Thermodynamic Studies of Complexes in Cu(II)/Uridine-5'-Diphosphoglucuronic Acid System.

A binary system of uridine-5'-diphosphoglucuronic acid with copper (II) ions was studied. Potentiometric studies in aqueous solutions using computer data analysis were carried out. The pH of dominance, the overall stability constants (logß), and the equilibrium constants of the formation reaction (logKe) were determined for each complex compound formed in the studied system. Spectroscopic studies were carried out to determine the mode of coordination in the compounds studied. Cytotoxicity and metabolic activity tests of the compounds obtained showed an increase in the biological activity of the complexes tested against the free ligand. The current research may contribute to the knowledge of complex compounds of biomolecules found in the human body and may also contribute to the characterization of a group of complex compounds with potential anticancer properties.

The Unusual Role of Pro in Cu(II) Binding by His2-Cyclopentapeptide.

In this paper, we present findings from studying the interaction of copper(II) ions with the His2-cyclopentapeptide and the role of proline used for the purpose of potentiometric titration and UV-Vis, CD and EPR spectroscopic measurements. Experiments of two homodetic peptides differing by one amino acid residue were conducted for a ligand to metal ratio of 1:1 in the pH range 2.5-11.0. The presented studies reveal that peptides form only mononuclear complexes, and the CuH2L complex appears in the system first (for both L1 and L2). Study results show that the presence of Pro influences the structure of formed complexes and their stabilities and has a strong impact on the efficiency of copper(II) coordination.

The Role of the Disulfide Bridge in the Copper (II) Binding by the Cyclic His4-Peptide.

In this paper, we present studies on the influence of the disulfide bridge on the copper (II) ions' binding abilities by the cyclic His4-peptide. The studied ligand HKHPHRHC-S-S-C consists of nine amino acids. The cyclic structure was obtained through a disulfide bridge between two cysteinyl groups. Moreover, this peptide is characterized by the presence of four His residues in the sequence, which makes it an interesting ligand for transition metal ions. The potentiometric and spectroscopic (UV-Vis spectroscopy and circular dichroism spectroscopy (CD)) studies were carried out in various molar ligand to metal ratios: 2:1, 1:1, and 1:2, in the pH range of 2.5-11 at 25 °C. The results showed that the cyclic His4-peptide promotes dinuclear complexes in each of these systems and forms the final dinuclear species with the {NIm, 3N-amide}{NIm, 3N-amide} coordination mode. The obtained data shows that cyclization by the formation of the disulfide bond has an impact on the peptide chain flexibility and appearance of additional potential donors for metal ions and influences the copper (II) ions' coordination.

Influence of d-Electron Divalent Metal Ions in Complex Formation with L-Tartaric and L-Malic Acids.

Binary complexes of α-hydroxy acids (L-Tartaric acid and L-Malic acid) with d-electron metal ions (copper, cobalt, nickel) were investigated. Potentiometric measurements have been performed in aqueous solution with computer analysis of the data for determination of the stability constants of complexes formed in the studied systems. The coordination mode of the complexes was defined using spectroscopic methods: electron paramagnetic resonance (EPR), ultraviolet-visible (UV-Vis), circular dichroism (CD), and infrared (IR). Results of the equilibrium studies have provided evidence for the formation of dimers with copper(II) ions and monomers with cobalt(II) and nickel(II) ions.

Thermodynamic and Spectroscopic Studies of the Complexes Formed in Tartaric Acid and Lanthanide(III) Ions Binary Systems.

Binary complexes of tartaric acid with lanthanide(III) ions were investigated. The studies have been performed in aqueous solution using the potentiometric method with computer analysis of the data for detection of the complexes set, determination of the stability constants of these compounds. The mode of the coordination of complexes found was determined using spectroscopy, which shows: Infrared, circular dichroism, ultraviolet, visible as well as luminescence spectroscopy. The overall stability constants of the complexes as well as the equilibrium constants of the reaction were determined. Analysis of the equilibrium constants of the reactions and spectroscopic data allowed the effectiveness of the carboxyl groups in the process of complex formation.

The Influence of pH on Complexation Process of Copper(II) Phosphoethanolamine to Pyrimidine Nucleosides.

The influence of pH on the complex formation of phosphoethanolamine and pyrimidine nucleosides (uridine, cytidine and thymidine) with copper(II) ions was studied. All investigations were performed in aqueous solution. The overall stability constants of the complexes and non-covalent compounds were obtained using the potentiometric method with computer calculation of the data. Moreover, equilibrium constants of the reaction were determined. The mode of coordination was obtained using spectroscopic methods. Analysis of the potentiometric and spectroscopic data confirmed the involvement and effectiveness of phosphate groups in species formation as well as the influence of pH on the mode of coordination of the investigated biomaterials. In the next step, studied complexes will be applied as potential biomaterials with biological applications.

Miniaturized pH Sensors Based on Zinc Oxide Nanotubes/Nanorods.

ZnO nanotubes and nanorods grown on gold thin film were used to create pH sensor devices. The developed ZnO nanotube and nanorod pH sensors display good reproducibility, repeatability and long-term stability and exhibit a pH-dependent electrochemical potential difference versus an Ag/AgCl reference electrode over a large dynamic pH range. We found the ZnO nanotubes provide sensitivity as high as twice that of the ZnO nanorods, which can be ascribed to the fact that small dimensional ZnO nanotubes have a higher level of surface and subsurface oxygen vacancies and provide a larger effective surface area with higher surface-to-volume ratio as compared to ZnO nanorods, thus affording the ZnO nanotube pH sensor a higher sensitivity. Experimental results indicate ZnO nanotubes can be used in pH sensor applications with improved performance. Moreover, the ZnO nanotube arrays may find potential application as a novel material for measurements of intracellular biochemical species within single living cells.

The pH Response and Sensing Mechanism of n-Type ZnO/Electrolyte Interfaces.

Ever since the discovery of the pH-sensing properties of ZnO crystals, researchers have been exploring their potential in electrochemical applications. The recent expansion and availability of chemical modification methods has made it possible to generate a new class of electrochemically active ZnO nanorods. This reduction in size of ZnO (to a nanocrystalline form) using new growth techniques is essentially an example of the nanotechnology fabrication principle. The availability of these ZnO nanorods opens up an entire new and exciting research direction in the field of electrochemical sensing. This review covers the latest advances and mechanism of pH-sensing using ZnO nanorods, with an emphasis on the nano-interface mechanism. We discuss methods for calculating the effect of surface states on pH-sensing at a ZnO/electrolyte interface. All of these current research topics aim to explain the mechanism of pH-sensing using a ZnO bulk- or nano-scale single crystal. An important goal of these investigations is the translation of these nanotechnology-modified nanorods into potential novel applications.

New coordination compounds of citric acid and polyamines with lanthanide ions - potential application in monitoring the treatment of cancer diseases.

Non-covalent interaction in the binary systems of polyamines (putrescine, spermidine, spermine) with citric acid and complex formation in the binary as well as ternary systems of lanthanide(III) ions, citric acid and polyamine have been investigated. The studies were performed in aqueous solution. The overall stability constants of the complexes were determined using the potentiometric method with computer analysis of the data. Only mononuclear type of complexes were found in the ternary systems and polyamines were located in the outer as well as inner coordination sphere. Non-covalent interaction between biogenic amines and citric acid in the binary and ternary systems were confirmed on the basis of the equilibrium constants analysis and spectroscopic studies.

Carboxyl groups of citric acid in the process of complex formation with bivalent and trivalent metal ions in biological systems.

Binary complexes of citric acid (H3L - protonated form, H2L and HL - partly protonated forms, L - fully deprotonated) with d- and f-electron metal ions were investigated. The studies have been performed in aqueous solution using the potentiometric method with computer analysis of the data, electron paramagnetic resonance, infrared, visible as well as luminescence spectroscopies. The overall stability constants of the complexes were determined. Analysis of the equilibrium constants of the reactions and spectroscopic data has allowed determination of the type of coordination and effectiveness of the carboxyl groups in the process of complex formation. On the basis of potentiometric titration for d-electron were found dimeric and monomeric type of complexes and for f-electron four type of complexes: MHL, ML, ML(OH) and ML(OH)2.

Tandem mass spectroscopy as a tool for investigation of complexes of PNP-lariat ether derivative with metal ions.

The novel PNP-lariat ether L with cyclotriphosphazene ring incorporated in the macrocyclic structure was synthesized and checked by the electrospray mass spectrometry (ESI-MS) method for the ability to bind different types of ions Ag+ , Ca2+ , Cd2+ , Cu2+ , and Pb2+ . Furthermore, the stability constants of the abovementioned ion complexes with the investigated ligand have been determined by direct and competitive potentiometric methods. To evaluate the stability of various complex types and to confirm the way of metal cation binding, the tandem mass spectra of the investigated ligand and its complexes were taken. As a result, we obtained quite a good relationship between the number and main types of complex species observed in ESI-MS experiments and the forms of complexes for which the stabilization constants were determined by potentiometric methods. Moreover, we also concluded that in case of big discrepancies of stability constants, ESI-MS experiments could provide information about the most stable form of the complexes, but they fail when the differences between the strength of the coordination binding are slightly different.

The Coordination Abilities of New Cyclic Analogs of Somatostatin.

Two new somatostatin analogs with a characteristic part of the sequence -c(Cys-Phe-Trp-Lys-Thr-Cys)- and with two histidine and two aspartic acid moieties in their structures were synthesized and analyzed in terms of their coordination abilities with copper (II) ions. Both peptides bind Cu(II) effectively. Ligands form 4N complexes with [Formula: see text] binding mode in a basic range of pH. But in spite of very similar sequences of the two peptides a significant difference in the effectiveness of the binding of copper (II) ions was observed.

The integration of ion potentiometric measurements with chemical, structural, and morphological analysis to follow mineralization reactions in solution.

The solution crystallization of biominerals like calcium carbonate or calcium phosphate is a process that requires a high level of control over reaction kinetics. Ion potentiometric measurements are a way to follow and control reaction kinetics by measuring changes in pH and ion concentration, also allowing quantification of chemical compositions and solubility characteristics. By combining these measurements with various analysis techniques, one can acquire a complete spectrum of chemical, structural, and morphological data, even on metastable precursors. Therefore, in this chapter, the use of potentiometric measurements in standard solution crystallization experiments is described and the integration of these measurements with microscopy, spectroscopic and scattering analyses in such a way that the control over the reaction kinetics is maintained.

Ionization of Hydrofluoric Acid at 25 °C.

The ionization constant, K 1, for the reaction HF⇄H+ + F- was calculated on the basis of potentiometric measurements in the cell Ag; AgCl, Cl-, F-∥LaF3∥NaF, HCl, H2O∣KCl(Satd.), Hg2Cl2; Hg at 25 °C. A least squares procedure was applied to the experimental data yielding a best estimate for K 1 of 5.85 × 10-4 with a standard error of 0.03 × 10-4.