Magnetic property studies of manganese-phosphate complexes

Phosphoric acid forms two distinct coordination compounds with manganese salts in aqueous media, a two-dimensional layered structure, [Mn(HPO4).(H2O)3], 1, under ambient conditions, and a three-dimensional synthetic mineral, [Mn5(mu-OH2)2(HPO4)2(PO4)2(H2O)2], 2, under hydrothermal procedures, at 120 degrees C. In compound 1, the oxygen atom of the doubly deprotonated phosphoric acid interconnects the metal centers to form a layered structure. The neutral hydrophilic layers of 1 are separated by 5.5 A and may potentially intercalate hydrophilic organic guest molecules. The metal centers in 2 are octahedral and bridged by PO4(3-), HPO4(2-), and OH2 groups to form a complex three-dimensional network. XPS analysis on 1 and 2 confirms that manganese exists in the +2 oxidation state. Compound 2 is a poor ion exchanger, but some improvement is observed on partial dehydration. The magnetic properties of both 1 and 2 were studied in detail to examine the amplitude of the magnetic interactions through phosphate ligand bridges. While 1 reveals dominant antiferromagnetic interactions between the spin carriers, a complete investigation of the magnetic properties of 2 revealed its true nature to be a glassy magnet.     

Fractional Diffusion Limit for Collisional Kinetic Equations

This paper is devoted to diffusion limits of linear Boltzmann equations. When the equilibrium distribution function is a Maxwellian distribution, it is well known that for an appropriate time scale, the small mean free path limit gives rise to a diffusion equation. In this paper, we consider situations in which the equilibrium distribution function is a heavy-tailed distribution with infinite variance. We then show that for an appropriate time scale, the small mean free path limit gives rise to a fractional diffusion equation.     

Photooxidation of glycated and non‐glycated phosphatidylethanolamines monitored by mass spectrometry

Phosphatidylethanolamines (PE) are one of the major components of cells membranes, namely in skin and in retina, that are continuously exposed to solar UV radiation being major targets of photooxidation damage. In addition, due to the presence of the free amine group, PE can also undergo glycation, in hyperglycemic conditions which may increase the susceptibility to oxidation. The aim of this study is to develop a model, based on mass spectrometry (MS) analysis, to identify photooxidative degradation of selected PE (POPE: PE 16:0/18:1, PLPE: PE 16:0/18:2, PAPE: PE 16:0/20:4) and glycated PEs due to UV irradiation. Photooxidation products were analysed by electrospray ionization MS (ESI‐MS) and tandem MS (ESI‐MS/MS) in positive and negative mode. Emphasis is placed in the influence of glycation in the generation of distinct photooxidation products. ESI‐MS spectra of PE after UV photo‐irradiation showed mainly hydroperoxy derivatives, due to oxidation of unsaturated fatty acyl chains. Glycated PE gave rise to several new photooxidation products formed due to oxidative cleavages of the glucose moiety, namely between C1 and C2, C2 and C3, and C5 and C6 of this sugar unit. These new products were identified by ESI‐MS/MS in positive mode showing distinct neutral loss depending on the different structure of the polar head group. These new identified advanced glycated photooxidation products may have a deleterious role in the etiology of diabetic retinopathy and in diabetic retinal microvascular complications. Copyright © 2013 John Wiley & Sons, Ltd.     

A memetic algorithm for multi-objective dynamic location problems

This paper describes a new multiobjective interactive memetic algorithm applied to dynamic location problems. The memetic algorithm integrates genetic procedures and local search. It is able to solve capacitated and uncapacitated multi-objective single or multi-level dynamic location problems. These problems are characterized by explicitly considering the possibility of a facility being open, closed and reopen more than once during the planning horizon. It is possible to distinguish the opening and reopening periods, assigning them different coefficient values in the objective functions. The algorithm is part of an interactive procedure that asks the decision maker to define interesting search areas by establishing limits to the objective function values or by indicating reference points. The procedure will be applied to some illustrative location problems.     

An Interactive Method for 0-1 Multiobjective Problems Using Simulated Annealing and Tabu Search

This paper presents an interactive method for solving general 0-1 multiobjective linear programs using Simulated Annealing and Tabu Search. The interactive protocol with the decision maker is based on the specification of reservation levels for the objective function values. These reservation levels narrow the scope of the search in each interaction in order to identify regions of major interest to the decision maker. Metaheuristic approaches are used to generate potentially nondominated solutions in the computational phases. Generic versions of Simulated Annealing and Tabu Search for 0-1 single objective linear problems were developed which include a general routine for repairing unfeasible solutions. This routine improves significantly the results of single objective problems and, consequently, the quality of the potentially nondominated solutions generated for the multiobjective problems. Computational results and examples are presented.     

A study of frost growth and densification on flat surfaces

The present study advances a theoretical and experimental investigation of the frost growth and densification on flat surfaces. This study focuses on the most important factors affecting the frost formation process, i.e. the surrounding air temperature, humidity and velocity, and the surface temperature. The processes of frost growth and densification were investigated experimentally in order to provide a physical basis for the development of a theoretical model to predict the variation of the frost layer thickness and mass with time. The mathematical model was based on mass and energy balances within the frost layer, assuming the frost as a porous medium and accounting for the supersaturation of the moist air on the frost surface. The governing equations for mass and heat diffusion were integrated analytically, giving rise to a semi-algebraic formulation which requires numerical integration of only one time dependent ordinary differential equation. When compared with experimental data, the model predictions of the frost thickness as a function of time agreed to within ±10% error bands. The experimentally-validated model was then used to predict the frost layer growth and densification with respect to the operation conditions such as plate surface temperature, air stream temperature, humidity and velocity.     

Crystal structure and theoretical calculations of Julocrotine,a natural product with antileishmanial activity

Julocrotine, N‐(2,6‐dioxo‐1‐phenethyl‐piperidin‐3‐yl)‐2‐methyl‐butyramide, is a potent antiproliferative agent against the promastigote and amastigote forms of Leishmania amazonensis (L.). In this work, the crystal structure of Julocrotine was solved by X‐ray diffraction, and its geometrical parameters were compared with theoretical calculations at the B3LYP and HF level of theory. IR and NMR spectra also have been obtained and compared with theoretical calculations. IR absorptions calculated with the B3LYP level of theory employed together with the 6‐311G+(d,p) basis set, are close to those observed experimentally. Theoretical NMR calculations show little deviation from experimental results. The results show that the theory is in accordance with the experimental data. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

A meta-model for multiobjective routing in MPLS networks

MPLS (Multiprotocol Label Switching) enables the utilisation of explicit routes and other advanced routing mechanisms in multiservice packet networks, capable of dealing with multiple and heterogeneous QoS (Quality of Service) parameters. Firstly the paper presents a discussion of conceptual and methodological issues raised by multiobjective routing optimisation models for MPLS networks. The major contribution is the proposal of a multiobjective routing optimisation framework for MPLS networks. The major features of this modelling framework are: the formulation of a three-level hierarchical routing optimisation problem including network and service performance objectives, the inclusion of fairness objectives in the different levels of optimisation and a two-level stochastic representation of the traffic in the network (traffic flow and packet stream levels). A variant of the general model for two classes of traffic flows, QoS traffic and Best Effort traffic, is also presented. Finally a stochastic teletraffic modelling approach, underlying the optimisation model, is fully described. Work partially supported by programme POSI of the III EC programme cosponsored by FEDER and national funds.     

Structure determination of slowly exchanging conformers in solution using high‐resolution NMR,computational modeling and DFT‐GIAO chemical shielding: application to an erythronolide A derivative

We discuss and demonstrate the potential of HSQC‐TOCSY and HSQC‐NOESY experiments to offer solutions for overlap problems in COSY and NOESY spectra, leading to improved signals that can be unambiguously assigned to individual carbons. Direct comparison of experimental ¹H and ¹³C chemical shielding with density functional theory (DFT)‐calculated values are uninformative; in contrast, the relative differences in experimental shielding between pairs of molecules correlates well with the relative differences in DFT‐GIAO shielding for the computed lowest energy conformers. A detailed application of both experimental and theoretical techniques is illustrated for slowly exchanging conformers of an erythronolide A derivative, which demonstrates that structure determination can strongly benefit from the interplay between experiment and theory. Copyright © 2009 John Wiley & Sons, Ltd.     

1D to 3D NMR study of microporous alumino‐phosphate AlPO4‐40

From one‐ to two‐ and three‐dimensional MAS NMR solid‐state experiments involving ³¹P and ²⁷Al, we show that the structure of microporous alumino‐phosphate AlPO₄‐40 contains at least four times more sites than expected, and we attribute two types of Al_IV sites. The newly described ²⁷Al‐³¹P MQ‐HMQC opens new possibilities of describing details of three‐dimensional bounded networks. Copyright © 2009 John Wiley & Sons, Ltd.