Modification of Glassy Carbon Electrodes with Complexes of Manganese(II) with Some Phenanthroline Derivatives Immobilized in Nafion Layer.

Manganese(II) complexes with phenanthroline derivatives modified with different substituents were synthesized and incorporated into Nafion layers covering the surfaces of glassy carbon electrodes and were studied electrochemically. Formal potentials and apparent diffusion coefficients were calculated and discussed. The suitability for electrocatalytic oxidation of ascorbic acid and glycolic acid was examined. The surfaces of modified electrodes were characterized using atomic force microscopy.

The Influence of Electrolyte Type on Kinetics of Redox Processes in the Polymer Films of Ni(II) Salen-Type Complexes.

Electrodes modified with polymers derived from the complexes [Ni(salcn)], [Ni(salcn(Me))] and [Ni(salcn(Bu))] were obtained in order to study the kinetics of electrode processes occurring in polymer films, depending on the thickness of the films, the type of electrolyte and the solvent. FTIR and EQCM methods were used to determine the type of mass transported into polymer films during anode processes and the number of moles of ions and solvent. The rate of charge transport through films was determined by the cyclic voltammetry method, by the quantity cD1/2. It was shown that the charge transport was determined by the transport of anions. The kinetics were most efficient for poly[Ni(salcn(Bu))] modified electrodes, obtained from TBAPF6 and working in TBAClO4 and TBABF4. It was also shown that a solvent with a higher DN value and lower viscosity (MeCN) facilitated the transport of the charge through polymer films.

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.

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 Determination of Protonation Constants of Peptidomimetic Cyclophanes in Binary Methanol-Water Mixtures.

The protonation constants of new group of peptidomimetic cyclophanes with valine or phenylalanine moieties incorporated into the macrocyclic skeleton as well as their linear analogues were determined by potentiometric measurements in solutions of methanol-water mixtures at 25°C and constant ionic strength. The influence of cavity size, location of protonation sites, and attached substituents of the macrocyclic ligands on the protonation constants were discussed on the basis of potentiometric measurement as well as H(1)-NMR results.

Silver complexes of peptidomimetic polyazapyridinophanes. The influence of the bonding cavity size and the nature of side chains.

Several peptidomimetic macrocycles containing a pyridine spacer and ring sizes ranging from 15 to 17 have been efficiently synthesized starting from valine and phenylalanine. The complexes formed have been investigated by potentiometry and NMR. Log K values show that phenylalanine derivatives are consistently more stable than valine derivatives , whilst macrocycles with ring sizes of 16 members are the most appropriate for the complexation. The NMR data, in combination with molecular modeling, allow rationalization of the structure of the complexes formed and the participation of the aromatic rings from the side chain of phenylalanine in pi-Ag+ interactions to be discarded.