Oxidation properties of β-substituted pyrroles

Pyrroles represent building blocks of conjugated poly(heterocycles) which, as organic conductors, are potential materials for organic electronics. Oxidation of β-substituted pyrroles constitutes an important first step in the process of electropolymerization. Ionization energy and the electron spin density distribution are two the most important properties regarding monomers. These properties are studied as a function of electron-withdrawing and electron-donating substituents of pyrrole ring. Evolution of molecular structure, nature of bonding, and electronic density are studied as an effect of ionization process.     

Naringenin Schiff base: antioxidant activity,acid–base profile,and interactions with DNA

A Schiff base derived from naringenin (NTSC) and its complex with Cu(II) ([Cu(H₃L)(OAc)]·H₂O, Cu(II)–NTSC) have been synthesized and characterized by physicochemical and spectroscopic methods. EPR studies confirmed that nitrogen, oxygen, and sulfur are the donor atoms bound to Cu(II) in the complex. The geometry of the complex has been modelled using DFT methods. Furthermore, naringenin and NTSC were used for the formation of Cu(II) complexes in solution, for comparison of biological activities. Antioxidant studies confirmed better radical scavenging activity of both NTSC and its Cu(II) complex compared to naringenin. The interaction of these compounds with calf thymus DNA was monitored by UV–Vis spectroscopy.     

Properties of a Ring Critical Pointas Measures of Intramolecular H-Bond Strength

Summary.  The topological parameters derived from the Bader theory such as the electron density and its Laplacian at the ring critical point (RCP) are analysed here as possible measures of the H-bond stength for intramolecular H-bonds. The parameters of RCP correlate well with the other properties of intramolecular H-bonds which are known as good measures of the H-bond strength. The calculations were performed on two samples of compounds with intramolecular H-bonds: the derivatives of malonaldehyde and the derivatives of o-hydroxybenzaldehyde. MP2 and HF calculations were carried out using a 6-311++G^** basis set. E-mail: slagra@krysia.uni.lodz.pl Received February 18, 2002; accepted (revised) May 27, 2002     

Apparent Molar Volumes of Multicharged Cations in Dimethyl Sulfoxide Solutions at 25°C

Densities for DMSO solutions of iron(III), aluminium(III), beryllium(II) and magnesium(II) perchlorates and silver nitrate are reported. Densities for DMSO solutions of tetraethylammonium perchlorate and nitrate and tetrabutylammonium perchlorate and tetraphenylborate are also presented. The partial molar volumes of the DMSO-solvated cations are derived and discussed in terms of variation with the charge number.     

Radon-222 and 226Ra concentrations in mineralized groundwaters of Gorzanów (Kłodzko Basin, Sudeten Mountains, SW Poland)

This work characterizes the occurrence of radionuclides ²²²Rn and ²²⁶Ra in the mineralized groundwaters of Gorzanów. The village is situated in the Sudeten Mountains, which are known in Poland for having increased concentrations of the aforesaid radionuclides in their groundwaters. However, in Gorzanów, the measured concentrations of ²²⁶Ra were low both in the reservoir rocks and mineralized waters. Consequently, the ²²²Rn concentration in the groundwaters also turned out to be low. The ²²⁶Ra content of these waters should mainly be associated with the dissolution of this nuclide, together with other main ions, at large depths, at slightly enhanced temperature. Radon-222, on the other hand, penetrates into the water during its outflow to the surface, in the zones of intensive friable deformations near fault zones. Thus, in the groundwaters of Gorzanów, the concentrations of these nuclides, subsequent in the uranium series, do not have a common genesis and they are not correlated with each other.     

Lanthanide Complexes with Multidentate Oxime Ligands as Single‐Molecule Magnets and Atmospheric Carbon Dioxide Fixation Systems

The synthesis, structure, and magnetic properties of five lanthanide complexes with multidentate oxime ligands are described. Complexes 1 and 2 ( 1 : [La₂(pop)₂(acac)₄(CH₃OH)], 2 : [Dy₂(pop)(acac)₅]) are synthesized from the 2‐hydroxyimino‐N‐[1‐(2‐pyridyl)ethylidene]propanohydrazone (Hpop) ligand, while 3 , 4 , and 5 ( 3 : [Dy₂(naphthsaoH)₂(acac)₄H(OH)]?0.85 CH₃CN?1.58 H₂O; 4 : [Tb₂(naphthsaoH)₂(acac)₄H(OH)]?0.52 CH₃CN?1.71 H₂O; 5 : [La₆(CO₃)₂(naphthsao)₅ (naphthsaoH)_0.5(acac)₈(CO₃)_0.5(CH₃OH)_2.76H_5.5(H₂O)_1.24]?2.39 CH₃CN?0.12 H₂O) contain 1‐(1‐hydroxynaphthalen‐2‐yl)‐ethanone oxime (naphthsaoH₂). In 1 – 4 , dinuclear [Ln₂] complexes crystallize, whereas hexanuclear La^III complex 5 is formed after fixation of atmospheric carbon dioxide. Dy^III‐based complexes 2 and 3 display single‐molecule‐magnet properties with energy barriers of 27 and 98 K, respectively. The presence of a broad and unsymmetrical relaxation mode observed in the ac susceptibility data for 3 suggest two different dynamics of the magnetization which might be a consequence of independent relaxation processes of the two different Dy³⁺ ions.     

EXAFS studies on the reaction of gold (III) chloride complex ions with sodium hydroxide and glucose

EXAFS and QEXAFS experiments were carried out at Hasylab laboratory in DESY center (X1 beamline, Hamburg, Germany) to monitor the course of the hydrolysis reactions of [AuCl(4)](-) complex ions as well as their reduction using glucose. As a result, changes in the spectra of [AuCl(4)](-) ions and disappearance of absorption Au-L(3) edge were registered. From the results of the experiments we have carried out, the changes in bond lengths between Au(3+) central ion and Cl(-) ligands as well as the reduction of Au(3+) to metallic form (colloidal gold was formed in the system) are evident. Good quality spectra obtained before and after the reactions gave a chance to determine the bond length characteristic of Au-Cl, Au-OH and Au-Au pairs. Additionally, the obtained results were compared with the simulated spectra of different gold (III) complex ions, possibly present in the solution. Finally, the mechanism of these reactions was suggested. Unfortunately, it was not possible to detect the changes in the structure of gold (III) complex ions within the time of reaction, because of too high rates of both processes (hydrolysis and reduction) as compared with the detection time.     

Isomerical and structural determination of N-hydroxyurea: a matrix isolation and theoretical study

The structure, isomerization pathways and vibrational spectra of the important N-hydroxyurea (HU) molecule were studied by matrix isolation FT-IR spectroscopy and molecular orbital calculations undertaken at the MP2/6-311++G(2d,2p) level of theory. In agreement with theoretical predictions, 1Ea represents the most stable keto isomer in the gas-phase, being the dominant species trapped in argon matrices, while the 1Za isomer also contributes to the spectrum of isolated HU molecules. According to the calculated abundance values at the temperature of evaporation of the compound (393 K), the 1Ea and 1Za isomers together with a small contribution of 1Eb are expected to appear in the experimental spectra. Since the barrier for interconversion 1Ea? 1Eb is only ～2 kJ mol(-1), these two isomers are in equilibrium in the matrices and, at low temperature, the population of the less stable 1Eb form is too small to be observed. Full assignment of the observed spectra of N-hydroxyurea and its deuterium analogue was undertaken on the basis of comparison with theoretical data.