Structure and magnetic properties of a non-heme diiron complex singly bridged by a hydroxo group

The synthesis of the first singly bridged non-heme diiron complex with a mu-hydroxo bridging ligand, [{(salten)Fe}2(OH)][B(C6H5)4].(CH3CN)x.(H2O)y (1) [H2salten = 4-azaheptane-1,7-bis(salicylideneiminate)], is reported. The complex has been characterized with X-ray crystallography, FTIR, magnetic susceptibility measurements, and M?ssbauer spectroscopy. The data have been compared with the results of DFT calculations on both 1 and a model with an unsupported mu-oxo bridge (2) to verify the formulation of the complex as a mu-hydroxo-bridged species. The X-ray structure [Fe-O(H) = 1.997(1) A and Fe-O(H)-Fe = 159 degrees ] is consistent with the DFT-optimized geometry of 1 [Fe-O(H) = 2.02 A and Fe-O(H)-Fe = 151 degrees ]; the Fe-O(H) distance in 1 is about 0.2 A longer than the Fe-O separations in the optimized geometry of 2 (1.84 A) and in the crystallographic structures of diiron(III) compounds with unsupported mu-oxo bridges (1.77-1.81 A). The formulation of 1 as a hydroxo-bridged compound is also supported by the presence of an O-H stretch band in the FTIR spectrum of the complex. The magnetic susceptibility measurements of 1 reveal antiferromagnetic exchange (J = 42 cm(-1) and H(ex) = JS(1).S(2)). Nearly the same J value is obtained by analyzing the temperature dependence of the M?ssbauer spectra (J = 43 cm(-1); other parameters: delta = 0.49 mm s(-1), DeltaE(Q) = -0.97 mm s(-1), and eta = 0.45 at 4.2 K). The experimental J values and M?ssbauer parameters agree very well with those obtained from DFT calculations for the mu-hydroxo-bridged compound (J = 46 cm(-1), delta = 0.48 mm s(-1), DeltaE(Q) = -1.09 mm s(-1), and eta = 0.35). The exchange coupling constant in 1 is distinctly different from the value J approximately 200 cm(-1) calculated for the optimized mu-oxo-bridged species, 2. The increased exchange-coupling in 2 arises primarily from a decrease in the Fe-O bond length.     

Nonheme oxoiron(IV) complexes of tris(2-pyridylmethyl)amine with cis-monoanionic ligands

Treatment of [Fe(IV)(O)(TPA)(NCMe)](CF3SO3)2 [TPA, N,N,N-tris(2-pyridylmethyl)amine] with 3 equiv of NR4X (X = CF3CO2, Cl, or Br) in MeCN at -40 degrees C affords a series of metastable [Fe(IV)(O)(TPA)(X)]+ complexes. Some characteristic features of the S = 1 oxoiron(IV) unit are quite insensitive to the ligand substitution in the equatorial plane, namely, the Fe-O distances (1.65-1.66 A), the energy ( approximately 7114.5 eV) and intensity [25(2) units] of the 1s-to-3d transition in the X-ray absorption spectra, and the M?ssbauer isomer shifts (0.01-0.06 mm.s(-1)) and quadrupole splittings (0.92-0.95 mm.s(-1)). The coordination of the anionic X ligand, however, is evidenced by red shifts of the characteristic near-IR ligand-field bands (720-800 nm) and spectroscopic observation of the bound anion by (19)F NMR for X = CF3CO2 and by EXAFS analysis for X = Cl (r(Fe-Cl) = 2.29 A) and Br (r(Fe-Br) = 2.43 A). Density functional theory calculations yield M?ssbauer parameters and bond lengths in good agreement with the experimental data and produce excited-state energies that follow the trend observed in the ligand-field bands. Despite mitigating the high effective charge of the iron(IV) center, the substitution of the MeCN ligand with monoanionic ligands X- decreases the thermal stability of [Fe(IV)(O)(TPA)]2+ complexes. These anion-substituted complexes model the cis-X-Fe(IV)=O units proposed in the mechanisms of oxygen-activating nonheme iron enzymes.     

Synthesis and Antitumor Evaluation of Some New Fused and Binary Pyridines

Syntheses of some new heterocyclic compounds containing pyridone, thioxopyridine, halogenated‐pyridine‐carbonitriles, pyrazolopyridine, and pyridine derivatives were achieved. Besides, a modified synthetic method for the synthesis of 2‐chloro‐4,6‐dimethyl‐nicotinonitrile ( 3 ) through the reaction of acetylacetone and malononitrile as starting materials was implemented. The reaction of 2‐chloronicotinonitrile 3 with substituted amines to 2‐aminonicotinonitrile were also investigated. Fused or binary pyridines were tested for cytotoxicity against well‐known established model Ehrlich ascites cells in vitro. Compound 13 exhibited a high antitumor activity compared with 5‐fluorouracil.     

IMPROVEMENT OF THE SEMI-ANALYTICAL METHOD, FOR DETERMINING THE GEOMETRICALLY NON-LINEAR RESPONSE OF THIN STRAIGHT STRUCTURES: PART II—FIRST AND SECOND NON-LINEAR MODE SHAPES OF FULLY CLAMPED RECTANGULAR PLATES

In a previous series of papers, a semi-analytical model based on Hamilton's principle and spectral analysis has been developed for geometrically non-linear free vibrations occurring at large displacement amplitudes of clamped-clamped beams and fully clamped rectangular homogeneous and composite plates. In Part I of this series of papers, concerned with geometrically non-linear free and forced vibrations of various beams, a practical simple “multi-mode theory”, based on the linearization of the non-linear algebraic equations, written in the modal basis, in the neighbourhood of each resonance has been developed. Simple explicit formulae, ready and easy to use for analytical or engineering purposes have been derived, which allows direct calculation of the basic function contributions to the first three non-linear mode shapes of the beams considered. Also, various possible truncations of the series expansion defining the first non-linear mode shape have been considered and compared with the complete solution, which showed that an increasing number of basic functions has to be used, corresponding to increasingly sized intervals of vibration amplitudes; starting from use of only one function, i.e., the first linear mode shape, corresponding to very small amplitudes, for which the linear theory is still valid, and ending by the complete series, involving six functions, corresponding to maximum vibration amplitudes at the beam middle point up to once the beam thickness. For higher amplitudes, a complementary second formulation has been developed, leading to reproduction of the known results via the solution of reduced linear systems of five equations and five unknowns. The purpose of this paper is to extend and adapt the approach described above to the geometrically non-linear free vibration of fully clamped rectangular plates in order to allow direct and easy calculation of the first, second and higher non-linear fully clamped rectangular plate mode shapes, with their associated non-linear frequencies and non-linear bending stress patterns. Also, numerical results corresponding to the first and second non-linear modes shapes of fully clamped rectangular plates with an aspect ratio α=0·6 are presented. Data concerning the higher non-linear modes, the aspect ratio effect, and the forced vibration case will be presented later.     

Modulations of exchange coupling in oxoferrylporphyrin cation radical complexes detected by Mössbauer and EPR measurements

Oxoferrylporphyrin cation radical complexes were generated using the prophyrin dianions: tetrakis 2,6-dichlorophenyl (TDCPP) and tetrakis 2,4,6-trimethoxyphenyl (TTMPP). Spin coupling between ferryl iron (S=1) and porphyrin radical S′=1/2), ligand field interaction and hyperfine parameters of iron were studied by Mössbauer and EPR measurements and corresponding spin Hamiltonian analyses. Samples of [Fe^IV=0 TDCPP], which had to be prepared in CH₂Cl₂, were “vacuum dried” in order to obtain Mössbauer spectra.     

On the Spectrum of a Class of Strongly Coupled p-Laplacian Systems

Consider the nonlinear coupled elliptic system     

The absorption spectrum of 12C2H2 IV. The regions 7600–9200 cm−1 and 10600–11500 cm−1

The absorption spectrum of ¹²C₂H₂ has been recorded by intracavity laser absorption spectroscopy (ICLAS) in the 10600–11 500 cm^?1 spectral region, where no absorption bands were previously reported. Fifteen bands starting from the vibrational ground state are observed and rotationally analysed. All corresponding excited vibrational levels were assigned using the polyad model, the so-called cluster model (El Idrissi, M.I., Liévin, J., Campargue, A., and Herman, M., 1999, J. chem. Phys., 110, 2074) which allows vibrational energies, rotational B_v constants and, to some respect, relative band intensities to be predicted. Additional data and constants are also provided in the range 7600–9200cm^?1, whenever improving the literature results, from spectra recorded previously at ULB using Fourier transform spectroscopy. The assignment procedure in the range recorded by ICLAS is detailed, leading to a deeper understanding of vibration-rotation and intensity features of the absorption bands within the frame of the cluster model.     

Stability-Indicating Spectrofluorimetric Method for Determination of Itopride Hydrochloride in Raw Material and Pharmaceutical Formulations

A simple, sensitive and rapid spectrofluorimetric method for determination of itopride hydrochloride in raw material and tablets has been developed. The proposed method is based on the measurement of the native fluorescence of the drug in water at 363 nm after excitation at 255 nm. The relative fluorescence intensity-concentration plot was rectilinear over the range of 0.1–2 μg/mL (2.5?×?10^?7–5.06?×?10^?6 mole/L), with good correlation (r?=?0.9999), limit of detection of 0.015 μg/mL and a lower limit of quantification of 0.045 μg/mL. The described method was successfully applied for the determination of itopride hydrochloride in its commercial tablets with average percentage recovery of 100.11?±?0.32 without interference from common excipients. Additionally, the proposed method can be applied for determination of itopride in combined tablets with rabeprazole or pantoprazole without prior separation. The method was extended to stability study of itopride. The drug was exposed to acidic, alkaline, oxidative and photolytic degradation according to ICH guidelines. Moreover, the method was utilized to investigate the kinetics of the alkaline, acidic and oxidative degradation of the drug. A proposal for the degradation pathways was postulated.     

Optical investigations on the existence of phase transition in ZnO:Li thin films prepared by DC sputtering method

We investigated the effect of temperature on the absorption spectra of Zn_0.8Li_0.2O thin films (ZnO:Li), deposited at 573 K, in the wavelength range 190‐800 nm. The films were deposited on sapphire, MgO or quartz substrates by DC sputtering method. The results show a shift of the optical energy gap (E_g), with direct allowed transition type near the fundamental edge, to lower wavelengths as the temperature increases. The temperature rate of E_g changes considerably showing an anomaly around 320 K depending on type of substrate. The founded results indicated that replacement of Zn ions with Li ions induces a ferroelectric phase in the ZnO wurtzite‐type semiconductor. The exponential dependence of the absorption coefficient on the incident photon energy suggests the validity of the Urbach rule. (© 2007 WILEY ‐VCH Verlag GmbH & Co. KGaA, Weinheim)