scholarly journals Synthesis and stability of the dirhenium(III) cluster compounds with isoleucine, serine and proline in aqueous solutions

2020 ◽  
pp. 38-43
Author(s):  
Y.V. Husak ◽  
◽  
A.A. Ovcharenko ◽  
A.A. Golichenko ◽  
A.V. Shtemenko ◽  
...  
Keyword(s):  
Aqueous Solutions ◽  
Electronic Absorption Spectra ◽  
Complex Compounds ◽  
Biologically Active ◽  
Cluster Compounds ◽  
Imino Group ◽  
Bending Vibrations ◽  
Oh Groups ◽  
Carboxylate Groups ◽  
The Stability

The previously developed methods for the synthesis of cis-tetrachlorodi--carboxylates of dirhenium(III) were modified, due to which the derivatives of Re26+ with proteinogenic amino acids (AA) isoleucine, serine and proline were synthesized for the first time. The composition and structure of these substances with the general formula cis-[Re2(АA)2Cl4(CH3CN)2]Cl2 were confirmed by elemental analysis, electron adsorption and IR spectroscopy. The presence of a characteristic peak, which corresponds to the *-electronic transition of the Re–Re quadruple bond for compounds with the cis-arrangement of two bridging-coordinated carboxylate groups in the ligand environment of the Re26+ cluster, was showed by using the data on the electronic absorption spectra of solutions of the synthesized compounds. The IR spectrum contains an intense, weakly split band in the region of 1466–1458 cm–1, which is attributed to the s(CO) coordinated carboxyl group and indicates its bridging coordination to the binuclear Re26+ fragment. The spectra exhibited the presence of bands of stretching (NH3+) and bending vibrations (NH3+) of protonated amino groups in complex compounds of isoleucine and serine and the presence of bands of stretching (NH2+) and bending vibrations (NH2+) of the protonated imino group of proline. The stability of the prepared complex compounds in aqueous solutions was investigated. It is shown that the hydrolysis of the synthesized substances occurs within 9–14 days with a decrease in the pH of the reaction solution due to a gradual replacement of labile chloride ligands by OH–-groups at the first stages of interaction with water. The resistance to hydrolysis is an important parameter of biologically active substances; the determination of the resistance to hydrolysis will expand understanding of the possible mechanisms of their specific biological activity.

scholarly journals HYDROLYSIS OF RHENIUM(III) CLUSTER COMPOUNDS

2019 ◽  
Vol 85 (3) ◽  
pp. 27-34
Author(s):  
Alexander Golichenko ◽  
Alexander Shtemenko
Keyword(s):  
Complex Compound ◽  
Biological Activities ◽  
Electron Transition ◽  
Complex Compounds ◽  
Biologically Active ◽  
Cluster Compounds ◽  
Hydrolysis Rate ◽  
Oh Groups ◽  
Chloride Ligands ◽  
Hydrolysis Of

Study of hydrolysis of cis-tetrachlorodi-m-carboxylates of dirhenium (III) was carried out due to the electronic adsorption and IR spectroscopy and pHmeter. As a result, itwas shown that the hydrolysis is a multistage process which can be attributed to the reactions of the pseudo-first order. It is also shown that the electronic absorption spectroscopy (EAS) is a reliable method of investigation to study the hydrolysis of rhenium (III) complex compounds. This conclusion is based on the fact that in the systems with halide and carboxylic ligands, each of the five structural types can be clearly identified by the EAS in the region of both d–d* electron transition and charge transfer transition of L*Hal ®Re type. It is shown that with the increase in the length of the alkyl group and in its branching, the hydrolysis rate decreases, as a result of a change in the positive inductive effect of these groups and, consequently, an increase in the strengthening of quadruple Re–Re bond. In addition, with the help of the EAS, a transition of the chloride ligands to OHgroups can be observed. As a result of the study, a hydrolysis route, which initially leds to the gradual replacement of the chloride ligands of a complex compound with OH groups, and subsequently to the conversion of Re(III) compounds into the derivative of Re(IV) was proposed. The dependence of resistance to hydrolysis on the structure of the complex compound, the temperature and pH was determined. It allowed to predict the stability of the investigated compounds while their usage as biologically active substances and reagents in the synthesis of new compounds. The obtained results allow us to presence of anticancer, cytostabilizing and other biological activities is the coordination of Re(III) complex compounds with the components of biomolecules (proteins, DNA).

scholarly journals HYDROLYSIS OF RHENIUM(III) CLUSTER COMPOUNDS

2019 ◽  
Vol 85 (3) ◽  
pp. 27-34 ◽  
Author(s):  
Alexander Golichenko ◽  
Alexander Shtemenko
Keyword(s):  
Complex Compound ◽  
Biological Activities ◽  
Electron Transition ◽  
Complex Compounds ◽  
Biologically Active ◽  
Cluster Compounds ◽  
Hydrolysis Rate ◽  
Oh Groups ◽  
Chloride Ligands ◽  
Hydrolysis Of

Study of hydrolysis of cis-tetrachlorodi-m-carboxylates of dirhenium (III) was carried out due to the electronic adsorption and IR spectroscopy and pHmeter. As a result, itwas shown that the hydrolysis is a multistage process which can be attributed to the reactions of the pseudo-first order. It is also shown that the electronic absorption spectroscopy (EAS) is a reliable method of investigation to study the hydrolysis of rhenium (III) complex compounds. This conclusion is based on the fact that in the systems with halide and carboxylic ligands, each of the five structural types can be clearly identified by the EAS in the region of both d–d* electron transition and charge transfer transition of L*Hal ®Re type. It is shown that with the increase in the length of the alkyl group and in its branching, the hydrolysis rate decreases, as a result of a change in the positive inductive effect of these groups and, consequently, an increase in the strengthening of quadruple Re–Re bond. In addition, with the help of the EAS, a transition of the chloride ligands to OHgroups can be observed. As a result of the study, a hydrolysis route, which initially leds to the gradual replacement of the chloride ligands of a complex compound with OH groups, and subsequently to the conversion of Re(III) compounds into the derivative of Re(IV) was proposed. The dependence of resistance to hydrolysis on the structure of the complex compound, the temperature and pH was determined. It allowed to predict the stability of the investigated compounds while their usage as biologically active substances and reagents in the synthesis of new compounds. The obtained results allow us to presence of anticancer, cytostabilizing and other biological activities is the coordination of Re(III) complex compounds with the components of biomolecules (proteins, DNA).

scholarly journals COMPARISON OF L-ASPARAGINE INTERACTIONS WITH PYRIDINE DERIVATIVES, PYRIDOXAL- 5'-PHOSPHATE AND PYRIDOXINE, IN AQUEOUS SOLUTIONS: THERMODYNAMIC ASPECTS

2021 ◽  
Vol 64 (5) ◽  
pp. 12-18
Author(s):  
Elena Yu. Tyunina ◽  
Olga N. Krutova ◽  
Alexandr I. Lytkin
Keyword(s):  
Aqueous Solution ◽  
Aqueous Solutions ◽  
Aspartic Acid ◽  
Acid Amide ◽  
The Body ◽  
Biologically Active ◽  
Stable Complex ◽  
Thermochemical Study ◽  
Oh Groups ◽  
Heat Effects

Interactions of proteins with various biologically active substances (hormones, drugs, enzymes, etc.) underlie many biochemical processes in the body. As part of the long-term task to studying various aspects of the interaction between model protein compounds and heterocyclic compounds that are into the structure of many enzymes and drugs, the thermochemical study of aqueous solutions containing aspartic acid amide (L-asparagine) and peridoxal-5¢-phosphate was carried out. Calorimetric measurements of the enthalpy of L-asparagine dissolution in an aqueous solution with pyridoxal-5¢-phosphate additives were performed on an ampoule-type isoperibolic dissolution calorimeter at 298.15 K. The error of measuring single heat effects was below 0.2%. The relative combined uncertainty in the measurements of the enthalpies of dissolution was not more than 0.7%. Based on the obtained experimental data and the using the HEAT computer program, the binding constants and thermodynamic parameters (lgK, ΔcG, ΔcH, ΔcS) of the complex formation between the reagents under study were calculated. A comparison of the affinity of amino acids to interaction with pyridoxal-5¢-phosphate and pyridoxine was carried out. The features of their behavior in an aqueous solution are revealed. It is shown that the interaction of L-asparagine with pyridoxine leads to the formation of a more stable complex than with peridoxal-5¢-phosphate. This fact may be explained in terms of a bulky phosphate group that hinders apparently the interaction of POP with aspartic acid amide. In addition, the peridoxal-5¢-phosphate molecule contains intramolecular hydrogen bonds between aldehyde CHO and phenolic OH groups, which must be destroyed by the interaction of peridoxal-5' - phosphate with an amino acid, which requires additional energy expenses. Thus, the selectivity of the interaction and the stability of the formed complexes are mainly regulated by the factors of structural and energy complementarity.

scholarly journals STABILITY CONSTANTS OF L-ASPARAGINE AND L-LEUCINE COMPLEXES WITH SOME LANTHANIDE IN AQUEOUS SOLUTIONS AT 298.15 K

2017 ◽  
Vol 61 (1) ◽  
pp. 37
Author(s):  
Alexandr I. Lytkin ◽  
Natalya V. Chernyavskaya ◽  
Darya K. Smirnova
Keyword(s):  
Amino Acids ◽  
Aqueous Solutions ◽  
Stability Constants ◽  
Quantitative Estimation ◽  
A Priori ◽  
Complex Compounds ◽  
Complexing Agent ◽  
Stability Of Complexes ◽  
Biological Substrates ◽  
The Stability

Lanthanides have a high affinity toward ligands containing donor oxygen atoms, especially amino acids and complexons. The study of the processes of complexation of amino acids with f-element cations provides valuable information for solving problems of supramolecular chemistry, molecular recognition and chiral sensitivity of biological substrates. As a rule, f-elements are not components of biopolymers, but they are spectral label probes, which are important in the bioinorganic chemistry of metals. Quantitative estimation of the stability of complexes is necessary, first of all, to search for an internal connection between the constants themselves and then to find correlations between the stability of complexes and the properties of the complexing agent, the ligand, and the system as a whole. Such correlation dependencies make it possible to calculate a priori, or at least estimate the stability constants of new complexes, and also to better understand the influence of the nature of the chemical bond and the properties of the system as a whole on the formation and stability of complex compounds. In the present work, the complexation of neodymium, lanthanum with L-asparaginat ion and samarium, cerium with L-leucinat ion at 298.15 K and ionic strength values of 0.5 mol/l was studied by potentiometric titration and the stability constants of the complexes formed were determined. The values of the stability constants found allow us to perform rigorous thermodynamic calculations of the equilibria of these amino acids in salt solutions. The data obtained, in particular, can be used to reliably interpret the results of calorimetric studies of the complexation of lanthanides with the participation of the studied amino acids.Forcitation:Lytkin A.I., Chernyavskaya N.V., Smirnova D.K. Stability constants of L-asparagine and L-leucine complexes with some lanthanide in aqueous solutions at 298.15 K. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 1. P. 37-41

STUDY ON NEW COMPLEX COMPOUNDS OF Ti(IV) AND Zr(IV) IN AQUEOUS SOLUTIONS: SYNTHESIS, STABILITY AND APPLICATION IN CLEANER TECHNOLOGIES OF NATURAL LEATHER

2008 ◽  
Vol 7 (3) ◽  
pp. 241-248 ◽  
Author(s):  
Doina Sibiescu ◽  
Ioan Rosca ◽  
Daniel Sutiman ◽  
Marian Crudu ◽  
Adrian Cailean ◽  
...  
Keyword(s):  
Aqueous Solutions ◽  
Complex Compounds ◽  
Cleaner Technologies

Synthesis, Conformational Analysis, Infrared, Raman and UV-Visible Spectra of Novel Schiff Bases compiled with DFT Calculations

2020 ◽  
Vol 23 (7) ◽  
pp. 568-586
Author(s):  
Samy M. Ahmed ◽  
Ibrahim A. Shaaban ◽  
Elsayed H. El-Mossalamy ◽  
Tarek A. Mohamed
Keyword(s):  
Schiff Bases ◽  
1H Nmr ◽  
Electronic Absorption Spectra ◽  
Chemical Shifts ◽  
Basis Set ◽  
Oh Groups ◽  
Vibrational Assignments ◽  
Cartesian Coordinate ◽  
Surface Scan ◽  
Ir And Raman

Objective: Two novel Schiff bases named, 2-((2-Hydroxybenzylidene)amino)-4,5,6,7- tetrahydrobenzo[b] thiophene-3-carbonitrile (BESB1) and 2-((Furan-2-ylmethylene)amino)-4,5,6, 7-tetrahydro-benzo[b]thiophene-3-carbonitrile (BESB2) were synthesized. Methods: The structures were characterized based on CHN elemental analysis, mid-infrared (400– 4000 cm-1), Raman (100-4000 cm-1), 1H NMR, mass and UV-Vis spectroscopic measurements. In addition, quantum mechanical calculations using DFT-B3LYP method at 6-31G(d) basis set were carried out for both Schiff bases. Initially, we have carried out complete geometry optimizations followed by frequency calculations for the proposed conformational isomers; BESB1 (A–E) and BESB2 (F–J) based on the orientations of both CN and OH groups against the azomethine lonepair (NLP) in addition to the 3D assumption. Results: The computational outcomes favor conformer A for BESB1 in which the C≡N and OH moieties are cis towards the NLP while conformer G is preferred for BESB2 (the C≡N/furan-O are cis/trans towards the NLP) which was found consistent with the results of relaxed potential energy surface scan. Aided by normal coordinate analysis of the Cartesian coordinate displacements, we have suggested reliable vibrational assignments for all observed IR and Raman bands. Moreover, the electronic absorption spectra for the favored conformers were predicted in DMSO solution using TD-B3LYP/6-31G(d) calculations. Similarly, the 1H NMR chemical shifts were also estimated using GIAO approach implementing PCM including solvent effects (DMSO-d6). Conclusion: Proper interpretations of the observed electronic transition, chemical shifts, IR and Raman bands were presented in this study.

On the Structure of Lead(II) Complexes in Aqueous Solutions. I. Trinuclear Clusters

1995 ◽  
Vol 60 (4) ◽  
pp. 527-536 ◽  
Author(s):  
Martin Breza ◽  
Alena Manová
Keyword(s):  
Quantum Chemistry ◽  
Aqueous Solutions ◽  
Electronic Structures ◽  
Mndo Method ◽  
Model Systems ◽  
Trinuclear Clusters ◽  
The Stability ◽  
Semiempirical Mndo

Using semiempirical MNDO method of quantum chemistry the optimal geometries and corresponding electronic structures of [Pb3(OH)n]6-n model systems as well as of their hydrated [Pb3(OH)n(H2O)8-n]6-n analogues (n = 4, 5) are investigated. The most stable trinuclear lead(II) complexes present in aqueous solutions correspond to cyclo-(μ3-OH)(μ2-OH)3Pb32+, Pb(μ-OH)2Pb(μ-OH)2Pb2+, cyclo-(μ3-OH)2(μ2-OH)3Pb3+, Pb(OH)(μ-OH)2Pb(μ-OH)Pb(OH)+ and Pb(OH)(μ-OH)2Pb(μ-OH)2Pb+ systems. The key role of OH bridges (by vanishing direct Pb-Pb bonds) on the stability of individual isomers is discussed.

scholarly journals Development of TLC Chromatographic-Densitometric Procedure for Qualitative and Quantitative Analysis of Ceftobiprole

Processes ◽  
2021 ◽  
Vol 9 (4) ◽  
pp. 708
Author(s):  
Żaneta Binert-Kusztal ◽  
Małgorzata Starek ◽  
Joanna Żandarek ◽  
Monika Dąbrowska
Keyword(s):  
High Sensitivity ◽  
Biologically Active ◽  
Fifth Generation ◽  
Ich Guidelines ◽  
Relative Standard ◽  
Lipophilicity Parameter ◽  
Alkaline Environments ◽  
Acetic Acid Water ◽  
Cephalosporin Antibiotics ◽  
The Stability

Currently, there is still a need for broad-spectrum antibiotics. The new cephalosporin antibiotics include, among others, ceftobiprole, a fifth-generation gram-positive cephalosporin, active against Staphylococcus aureus methicillin agonist (MRSA). The main focus of the work was to optimize the conditions of ceftobiprole qualitative determination and to validate the developed procedure according to ICH guidelines. As a result of the optimization process, HPTLC Cellulose chromatographic plates as a stationary phase and a mixture consisting of ethanol:2-propanol: glacial acetic acid: water (4:4:1:3, v/v/v/v) as a mobile phase were chosen. The densitometric detection was carried out at maximum absorbance of ceftobiprole (λ = 232 nm). Next, the validation process of the developed procedure was carried out. The relative standard deviation (RSD) for precision was less than 1.65%, which proves the high compatibility of the results, as well as the LOD = 0.0257 µg/spot and LOQ = 0.0779 µg/spot values, which also confirm the high sensitivity of the procedure. The usefulness of the developed method for the stability studies of ceftobiprole was analyzed. Study was carried out under stress conditions, i.e., acid and alkaline environments, exposure to radiation imitating sunlight and high temperature (40–60 °C). It was found that cefotbiprole is unstable in an alkaline environment and during exposure to UV-VIS radiation. Moreover, the lipophilicity parameter, as a main physicochemical property of the biologically active compound, was determined using experimental and computational methods.

scholarly journals Effective replacement of cetyltrimethylammonium bromide (CTAB) by mercaptoalkanoic acids on gold nanorod (AuNR) surfaces in aqueous solutions

Nanoscale ◽  
2020 ◽  
Vol 12 (2) ◽  
pp. 658-668 ◽  
Author(s):  
Rafael del Caño ◽  
Jose M. Gisbert-González ◽  
Jose González-Rodríguez ◽  
Guadalupe Sánchez-Obrero ◽  
Rafael Madueño ◽  
...  
Keyword(s):  
Aqueous Solutions ◽  
Gold Nanorods ◽  
Ligand Exchange ◽  
Cetyltrimethylammonium Bromide ◽  
Gold Nanorod ◽  
Experimental Conditions ◽  
Seed Mediated ◽  
The Stability

The highly packed cetyltrimethylammonium bromide bilayer on the surface of gold nanorods synthesized by the seed-mediated procedure hampers the complete ligand exchange under experimental conditions that preserves the stability of the dispersions.

scholarly journals Investigations of ternary complexes of Co(II) and Ni(II) with thiodiacetate anion and 1,10-phenanthroline or 2,2’-bipyridine in aqueous solutions

2014 ◽  
Vol 13 (1) ◽  
Author(s):  
Dariusz Wyrzykowski ◽  
Joanna Pranczk ◽  
Dagmara Jacewicz ◽  
Aleksandra Tesmar ◽  
Bogusław Pilarski ◽  
...  
Keyword(s):  
Aqueous Solutions ◽  
Substitution Reactions ◽  
Experimental Conditions ◽  
Kinetic Measurements ◽  
Hydroxo Complexes ◽  
Binary Complexes ◽  
Vis Spectroscopy ◽  
Potentiometric Titration Method ◽  
The Stability ◽  
Ph Range

AbstractA potentiometric titration method (PT) and a stopped-flow kinetic technique monitored by a UV−Vis spectroscopy have been used to characterize the stability of series of Co(II)- and Ni(II)-thiodiacetato complexes, M(TDA), in the presence of 1,10-phenanthroline (phen) or 2,2’-bipyridine (bipy) in aqueous solutions. The stability constants of the binary (1:1), ternary (1:1:1) as well as the resulting hydroxo complexes were evaluated and compared to the corresponding oxydiacetate complexes. Based on the species distribution as a function of pH the relative predominance of the species in the system over a pH range was discussed. Furthermore, the kinetic measurements of the substitution reactions of the aqua ligands to phen or bipy in the coordination sphere of the binary complexes M(TDA) were performed in the 288–303 K temperature range, at a constant concentration of phen or bipy and at seven different concentrations of the binary complexes (0.2–0.5 mM). The kinetic stability of the M(TDA) complexes was discussed in relation to the experimental conditions and the kind of the auxiliary ligands (phen/bipy). Moreover, the influence of the type of primary ligand (thiodiacetate/oxydiacetate) on the substitution rate of the auxiliary ligands was also compared.

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