Triesterase and Promiscuous Diesterase Activities of a Di‐CoII‐Containing Organophosphate Degrading Enzyme Reaction Mechanisms

The reaction mechanism for the hydrolysis of trimethyl phosphate and of the obtained phosphodiester by the di‐Co^II derivative of organophosphate degrading enzyme from Agrobacterium radiobacter P230(OpdA), have been investigated at density functional level of theory in the framework of the cluster model approach. Both mechanisms proceed by a multistep sequence and each catalytic cycle begins with the nucleophilic attack by a metal‐bound hydroxide on the phosphorus atom of the substrate, leading to the cleavage of the phosphate‐ester bond. Four exchange‐correlation functionals were used to derive the potential energy profiles in protein environments. Although the enzyme is confirmed to work better as triesterase, as revealed by the barrier heights in the rate‐limiting steps of the catalytic processes, its promiscuous ability to hydrolyze also the product of the reaction has been confirmed. The important role played by water molecules and some residues in the outer coordination sphere has been elucidated, while the binuclear Co^II center accomplishes both structural and catalytic functions. To correctly describe the electronic configuration of the d shell of the metal ions, high‐ and low‐spin arrangement jointly with the occurrence of antiferromagnetic coupling, have been herein considered.     

Functional Carbazole Liquid‐Crystal Block Codendrimers with Optical and Electronic Properties

The synthesis and characterisation of a family of block codendrimers consisting of highly versatile mesogenic and carbazole‐containing 2,2‐bis(hydroxymethyl)propionic acid (bis‐MPA) dendrons are reported. The liquid‐crystal behaviour was investigated by means of differential scanning calorimetry, polarised‐light optical microscopy and X‐ray diffraction. Depending on the chemical structure of the constituent dendrons, the codendrimers show lamellar or columnar mesophases. On the basis of the experimental results, models both at the molecular level and in the mesophase are proposed. The physical properties of the block codendrimers derived from the presence of the carbazole moiety in their structure were investigated: photoluminescence in solution and in the mesophase, electrochemical behaviour and hole transport. Electrodeposition of carbazole dendrons afforded a globular supramolecular conformation in which the mesogenic molecular side plays a key role.     

Functional Binding Surface of a β‐Hairpin VEGF Receptor Targeting Peptide Determined by NMR Spectroscopy in Living Cells

In this study, the functional interaction of HPLW peptide with VEGFR2 (Vascular Endothelial Growth Factor Receptor 2) was determined by using fast ¹⁵N‐edited NMR spectroscopic experiments. To this aim, ¹⁵N uniformly labelled HPLW has been added to Porcine Aortic Endothelial Cells. The acquisition of isotope‐edited NMR spectroscopic experiments, including ¹⁵N relaxation measurements, allowed a precise characterization of the in‐cell HPLW epitope recognized by VEGFR2.     

Competing kinetic pathways in the bromine addition to allylic ethers in 1,2‐dichloroethane: Opposite temperature effects

The kinetics of the electrophilic bromination of three allylic ethers in a nonprotic solvent, 1,2‐dichloroethane, has been investigated. Two of them followed a prevalent second‐order pathway, while the third one exhibited a classical, clean third order. The second‐order pathway in the first two olefins is attributed to electrophilic assistance of the ethereal oxygen to the attacking bromine molecule. In the molecular bromination of 2,4‐cis‐dimethyl‐8‐oxabicyclo[3.2.1]‐6‐octen‐3‐cis‐ol, opposite temperature dependences were found for the two different kinetic pathways. An exoergonic process for the second‐order reaction was explained by the lesser stability of the bromiranium–bromide ionic intermediate, compared to the bromiranium–tribromide in the third‐order profile. © 2007 Wiley Periodicals, Inc. 39: 197–203, 2007     

Involutions for upper triangular matrix algebras

In this paper we describe completely the involutions of the first kind of the algebra UT_n(F) of n×n upper triangular matrices. Every such involution can be extended uniquely to an involution on the full matrix algebra. We describe the equivalence classes of involutions on the upper triangular matrices. There are two distinct classes for UT_n(F) when n is even and a single class in the odd case.Furthermore we consider the algebra UT₂(F) of the 2×2 upper triangular matrices over an infinite field F of characteristic different from 2. For every involution *, we describe the *-polynomial identities for this algebra. We exhibit bases of the corresponding ideals of identities with involution, and compute the Hilbert (or Poincaré) series and the codimension sequences of the respective relatively free algebras.Then we consider the *-polynomial identities for the algebra UT₃(F) over a field of characteristic zero. We describe a finite generating set of the ideal of *-identities for this algebra. These generators are quite a few, and their degrees are relatively large. It seems to us that the problem of describing the *-identities for the algebra UT_n(F) of the n×n upper triangular matrices may be much more complicated than in the case of ordinary polynomial identities.     

Spectral Properties of Four-Dimensional Compact Flat Manifolds

We study the spectral properties of a large class of compact flat Riemannian manifolds of dimension 4, namely, those whose corresponding Bieberbach groups have the canonical lattice as translation lattice. By using the explicit expression of the heat trace of the Laplacian acting on p-forms, we determine all p-isospectral and L-isospectral pairs and we show that in this class of manifolds, isospectrality on functions and isospectrality on p-forms for all values of p are equivalent to each other. The list shows for any p, 1 ≤ p ≤ 3, many p-isospectral pairs that are not isospectral on functions and have different lengths of closed geodesics. We also determine all length isospectral pairs (i.e. with the same length multiplicities), showing that there are two weak length isospectral pairs that are not length isospectral, and many pairs, p-isospectral for all p and not length isospectral. Mathematics Subject Classifications (2000): 58J53, 58C22, 20H15.     

Quantum Conservative Gates for Finite-Valued Logics

We introduce some conservative gates for finite-valued logics which are able to realize all the main connectives of the many-valued logics of ?ukasiewicz, the MV-algebras of Chang and Brower–Zadeh algebras. After a brief exposition of the motivations for this work, the gates are defined and their properties are explored. Finally, a possible quantum realization of them is proposed, using three techniques: a “brute force” method--an extension of the Conditional Quantum Control argument, and a new technique which we call the Constants Method. For all these techniques, the unitary operator which describes the gate is a sum of local operators.