Initial members of the family of molecular mid-valent high-nuclearity iron nitrides: [Fe4N2X10]4- and [Fe10N8X12]5- (X = Cl-, Br-)

Current theoretical and experimental evidence points toward X = N as the identity of the interstitial atom in the [MoFe7S9X] core of the iron-molybdenum cofactor cluster of nitrogenase. This atom functions with mu6 bridging multiplicity to six iron atoms and, if it is nitrogen as nitride, raises a question as to the existence of a family of molecular iron nitrides of higher nuclearity than known dinuclear Fe(III,IV) species with linear [Fe-N-Fe]5+,4+ bridges. This matter has been initially examined by variation of reactant stoichiometry in the self-assembly systems [FeX4]1-/(Me3Sn)3N (X = Cl-, Br-) in acetonitrile. A 2:1 mol ratio affords [Fe4N2Cl10]4- (1), isolated as the Et4N+ salt (72%). This cluster has idealized C2h symmetry with a planar antiferromagnetically coupled [Fe(III)4(mu3-N)2]6+ core containing an Fe2N2 rhombus to which are attached two FeCl3 units. DFT calculations have been performed to determine the dominant magnetic exchange pathway. An 11:8 mol ratio leads to [Fe10N8Cl12]5- (3) as the Et4N+ salt (37%). The cluster possesses idealized D2h symmetry and is built of 15 edge- and vertex-shared rhomboids involving two mu3-N and six mu4-N bridging atoms, and incorporates two of the core units of 1. Four FeN2Cl2 and four FeN3Cl sites are tetrahedral and two FeN5 sites are trigonal pyramidal. The cluster is mixed-valence (9Fe(III) + Fe(IV)); a discrete Fe(IV) site was not detected by crystallography or M?ssbauer spectroscopy. The corresponding clusters [Fe4N2Br10]4- and [Fe10N8Br12]5- are isostructural with 1 and 3, respectively. Future research is directed toward defining the scope of the family of molecular iron nitrides.     

Antisymmetric exchange in [2Fe-2S]1+ clusters: EPR of the Rieske protein from Thermus thermophilus at pH 14

[2Fe-2S] clusters found in the xanthine oxidase family of proteins exhibit an S = 1/2 EPR feature, called signal II, for which one g-value is significantly above g = 2.0. The g-values of signal II cannot be explained with the standard spin coupling model that has been so successful in describing the g = 1.94 signals of [2Fe-2S] ferredoxins. We have studied the EPR spectra of the Rieske protein from Thermus thermophilus at pH 14 and observed a signal II-type EPR spectrum, with g-values at 1.81, 1.94, and 2.14. It is shown that the g-values of signal II can be explained by including an antisymmetric exchange term, d.S1xS2, in the spin Hamiltonian. The presence of this term is sensed by EPR if the isotropic exchange coupling constant J is sufficiently small. For the Rieske protein we determined J = 43 cm-1 which is at least 4 times smaller than the J values reported for [2Fe-2S] clusters that yield standard g = 1.94 signals.     

IMPROVEMENT OF THE SEMI-ANALYTICAL METHOD, FOR DETERMINING THE GEOMETRICALLY NON-LINEAR RESPONSE OF THIN STRAIGHT STRUCTURES. PART I: APPLICATION TO CLAMPED-CLAMPED AND SIMPLY SUPPORTED-CLAMPED BEAMS

In a previous series of papers (Benamar 1990 Ph.D. Thesis, University of Southampton; Benamaret al. 1991 Journal of Sound and Vibration149, 179-195;164, 399-424 [1-3]) a general model based on Hamilton's principle and spectral analysis has been developed for non-linear free vibrations occurring at large displacement amplitudes of fully clamped beams and rectangular homogeneous and composite plates. The results obtained with this model corresponding to the first non-linear mode shape of a clamped-clamped (CC) beam and to the first non-linear mode shape of a CC plate are in good agreement with those obtained in previous experimental studies (Benamaret al. 1991 Journal of Sound and Vibration 149, 179-195;164, 399-424 [2, 3]). More recently, this model has been re-derived (Azar et al. 1999 Journal of Sound and Vibration224, 377-395; submitted [4, 5]) using spectral analysis, Lagrange's equations and the harmonic balance method, and applied to obtain the non-linear steady state forced periodic response of simply supported (SS), CC, and simply supported-clamped (SSC) beams. The practical application of this approach to engineering problems necessitates the use of appropriate software in each case or use of published tables of data, obtained from numerical solution of the non-linear algebraic system, corresponding to each problem. The present work was an attempt to develop a more practical simple “multi-mode theory” based on the linearization of the non-linear algebraic equations, written on the modal basis, in the neighbourhood of each resonance. The purpose was to derive simple formulae, which are easy to use, for engineering purposes. In this paper, two models are proposed. The first is concerned with displacement amplitudes of vibrationW_max /H, obtained at the beam centre, up to about 0·7 times the beam thickness and the second may be used for higher amplitudes W_max/H up to about 1·5 times the beam thickness. This new approach has been successfully used in the free vibration case to the first, second and third non-linear modes shapes of CC beams and to the first non-linear mode shape of a CSS beam. It has also been applied to obtain the non-linear steady state periodic forced response of CC and CSS beams, excited harmonically with concentrated and distributed forces.     

Embedding Uq(sl(2)) and Sine Algebras in Generalized Clifford Algebras

We establish the connection between certain quantum algebras and generalizedClifford algebras (GCA). To be precise, we embed the quantum tori Lie algebraand U _q (sl(2)) in GCA.     

Synthesis,characterization, and photovoltaic properties of dithienylbenzobisazole‐dithienylsilole copolymers

Three conjugated polymers comprised of dioctyl‐dithieno‐[2,3‐b:2',3'‐d]silole and a donor‐acceptor‐donor triad of either cis‐benzbisoxazole, trans‐benzobisoxazole or trans‐benzobisthiazole were synthesized via the Stille cross‐coupling reaction. The impact of varying the heteroatoms and/or the location within the benzobisazole moiety on the optical and electronic properties of the resulting polymers was evaluated via cyclic voltammetry and UV‐Visible spectroscopy. All of the polymers have similar optical band‐gaps of ～1.9 eV and highest occupied molecular orbital levels of ? 5.2 eV. However, the lowest unoccupied molecular orbitals (LUMO) ranged from ? 3.0 to ? 3.2 eV. Interestingly, when the polymers were used as donor materials in bulk‐heterojunction photovoltaic cells with PC₇₁BM as the electron‐acceptor, the benzobisoxazole‐based polymers gave slightly better results than the benzobisthiazole‐containing polymers with power conversion efficiencies up to 3.5%. These results indicate that benzobisoxazoles are promising materials for use in OPVs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1533–1540     

COMBINED EFFECTS IN A SEMILINEAR POLYHARMONIC PROBLEM IN THE UNIT BALL

Let m be a positive integer and B be the unit ball of Rn(n ≥ 2). We investigate the existence, uniqueness and the asymptotic behavior of a positive continuous solution to the following semilinear polyharmonic boundary value problem(-△)mu = a1(x)uα1+ a2(x)uα2, lim|x|→1u(x)(1- |x|)m-1= 0,where α1, α2 ∈(-1, 1) and a1, a2 are two nonnegative measurable functions on B satisfying some appropriate assumptions related to Karamata regular variation theory.     

Spectrofluorometric Determination of Methocarbamol in Pharmaceutical Preparations and Human Plasma

A simple, sensitive and rapid spectrofluorometric method for determination of methocarbamol in pharmaceutical formulations and spiked human plasma has been developed. The proposed method is based on the measurement of the native fluorescence of methocarbamol in methanol at 313 nm after excitation at 277 nm. The relative fluorescence intensity-concentration plot was rectilinear over the range of 0.05–2.0 μg/mL, with good correlation (r = 0.9999), limit of detection of 0.007 μg/ mL and a lower limit of quantification of 0.022 μg/ mL. The described method was successfully applied for the determination of methocarbamol in its tablets without interference from co-formulated drugs, such as aspirin, diclofenac, paracetamol and ibuprofen, The results obtained were in good agreement with those obtained using the official method (USP 30).The high sensitivity of the method allowed the determination of the studied drug in spiked human plasma with average percentage recovery of 99.42 ± 3.84.