Magnetically Active Carbon Nanotubes at Work

Endohedral and exohedral assembly of magnetic nanoparticles (MNPs) and carbon nanotubes (CNTs) recently gave birth to a large body of new hybrid nanomaterials (MNPs–CNTs) featuring properties that are otherwise not in reach with only the graphitic or metallic cores themselves. These materials feature enhanced magnetically guided motions (rotation and translation), magnetic saturation and coercivity, large surface area, and thermal stability. By guiding the reader through the most significant examples in this Concept paper, we describe how researchers in the field engineered and exploited the synergistic combination of these two types of nanoparticles in a large variety of current and potential applications, such as magnetic fluid hyperthermia therapeutics and in magnetic resonance imaging to name a few.     

Carbon–Phosphorus Coupling from C^N Cyclometalated AuIII Complexes

With the aim of exploiting new organometallic species for cross-coupling reactions, we report here on the Au^III-mediated C_aryl−P bond formation occurring upon reaction of C^N cyclometalated Au^III complexes with phosphines. The [Au(C^N)Cl₂] complex 1 featuring the bidentate 2-benzoylpyridine (C^CON) scaffold was found to react with PTA (1,3,5-triaza-7-phosphaadamantane) under mild conditions, including in water, to afford the corresponding phosphonium 5 through C−P reductive elimination. A mechanism is proposed for the title reaction based on in situ ³¹P{¹H} NMR and HR-ESI-MS analyses combined with DFT calculations. The C−P coupling has been generalized to other C^N cyclometalated Au^III complexes and other tertiary phosphines. Overall, this work provides new insights into the reactivity of cyclometalated Au^III compounds and establishes initial structure–activity relationships to develop Au^III-mediated C−P cross-coupling reactions.     

Decarboxylative Conjunctive Cross-coupling of Vinyl Boronic Esters using Metallaphotoredox Catalysis

The synthesis of complex alkyl boronic esters through conjunctive cross-coupling of vinyl boronic esters with carboxylic acids and aryl iodides is described. The reaction proceeds under mild metallaphotoredox conditions and involves an unprecedented decarboxylative radical addition/cross-coupling cascade of vinyl boronic esters. Excellent functional-group tolerance is displayed, and application of a range of carboxylic acids, including secondary α-amino acids, and aryl iodides provides efficient access to highly functionalized alkyl boronic esters. The decarboxylative conjunctive cross-coupling was also applied to the synthesis of sedum alkaloids.     

A methodology to investigate heterogeneous oxidation of thermally aged cross-linked polyethylene by ToF-SIMS

Artificial ageing of polymeric insulation jackets is routinely performed in order to assess end-of-life material characteristics. Practical constraints including high temperatures/short times ageing treatments lead to strong influence of diffusion-limited oxidation (DLO) resulting in unreliable life-time predictions. This study proposes a new experimental approach to the investigation of cable insulation ageing, exploiting analytical techniques capable of resolving chemistry at the length scale relevant for DLO (nano-microscale). When studying the potential effects of DLO using time of flight secondary ion mass spectrometry (ToF-SIMS) sample preparation becomes crucial. This paper presents the development of a methodology to generate suitable specimens to investigate the DLO effect using ToF-SIMS. A reference polymeric material has been thermally aged in various DLO conditions. Cross sections of aged samples were generated using three different methods. In order to assess the most suitable approach for this study, cross-section topography were scanned using a profilometer and the surface chemistry was investigated using ToF-SIMS together with multivariate analysis methods.     

Morphometry of E-PTA stained synapses at the periphery of pathological lesions

We carried out a novel application of the disector sampling and counting method, in a biopsy material from the pathologic human brain, to estimate the synaptic structural dynamics, quantitatively. Parietal cortex biopsies of adult (mean age: 40.0 years) and old (mean age: 66.2 years) patients having undergone surgical intervention were investigated. The tissue samples were excised at the periphery of meningioma masses. Synaptic contact zones were stained en bloc by the ethanol phosphotungstic acid (E-PTA) preferential technique which selectively enhances both the pre- and post-synaptic paramembranous material separated by a sharp cleft against a very faint background, thus facilitating and objectifying synaptic morphometry. The disector method, associated with currently used morphometric formulas, enabled us to measure the number of synapses/m3 of tissue (numeric density: Nv); the total area of the synaptic contact zones/m3 of tissue (surface density: Sv) and the average synaptic size (S). In old vs. adult patients, Nv decreased by 7.5% (Mean (SEM): Adult 2.0040(0.0452); Old 1.6780(0.0623)), while S increased by 17.5% (Adult 0.0203(0.0026); Old 0.0246(0.0035)). Sv did not show any age-related difference. The same negative correlation between Nv and S has also been reported in physiological aging, and this suggests the active presence of age-related synaptic restructuring mechanisms in the nervous tissue surrounding a tumoral mass.     

Use of rotating ion-collectors for the preparation of isotopically pure targets

The rotating ion collectors of E.M. isotope separators offer interesting possibilities to produce thin. very extended and uniform mono-isotopic layers deposited on thin A1 backings. Such targets are needed for high resolution electron spectroscopy studies following neutron eapture reactions induced by high flux neutron beams.     

A Monge–Kantorovich mass transport problem for a discrete distance

This paper is concerned with a Monge-Kantorovich mass transport problem in which in the transport cost we replace the Euclidean distance with a discrete distance. We fix the length of a step and the distance that measures the cost of the transport depends of the number of steps that is needed to transport the involved mass from its origin to its destination. For this problem we construct special Kantorovich potentials, and optimal transport plans via a nonlocal version of the PDE formulation given by Evans and Gangbo for the classical case with the Euclidean distance. We also study how these problems, when rescaling the step distance, approximate the classical problem. In particular we obtain, taking limits in the rescaled nonlocal formulation, the PDE formulation given by Evans-Gangbo for the classical problem.     

Orbital branching

We introduce orbital branching, an effective branching method for integer programs containing a great deal of symmetry. The method is based on computing groups of variables that are equivalent with respect to the symmetry remaining in the problem after branching, including symmetry that is not present at the root node. These groups of equivalent variables, called orbits, are used to create a valid partitioning of the feasible region that significantly reduces the effects of symmetry while still allowing a flexible branching rule. We also show how to exploit the symmetries present in the problem to fix variables throughout the branch-and-bound tree. Orbital branching can easily be incorporated into standard integer programming software. Through an empirical study on a test suite of symmetric integer programs, the question as to the most effective orbit on which to base the branching decision is investigated. The resulting method is shown to be quite competitive with a similar method known as isomorphism pruning and significantly better than a state-of-the-art commercial solver on symmetric integer programs.     

Groupoid quantales: A non-étale setting

We establish a bijective correspondence involving a class of unital involutive quantales and a class of groupoids whose space of units is a sober space. This class includes equivalence relations that arise from group actions. The resulting axiomatization of the class of quantales, as well as the correspondence defined here, extend the theory of étale groupoids and their quantales (Resende (2007) [10]) to a point-set, non-étale setting.