The acidobasic and complexing properties of 1-methyl-2-mercaptoimidazole (Methimazole, an anti-thyroid drug) were investigated. The pKa 11.49 ± 0.03 was estimated by molecular absorption spectroscopy (I = 0.10 M NaCl, t = 25.0 ± 0.1 °C). This value is in good agreement with the value 11.58 ± 0.05, obtained using the solvent-extraction technique. Theoretical (LFER and quantum chemical calculations) and experimental (1H/13C NMR spectroscopy) methods confirmed that the ligand prefers to be in the thion form, and the proton dissociation takes place on the nitrogen atom. Using glass electrode potentiometry, the complexation of the Pd(II) ion by the methimazole ligand occurs without the participation of protons. The best chemical model considers the [Pd(HL)]2+, [Pd(HL)2]2+ and [Pd(HL)3]2+ complex species, whose stability constants were also determined using spectroscopy and capillary zone electrophoretic (CZE) measurements. The metal complexes dissociate at -log [H+] > 7, where an uncharged palladium(II) hydroxide is formed. The formation kinetics of the palladium(II) complex with methimazole were studied in perchloric and hydrochloric acids (I = 1.00 M, t = 15-40 °C) and the determined rate constants and activation parameters are consistent with literature values determined for the reactions of the Pd(II) ion with thiourea derivatives. The rate constants decrease by two orders of magnitude in both media, which can be assigned to a lower tendency of the chloride ion to dissociate from the [PdCl4]2- complex species than the water molecule from the [Pd(H2O)4]2+ ion. The presented results can be utilized for the design of new Pd and Pt metallodrugs.

• Klíčová slova
• Anti-thyroid drug (methimazol, tapazol): 1-methyl-2-mercaptoimidazole, Complexation properties, Equilibria/kinetics, Metallodrug, Pd(II) ion, Protonation,
• MeSH
• kinetika MeSH
• komplexní sloučeniny * chemie   chemická syntéza   MeSH
• methimazol * chemie   MeSH
• palladium * chemie   MeSH
• termodynamika * MeSH
• thyreostatika chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• komplexní sloučeniny * MeSH
• methimazol * MeSH
• palladium * MeSH
• thyreostatika MeSH

A detailed study of diastereomeric complexes of chiral ureido-1,1'-binaphthalene derivatives with chiral 1-phenylethanol showed that a derivative bearing only one urea unit makes five times more stable complex with (S)-enantiomer than with (R)-enantiomer of the alcohol. This phenomenon could be used in chiral discrimination processes. The influence of individual parts of the structure on the complexation properties is shown. The probable structure of diastereomeric complexes based on experimental results and computational methods is proposed.

• Klíčová slova
• [6]helicene, binaphthalene, calix[4]arene, enantioselective complexation, urea,
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH

This study investigates the mechanisms of Cr(VI) adsorption on natural clay (illite and kaolinite) and synthetic (birnessite and ferrihydrite) minerals, including its speciation changes, and combining quantitative thermodynamically based mechanistic surface complexation models (SCMs) with spectroscopic measurements. Series of adsorption experiments have been performed at different pH values (3-10), ionic strengths (0.001-0.1M KNO3), sorbate concentrations (10(-4), 10(-5), and 10(-6)M Cr(VI)), and sorbate/sorbent ratios (50-500). Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy were used to determine the surface complexes, including surface reactions. Adsorption of Cr(VI) is strongly ionic strength dependent. For ferrihydrite at pH <7, a simple diffuse-layer model provides a reasonable prediction of adsorption. For birnessite, bidentate inner-sphere complexes of chromate and dichromate resulted in a better diffuse-layer model fit. For kaolinite, outer-sphere complexation prevails mainly at lower Cr(VI) loadings. Dissolution of solid phases needs to be considered for better SCMs fits. The coupled SCM and spectroscopic approach is thus useful for investigating individual minerals responsible for Cr(VI) retention in soils, and improving the handling and remediation processes.

• Klíčová slova
• Adsorption, Chromate, Soil minerals, Spectroscopy, Surface complexation modeling,
• Publikační typ
• časopisecké články MeSH

The interaction of α-cyclodextrin (α-CD) with ten ionic surfactants (S) in water was systematically examined using isothermal titration calorimetry. The S comprised cationic and anionic head groups while the hydrocarbon alkyl chain length varied from eight to fourteen carbon atoms. The heat data were measured at five temperatures ranging from 283.15K to 318.15K and were treated simultaneously allowing the estimation of a thermodynamically consistent temperature dependence of the equilibrium constant, as well as the enthalpy and heat capacity for the sequential formation of the [α-CD·S] and the [α-CD2·S] inclusion complexes. All attempts to fit the data assuming that only [α-CD·S] complexes are present failed. It was found that the thermodynamic footprint of the [α-CD·S] complexes does not depend importantly on the head group, while the formation and stabilization of the [α-CD2·S] complexes is strongly influenced by the chemical nature of the polar head group. Several contributions to the thermodynamic parameters are discussed in detail. Among the studied surfactants, the decyl- and octylsulfates were identified as those with a predominant content of [α-CD2·S] complexes and hence they are promising candidates to form viscoelastic films at the liquid/air interface, as it was found previously for the dodecylsulfate surfactant.

• Klíčová slova
• -Cyclodextrin, Complexation, Inclusion complex, Isothermal titration calorimetry, Surfactant, Thermodynamic,
• Publikační typ
• časopisecké články MeSH

The acid-base and complexation properties of humic acids (HAs) extracted from bohemian brown coals were studied. The acid-base behavior corresponds with the model of HA as a mixture of mono- and diprotic acids. This model was also verified on commercial HA substances (Aldrich and Fluka). HA binds strongly with heavy metal ions and the highest stability constant of HA-metal ion complexes was observed for copper(II). Stability constant values were found to decrease in the order: Cu(2+)>Ba(2+)>Pb(2+)>Cd(2+)>Ca(2+). Both acidobasic models for HA alone and those for HA-metal ion interactions were proposed and the computational methodology for polyelectrolyte equilibria studies demonstrated.

• Publikační typ
• časopisecké články MeSH

By potentiometric study using a specific uranyl ion-selective electrode, the formation of 1:1 and 1:2 (metal:ligand) complexes of uranyl with various humic acids (HAs) was found. The conditional stability constants were calculated using the LETAGROP-ETITR program. Possible structures of the complexes are proposed. Stability constants were found to be rather high indicating that immobilized HA can be used, for example, to remove traces of uranyl from waste waters.

• Publikační typ
• časopisecké články MeSH

In this study, the complexation rates of two new phosphinate H(4)dota (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) analogs, H(5)do3ap(PrA) and H(4)do3ap(ABn), and H(4)dota itself were compared under identical conditions (H(5)do3ap(PrA)=10-{[(2-carboxyethyl)hydroxyphosphoryl]methyl}-1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid; H(4)do3ap(ABn)=10-{[(4-aminophenyl)hydroxyphosphoryl]methyl}-1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid). The biodistribution of their (111)In and (90)Y complexes in healthy rats was also studied. Unlike the observation obtained under "chemical" conditions where differences between the ligands were observed no such differences in complexation rates were found under radiochemical conditions. The ligands bind the radiometals similarly to H(4)dota. So, "chemical" formation kinetic data should be transferred into radiochemical conditions only with high care and "radiochemical" complexation experiments should be run as part of standard in vitro studies with new ligands considered as potential radiopharmaceuticals. Pharmacokinetic studies in rats showed similar distribution characteristics for both phosphinate H(4)dota analogs radiolabelled with (111)In and (90)Y when compared with that of the (111)In-H(4)dota complex. No specific uptake in any organ and tissue of rats was determined. The phosphinate complexes are not accumulated in calcified tissues.

• MeSH
• heterocyklické sloučeniny monocyklické chemie   farmakokinetika   MeSH
• krysa rodu Rattus MeSH
• kyseliny fosfinové chemie   farmakokinetika   MeSH
• organokovové sloučeniny chemie   farmakokinetika   MeSH
• radiofarmaka chemie   farmakokinetika   MeSH
• radioizotopy india chemie   farmakokinetika   MeSH
• radioizotopy ytria chemie   farmakokinetika   MeSH
• tkáňová distribuce MeSH
• zvířata MeSH
• Check Tag
• krysa rodu Rattus MeSH
• zvířata MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• heterocyklické sloučeniny monocyklické MeSH
• kyseliny fosfinové MeSH
• organokovové sloučeniny MeSH
• radiofarmaka MeSH
• radioizotopy india MeSH
• radioizotopy ytria MeSH

Solid complexes of D-galacturonic acid (GalA) with cobalt(II), copper(II), nickel(II) and oxovanadium(IV) (1-4) were prepared and characterised. The metal-to-ligand molar ratio was 1:2 for complexes 1-3 and 1:1 for complex 4. The alpha- and beta-anomers of GalA were detected in all the complexes in solid state and in solutions. An addition of small amounts of the paramagnetic complexes to the D2O solution of pure ligand led to NMR line broadening of some 1H and 13C nuclei. This broadening was sensitive to the anomeric state of GalA in the case of complexes 1 and 4. NMR and vibrational spectroscopic data indicate the formation of carboxylate complexes of all the cations, while noncarboxylic oxygens are also involved into the metal bonding in some cases. VCD spectra of complexes 1-4 in D2O and Me2SO-d6 solutions confirm that GalA carboxylic group may participate in the formation of optically active species around the metal cation. Possible ways of GalA coordination by metal cations of this study were proposed and discussed.

• MeSH
• kationty dvojmocné chemie   MeSH
• kyseliny hexuronové chemie   MeSH
• magnetická rezonanční spektroskopie MeSH
• molekulární struktura MeSH
• roztoky MeSH
• těžké kovy chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• galacturonic acid MeSH Prohlížeč
• kationty dvojmocné MeSH
• kyseliny hexuronové MeSH
• roztoky MeSH
• těžké kovy MeSH

The interactions of valinomycin, macrocyclic depsipeptide antibiotic ionophore, with ammonium cation NH4+ have been investigated. Using quantum mechanical density functional theory (DFT) calculations, the most probable structure of the valinomycin-NH4+ complex species was predicted. In this complex, the ammonium cation is bound partly by three strong hydrogen bonds to three ester carbonyl oxygen atoms of valinomycin and partly by somewhat weaker hydrogen bonds to the remaining three ester carbonyl groups of the valinomycin ligand. The strength of the valinomycin-NH4+ complex was evaluated experimentally by capillary affinity electrophoresis. From the dependence of valinomycin effective electrophoretic mobility on the ammonium ion concentration in the background electrolyte, the apparent binding (association, stability) constant (Kb) of the valinomycin-NH4+ complex in methanol was evaluated as log Kb = 1.52 +/- 0.22.

• MeSH
• antibakteriální látky chemie   MeSH
• kationty chemie   MeSH
• kvantová teorie MeSH
• kvartérní amoniové sloučeniny chemie   MeSH
• molekulární konformace MeSH
• molekulární modely MeSH
• valinomycin chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• antibakteriální látky MeSH
• kationty MeSH
• kvartérní amoniové sloučeniny MeSH
• valinomycin MeSH

The character of the hydrogen bonding and the excited state proton transfer (ESPT) in the model system HCN...H(2)O is investigated. The PES of the two lowest excited states of the H(2)O...HCN complex was calculated using the CASPT2 method. The nonadiabatic coupling of the two states of the (pi-->pi*) and (pi-->sigma*) character is responsible for the excited state proton/hydrogen transfer. Compared to the ground state, the barrier for this process is significantly smaller. An increased number of water molecules in the complex with cyclic hydrogen-bonded network causes a large blue shift of the state of the (pi-->sigma*) character. The question of the dissociation of the complex in its excited state is also addressed.

• MeSH
• chemické modely * MeSH
• fotochemie MeSH
• kvantová teorie MeSH
• kyanovodík chemie   MeSH
• počítačová simulace MeSH
• protony MeSH
• voda chemie   MeSH
• vodíková vazba MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• kyanovodík MeSH
• protony MeSH
• voda MeSH