Solvent effects on the redox properties of tris-(1,10-phenanthroline)iron(II/III) complexes

The redox properties of the system Fe(tmphen)₃(II/III) (tmphen=3,4,7,8-tetramethyl-1,10-phenanthroline) have been studied in the solvents nitromethane, acetonitrile, propanediol-1,2-carbonate, dimethylformamide, dimethylacetamide, dimethylsulfoxide and of the systems Fe(phen)₃(II/III) (phen=1,10-phenanthroline) and Fe(niphen)₃(II/III) (niphen=5-nitro-1,10-phenanthroline) in the solvents nitromethane, acetonitrile, propanediol-1,2-carbonate and acetone. The redox potentials of Fe(tmphen)₃(II/III) are nearly independent of the solvent suggesting that the system might be used as a reference redox couple similar to the systems ferrocene/ferricinium or bisbiphenylchromium(0/I). In contrast the redox potentials of Fe(niphen)₃(II/III) show a significant decrease with increasing donor number of the solvent which can be explained by nucleophilic attack of solvent molecules at the iron. It is shown that such a mechanism is consistent with the known solvent and salt effects on the kinetics of dissociation of ferroin and ferriin type complexes.     

Spectral and electrochemical study of coordination molecules Cu4OX6L4: 3-Methylpyridine and 4-Methylpyridine Cu4OBrnCl(6−n)L4 complexes

The tetranuclear Cu₄OBr_nCl_(6-n)L₄ complexes, where L = 3-methylpyridine (3-Mepy), 4-methylpyridine (4-Mepy) and n=0–6 with trigonal bipyramidal coordination of copper(II) were prepared and their infrared and electronic absorption spectra as well as cyclic voltammograms in nitromethane solutions were measured. The polyhedra in Cu₄OBr_nCl_(6−n) (3-Mepy)₄ molecules are less distorted comparing with those of 4-Mepy analogues as indicated by infrared Cu₄O absorptions, far infrared Cu—Br, Cu—Cl, and Cu—N absorptions, d—d bands in electronic spectra and potentials, measured by cyclic voltammetry. The 3-Mepy complexes exhibit strong single infrared Cu₄O absorptions, while for related 4-Mepy complexes doubly split Cu₄O bands were observed. Two strongly overlapped d—d bands in electronic absorption spectra of the 3-and 4-Mepy complexes in nitromethane were resolved by Gaussian fitting. The 4-Mepy ligand produces slightly stronger ligand field than its 3-Mepy analogue. The maxima of high-energy d—d bands are in a linear correlation with the number of bromide ligands. The correlations for corresponding low-energy bands are considerably deviated from linearity. The halfwave potentials of the complexes in nitromethane correlate with both the number of bromides and the data of electronic absorption spectra suggesting that the reducing electron at the electrode process enters the half-filled d _{z 2} orbital of the copper(II) atom. The origin of a difference between the 3-and 4-Mepy complexes in their spectral and electrochemical properties is also discussed.     

Electrochemical behaviour of a series of Fe(III) complexes with tetradentate Schiff base ligands

Summary The electrochemical reduction of the Fe(III) complexes with a series of substituted N,N-Ethylenebisacetonimines was investigated by cyclic voltammetry in acetonitrile solution at a platinum electrode. The substituent does not significantly influence the redox properties of the studied complexes. The symmetry of the redox orbital is responsible for the observed behaviour of the complexes.

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Elektrochemisches Verhalten einer Reihe von Fe(III)-Komplexen mit vierzähnigen Schiffschen Basen als Liganden

Zusammenfassung Die elektrochemische Reduktion der Fe(III)-Komplexe einer Reihe von substituierten N,N-Ethylenbisacetoniminen wurde mittels cyclischer Voltammetrie in Acetonitril an einer Platinelektrode untersucht. Der Substituent beeinflußt die Redoxeigenschaften der untersuchten Komplexe nicht signifikant. Das beobachtete Verhalten der Komplexe wird von der Symmetrie des Redoxorbitals bestimmt.

     

IMEX Runge–Kutta schemes for reaction–diffusion equations

A fundamental research is carried out into convergence and stability properties of IMEX (implicit–explicit) Runge–Kutta schemes applied to reaction–diffusion equations. It is shown that a fully discrete scheme converges if it satisfies certain conditions using a technique of the B-convergence analysis, developed by Burrage, Hundsdorfer and Verwer in 1986. Stability of the schemes is also examined on the basis of a scalar test equation, proposed by Frank, Hundsdorfer and Verwer in 1997.     

Influence of tetraalkylammonium ions on structure of nonaqueous solvents

Summary The half-wave potentials of the redox system [Co(en)₃]³⁺/[Co(en)₃]²⁺ have been influenced by the tetraalkylamonium cation of the supporting electrolyte used. This was explained with the specific interactions (solvation) of the tetraalkylamonium ion with the nonaqueous solvent.

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Einfluß von Tetraalkylammoniumionen auf die Struktur nichtwäßriger Lösungsmittel (Kurze Mitt.)

Zusammenfassung Das Halbwellenpotential des Redoxsystems [Co(en)₃]³⁺/[Co(en)₃]²⁺ wird von Tetraalkylammonium-Ionen des Stützelektrolyten beeinflußt. Dies wird durch die spezifischen Wechselwirkungen (Solvatation) der Ionen mit dem nichtwäßrigen Lösungsmittel erklärt.

     

Cofactor Biogenesis in Cysteamine Dioxygenase: C−F Bond Cleavage with Genetically Incorporated Unnatural Tyrosine

Cysteamine dioxygenase (ADO) is a thiol dioxygenase whose study has been stagnated by the ambiguity as to whether or not it possesses an anticipated protein‐derived cofactor. Reported herein is the discovery and elucidation of a Cys‐Tyr cofactor in human ADO, crosslinked between Cys220 and Tyr222 through a thioether (C?S) bond. By genetically incorporating an unnatural amino acid, 3,5‐difluoro‐tyrosine (F₂‐Tyr), specifically into Tyr222 of human ADO, an autocatalytic oxidative carbon–fluorine bond activation and fluoride release were identified by mass spectrometry and ¹⁹F NMR spectroscopy. These results suggest that the cofactor biogenesis is executed by a powerful oxidant during an autocatalytic process. Unlike that of cysteine dioxygenase, the crosslinking results in a minimal structural change of the protein and it is not detectable by routine low‐resolution techniques. Finally, a new sequence motif, C‐X‐Y‐Y(F), is proposed for identifying the Cys‐Tyr crosslink.     

Structural and electronic effects involving pyridine rings in 4-methylpyridine Cu4OX6L4 complexes. II. Correlations based on molecular structure of the Cu4OCl6(4-Mepy)4 complex

Correlations involving bond lengths and bond angles in the molecular structure of the Cu₄OCl₆(4-Mepy)₄ complex (4-Mepy = 4-methylpyridine) with four symmetrically independent molecules present in the unit cell showed that the donor-acceptor behavior involving the π-back donation into the pyridine rings of the 4-Mepy ligands is most effectively stimulated by a suitable orientation of the pyridine rings in the trigonal bipyramidal geometry. The pyridine ring planes are almost in parallel orientation with one of the three Cu-Cl bonds. The bond lengths of these Cu-Cl bonds are in a significant linear correlation with the Cu-N bond lengths and the bonds lengths of the pyridine rings. The pyridine rings orientation is affected by distortion of the trigonal bipyramidal geometry to tetragonal pyramidal coordination, by out-of plane pyridine rings deviation and in-plane pyridine rings tilting, by puckering of the pyridine rings and by the effects of the methyl groups. The pyridine rings in at least seven of the sixteen trigonal bipyramidal coordinations exhibit an orientation supporting the π-back bonding between the Cu(II) atoms and the pyridine rings.     

Calorimetric Investigation of Conversion to The Most Stable Subgel Phase of Phosphatidylethanolamine-water System

The conversion of either the gel or the liquid crystal phase to the most stable subgel phase in dimyristoylphosphatidylethanolamine (DMPE)-water system at a water content of 25 mass% was studied by differential scanning calorimetry and isothermal calorimetry. The calorimetric experiments were performed for two samples depending on whether the thermal treatment of cooling to -60°C was adopted or not. In DSC of varying heating rate, exothermic peaks due to the partial conversion were observed at either temperatures just below the gel-to-liquid crystal phase transition at 50°C or temperatures where the liquid crystal phase is present as a metastable state. The enthalpies of conversion for both the gel and the liquid crystal phase were measured directly by the isothermal calorimetries at 47 and 53°C, respectively, where the exothermic peaks were observed by DSC and were compared with the enthalpy difference between the gel and subgel phases and that between the liquid crystal and subgel phases. This revised version was published online in July 2006 with corrections to the Cover Date.     

The contribution of anion disorder to ionic conductivity on single crystals of β-PbF2

The effect of the different cooling processes on the disorder of flourine ions and ionic conductivity in β-PbF₂ has been studied by X-ray method and ionic conductivity measurements on single crystals below the transition temperature T_c. The spike-like diffuse scattering was observed along the <111>¹ directions around the Bragg reflections. The activation energies for the conduction process are 0.40 eV for the sample quenched from 970 K and 0.54 eV for the one from 720 K. The higher the quenching temperature is, the higher the conductivity and the lower the activation energy become. The dependence of conductivity on the different cooling processes is more evident in single crystals than in polycrystalline samples. The contribution of the different cooling processes to ionic conductivity can be quantitatively explained by the extent of ordering of mobile fluorine ions. Time dependence of ionic conductivity has not been observed.     

NP-stability of Runge-Kutta methods based on classical quadrature

Recently Bellen, Jackiewicz and Zennaro have studied stability properties of Runge-Kutta (RK) methods for neutral delay differential equations using a scalar test equation. In particular, they have shown that everyA-stable collocation method isNP-stable, i.e., the method has an analogous stability property toA-stability with respect to the test equation. Consequently, the Gauss, Radau IIA and Lobatto IIIA methods areNP-stable. In this paper, we examine the stability of RK methods based on classical quadrature by a slightly different approach from theirs. As a result, we prove that the Radau IA and Lobatto IIIC methods equipped with suitable continuous extensions are alsoNP-stable by virtue of fundamental notions related to those methods such as simplifying conditions, algebraic stability, and theW-transformation.