Synthesis and anti‐inflammatory activity of 8H‐1‐thia‐8‐aza‐dibenzo[e,h]azulenes

Synthesis of a novel class of fused heterotetracyclic compounds, 8H‐1‐thia‐8‐aza‐dibenzo[e,h]azulenes ( VII ), is described. Starting N‐benzoyl‐protected 5H‐dibenzo[b,f]azepine ( XI , PG = Bz) was oxidized to 5‐benzoyl‐10,11‐epoxy‐10,11‐dihydro‐5H‐dibenzo[b,f]azepine ( 2 ), which subsequently rearranged in Lewis acid‐induced epoxide ring opening to give 5‐benzoyl‐5,11‐dihydro‐10H‐dibenzo[b,f]azepin‐10‐one ( 3 ). Vilsmeier reaction of 3 provided β‐chlorovinyl aldehyde 4 that readily cyclized with ethyl 2‐mercaptoacetate to form dibenzazepino[4,5]‐fused thiophene structure 5 . Further transformation of substituent at C‐2 position of 5 and N‐deprotection led to final aminoalkoxy derivatives 9 . All compounds with tetracyclic skeleton were tested in vitro for their anti‐inflammatory activity. J. Heterocyclic Chem., (2011).     

Detailed mechanism of the autoxidation of N-hydroxyurea catalyzed by a superoxide dismutase mimic Mn(iii) porphyrin: formation of the nitrosylated Mn(ii) porphyrin as an intermediate

The in vitro autoxidation of N-hydroxyurea (HU) is catalyzed by Mn(III)TTEG-2-PyP(5+), a synthetic water soluble Mn(iii) porphyrin which is also a potent mimic of the enzyme superoxide dismutase. The detailed mechanism of the reaction is deduced from kinetic studies under basic conditions mostly based on data measured at pH = 11.7 but also including some pH-dependent observations in the pH range 9-13. The major intermediates were identified by UV-vis spectroscopy and electrospray ionization mass spectrometry. The reaction starts with a fast axial coordination of HU to the metal center of Mn(III)TTEG-2-PyP(5+), which is followed by a ligand-to-metal electron transfer to get Mn(II)TTEG-2-PyP(4+) and the free radical derived from HU (HU˙). Nitric oxide (NO) and nitroxyl (HNO) are minor intermediates. The major pathway for the formation of the most significant intermediate, the {MnNO} complex of Mn(II)TTEG-2-PyP(4+), is the reaction of Mn(II)TTEG-2-PyP(4+) with NO. We have confirmed that the autoxidation of the intermediates opens alternative reaction channels, and the process finally yields NO(2)(-) and the initial Mn(III)TTEG-2-PyP(5+). The photochemical release of NO from the {MnNO} intermediate was also studied. Kinetic simulations were performed to validate the deduced rate constants. The investigated reaction has medical implications: the accelerated production of NO and HNO from HU may be utilized for therapeutic purposes.     

Thermal Lens Spectrometric Detection in Flow Injection Analysis and Separation Techniques

Abstract

Recent applications of thermal lens spectrometry in liquid chromatography (HPLC, ion chromatography), capillary electrophoresis, and flow injection analysis are reviewed. Possible effects of performing TLS measurements in flows are discussed initially for different TLS configurations. The emphasis is given to the analysis of real samples, and the performances of various detection schemes in combination with chromatographic techniques and FIA are discussed particularly in terms of sensitivity, sample throughput, and eventual interferences from complex matrices. Coaxial TLS detection with continuous wave excitation is most suitable for detection in HPLC, ion chromatography, and FIA using long‐path length cells, when large volume samples are available. On the other hand, transverse or crossed beam TLS was found most suitable for detection in CE where it provides low absolute LODs, which are lowered even further by thermal lens microscopy on microchips, where the capability of detecting a single molecule in the detection volume was demonstrated.     

Homogenization results for a coupled system modelling immiscible compressible two-phase flow in porous media by the concept of global pressure

A model for immiscible compressible two-phase flow in heterogeneous porous media is considered. Such models appear in gas migration through engineered and geological barriers for a deep repository for radioactive waste. The main feature of this model is the introduction of a new global pressure and it is fully equivalent to the original equations. The resulting equations are written in a fractional flow formulation and lead to a coupled degenerate system which consists of a nonlinear parabolic (the global pressure) equation and a nonlinear diffusion–convection one (the saturation) equation with rapidly oscillating porosity function and absolute permeability tensor. The major difficulties related to this model are in the nonlinear degenerate structure of the equations, as well as in the coupling in the system. Under some realistic assumptions on the data, we obtain a nonlinear homogenized problem with effective coefficients which are computed via a cell problem and give a rigorous mathematical derivation of the upscaled model by means of two-scale convergence.     

Large scale structural synthesis

A general purpose optimization program is coupled to a large scale finite element program to provide an efficient tool for structural synthesis. The resulting interface program may be used to design structures for minimum weight, subject to constraints on stress, displacement, and vibration frequencies. A variety of state-of-the-art techniques are employed, including design variable linking, constraint deletion, reciprocal variables, and formal approximations. The capability is demonstrated with the design of a gear housing using 30 design variables and over 5000 nonlinear inequality constraints. The finite element model consists of over 1600 elements and 7000 displacement degrees of freedom. The design required six detailed finite element analyses and approximately one hour on a Cray-1s supercomputer. It is concluded that structures of practical size and complexity can be efficiently designed using numerical optimization.     

Proper actions of lattices on contractible manifolds

Every lattice Γ in a connected semi-simple Lie group G acts properly discontinuously by isometries on the contractible manifold G/K (K a maximal compact subgroup of G). We prove that if Γ acts on a contractible manifold W and if either?1) the action is properly discontinuous, or?2) W is equipped with a complete Riemannian metric, the action is by isometries and with unbounded orbits, G is simple with finite center and rank >1,?then dimW≥dimG/K. Oblatum 19-I-2001 & 24-IV-2002?Published online: 5 September 2002 RID="*" ID="*"The authors gratefully acknowledge support from the National Science Foundation.     

Tension spline collocation methods for singularly perturbed Volterra integro-differential and Volterra integral equations

We consider the numerical discretization of singularly perturbed Volterra integro-differential equations (VIDE)

(*)

and Volterra integral equations (VIE)

(**)

by tension spline collocation methods in certain tension spline spaces, where is a small parameter satisfying 0<1, and q₁, q₂, g and K are functions sufficiently smooth on their domains to ensure that Eqs. (*) and (**) posses a unique solution.We give an analysis of the global convergence properties of a new tension spline collocation solution for 0<1 for singularly perturbed VIDE and VIE; thus, extending the existing theory for =1 to the singularly perturbed case.     

Orthomodular Lattices and a Quantum Algebra

We show that one can formulate an algebra with lattice ordering so as to contain one quantum and five classical operations as opposed to the standard formulation of the Hilbert space subspace algebra. The standard orthomodular lattice is embeddable into the algebra. To obtain this result we devised algorithms and computer programs for obtaining expressions of all quantum and classical operations within an orthomodular lattice in terms of each other, many of which are presented in the paper. For quantum disjunction and conjunction we prove their associativity in an orthomodular lattice for any triple in which one of the elements commutes with the other two and their distributivity for any triple in which a particular element commutes with the other two. We also prove that the distributivity of symmetric identity holds in Hilbert space, although whether or not it holds in all orthomodular lattices remains an open problem, as it does not fail in any of over 50 million Greechie diagrams we tested.     

Multiplicity distributions in proton-nucleus collisions at 67 and 200 GeV

New data, concerning multiplicities in collisions of 67 and 200 GeV protons in emulsions are presented. Various parameters of multiplicity distributions in collisions of protons with nuclei of photographic emulsion at primary energies between a few and about 1000 GeV are compared with p-p collisions.