Synthesis and crystal structure of some 3,5-pyrazolidinediones

Syntheses of various derivatives of 3,5-pyrazolidenedione are reported. This includes 4-arylidene (alkylidene or aralkylidene)-3,5-pyrazolidinediones, which on epoxidation gave unreported oxiranes. The syntheses of these derivatives were based on either the Knoevenagel reaction of carbonyl derivatives with 3,4-pyrazolidinedione or cyclization of arylidene (alkylidene) malonic acid hydrazide with glacial acetic acid. 4-Arylazo-3,5-pyrazolidinedione derivatives were also prepared by coupling of aryldiazonium salts with 3,5-pyrazolidinedione or cyclization of arylazomalonic acid hydrazide. Reduction of 4-benzylidene derivatives gave the corresponding benzyl derivatives. The structure of the new products was confirmed by elemental and spectral analyses and X-ray crystallography.     

Kinetics of Oxidation of L‐Cysteine by trans‐ and cis‐CoIII and FeIII Complexes based on α‐ and γ‐Diimine Schiff Base Ligands

Kinetics of oxidation of L ‐cysteine by Co^III and Fe^III complexes based on α‐ and γ‐diimine Schiff base ligands were studied in aqueous solution. Pairs of trans and cis isomers of the metal complexes were used in the studies. Kinetic measurements were performed at 25 °C and constant pH and ionic strength under pseudo‐first order condition, in which the concentration of cysteine was around two orders of magnitude greater than that of the metal complex. The observed rate constant was obtained by following the change in absorbance of the reaction mixture with time at a predetermined wavelength. The overall rate constant and order of the reaction with respect to cysteine and metal complex were determined. For both metal ions studied, the oxidation rate constant for the trans isomer was higher than that for the cis isomer. This was attributed to the contribution of the steric factor and the trans effect. The effects of substituents and the nature of the metal ion on the reaction rate are discussed.     

Characterization and de novo sequencing of snow crab tropomyosin enzymatic peptides by both electrospary ionization and matrix‐assisted laser desorption ionization QqToF tandem mass spectrometry

The protein tropomyosin (TM) is a known major allergen present in shellfish causing frequent food allergies. TM is also an occupational allergen generated in the working environment of snow crab (Chionoecetes opilio) processing plants. The TM protein was purified from both claw and leg meats of snow crab and analyzed by electrospray ionization and matrix‐assisted laser desorption/ionization (MALDI) using hybrid quadruple time‐of‐flight tandem mass spectrometry (QqToF‐MS). The native polypeptide molecular weight of TM was determined to be 32 733 Da. The protein was further characterized using the ‘bottom‐up’ MS approach. A peptide mass fingerprinting was obtained by two different enzymatic digestions and de novo sequencing of the most abundant peptides performed. Any post‐translational modifications were identified by searching their calculated and predicted molecular weights in precursor ion spectra. The immunological reactivity of snow crab extract was evaluated using specific antibodies and allergenic reactivity assessed with serum of allergic patients. Subsequently, a signature peptide for TM was identified and evaluated in terms of identity and homology using the basic local alignment search tool (BLAST). The identification of a signature peptide for the allergen TM using MALDI‐QqToF‐MS will be critical for the sensitive and specific quantification of this highly allergenic protein in the work place. Copyright © 2010 John Wiley & Sons, Ltd.     

LIMIT CYCLES TO A FOUR-DIMENSIONAL LINEAR CENTER

In this paper we study a four-dimensional linear center. Based on the averaging theory, we investigate the existence of limit cycles of the system.     

Theoretical investigation of the proton affinities of benzazoles in the gas phase and in solution

The ground‐state equilibrium geometries of benzothiazole, benzoxazole, and benzimidazole were optimized at the density functional theory (DFT)/6‐31G** level of theory. Proton affinities on each of the possible sites in the studied series of compounds have been calculated at the DFT/6‐31G**/6‐311++G** level. The results indicate clearly that N‐site protonation is strongly favored over X‐site protonation (X = NH, O, S) for the series studied. Correlation of the computed proton affinities to the energy (E_HOMO) of the highest occupied MO in the gas phase and in solution has been explored and discussed. A comprehensive investigation of the effect of solvent on the process of protonation of the studied compounds has been performed. Different dielectric continuum models (i.e., Onsager, PCM, and IPCM) have been tested; their performance and range of applicability are reported and discussed. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

CO adsorption on MgO, CaO and SrO crystals periodic Hartree-Fock calculations

The adsorption of carbon monoxide at the defect-free (1 0 0), (1 1 0) and (2 1 0) five-atomic layer slab of the three oxides: MgO, CaO, and SrO has been investigated using the periodic Hartree-Fock level of ab initio theory, together with the 1 × 1 supercell model. All the calculated CO/oxide interaction energies exhibit exothermic character. The HF interaction energies increase monotonically in the order MgO < CaO < SrO. The surface morphology of adsorbate/substrate interaction is confirmed by considering relaxation energies, Mulliken population analysis, charge density contours, and electrostatic potential maps.     

Nonlinear electrohydrodynamic Kelvin-Helmholtz and Marangoni instabilities near the marginal state

The effects of surface tension and adsorption on the electrohydrodynamic Kelvin-Helmholtz instability are studied. The system is stressed by a normal electric field such that it allows for the presence of surface charges at the interface. The method used is that of multiple scales. The nonlinear Schrödinger equation describing the behavior of the disturbed system is derived. The stability of the perturbed system is discussed both analytically and numerically and the stability diagrams are obtained. At the critical point, a generalized formulation of the evolution equation is developed, which leads to the nonlinear Klein-Gordon equation. The various stability criteria are derived from this equation.     

On directional monogeneity sets

We introduce and investigate some new differential properties of functions by using geometrical properties of directional monogeneity sets.¹ University of Cairo, Giza, Egypt. Published in Ukrainskii Matematicheskii Zhurnal, Vol. 49, No. 4, pp. 517–522, April, 1997.     

Exploiting the 1,2,3‐Triazole Moiety to Generate Carbazole Molecular Architectures through Click Approach

Reaction of 3,6‐dichlorocarbazole with propargyl bromide in the presence of a basic medium gave an N‐propargylated carbazole. The latter compound was converted into molecular architectures containing 1,2,3‐triazole moiety through Cu(I)‐catalyzed 1,3‐cycloaddition reaction with different azides. Similarly, 2‐azidomethyl benzothiazole was cliched with N‐Boc‐protected N´‐propargyl glutamate to give the biomolecule 2‐triazolylmethyl product.