Bifurcation of limit cycles from a 4-dimensional center in 1:n resonance

We study the bifurcation of limit cycles from the periodic orbits of a linear differential system in R⁴ in resonance 1:n perturbed inside a class of piecewise linear differential systems, which appear in a natural way in control theory. Our main result shows that at most 1 limit cycle can bifurcate using expansion of the displacement function up to first order with respect to a small parameter. This upper bound is reached. For proving this result we use the averaging theory in a form where the differentiability of the system is not needed.     

Surface supramolecular organization of a terbium(III) double-decker complex on graphite and its single molecule magnet behavior

The two-dimensional self-assembly of a terbium(III) double-decker phthalocyanine on highly oriented pyrolitic graphite (HOPG) was studied by atomic force microscopy (AFM), and it was shown that it forms highly regular rectangular two-dimensional nanocrystals on the surface, that are aligned with the graphite symmetry axes, in which the molecules are organized in a rectangular lattice as shown by scanning tunneling microscopy. Molecular dynamics simulations were run in order to model the behavior of a collection of the double-decker complexes on HOPG. The results were in excellent agreement with the experiment, showing that-after diffusion on the graphite surface-the molecules self-assemble into nanoscopic islands which align preferentially along the three main graphite axes. These low dimension assemblies of independent magnetic centers are only one molecule thick (as shown by AFM) and are therefore very interesting nanoscopic magnetic objects, in which all of the molecules are in interaction with the graphite substrate and might therefore be affected by it. The magnetic properties of these self-assembled bar-shaped islands on HOPG were studied by X-ray magnetic circular dichroism, confirming that the compounds maintain their properties as single-molecule magnets when they are in close interaction with the graphite surface.     

Playing with organic radicals as building blocks for functional molecular materials

The literature has shown numerous contributions on the synthesis and physicochemical properties of persistent organic radicals but there are a lesser number of reports about their use as building blocks for obtaining molecular magnetic materials exhibiting an additional and useful physical property or function. These materials show promise for applications in spintronics as well as bistable memory devices and sensing materials. This critical review provides an up-to-date survey to this new generation of multifunctional magnetic materials. For this, a detailed revision of the most common families of persistent organic radicals-nitroxide, triphenylmethyl, verdazyl, phenalenyl, and dithiadiazolyl-so far reported will be presented, classified into three different sections: materials with magnetic, conducting and optical properties. An additional section reporting switchable materials based on these radicals is presented (257 references).     

Chemical synthesis of oriented ferromagnetic LaSr-2 × 4 manganese oxide molecular sieve nanowires

We report a chemical solution based method using nanoporous track-etched polymer templates for producing long and oriented LaSr-2 × 4 manganese oxide molecular sieve nanowires. Scanning transmission electron microscopy and electron energy loss spectroscopy analyses show that the nanowires are ferromagnetic at room temperature, single crystalline, epitaxially grown and self-aligned.     

GC‐MS of amaryllidaceous galanthamine‐type alkaloids

Galanthamine‐type alkaloids produced by plants of the Amaryllidaceae family are potent acetylcholinesterase inhibitors. One of them, galanthamine, has been marketed as a hydrobromide salt for the treatment of Alzheimer's disease. In the present work, gas chromatography with electron impact mass spectrometry (GC‐EIMS) fragmentation of 12 reference compounds isolated from various amaryllidaceous plants and identified by spectroscopic methods (1D and 2D nuclear magnetic resonance, circular dichroism, high‐resolution MS (HRMS) and EIMS) was studied by tandem mass spectrometry (GC‐MS/MS) and accurate mass measurements (GC‐HRMS). The studied compounds showed good peak shape and efficient GC separation with a GC‐MS fragmentation pattern similar to that obtained by direct insertion probe. With the exception of galanthamine‐N‐oxide and N‐formylnorgalanthamine, the galanthamine‐type compounds showed abundant [M]^+. and [M‐H]⁺ ions. A typical fragmentation pattern was also observed, depending on the substituents of the skeleton. Based on the fragmentation pathways of reference compounds, three other galanthamine‐type alkaloids, including 3‐O‐(2′‐butenoyl)sanguinine, which possesses a previously unelucidated structure, were identified in Leucojum aestivum ssp. pulchelum, a species endemic to the Balearic islands. GC‐MS can be successfully applied to Amaryllidaceae plant samples in the routine screening for potentially new or known bioactive molecules, chemotaxonomy, biodiversity and identification of impurities in pharmaceutical substances. Copyright © 2012 John Wiley & Sons, Ltd.     

Growth hormone secretagogues: out of competition

Growth hormone secretagogues (GHS) constitute a new GH deficiency treatment increasing exponentially in number and improved potency and bioavailability over the last decade. The growth hormone releasing activity makes these compounds attractive for the artificial improvement of the human sports skills, now that recombinant human growth hormone (rhGH) administration is effectively detected. The GHS family is extremely diverse both in number and chemical heterogeneity and keeps growing continuously. In this paper, a general screening test is proposed. To develop a universal method, the single common property of growth hormone secretagogues has been targeted: their capacity to bind to the GHS receptor 1a (GHS-R1a). Pretreated urine samples have been tested in a competition assay where eventually the GHS presence detached a radiolabelled ligand from the receptor in a dose-dependent manner. Blank urine samples were processed to determine potential age, gender and exercise effects, and to define a threshold beyond which a specimen is considered positive. Samples from a growth hormone releasing peptide 2 (GHRP-2) excretion study corroborated the screening assay applicability with a detection window of approximately 4.5 h, and results were confirmed by comparison with a dedicated LC–MS quantification of the intact compound.     

Kinetico-mechanistic studies of cyclometalating C-H bond activation reactions on Pd(ii) and Rh(ii) centres: The importance of non-innocent acidic solvents in the process

The activation of C-H bonds in homogeneous systems has been the subject of study for many years due to its involvement in important industrial catalytic processes. A large number of reviews on the different areas involved have appeared, but those dealing with kinetic studies, including activation parameters, are rather scarce due to the severe difficulties in interpreting experimental data. In this perspective, the information available from kinetico-mechanistic studies of cyclometalation reactions on Pd(ii) and Rh(ii) centres via C-H bond activation is considered. Experimental results from studies performed on complexes of these metal centres indicate that the historically accepted electrophilic substitution classification is not a satisfactory mechanistic term for the process occurring during the reaction. A definite acid-assisted phenomenon is evident for all the processes studied, which contradicts the expected need for a proton abstractor in the reaction. This is even more surprising when considering the expected hydrolysis of M-C bonds in such acidic media, indicating that metalation prevails under these conditions. Only the presence of coordinated acid molecules in solvolytic carboxylic acid media can explain the observations. The fine tuning between the proton abstraction capacity of a coordinated RCO(2)H molecule and its Lewis basicity results in a unique reactivity trend. DFT calculations carried out for these acid-assisted processes fully agree with the experimental trends observed.     

Selective Metal‐Cation Recognition by [2.2]Ferrocenophanes: The Cases of Zinc‐ and Lithium‐Sensing

The synthesis, electrochemical, optical, and cation‐sensing properties of [2.2]ferrocenophanes, in which the two ferrocene subunits are linked through two aldiminic or iminophosphorane moieties, are reported. The new compounds show remarkably selective cation‐sensing properties due to the presence of redox‐active units (ferrocene) and aza‐unsaturated functionalities that are able to act as putative cation‐binding sites. In this structural motif, the aldimine groups act as a highly selective binding site for Zn²⁺ cations, whereas the iminophosphorane bridges display an unusually strong binding affinity towards Li⁺ cations, which could be explained by an additional Li???Fe interaction. The X‐ray structure of the complex 4? Li⁺ as well as detailed NMR spectroscopic studies, both in solution and in the solid state, support this assessment. Experimental data and conclusions about the cation‐sensing capabilities of this family of compounds are supported by DFT calculations.     

Argue to agree: A case-based argumentation approach

The capability of reaching agreements is a necessary feature that large computer systems where agents interoperate must include. In these systems, agents represent self-motivated entities that have a social context, including dependency relations among them, and different preferences and beliefs. Without agreement there is no cooperation and thus, complex tasks which require the interaction of agents with different points of view cannot be performed. In this work, we propose a case-based argumentation approach for Multi-Agent Systems where agents reach agreements by arguing and improve their argumentation skills from experience. A set of knowledge resources and a reasoning process that agents can use to manage their positions and arguments are presented. These elements are implemented and validated in a customer support application.     

A note on Liouvillian first integrals and invariant algebraic curves

In this work we study the existence and non-existence of finite invariant algebraic curves for a complex planar polynomial differential system having a Liouvillian first integral.