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.     

Sensitive targeted multiple protein quantification based on elemental detection of Quantum Dots

A generic strategy based on the use of CdSe/ZnS Quantum Dots (QDs) as elemental labels for protein quantification, using immunoassays with elemental mass spectrometry (ICP-MS), detection is presented. In this strategy, streptavidin modified QDs (QDs-SA) are bioconjugated to a biotinylated secondary antibody (b-Ab₂). After a multi-technique characterization of the synthesized generic platform (QDs-SA-b-Ab₂) it was applied to the sequential quantification of five proteins (transferrin, complement C3, apolipoprotein A1, transthyretin and apolipoprotein A4) at different concentration levels in human serum samples. It is shown how this generic strategy does only require the appropriate unlabeled primary antibody for each protein to be detected. Therefore, it introduces a way out to the need for the cumbersome and specific bioconjugation of the QDs to the corresponding specific recognition antibody for every target analyte (protein). Results obtained were validated with those obtained using UV–vis spectrophotometry and commercial ELISA Kits.     

Topology optimization of composite hyperelastic material using SPIMFO-method

Meccanica - Fiber reinforced materials are used in assorted engineering application and for this reason, new additive manufacturing technologies have been developed for this type of materials. With...     

New inequalities from classical Sturm theorems

Inequalities satisfied by the zeros of the solutions of second-order hypergeometric equations are derived through a systematic use of Liouville transformations together with the application of classical Sturm theorems. This systematic study allows us to improve previously known inequalities and to extend their range of validity as well as to discover inequalities which appear to be new. Among other properties obtained, Szegő's bounds on the zeros of Jacobi polynomials for , are completed with results for the rest of parameter values, Grosjean's inequality (J. Approx. Theory 50 (1987) 84) on the zeros of Legendre polynomials is shown to be valid for Jacobi polynomials with |β|1, bounds on ratios of consecutive zeros of Gauss and confluent hypergeometric functions are derived as well as an inequality involving the geometric mean of zeros of Bessel functions.     

Paradigms and Paradoxes: Energetics of Aqueous Oxyanions of Nonmetals and Metalloids

The enthalpies of formation of simple nonmetal or metalloid oxyanions in aqueous solution are discussed. Archival values are cited and estimates are made. Trends prove evasive.     

Theoretical study on the structures and electronic spectra of TCNE2-.

Investigations into the charge-separated states and electron-transfer transitions in tetracyanoethylene (TCNE) complexes have recently generated much interest. In this work we present theoretical calculations showing that the most stable structure of the dianion TCNE2- has D2d symmetry in vacuum as well as in the solvents dichloromethane and acetonitrile. By means of the coupled cluster linear response, we compute the vertical electronic spectrum in both the gas phase and solution. The theoretical results are compared to the experimental data and good agreement is achieved.     

A new analytical method for anchoring quantification of amines on resin support

A rapid and quantitative method for monitoring the efficiency of coupling of amino compounds to polystyrene resin through a carbamate linker has been developed. para-Nitrophenyl carbonate activating group has been shown to release a valuable chromophore for quantitatively monitoring the progress and the yield of the reaction.     

Necessary conditions and duality for inexact nonlinear semi-infinite programming problems

First order necessary conditions and duality results for general inexact nonlinear programming problems formulated in nonreflexive spaces are obtained. The Dubovitskii–Milyutin approach is the main tool used. Particular cases of linear and convex programs are also analyzed and some comments about a comparison of the obtained results with those existing in the literature are given.     

Some Questions of Heinrich on Ultrapowers of Locally Convex Spaces

In this note we treat some open problems of Heinrich on ultrapowers of locally convex spaces. In section 1 we investigate the localization of bounded sets in the full ultrapower of a locally convex space, in particular the coincidence of the full and the bounded ultrapower, mainly concentrating in the case of (DF)-spaces. In section 2 we provide a partial answer to a question of Heinrich on commutativity of strict inductive limits and ultrapowers. In section 3 we analyze the relation between some natural candidates for the notion of superreflexivity in the setting of Fréchet spaces. We give an example of a Fréchet-Schwartz space which is not the projective limit of a sequence of superreflexive Banach spaces.