Multienergetic continuous time random walk

We have extended the CTRW theory of Montroll and Weiss including the effect of extra variables, like the energy. This MCTRW scheme can be written in a simple matrix notation, that simplifies its solution. As an example of their usefulness we have studied a two-energy-group neutron diffusion problem. This has shown the peculiarities of the transient behaviour for the variance of the probability distribution, due to the coupling between the groups.Comisión Nacional de Energiá AtómicaComisión Nacional de Energía Atómica and Universidad Nacional de Cuyo     

Synthesis of 3-alkyl-5-hydroxycyclohex-2-enones via aldolic addition/sulfinate elimination tandem reactions

The first synthesis of 3-alkyl-5-hydroxycyclohex-2-enones is reported. An intramolecular cyclization by means of an aldolic addition/sulfinate elimination tandem reactions, performed under mild basic conditions was the key step.     

Comparative study of 2‐amino and 3‐aminobenzoic acid copolymerization with aniline synthesis and copolymer properties

Polyanilines soluble in an aqueous basic medium were synthesised by copolymerization of aniline (ANI) with both 2 and 3‐aminobenzoic acids (ABA). Different composition copolymers were prepared by varying the ANI/ABA feed ratio. Poly(aniline‐co‐2‐aminobenzoic acid) (PANI2ABA) and poly(aniline‐co‐3‐aminobenzoic acid) (PANI3ABA) displayed differences in their properties, such as specific charge and fluorescence behavior because the reactivity of 2‐aminobenzoic (2ABA) and 3‐aminobenzoic (3ABA) acids are very different. The new materials were characterized by X‐ray photoelectron, Fourier transform infrared, and Raman spectroscopies. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5587–5599, 2004     

Membrane triangles with corner drilling freedoms—I. The EFF element

This paper is the first of a three-part series that studies the formulation of 3-node, 9-dof membrane elements with normal-to-element-plane rotations (the so-called drilling freedoms) within the context of parametrized variational principles. These principles supply a unified basis for several advanced element-construction techniques; in particular: the free formulation (FF), the extended free formulation (EFF) and the assumed natural deviatoric strain (ANDES) formulation. In Part I we construct an element of this type using the EFF. This derivation illustrates the basic steps in the application of that formulation to the construction of high-performance, rank-sufficient, nonconforming elements with corner rotations. The element is initially given the twelve degress of freedom of the linear strain triangle (LST), which allows the displacement expansion to be a complete quadratic in each component. The expansion basis contains the six linear basic functions and six energy-orthogonal quadratic higher-order functions. Three degrees of freedom, defined as the midpoint deviations from linearity along the triangle-median directions, are eliminated by kinematic constraints. The remaining hierarchical midpoint freedoms are transformed to corner rotations. The performance of the resulting element is evaluated in Part III.     

Investigation of 3D Contour Map and Intermolecular Interaction of Dopamine with β-Cyclodextrin and 2-Hydroxypropyl-β-cyclodextrin

The interactions of the neurotransmitter dopamine (DA) with β-cyclodextrin and 2-hydroxypropyl-β-cyclodextrin (HP-β-CD) was characterized using UV–visible, 2D fluorescence, 3D fluorescence, FT–IR, PXRD and SEM techniques. PM3, PM7 and DFT methods were used to optimize the structures of the inclusion complexes in the gas phase. The absorbance and fluorescence intensities of DA increased in the presence of CDs in aqueous solution. The binding energy, HOMO–LUMO energy gap and Mulliken atomic charges were computed for the inclusion complexes. NBO analysis revealed a greater number of intermolecular hydrogen bonds in DA:HP-β-CD. Experimental and theoretical results suggested that the DA molecule is deeply embedded in the cavities of both CDs.     

Lone pair···π interactions on the stabilization of intra and intermolecular arrangements of coordination compounds with 2-methyl imidazole and benzimidazole derivatives

Abstract

Spectroscopic and single crystal X-ray diffraction studies of coordination compounds of Co^II, Ni^II, Zn^II, and Pd^II with phenylsulfonyl imidazole and benzimidazole derivatives (2-mfsiz, 2-mfsbz) were performed. The relevance of non-covalent interactions on the stabilization of intra and intermolecular arrangements in the ligands and their coordination compounds was investigated. The imidazole 2-mfsiz ligand presents two enantiomeric conformers, where the ethylphenylsulfone moiety stabilizes intermolecular lone pair···π (S–O···π_(phe)) and H···π contacts, while its tetrahedral coordination compounds, [M(2-mfsiz)₂X₂] (M²⁺?=?Co, Ni, Zn; X?=?Cl, Br) showed intramolecular lone pair···π interactions (S–O···π_(iz)). On the other hand, compounds [Cu₂(2-mfsiz)₂(µ₂-AcO)₄] and trans-[Pd(2-mfsiz)₂Cl₂] do not present lone pair···π interactions due to the metal ion geometry (square base pyramidal or square planar), which leads to formation of π_(iz)···π_(phe) interactions. For the benzimidazole ligand 2-mfsbz, an intramolecular, H_(phe)···π_(bz) contact was observed, remaining in its tetrahedral and octahedral coordination compounds, [M(2-mfsbz)₂X₂] (M²⁺?=?Co, Zn; X?=?Cl, Br, NO₃). This interaction limits the free rotation of the ethylphenylsulfone moiety for stabilization of an intermolecular lone pair···π interaction (S–O···π_(iz)). The dimeric [Zn₂(2-mfsiz)₂(µ²-AcO)₄] compound has a π_(bz)···π_(phe) contact. Theoretical calculations confirmed the non-covalent interactions in the ligands and their coordination compounds.     

Immobilization of Carboxypeptidase A into Modified Chitosan Matrixes by Covalent Attachment

Carboxypeptidase A (CPA) is a metalloexopeptidase that catalyzes the hydrolysis of the peptide bonds that are adjacent to the C-terminal end of a polypeptide chain. The enzyme preferentially cleaves over C-terminal L-amino acids with aromatic or branched side chains. This is of main importance for food industry because it can be employed for manufacturing functional foods from different protein sources with reduced hydrophobic amino acid content for patients with deficiencies in the absorption or digestion of the corresponding amino acids. In that way, strategies for effective multipoint covalent immobilization of CPA metalloenzyme on chitosan beads have been developed. The study of the ability to produce several chemical modifications on chitosan molecules before, during and after its coagulation to form carrier beads lead in a protective effect of the polymer matrix. The chemical modification of chitosan through the use of an N-alkylation strategy produced the best derivatives. N-alkyl chitosan derivative beads with D-fructose presented values of 0.86 for immobilization yield, 314.6 IU g^?1 bead for initial activity of biocatalyst and were 5675.64-fold more stable than the free enzyme at 55 °C. Results have shown that these derivatives would present a potential technological application in hydrolytic processes due to both their physical properties, such as low swelling capacity, reduced metal chelation ability and bulk mesoporosity, and increased operational stability when compared with soluble enzyme.     

Investigation of New Ion-Conducting ORMOLYTES: Structure and Properties

Two families of hybrid organic-inorganic composites exhibiting Li⁺ ionic conduction (ORMOLYTES) have been prepared by the sol-gel process. The first family, prepared from a mixture of 3-isocyanatopropyltriethoxysilane, O,O Bis (2-aminopropyl)-polyethyleneglycol (or O,O Bis (2-aminopropyl)-polypropyleneglycol) and lithium salt, presents chemical bonds between the organic and the inorganic phase and an ionic conductivity higher than 10^-4 S m^-1 at room temperature. Their properties have been related to their structure using liquid state NMR measurements of ⁷Li between -100°C and +100°C and the DMTA technique. In the second family, prepared by ultrasonic method from a mixture of tetraethoxysilane (TEOS), polyethyleneglycol (PEG) and lithium salt, the organic and inorganic phases are not chemically bonded. Ionic conductivity has been studied as a function of the polymer chain length and concentration. Values of up to 10^-2 S m^-1 at room temperature have been obtained (with a silica-PEG₃₀₀ system, PEG/TEOS = 40% in weight). Again, structure was investigated by liquid state ⁷Li NMR measurements.     

Kinetic determinations of reactants utilizing uncatalyzed reactions

Kinetic-based determinations of reactants utilizing uncatalyzed chemical reactions do not match the polularity of catalytic methods for the determination of catalysts (particularly transition metal ions) or reactants (e.g., in enzymatic reactions) and this reflects on the scarcity of reviews on the topic. In some cases, however, advances in instrumentation and data manipulation provide competitive alternatives to nonkinetic-based methods for single as well as multispecies determinations. Such advances are reviewed here and applications illustrated.     

Pauli-Dirac matrix generators of Clifford Algebras

This article presents a Pauli-Dirac matrix approach to Clifford Algebras. It is shown that the algebra C₂ is generated by two Pauli matrices i₂ and i₃; C₃ is generated by the three Pauli matrices ₁, ₂, ₃; C₄ is generated by four Dirac matrices ₀, ₁, ₂, ₃ and C₅ is generated by five Dirac matrices i₀, i₁, i₂, i₃, i₅. The higher dimensional anticommuting matrices which generate arbitrarily high order Clifford algebras are given in closed form. The results obtained with this Clifford algebra approach are compared with the vector product method which was described in a recent article [Found. Phys. 10, 531–553 (1980) by Poole, Farach and Aharonov] and with the Dirac, Rashevskii and Ramakrishnan methods of matrix generation.Supported by the National Science Foundation under Grant ISP-80-11451.