Inhomogeneous Gevrey classes and ultradistributions

The inhomogeneous Gevrey classes, defined in terms of Fourier transform, are a natural extension of the standard Gevrey classes. We find equivalent characterizations and discuss algebraic and topological properties. We therefore introduce the dual spaces, the inhomogeneous ultradistributions, giving some equivalent definitions and corresponding algebraic and topological properties; in particular, a version of the Paley-Wiener-Schwartz theorem is proved in our framework. Finally, as an important example, the multianisotropic Gevrey classes and ultradistributions are considered.     

A decomposition heuristics for the container ship stowage problem

In this paper we face the problem of stowing a containership, referred to as the Master Bay Plan Problem (MBPP); this problem is difficult to solve due to its combinatorial nature and the constraints related to both the ship and the containers. We present a decomposition approach that allows us to assign a priori the bays of a containership to the set of containers to be loaded according to their final destination, such that different portions of the ship are independently considered for the stowage. Then, we find the optimal solution of each subset of bays by using a 0/1 Linear Programming model. Finally, we check the global ship stability of the overall stowage plan and look for its feasibility by using an exchange algorithm which is based on local search techniques. The validation of the proposed approach is performed with some real life test cases. This work has been developed within the research area: “The harbour as a logistic node” of the Italian Centre of Excellence on Integrated Logistics (CIELI) of the University of Genoa, Italy     

Membrane-immobilized haptoglobin as affinity matrix for a hemoglobin-A1c immunosensor

An amperometric immunosensor for hemoglobin-A1c (HbA1c) determination has been developed utilizing membrane-immobilized haptoglobin as affinity matrix fixed in front of a Pt-working electrode. The HbA1c assay was carried out in a two-step procedure including the selective hemoglobin enrichment on the sensor surface and the specific HbA1c detection by a glucose oxidase (GOx) labeled anti-HbA1c antibody. Hydrogen peroxide generated by the enzyme label was oxidized at +600 mV versus Ag/AgCl. A standard curve for HbA1c was obtained with a linear range between 0 and 25% HbA1c of total hemoglobin which correspond to 7.8–39 nM. ELISA studies confirmed the advantage of a sandwich-type format with haptoglobin as capture molecule for selective hemoglobin binding over the direct adsorption method. Results by the sandwich immunoassay showed a linear correlation within the clinically relevant range 5–20% (CV < 3). For sensor application the immobilization procedure of haptoglobin onto CDI-activated cellulose membranes was optimized.     

The effect of the anion on the physical properties of trihalide-based N,N-dialkylimidazolium ionic liquids

Low viscosity, high density trihalide-based 1-n-butyl-3-methylimidazolium ionic liquids have been prepared and characterised. Key physical properties (density, conductivity, melting point, refractive index, surface tension and diffusion coefficient) of the ionic liquids have been determined and are compared with those of other 1,3-dialkylimidazolium molten salts. The relationship between anion identity and the physical properties of the ionic liquids under investigation is discussed.     

Effect of support on the synergy in HDS of thiophene and HDN of pyridine over Mo sulfide catalysts promoted by Rh

The effect of support (SiO₂-Al₂O₃, Al₂O₃,MgO) of the Rh-Mo(S) sulfide catalysts on the synergy in hydrodesulfurization (HDS) of thiophene and hydrodenitrogenation (HDN) of pyridine was studied. The synergy in HDS was between 7–10 regardless of the kind of support used. The synergy in HDN varied from none over the MgO supported sample to about 3 over SiO₂-Al₂O₃ supported catalyst, in accord with the positive effect of increasing support acidities. This revised version was published online in June 2006 with corrections to the Cover Date.     

Reactivity of 3d transition metal cations in diethylene glycol solutions. Synthesis of transition metal ferrites with the structure of discrete nanoparticles complexed with long-chain carboxylate anions

Study of the reactivity of 3d transition metal cations in diethylene glycol solutions revealed several key features that made it possible to develop a new method for synthesis of the nanocrystalline transition metal ferrites. The 3-7 nm particles of [MFe2O4]n[O2CR]m, where M = Mn, Fe, Co, Ni, and Zn, ligated on their surface with long-chain carboxylate anions, have been obtained in an isolated yield of 75-90%. The key features are the following. Complexation of the first-row transition metal cations with diethylene glycol at a presence of alkaline hydroxide is sufficient to enable control over the rate of their hydrolysis. The reaction of hydrolysis leads to the formation of metal oxide nanocrystals in colloidal solution. The nanoparticles growth is terminated by an added long-chain carboxylic acid, which binds to their surface and acts as a capping ligand. The isolated nanocrystalline powders are stable against agglomeration and highly soluble in nonpolar organic solvents.     

Electrospray mass and tandem mass spectrometry of homologous and isomeric singly, doubly, triply and quadruply charged cationic ruthenated meso-(phenyl)m-(meta- and para-pyridyl)n (m + n = 4) macrocyclic porphyrin complexes

Ten homologous or isomeric singly, doubly, triply and quadruply charged cationic macrocyclic complexes I-Va, bn+ (n = 1-4) formed by the coordination of [Ru(bipy)2Cl]+ to the pyridyl N-atoms of a series of meso-(phenyl)m-(meta or para-pyridyl)n-porphyrins (m + n = 4) were transferred to the gas phase and structurally characterized by electrospray ionization (ESI) mass (MS) and tandem mass (MS/MS) spectrometry. Previously known to be stable in solution and in the solid state, I-Va, bn+ are found to constitute also a new class of stable, long-lived multiply charged gas-phase ions with spatially separated charge sites. Increasing intramolecular electrostatic repulsion from Ia, b+ to IVa, b3+ facilitates in-source and tandem collision-induced dissociation (CID). However, for the quadruply charged ions Va, b4+, electrostatic repulsion is alleviated mainly by ion pairing with the CF3SO3- counterion forming the salt clusters [Va,b/CF3SO3]3+ and [Va,b/(CF3SO3)2]2+ with reduced charge states. Ion-pairing that yields [IVa,b/CF3SO3]2+ is also observed as a minor ESI process for the triply charged ions IVa, b3+. The gaseous ions I-Va, bn+ (n = 2, 3 or 4) dissociate by sequential 'charge partitioning' with the formation of two cationic fragments by the release of [Ru(bipy)2Cl]+. The meta (a) and para (b) isomers and the positional isomers II2+ and III2+ display nearly identical ESI-MS and ESI-MS/MS spectra. ESI-MS/MS of I-Va, bn+ shows that the Ru-py(P) is, intrinsically, the weakest bond since this bond breaks preferentially upon CID.     

Unusual heme-histidine bond in the active site of a chaperone

The heme chaperone CcmE is essential for the delivery of heme to c-type cytochromes. It forms an unusual transient, yet covalent, bond between an essential histidine, H130, and heme. We report on the discovery of the chemical structure of this bond solved by NMR, where the heme vinyl is cross-linked at the beta carbon to the Ndelta1 of H130. As this type of heme linkage has not been described previously in any cytochrome or hemoprotein, it represents a novel type of heme-histidine complex.     

Total synthesis of (±)-cyclooroidin

The first total synthesis of (±)-cyclooroidin, a member of the pyrrole-imidazole alkaloid family recently isolated from the sponge Agelas oroides in optically pure form, is described. The synthesis was achieved in nine linear steps, with an overall yield of 10%. Key step was a Wolff bromoketone synthesis performed on the intermediate longamide B.