Stability Constants Of Complexes Research Articles

A Combined Thermodynamic and Computational Study of Alkaline Earth Metal Cations Complexation by a Fluorescent Calix[4]arene Receptor

Complexation of alkaline earth metal cations with fluorescent tertiary-amide lower-rim calix[4]arene derivative bearing two phenanthridine moieties was studied experimentally (UV spectrophotometry, fluorimetry, isothermal microcalorimetry, NMR spectroscopy) and computationally (classical molecular dynamics and DFT calculations) at 25 °C. The complexation reactions were studied in acetonitrile, methanol, and ethanol, whereby the solvent effect on cation-binding processes was particularly addressed. The complex stability constants and standard reaction thermodynamic quantities (Gibbs energies, enthalpies, and entropies) were determined. The receptor exhibited particularly high affinity towards alkaline earth metal cations in acetonitrile, with peak affinity for Ca2+. The stability of all complexes was significantly lower in ethanol and methanol, where the most stable complex was formed with Sr2+. The decrease in cation-binding abilities was a consequence of the differences in solvation of the reactants and products of the complexation reactions (involving inclusion of the solvent molecule in the calixarene cone), cation charge density, as well as the cation–ligand binding site compatibility. The reactions were enthalpically controlled in acetonitrile, whereas in methanol and ethanol, the binding processes were endothermic and thus entropy driven. The results of 1H NMR measurements, MD simulations, and DFT calculations provided an insight into the structure of the complexes and the corresponding adducts with solvent molecules, as well as the structural aspects behind the differences in complexation thermodynamics. Due to the significant increase in its fluorescence upon cation binding, the studied calixarene derivative was proven to be a promising luminescent sensor for alkaline earth metal cations.

Comprehensive Chemical Analysis of the Methyl 3-Nitrogen-2,3-Dideoxysaccharides Derivatives with d-ribo-Configuration: Synthesis, Reactivity of HIV-1 Reverse Transcriptase Inhibitors.

This study extends previous research, particularly focusing on patented scientific objects No. ID: PL 240 353 B1, investigating the physicochemical properties of the methyl 3-azido- and 3-amino-2,3-dideoxysaccharides with a nucleoside scaffold similar to 3'-azidothymidine (AZT). The study utilizes multiwavelength spectrophotometric and potentiometric methods to evaluate the ionization of the saccharide units in aqueous solutions. pKa values, obtained from two independent methods, reveal significant sugar ionization effects on UV spectra with varying pH levels. Stability constants for divalent metal ion complexes (Cu2+ and Ni2+) with the saccharide isomers indicate that complex stoichiometries and stabilities are highly dependent on the configuration of sugar ring substituents. Spectrophotometric results show a descending order of CT-DNA-binding affinity: BRNH2OMe > BRN3OMe > ARN3OMe > ARNH2OMe, suggesting varied interaction strengths. Molecular docking of models of synthesized O-glycosides confirmed their potential as reverse transcriptase inhibitors. Among the derivatives tested, the compound BRN3OMe displays the highest interaction with the enzyme active site residues and DNA, suggesting it may possess the greatest efficacy. Our reported results highlight the promising inhibitory properties of novel O-glycosides against HIV reverse transcriptase, supporting their potential development as antiviral agents.

Linear free energy relationship modelling for predicting metal-ligand stability constants by thermodynamic radii

ABSTRACT The thermodynamic radii of 15 metal ions Ag+, Al3+, Am3+, Ba2+, Be2+, Fe3+, Ga3+, Hg2+, In3+, K+, Li+, Na+, NpO2 +, Sr2+, and UO2 2+ were calculated by linear free energy relationship modelling using 8269 experimental stability constants (logK) of ML complexes of 42 metal ions (M) and 1990 diverse organic ligands (L) in water. The predictive performance of relationships on the base of the thermodynamic radii was estimated on 5272 combinations of ligands and metal ion pairs of external test sets. Squared determination coefficient ( R d e t 2 ) and root mean squared error (RMSE) of logK predictions are 0.801 and 2.4 for combined data of the test sets, respectively. The corresponding performances for the 3003 combinations of training data are R d e t 2 0.921 and RMSE 1.7.

Kratom Alkaloids: A Blood-Brain Barrier Specific Membrane Permeability Assay-Guided Isolation and Cyclodextrin Complexation Study.

Mitragynine is an "atypic opioid" analgesic with an alternative mechanism of action and a favorable side-effect profile. Our aim was to optimize the alkaloid extraction procedure from kratom leaves and to determine and isolate the most relevant compounds capable of penetrating the central nervous system. The PAMPA-BBB study revealed that mitragynine and its coalkaloids, speciociliatine, speciogynine, and paynantheine, possess excellent in vitro BBB permeability. An optimized sequence of CPC, flash chromatography, and preparative HPLC methods was used to isolate the four identified BBB+ alkaloids. To improve the bioavailability of the isolated alkaloids, their cyclodextrin (CD) complexation behavior was investigated via affinity capillary electrophoresis using almost 40 CD derivatives. The apparent alkaloid-CD complex stability constants were determined and compared, and the most relevant CDs phase-solubility studies were also performed. Both the neutral and negatively charged derivatives were able to form complexes with all four kratom alkaloids. It was found that cavity size, substituent type, and degree of substitution also influenced complex formation. The negatively charged Sugammadex, Subetadex, and the sufoalkylated-beta-CD analogs were able to form the most stable complexes, exceeding 1000 M-1. These results serve as a good basis for further solubility and stability enhancement studies of kratom alkaloids.

Preparation, characterization, and in vitro cytogenotoxic evaluation of a novel dimenhydrinate-β-cyclodextrin inclusion complex.

Dimenhydrinate (DMH), used to alleviate motion sickness symptoms such as nausea, vomiting, dizziness, and vertigo, encounters limitations in oral pharmaceutical formulations due to its poor water solubility and bitter taste. Our research hypothesized that inclusion complexation with β-cyclodextrin (β-CD) might address these drawbacks while ensuring that the newly formed complexes exhibit no cytotoxic or genotoxic effects on peripheral blood mononuclear cells (PBMCs). Inclusion complexes were prepared using the kneading method and the solvent evaporation method. The phase solubility analysis, attenuated total reflectance-fourier transform infrared spectroscopy (ATR-FTIR), and differential scanning calorimetry (DSC) were conducted to evaluate the complexation efficacy and stability constant of the new binary systems. The results demonstrated that both methods provided complete and efficient complexation. Cytogenotoxic analysis, including the 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl tetrazolium bromide (MTT) assay, alkaline comet assay, and cytokinesis-block micronucleus cytome (CBMN-cyt) assay, was conducted to assess the cytogenotoxic potential of DMH-β-CD inclusion complexes, a topic previously unexamined. No cytotoxic or genotoxic effects were observed within the concentration range of 36.36 to 109.09 ng/mL. Cell viability of treated PBMCs exceeded 85% for all tested concentrations. No significant increases in DNA strand breaks were observed at any dose, and tail intensity of all complexes remained lower or up to 2.2% higher than the negative control. Parameters indicating genotoxic effects, as well as cytotoxic and cytostatic potential in the CBMN-cyt assay, did not significantly differ from untreated controls. These results suggest that inclusion complexation with β-CD might be a safe and promising solution to overcome the limitations of poor solubility and unpleasant taste of DMH, potentially providing opportunities for new and improved oral pharmaceutical dosage forms.

Temperature Changes in Luminescence of Mixed Complexes of Terbium and Samarium with Organic Ligands Based on 2,2-bipyridyldicarboxamides

Solutions in acetonitrile of three mixed complexes of rare earth elements (terbium and samarium) with organic ligands with various pyridine substituents were studied in this work. The ratios of ligands and metals in the resulting complexes were determined, and the stability constants of samarium complexes were calculated using the spectrophotometric titration method. Measurements of absorption, emission and excitation spectra of luminescence, luminescence kinetics of solutions of mixed complexes of rare earth elements with an excess of metal relative to the ligand were carried out at various temperatures in the range 298–328 K. An increase of luminescence intensity of a samarium ion in complex upon heating has been discovered for the first time. The dependences of the luminescence quantum yield and lifetime of mixed complexes on temperature were obtained. A thermometric parameter — the ratio of the integral luminescence intensities of samarium and terbium ions — was proposed, and the temperature sensitivity coefficient of this parameter was determined for different complexes.

Cyclic voltammetry analysis of mercuric chloride redox reactions with orange G dye

This study investigates the redox behavior of bulk and nano mercuric chloride (HgCl2) using cyclic voltammetry in the presence and absence of Orange G dye, employing 0.1 M KCl as the supporting electrolyte at room temperature. The effects of varying scan rates on electrode processes and redox reaction kinetics were analyzed, revealing that the choice of electrode material, specifically a glassy carbon electrode, significantly influences reproducibility and sensitivity. The study has implications for various applications, including environmental and analytical chemistry. The interaction between mercuric chloride and Orange G was characterized through specific scan rates, highlighting distinct redox peaks and current changes. This research underscores cyclic voltammetry as a powerful technique for probing redox reactions, electroactive species, and complexation processes. Additionally, the determination of complexation stability constants and Gibbs free energies provides valuable insights into the nature of these interactions, paving the way for future applications in environmental and analytical chemistry.Environmental Implication: The redox behaviour of hazardous substance mercuric chloride in the presence of orange G dye has been studied, and the results have important environmental implications. By studying the electrode processes and redox reaction kinetics using cyclic voltammetry, researchers can gain a better understanding of how mercuric chloride behaves in different environmental conditions.The environmental implications of this research are significant. Understanding how mercuric chloride interacts with organic dyes can inform strategies to mitigate mercury pollution, a pressing issue in environmental chemistry. The findings contribute to the broader goal of developing effective remediation strategies for contaminated ecosystems.

Influence of Sodium Lauryl Sulfate Anionic Micelles on the Complex Equilibria of Divalent Metal Ions with Isoleucine Amino Acid

The main objective of the present investigation is the formation analysis of metal-ligand complexes of isoleucine with divalent calcium, magnesium and zinc metal ions in various concentrations of sodium dodecyl sulphate (0.0, 0.5, 1.0, 1.5, 2.0 and 2.5 percent w/v). To look into the impact of the concentration of negatively charged micelles, the parameters were changed and the possible chemical species of isoleucine that interact with the metal ions, are being studied. The experiment was performed using pH meter at 303 K using NaCl to keep ionic strength stable at 0.16 mol dm-3 in the presence of anionic surfactant sodium dodecyl sulphate (SDS). The determination of the correction factor was conducted via the computer program SCPHD. The computational software MINIQUAD75 is utilized to determine the stability constants of ligand-metal complexes through the analysis of titration data. Based on statistical features such as skewness, 2, kurtosis and crystallographic R-factor, the best fit to the complicated speciation was selected. The metal ions Ca (II), Mg (II) and Zn (II) formed complexes ML, ML2 and ML2H2 for Ca (II), Mg(II) and ML, ML2 and ML2H for Zn (II) through the complexation of isoleucine. In order to validate the accuracy of the final established model, deliberate defects were introduced into the relevant components.

Evaluation of Stability constant of Binary complex of Tannic Acid with Fe(II) in Aqueous Solution: Potentiometric Study

In this study, the protonation equilibria of the tannic acid was determined and used for determining the stability constants of the binary complexes formed with iron (II) ions in the aqueous medium under the experimental conditions by potentiometric method using Irving and Rossotti equation, where Stability constant was 3.205 for Fe(II)–tannic acid complex, while Fe(II) was formed complexes with tannic acid of various stoichiometries, which in the 1:1 molar ratio at pH = 11.24. Furthermore, the ionic strength and the influence of temperature on the stability of the complexes is investigated, where stability constant in presence 0.1 M NaCl (ionic strength) of binary iron-Tan complex equal 3.254, and at different temperatures were log K1= 3.156 at 298.15 K, log K1 = 3.205 at 310.15 K, and log K1 = 3.256 at 313.15 K.

Stability of metal ion complexes with the synthetic phytosiderophore proline-2'-deoxymugineic acid.

Adequate micronutrient concentrations in crops are essential for human health and agricultural productivity. However, 30% of plants growing on cultivated soils worldwide are deficient in iron (Fe). Because of low micronutrient bioavailability, graminaceous plants have evolved to exude small molecules, called phytosiderophores, into the soil environment, which strongly complex and promote uptake of trace elements. The development of a synthetic phytosiderophore, proline-2'-deoxymugeneic acid (PDMA), has been shown to promote Fe uptake in rice plants; however, its binding capabilities with other metals, which may impact the ability to promote the uptake of Fe and other trace nutrient metals commonly found in soils, remain unknown. We conducted spectrophotometric titrations to determine the stability constants (logK) of PDMA complexes with Mn(II), Co(II), Cu(II), Ni(II), and Zn(II). We determined that PDMA complex stability constants correlated with: (1) the hydrolysis constants of metal ions (logKOH) in complexes; (2) the ionic potential of complexed metals; and (3) the corresponding complex stability constants of other mugineic acid type phytosiderophores, as well as the trishydroxamate microbial siderophore DFOB. These correlations demonstrate the potential, and limitations, on our ability to predict the stability of phytosiderophore complexes with metal ions with different physicochemical properties and with potentially different coordination structures.

Metal-Fluoride Complex Stability Constant in Acid Solution as an Indicator to Identify the Corrosion Behavior of Metal Cations on Titanium

The Ti was immersed in 0.058 mol/L NaF containing 1.68 mol/L H2SO4 solution with different metal cations (Ca2+, Cu2+, Fe2+, Mg2+, Mn2+, Ni2+, Zn2+, Al3+, and Fe3+) for 7 d to identify the role of metal cations on corrosion behavior of titanium. To elucidate the role of metal cations on the corrosion behavior of Ti in acid solution, the standard electrode potential, E0, hardness of metal cations, X, and metal-fluoride complex stability constant, Kn, were chosen as the potential indicator. It is found that the mass loss fraction obtained from the immersion tests as a function of the metal-fluoride complex stability constant, Kn, has the highest correlation coefficient (0.92). The metal cations (Al3+ and Fe3+) with higher stability constant of the metal-fluoride complex in acid solution, (Kn > 3.27), show corrosion inhibition effect on Ti in acid solution. The Kn could be a suitable indicator to understand the role of metal cations on the Ti corrosion mechanism.

Influence of Sodium Dodecyl Sulfate Anionic Micelles on The Complex Equilibria of Divalent Metal Ions with L-Leucine Amino Acid

The main objectives of the present investigation are the formation analysis of metal-ligand complexes of L-Leucine with divalent calcium, magnesium, and zinc metal ions in various concentrations of sodium dodecyl sulphate (0.0, 0.5, 1.0, 1.5, 2.0, and 2.5 percent w/v). To also look into the impact of the concentration of negatively charged micelles, the parameters that were changed, and the possible chemical species of L-Leucine that interact with the metal ions that were being studied. The experiment was performed using pH meter at 303 K using NaCl to keep your ionic strength stable of 0.16mol dm-3 in the presence of anionic surfactant, sodium dodecyl sulphate (SDS). The determination of the correction factor was conducted via the computer program SCPHD. The computational software MINIQUAD75 is utilized to determine the stability constants of ligand-metal complexes through the analysis of titration data. Based on statistical features such as skewness, 2, kurtosis, and crystallographic R-factor, the best fit to the complicated speciation was selected. The metal ions Ca (II), Mg (II), and Zn (II) formed complexes ML, ML2, and ML2H2 for Ca (II), and ML, ML2, and ML2H for Mg (II) and Zn (II) through the complexation of L-Leucine. In order to validate the accuracy of the final established model, deliberate defects were introduced into the relevant components.

Metal Complexes in Biology and Medicine: The System Cadmium (II)/ Iron (II)/ Zinc (II)- α- Aminobutyric Acid

Metal ions play an important role in biological systems. The importance of metal ions to essential functions of living systems and for wellbeing of living organisms is well known. Complexation reactions of α– aminobutyric acid with cadmium (II), iron (II) and zinc (II) have been studied in solution phase using paper ionophoretic technique. The present method is based upon the migration of a spot of metal ion on a paper strip at different pH values of background electrolyte containing 0.01M α -aminobutyric acid. A graph of pH against mobility was used to obtained information in the binary complexes and to calculate its stability constants. The logarithm stability constants of ML and ML2 complexes of α -aminobutyric acid were found to be (4.01 ± 0.02; 2.72 ± 0.01), (3.73 ± 0.03; 2.65 ± 0.09), (4.45 ± 0.02; 2.80 ± 0.03) for cadmium (II), iron (II) and zinc (II) complexes, respectively at ionic strength 0.1 molL-1 and a temperature of 35º C. Metal based drugs bioactivity can be increase by metal chelation, which in turn increase their absorbance and stability. Metal complexes can offer their action such as anti-inflammatory, anti-diabetic, antimicrobial, anticancer and ant thyroid compounds.

Seasonal studies of aquatic humic substances from Amazon rivers: characterization and interaction with Cu (II), Fe (II), and Al (III) using EEM-PARAFAC and 2D FTIR correlation analyses.

Aquatic humic substances (AHS) are defined asan important components of organic matter, being composed as small molecules in a supramolecular structure and can interact with metallic ions, thereby altering the bioavailability of these species. To better understand this behavior, AHS were extracted and characterized from Negro River, located near Manaus city and Carú River, that is situated in Itacoatiara city, an area experiencing increasing anthropogenic actions; both were characterized as blackwater rivers. The AHS were characterized by 13C nuclear magnetic ressonance and thermochemolysis GC-MS to obtain structural characteristics. Interaction studies with Cu (II), Al (III), and Fe (III) were investigated using fluorescence spectroscopy applied to parallel factor analysis (PARAFAC) and two-dimensional correlation spectroscopy with Fourier transform infrared spectroscopy (2D-COS FTIR). The AHS from dry season had more aromatic fractions not derived from lignin and had higher content of alkyls moities from microbial sources and vegetal tissues of autochthonous origin, while AHS isolated in the rainy season showed more metals in its molecular architecture, lignin units, and polysacharide structures. The study showed that AHS composition from rainy season were able to interact with Al (III), Fe (III), and Cu (II). Two fluorescent components were identified as responsible for interaction: C1 (blue-shifted) and C2 (red-shifted). C1 showed higher complexation capacities but with lower complexation stability constants (KML ranged from 0.3 to 7.9 × 105) than C2 (KML ranged from 3.1 to 10.0 × 105). 2D-COS FTIR showed that the COO- and C-O in phenolic were the most important functional groups for interaction with studied metallic ions.

17-β-Estradiol—β-Cyclodextrin complex as an aqueous solution: Structural and physicochemical characterization supported by MM and QM calculations

17-β-estradiol (EST) is an Active Pharmaceutical Ingredient characterized by a low water solubility. Complexation with β-cyclodextrin (βCD) enhances its bioavailability, hence such complex is an interesting research object from pharmaceutical point of view. However, basic facts like description of complex's structure and definition of its molar ratio, were debatable already for decades. This work for the first time justifies the EST:βCD molar ratio as 1:2 using the HRMS (high-resolution mass spectrometry) and phase solubility studies. The latter are used to define complex stability constant, as well. The structure and stability is analyzed using a variety of computational approaches: Quantum Mechanics (QM) based methods (DFT, semiempirical approaches) and MD/MMGBSA approach. In case of the QM, for the first time in the computational analysis of cyclodextrin complexes, a thorough benchmarking test is presented. Different computational parameters (solvent model, presence/absence of dispersion correction etc.) are used. Obtained results are compared with the experimental data.

Metal Complexes in Biology and Medicine the System Cadmium (II) / Iron (II) /Zinc (II) - Proline

Metal ions are fundamental elements for the maintenance of the life span’ s of the humans, animals and plants. In coordination compound studies, a knowledge of the magnitude of the stability constants of complexes is necessary for preliminary quantitative treatment. Present work described method that involves the use of paper electrophoretic technique for the study of the equilibria in binary complex systems in solution. This method is based on the movement of a spot of metal ion in an electric field at various pHs of the background electrolyte. A plot of overall mobility of metal / complex ion versus pH was used to obtain information on the formation of binary complexes and to calculate their stability constants. The stability constant of the ML and ML2 complexes of cadmium (II) – proline,iron(II) – proline and zinc(II) – proline, have been found to be (4.61 ± 0.01; 3.04 ± 0.03), (4.21 ± 0.01; 2.89 ± 0.09) and (4.98 ± 0.02; 2.44 ± 0.05) (logarithm constant values), respectively at 35 ºC and ionic strength 0.1 mol L-1. The first and second stability constants follow the order zinc (II) >cadmium (II) > iron (II). Metal complexes can offer their action such as anti-inflammatory, antidiabetic, antimicrobial, anticancer and ant thyroid compounds. Metal based drugs bioactivity can be increase by metal chelation, which in turn increase their absorbance and stability.

Heterocyclic fluorescent Schiff base chemosensors for the detection of Fe(III) and Cu(II) ions.

Two new Schiff bases were synthesized from 1-(2,4-dihydroxyphenyl)ethanone and pyridine derivatives. Both compounds were characterized using infrared, UV-Vis., 1H NMR, 13C NMR and mass spectral studies. Density functional theory (DFT) calculations were performed for both the Schiff bases with 6-31G(d, p) as the basis set. Vibrational frequencies calculated using the theoretical method were in good agreement with the experimental values. Both the Schiff bases were highly fluorescent in nature. The cation-recognizing profile of the compounds was investigated in aqueous methanol medium. The Schiff base 4-(1-(pyridin-4-ylimino)ethyl)benzene-1,3-diol (PYEB) was found to interact with Fe(III) and Cu(II) ions, whereas the Schiff base 4,4'-((pyridine-2,3-diylbis(azanylylidene))bis(ethan-1-yl-1-ylidene))bis(benzene-1,3-diol) (PDEB) was found to detect Cu(II) ions. The mechanism of recognition was established as combined excited state intramolecular proton transfer (ESIPT)-chelation-enhanced fluorescence (CHEF) effect and chelation-enhanced quenching (CHEQ) process for the detection of Fe(III) and Cu(II) ions, respectively. The stability constant of the metal complexes formed during the sensing process was determined. The limit of detection for Fe(III) and Cu(II) ions with respect to Schiff base PYEB was found to be 1.64 ×10-6 and 2.16 ×10-7M, respectively. With respect to Schiff base PDEB, the limit of detection for Cu(II) ion was found to be 4.54 ×10-4M. The Cu(II) ion sensing property of the Schiff base PDEB was applied in bioimaging studies for the detection of HeLa cells.

Combination Mechanism of Soil Dissolved Organic Matter and Cu2+ in Vegetable Fields, Forests and Dry Farmland in Lujiang County

Dissolved organic matter (DOM) serves as a critical link in the migration and transformation of heavy metals at the soil–solid interface, influencing the migration behaviour and transformation processes of Cu2+ in soil. There have been studies on the combination mechanisms between DOM and Cu2+ in paddy soils. However, the adsorption/complexation and redox processes between DOM and Cu2+ in other agricultural soil types (such as dry farmland and vegetable fields) are unclear. In order to reveal the combination process of DOM with Cu in different agricultural soil types and the dynamic changes in chemical behaviour that occur, this study analysed the variability of DOM components and structure in three soils using three-dimensional fluorescence spectroscopy and X-ray photoelectron spectroscopy. In addition, the priority order of different DOM compounds in combination with Cu and the change process in relation to the Cu valence state in the soil of Lujiang County, Anhui Province, was revealed based on laboratory experiments. The results showed that the composition of soil DOM was mainly composed of humic-like and fulvic-like substances with a clear terrestrial origin and that the organic matter showed a high degree of decomposition characteristics. The results indicated that the composition of soil DOM is mainly composed of humic and fulvic acid-like substances, and they have obvious characteristics of terrestrial origin. In addition, the soil organic matter showed high decomposition characteristics. The complex stability constants (lgKM) of humic acid-like substances with Cu2+ follow the order of forest land (lgKM = 5.21), vegetable land (lgKM = 4.90), and dry farmland (lgKM = 4.88). The lgKM of fulvic acid-like substances with Cu2+ is in the order of dry farmland (lgKM = 4.51) and vegetable land (lgKM = 4.39). Humic acid-like substances in soil DOM combine preferentially with Cu2+, showing a stronger chelating affinity than fulvic acid-like substances. Cu2+ complexes mainly include hydroxyl, phenolic hydroxyl and amino functional groups are included in soil DOM, accompanied by redox reactions. In comparison to dry farmland, the soil DOM in forest and vegetable fields undergoes more intense redox reactions simultaneously with the chelation of Cu2+. Therefore, the application of organic fertilisers to vegetable and forest soils may lead to uncertainties concerning the fate of heavy metals with variable chemical valence. These results contribute to a deeper understanding of the interaction mechanisms between DOM and Cu2+ in agricultural soils.

Metal Complexes in Biology and Medicine: The System Cadmium ((II))/ Iron ((II))/ Zinc ((II)) - α - Aminobutenoic Acid

Metal ions play an important role in biological system. The importance of metal ions to essential functions of living systems and for wellbeing of living organisms is well known. Metal ions are fundamental elements for the maintenance of life spans of the human, animals, and plants. Recent advances in inorganic chemistry have made possible formation of number of transition metal complexes with organic ligand of interest, which can be used as therapeutic agent. In coordination compounds studies, knowledge of the stability constants of complexes is necessary for preliminary quantitative treatment. The present technique involving the use of paper electrophoresis is described for the study of equilibria in binary complex systems in solution. The method is based on the movement of a spot of a metal ion in an electric field at various pH’s of background electrolyte. A graph of pH versus mobility was used to obtained information in the binary complexes and to calculate its stability constants. Using this method , the stability constants of binary complexes metal (II) – α – aminobutenoic acid have been determined to be ( 3.78 ± 0.01, 2.48 ± 0.03 ); ( 3.27 ± 0.04, 2.33 ± 0.07 ); and (4.45 ± 0.02, 2.66 ± 0.05); (logarithm stability constant values) for cadmium (II), iron (II) and zinc (II) complexes, respectively, at ionic strength 0.01 Mol / L and a temperature of 35º C.

Prediction of stability constants of metal-ligand complexes by machine learning for the design of ligands with optimal metal ion selectivity.

The new LOGKPREDICT program integrates HostDesigner molecular design software with the machine learning (ML) program Chemprop. By supplying HostDesigner with predicted logK values, LOGKPREDICT enhances the computer-aided molecular design process by ranking ligands directly by metal-ligand binding strength. Harnessing reliable experimental data from a historic National Institute of Standards and Technology (NIST) database and data from the International Union of Pure and Applied Chemistry (IUPAC), we train message passing neural net algorithms. The multi-metal NIST-based ML model has a root mean square error (RMSE) of 0.629 ± 0.044 (R2 of 0.960 ± 0.006), while two versions of lanthanide-only IUPAC-based ML models have, respectively, RMSE of 0.764 ± 0.073 (R2 of 0.976 ± 0.005) and 0.757 ± 0.071 (R2 of 0.959 ± 0.007). For relative logK predictions on an out-of-sample set of six ligands, demonstrating metal ion selectivity, the RMSE value reaches a commendably low 0.25. We showcase the use of LOGKPREDICT in identifying ligands with high selectivity for lanthanides in aqueous solutions, a finding supported by recent experimental evidence. We also predict new ligands yet to be verified experimentally. Therefore, our ML models implemented through LOGKPREDICT and interfaced with the ligand design software HostDesigner pave the way for designing new ligands with predetermined selectivity for competing metal ions in an aqueous solution.