalate complexes is important not only to the understanding of uranium mobility in natural environments, but also to the performance assessment of nuclear waste disposal. Here we developed a thermodynamic model for the UO2 2+–Na+–H+–Cl––ClO4 ––C2O4 2––NO3 ––H2O system to ionic strength up to ∼11 mol•kg−1. We constrained the stability constants for UO2C2O4(aq) and UO2(C2O4)2 2− at infinite dilution based on our evaluation of the literature data over a wide range of ionic strengths up to ∼11 mol•kg−1. We also obtained the solubility constants at infinite dilution for solid uranyl oxalates, UO2C2O4•3H2O, based on the solubility data over a wide range of ionic strengths. The developed model will enable for the accurate stability assessment of oxalate complexes affecting uranium mobility under a wide range of conditions including those in deep geological repositories.

Synthesis, characterization, biological screening and determination of stability constants of N,N\u2032-Bis[1-(4-chlorophenyl)ethylidene]ethane-1,2-diamine

A Schiff base ligand, N,N′-bis[1-(4-chlorophenyl)ethylidene]ethane-1,2-diamine (SBL), was synthesized by condensation of 4-chloroacetophenone with ethylenediamine in methanol in the presence of H2SO4 as catalyst. The structure of SBL was elucidated by spectroscopic (1H-NMR, 13C-NMR, IR and MS) and elemental analyses, and also confirmed by XRD. The SBL was used to prepare metal complexes 1-2 with Pb+2 and Cd+2, respectively. The structures of the complexes were elucidated by IR, MS and elemental analyses. On the basis of electronic spectra and magnetic moment data, octahedral geometry was proposed for the synthesized complexes 1-2. The conductivity data showed the non-electrolytic nature of the complexes 1-2. The SBL and complexes 1-2 were subjected to measure their biological potential against Staphylococcus aureus, Bacillus subtilis and Escherichia coli bacteria. SBL showed non-significant anti-bacterial potential whereas complexes showed moderate potential as compared to standard impinium. In the toxicity with brine shrimp larvae, complexes showed more toxic effect than the SBL. In the experiments to determine the stability constants of SBL with CuCl2, Cu(OAc)2, CoCl2 and Co(NO3)2; SBL showed highest stability constants with Cu(OAc)2 which is 1.550 × 107 at 1:1 (L:M) and second highest with Co(NO3)2 which is 6.861 × 106 at 3:2 (L:M).

Determining Stability Constants of Complexes Between Ester Betulin Derivatives and β-Cyclodextrin by Affinity Capillary Electrophoresis

Inclusion complexes of ester betulin derivatives (pentacyclic lupane triterpenoids) with β-cyclodextrin (β-CD) were studied by affinity capillary electrophoresis. Stability constants were calculated from dependencies of viscosity-corrected effective electrophoretic mobilities on β-CD concentration (0-10 mM) in background electrolytes using nonlinear regression fitting. Logarithms of stability constants at 25 °C for 1:1 and 1:2 β-CD complexes of betulin 3,28-diphthalate, betulin 3,28-disuccinate and betulin 3,28-disulfate (95 % confidence interval) are 4.25 (4.16-4.32) and 7.27 (6.73-7.50), 4.38 (4.26-4.48) and 7.58 (6.90-7.84), 4.04 (4.00-4.08) and 5.91 (4.60-6.20), respectively

In support of hydroxycitrate being clinically investigated as a potential therapy of calcium nephrolithiasis: Theoretical modelling and in vitro investigation of thermodynamic effects

Hydroxycitrate (HCA), has been mooted as a potentially equivalent, if not superior therapy to citrate for calcium urolithiasis. However, past studies were mainly mechanistic while thermodynamic experiments were limited. We determined stability constants for HCA protonation and metal ion complexation, and measured HCA speciation by potentiometric titration. We modelled the effect of HCA, citrate and pH on calcium oxalate (CaOx) and calcium phosphate (CaP) supersaturation (SS) using the program JESS to which we had added our determined thermodynamic constants. Finally, we measured the effects of HCA on CaOx metastable limit (MSL) in artificial urine using turbidimetry. Our experiments showed that fully dissociated HCA is the dominant species at urinary pH 6. Modelling predicted that HCA decreases SS CaOx and CaP to a greater extent than citrate. In vitro experiments showed increases in the MSLs of CaOx and CaP thereby confirming favorable thermodynamic effects of HCA on SS. Clinical trials are warranted to investigate the promise of HCA for reducing this important risk factor for calcium nephrolithiasis.

Determination of Stability Constants and Thermodynamic Parameters for Ciprofloxacin-HCl With Some Transition Metal Ions by Potentiometric Titration Technique

This study included calculating the stability constants and stoichiometries of some binary complexes formed from the interaction of seven of metal ions (Cr+3,Mn+2,Co+2,Ni+2,Cu+2,Zn+2 and Cd+2) with Ciprofloxacin-HCl. This study was carried out using Potentiometric Titration Technique at different concentrations of the drug and the metal ion and at temperatures (288,298,310,318 and 328 K±0.1) in aqueous solution. Although, there are many methods available to study the stability of metal-ligand complexes, pH-metric is most frequently used to determine the stability constants. Hence, (Calvin - Bjerrum pH-metric titration technique) as adopted by Irving–Rossotti was used to calculate of stability constants. The results of the concentration effect study showed that the formation of complexes were more stable in dilute solutions, and through study of the temperature effect it was concluded that the stability of the complexes can be increased with raising temperature, and the stability constants value obtained were used in the calculation of thermodynamic parameters . The results of this study also showed that the ciprofloxacin tends to form two types of metal complexes in the solution (ML1),(ML2) and this indicates that the reaction ratio between the drug and the metal ion was (1:1) and (1:2)(M:L) respectively for all metal ions. These ratios depended on the nature of the ligand or the metal ion, and the stability of the complexes formed increases according to the following arrangement (Mn+ 2< Co+ 2< Ni+ 2< Cu+ 2> Zn+ 2) and this arrangement is compatible with Irving Williams’s arrangement for the stability of the elements.

Determination of Stability Constants of Iron(II) Complexes of as-Triazines Containing Ferroin-Yielding Chromogens

With the aim of determining stability constants of iron(II) complexes of 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine (PDT), 3-(2-pyridyl)-5,6-bis(p-methoxyphenyl)-1,2,4-triazine (PBMPT) and 3-(2-pyridyl)-5,6-bis(4-biphenyl)-1,2,4-triazine (PBBT), these organic reagents were prepared from commercially available relatively cheaper reactants. The absorptiometric characteristics of iron(II) complexes of these organic compounds; λmax and molar absorptivity (€max) were determined. The composition and stability constants of these iron(II) complexes were determined by both molar ratio and Job’s continuous variation methods. The mean logK values for iron(II) complexes of PDT, PBMPT and PBBT were found 16.48, 17.48 and 15.54 respectively reflecting the formation of very stable complexes. These are well comparable with the reported values for the iron(II) complexes of 2,2’-bipyridine, 1,10- phenanthroline, Ferrozine and Ferene. Higher sensitivity and stability constant values reflects the possibility of application of these compounds as promising chromogenic reagents for iron determination.&#x0D; Dhaka Univ. J. Sci. 68(2): 137-142, 2020 (July)

Thermodynamic Study on the Protonation and Complexation of the Neuroleptic Drug, Gabapentin with Na+, Ca2+ and Mg2+ at Various Temperatures and Ionic Strengths

The current work investigates the protonation constants of gabapentin (GP), 2-[1-(aminomethyl)cyclohexyl]acetic acid and the stability constants for the binding of GP to Ca2+ and Mg2+ in a wide range of temperature and ionic strength conditions [283.15 ≤ T/K ≤ 318.15 and ionic strengths of NaCl(aq), 0.12 ≤ I/mol·dm−3 ≤ 4.84]. The pH-potentiometric titration method was applied for gathering experimental data and determination of solution equilibrium constants. The ΔpK method was used for the determination of calcium and magnesium stability constants due to the low values which were predicted. A Debye–Huckel type equation, Specific Ion Interaction Theory, Pitzer and van’t Hoff equations were used for the modeling of ionic strength and temperature effects. Two species, ML and MHL, were found according to the best model for Ca2+ and Mg2+. Both protonation processes are exothermic based on the enthalpy values at 298.15 K and infinite dilution. A case study has been performed taking into account the speciation of GP in seawater.

Determination of stoichiometry and stability constants of iron complexes of phenanthroline, Tris(2-pyridyl)-s-triazine, and salicylate using a digital camera

The determination of stoichiometric ratios and stability constants of metal–ligand complexes is of great importance for physical, chemical, biochemical, and environmental studies and often require relatively expensive and sophisticated instruments. Herein, we introduce a simple, accurate, and low-cost method for determining these parameters by a conventional digital camera. The stoichiometric ratios and stability constants of iron complexes of 1,10-phenanthroline, 2,4,6-Tris(2-pyridyl)-s-triazine, and salicylate were determined, as model examples, using the molar ratio and the continuous variation methods. Digital images of solutions with various metal–ligand ratios were captured and analyzed, and the Yxy color absorbance and the ΔELUV color difference parameters were used as convenient analytical signals that favorably compete with conventional spectrophotometric signals. For the three studied iron complexes, the results of stoichiometric ratios and stability constants obtained from digital images were in excellent agreement with the spectrophotometric and the previously reported literature’s data.

Appropriate Buffers for Studying the Bioinorganic Chemistry of Silver(I)

Silver(I) is being largely studied for its antimicrobial properties. In parallel to that growing interest, some researchers are investigating the effect of this ion on eukaryotes and the mechanism of silver resistance of certain bacteria. For these studies, and more generally in biology, it is necessary to work in buffer systems that are most suitable, i.e., that interact least with silver cations. Selected buffers such as 4-(2-hydroxyethyl)-1-piperazineethane sulfonic acid (HEPES) were therefore investigated for their use in the presence of silver nitrate. Potentiometric titrations allowed to determine stability constants for the formation of (Ag(Buffer)) complexes. The obtained values were adapted to extract the apparent binding constants at physiological pH. The percentage of metal ions bound to the buffer was calculated at this pH for given concentrations of buffer and silver to realize at which extent silver was interacting with the buffer. We found that in the micromolar range, HEPES buffer is sufficiently coordinating to silver to have a non-negligible effect on the thermodynamic parameters determined for an analyte. Morpholinic buffers were more suitable as they turned out to be weaker complexing agents. We thus recommend the use of MOPS for studies of physiological pH.

Stability Series for the Complexation of Six Key Siderophore Functional Groups with Uranyl Using Density Functional Theory.

Determining stability constants of uranyl complexes with the principal functional groups in siderophores and identifying stability series is of great importance to predict which siderophore classes preferentially bind to UVI and, hence, impact uranium speciation in the environment. It also helps to develop resins for scavenging UVI from aqueous solutions. Here, we apply a recently developed computational approach to calculate log β values for a set of geochemically relevant uranium organometallic complexes using Density Functional Theory (DFT). We determined the stability series for catecholate, hydroxamate, α-hydroxycarboxylate, α-aminocarboxylate, hydroxy-phenyloxazolonate, and α-hydroxyimidazole with the uranyl cation. In this work, the stability constants (logβ110) of α-hydroxyimidazolate and hydroxy-phenyloxazolonate are calculated for the first time. Our approach employed the B3LYP density functional approximation, aug-cc-pVDZ basis set for ligand atoms, MDF60 ECP for UVI, and the IEFPCM solvation model. DFT calculated log β110 were corrected using a previously established fitting equation. We find that the siderophore functional groups stability decreases in the order: α-hydroxycarboxylate bound via the α-hydroxy and carboxylate groups (logβ110 = 17.08), α-hydroxyimidazolate (logβ110 = 16.55), catecholate (logβ110 = 16.43), hydroxamate (logβ110 = 9.00), hydroxy-phenyloxazolonate (logβ110 = 8.43), α-hydroxycarboxylate bound via the carboxylate group (logβ110 = 7.51) and α-aminocarboxylate (logβ110 = 4.73). We confirm that the stability for the binding mode of the functional groups decrease in the order: bidentate, monodentate via ligand O atoms, and monodentate via ligand N atoms. The stability series strongly suggests that α-hydroxyimidazolate is an important functional group that needs to be included when assessing uranyl mobility and removal from aqueous solutions.

Quantitative structure retention relationship modeling as potential tool in chromatographic determination of stability constants and thermodynamic parameters of β-cyclodextrin complexation process

When cyclodextrins (CDs) are used in chromatography analytes’ retention time is decreased with an increase in concentration of CD in the mobile phase. Thus complex stability constants can be determined from the change in retention time of the ligand molecule upon complexation. Since the preceding approach implies extensive and time-consuming HPLC experiments, the goal of this research was to investigate the possibility of using in silico prediction tools instead. Quantitative structure–retention relationship (QSRR) model previously developed to explain the retention behavior of risperidone, olanzapine and their structurally related impurities in β-CD modified HPLC system was applied to predict retention factor under different chromatographic conditions within the examined domains. Predicted retention factors were further used for calculation of stability constants and important thermodynamic parameters, namely standard Gibbs free energy, standard molar enthalpy and entropy, contributing to inclusion phenomenon. Unexpected prolonged retention with an increase in β-CD concentration was observed, in contrast to the employed chromatographic theory used for the calculation of the stability constants. Consequently, it led to failure in stability constants and thermodynamic parameters calculation for almost all analytes when acetonitrile content was 20% (v/v) across the investigated pH range. Moreover, ionization of investigated analytes and free stationary phase silanol groups are pH dependent, leading to minimization of secondary interactions if free silanol groups are non-ionized at pH lower than 3. In order to prove accuracy of predicted retention factors, HPLC verification experiments were performed and good agreement between predicted and experimental values was obtained, confirming the applicability of proposed in-silico tool. However, the obtained results opened some novel questions and revealed that chromatographic method is not overall applicable in calculation of stability constants and thermodynamic parameters indicating the complexity of β-CD modified systems.

Mass Spectrometry Reveals Complexing Properties of Modified PNP-Lariat Ether Containing Benzyl Derivative of (S)-Prolinamine.

In the investigation presented here the synthesis of new lariat ether derivative obtained from the modification of tetrapyrrolidinyl-PNP-crown ether macrocycle is described. The polyheterotopic molecular coreceptor consisted of the replacement of chlorine atoms with an optically active (S)-(1-benzylpyrrolidin-2-yl) methanamine. The structure was confirmed by using elemental analysis, mass spectrometry, and NMR spectroscopy. This work covers results concerning the complexing properties of the new ligand towards Ag+, Cu2+, Co2+, Ni2+, and Zn2+ ions. The formation of non-covalent complexes of 1:1 stoichiometry with the Cu2+, Co2+, Ni2+, and Zn2+ ions have been confirmed by mass spectrometry. Due to the previous work and application possibilities, a large emphasis was put on the investigation of the complexation ability of lariat ether with silver (I) cation to determine stability constants by direct potentiometric method. In this case, the formation of four different forms of complexes AgL, Ag2L, Ag3L, and Ag4L has been proved. The observed unusual binding through the nitrogen atoms from the exocyclic substituents may provide the structural unit to build a new coordination polymers.

Studies of the Complexation of Gluconate with Th(IV) in Acidic Solutions: Stability Constant Determination and Coordination Mode Analysis.

Gluconate is a multidentate ligand and its complexation with actinides has received increasing attention because of its existence in high level nuclear wastes as well as in nuclear waste repositories. In this work, the complexation of gluconate with Th(IV) was studied in deuterated water (D2O) by pD titrations and nuclear magnetic resonance (NMR) spectroscopy. In the pCD range 2.0-4.6, gluconate (GD4-) forms two 1:1 complexes with Th(IV), Th(GD3)2+ and Th(GD2)+. Their stability constants were determined to be log β(D)101(-1) = 1.04 ± 0.12 for Th4+ + GD4- = Th(GD3)3+ + D+ and log β(D)101(-2) = -(1.31 ± 0.09) for Th4+ + GD4- = Th(GD2)+ + 2D+ at I = 1.0 mol·L-1 NaClO4 and t = 22 °C. The coordination modes of these two complexes were also analyzed. In both complexes, the tridentate chelation forms through the binding of Th(IV) to one oxygen from the carboxylate group and two oxygens from α- and γ-hydroxyl groups. The difference is that in Th(GD2)+, both α- and γ-hydroxyl groups deprotonate, and in Th(GD3)2+, only the α-hydroxyl group deprotonates.

Speciation Studies of Bifunctional 3-Hydroxy-4-Pyridinone Ligands in the Presence of Zn2+ at Different Ionic Strengths and Temperatures.

The acid–base properties of two bifunctional 3-hydroxy-4-pyridinone ligands and their chelating capacity towards Zn2+, an essential bio-metal cation, were investigated in NaCl aqueous solutions by potentiometric, UV-Vis spectrophotometric, and 1H NMR spectroscopic titrations, carried out at 0.15 ≤ I/mol −1 ≤ 1.00 and 288.15 ≤ T/K ≤ 310.15. A study at I = 0.15 mol L−1 and T = 298.15 K was also performed for other three Zn2+/Lz− systems, with ligands belonging to the same family of compounds. The processing of experimental data allowed the determination of protonation and stability constants, which showed accordance with the data obtained from the different analytical techniques used, and with those reported in the literature for the same class of compounds. ESI-MS spectrometric measurements provided support for the formation of the different Zn2+/ligand species, while computational molecular simulations allowed information to be gained on the metal–ligand coordination. The dependence on ionic strength and the temperature of equilibrium constants were investigated by means of the extended Debye–Hückel model, the classical specific ion interaction theory, and the van’t Hoff equations, respectively.

Conformational Stability Effect of Polymeric Iron Chelators.

SummaryThe design and synthesis of metal chelators with extraordinary metal affinities is a basic and challenging scientific problem of both fundamental and practical importance. Here, we demonstrate a “conformational stability effect” that can significantly enhance the metal affinity of ligands after conjugation to polymer chains with the ability to spontaneously adopt a specific conformation as an optimal “soft” scaffold to ensure maximum thermodynamic stability of the metal complexes. Using iron chelators as models, we show that simple conjugation of small molecule catechol ligands to a polyallylamine chain resulted in more than 8–9 orders of magnitude enhancement of the iron-binding affinity, which is comparable to that of enterobactin, the strongest iron chelator ever known. This study demonstrates that flexible polymer chelators may realize the highest possible metal affinities of the conjugated ligands owing to their ability to achieve an optimal conformation, which could advance the identification of strong metal chelators.

The interaction of morin and morin-5’-sulfonic acid with lead(II): Study of the 1:1 complex formation process in aqueous solution

Abstract This article focuses on the aqueous complexation between two flavonoids (morin and morinsulfonate) and Pb2+ at constant ionic strength I=0.5 M (NaClO4). The determination of stability constants of ML complexes were performed at wide pH range. Two obtained constants are 14.8 ± 0.1 and 15.2 ± 0.1 logarithmic units for morin and morin-5’-sulfonic acid, respectively. For estimating the thermodynamic stability of the complexes studied, the Def2-SV(P)/DFT/PBE0/SMD method has been used. Different computational models were tested to describe the data obtained. The theoretical values of logK reproduce the experimental parameters within reasonable errors.

Determining Stability Constants Using the AKUFVE Technique

ABSTRACT The AKUFVE techniques were developed by Rydberg and co-workers in the 1960s. The main aim was to be able to perform a series of liquid-liquid extraction data varying one or more parameters and at the same time achieve very pure phases. As such, this technique was later used for short-lived isotope studies in the SISAK system, but also as a standalone unit for a large number of thermodynamic studies of extraction systems both for fundamental understanding as well as more applied investigations. In this paper, the apparatus with modifications made over the decades is described. In addition, studies with stability constant determinations for the zirconium-water-acetylacetone system as well as lanthanide extraction using bromodecanoic acid are exemplified to demonstrate the potential use of the technique. The results shown clearly demonstrate the versatility and ability of the AKUFVE system.