Bogoliubov Spectrum of Interacting Bose Gases

We study the large‐N limit of a system of N bosons interacting with a potential of intensity 1/N. When the ground state energy is to the first order given by Hartree's theory, we study the next order, predicted by Bogoliubov's theory. We show the convergence of the lower eigenvalues and eigenfunctions towards that of the Bogoliubov Hamiltonian (up to a convenient unitary transform). We also prove the convergence of the free energy when the system is sufficiently trapped. Our results are valid in an abstract setting, our main assumptions being that the Hartree ground state is unique and nondegenerate, and that there is complete Bose‐Einstein condensation on this state. Using our method we then treat two applications: atoms with “bosonic” electrons on one hand, and trapped two‐dimensional and three‐dimensional Coulomb gases on the other hand. © 2015 Wiley Periodicals, Inc.     

Microcrystalline testing used in combination with Raman micro‐spectroscopy for absolute identification of novel psychoactive substances

Two new psychoactive substances, namely 4‐methylmethcathinone (mephedrone) and 5,6‐methylenedioxy‐2‐aminoindane (MDAI) were analysed with a novel combination of microcrystalline tests followed by Raman micro‐spectroscopy to facilitate their absolute identification. The discrimination power of the proposed combination was successfully demonstrated through the analysis of the positional isomers 2‐ and 3‐methylmethcathinone. The addition of mercury dichloride as a microcrystalline test reagent produced specific microcrystals of each tested analyte. The robustness of the method was evaluated in the presence of common cutting agents (caffeine and benzocaine) as well as on street samples. The crystal lattice structures of mephedrone, 2‐methylmethcathinone and MDAI mercury dichloride microcrystals were determined by single crystal X‐ray diffraction. This confirmed the presence of both drug and reagent together in the lattice and accounts for the distinct habit of the observed microcrystals. Raman spectra of the formed microcrystals differed from those obtained from their standard salt form by loss and/or gain of some vibrational modes. Particularly important was the appearance of the mercury chloride link to each tested drug molecule which showed as strong bands at low wavenumbers. Its presence was corroborated by its detection in the crystal lattice. It was therefore concluded that microcrystalline testing followed by Raman micro‐spectroscopy satisfies the technique combination requirement for psychoactive substances recommended by the Scientific Working Group for the Analysis of Seized Drugs (SWGDRUG) and provides a rapid and cheap analysis route. The proposed technique combination also aids the development of new microcrystalline tests as it allows for confirmation of the uniqueness of the developed microcrystals almost in‐situ rather than growing single crystals for often long periods of time needed for single crystal X‐ray diffraction analysis. Copyright © 2016 John Wiley & Sons, Ltd.     

A Jahn–Teller analysis of K3 and Rb3 in the electronic states 1E′ and 1E″

The potential energy surfaces (PES) of the Jahn–Teller distorted doublet 1²E′ (1B₂/1A₁) ground state and 1²E″ (2B₁/1A₂) excited state of alkali metal trimers (K₃, Rb₃) are studied with three high-level computational chemistry methods whose results are compared: single-reference coupled cluster, equation-of-motion coupled cluster and multi-reference second-order Rayleigh–Schrödinger perturbation theory. The doubly degenerate E electronic state interacts with the twofold degenerate vibrational e mode. We use the E ⊗ e Jahn–Teller effect theory to analyze in detail one- and two-dimensional cuts of the PES as a function of the symmetry-adapted internal coordinates Q_s, Q_x and Q_y and we extract the associated Jahn–Teller parameters. Spin-orbit coupling is accounted for by means of the Effective-Core-Potential-LS technique and spin-orbit splitting constants are extracted. We also provide the geometries, the binding energies and tentative vibronic spectra for the 1²E″ ← 1²E′ transitions.     

Guidelines to design new spin crossover materials

This review focuses on new families of spin crossover (SCO) complexes based on polynitrile anions as new anionic ligands or on polyazamacrocycles as neutral macrocyclic ligands. We have shown that the structural and electronic characteristics (original coordination modes and high electronic delocalization) of the polynitrile anions can be tuned by slight chemical modifications such as substitution of functional groups or variation of the negative charge to design new discrete or polymeric SCO systems.In our ongoing work on the design of new molecular systems based on new ligands that can be fine-tuned via chemical modifications, another promising way which has been recently developed in our group concerns the use of new neutral polydentate ligands which are able to tune the ligand field energy around the metal centre. Here we report some recent original Fe(II) SCO complexes based on such polydentate ligands.     

Polynitrile anions as ligands: From magnetic polymeric architectures to spin crossover materials

The use of polynitrile anions as ligands (L) either alone or in combination with neutral co-ligands (L′) is a very promising and appealing strategy to get molecular architectures with different topologies and dimensionalities thanks to their ability to coordinate and bridge metal ions in many different ways. The presence of several potentially coordinating nitrile groups (or even other donor groups as –OH, –SH or –NH₂), their rigidity and their electronic delocalization allow the synthesis of original magnetic high dimensional coordination polymers with transition metals ions. Furthermore, these ligands have shown coordinating and bridging capabilities in novel discrete and polymeric bistable materials (materials showing original magnetic behaviours or spin crossover (SCO) transitions). Here we report an overview of the results obtained with some of these modified polynitrile ligands, showing their rich coordination chemistry and their crucial role in new molecular materials exhibiting unusual magnetic transitions.     

A Versatile Method for Quantification of Aflatoxins and Ochratoxin A in Dried Figs

JPC – Journal of Planar Chromatography – Modern TLC - Thin-layer chromatography is a rapid and reliable working method for quantification of mycotoxins which is suitable for checking EC...     

A Rigid Dinuclear Ruthenium(II) Complex as an Efficient Photoactive Agent for Bridging Two Guanine Bases of a Duplex or Quadruplex Oligonucleotide

The rigid dinuclear [(tap)₂Ru(tpac)Ru(tap)₂]⁴⁺ complex ( 1 ) (TAP=1,4,5,8‐tetraazaphenanthrene, TPAC=tetrapyridoacridine) is shown to be much more efficient than the mononuclear bis‐TAP complexes at photodamaging oligodeoxyribonucleotides (ODNs) containing guanine (G). This is particularly striking with the G‐rich telomeric sequence d(T₂AG₃)₄. Complex 1 , which interacts strongly with the ODNs as determined by surface plasmon resonance (SPR) and emission anisotropy experiments, gives rise under illumination to the formation of covalent adducts with the G units of the ODNs. The yield of photocrosslinking of the two strands of duplexes by 1 is the highest when the G bases of each strand are separated by three to four base pairs. This corresponds with each Ru(tap)₂ moiety of complex 1 forming an adduct with the G base. This separation distance of the G units of a duplex could be determined thanks to the rigidity of complex 1 . On the basis of results of gel electrophoresis, mass spectrometry, and molecular modelling, it is suggested that such photocrosslinking can also occur intramolecularly in the human telomeric quadruplex d(T₂AG₃)₄.     

Nanowires Formed by the Co‐Assembly of a Negatively Charged Low‐Molecular Weight Gelator and a Zwitterionic Polythiophene

Conjugated organic nanowires have been prepared by co‐assembling a carboxylate containing low‐molecular weight gelator (LMWG) and an amino acid substituted polythiophene derivative (PTT). Upon introducing the zwitterionic polyelectrolyte PTT to a basic molecular solution of the organogelator, the negative charges on the LMWG are compensated by the positive charges of the PTT. As a result, nanowires form through co‐assembly. These nanowires are visualized by both transmission electron microscopy (TEM) and atomic force microscopy (AFM). Depending on the concentration and ratio of the components these nanowires can be micrometers long. These measurements further suggest that the aggregates adopt a helical conformation. The morphology of these nanowires are studied with fluorescent confocal laser scanning microscopy (CLSM). The interactions between LMWG and PTT are characterized by steady‐state and time‐resolved fluorescence spectroscopy studies. The steady‐state spectra indicate that the backbone of the PTT adopts a more planar and more aggregated conformation when interacting with LMWG. The time‐ resolved fluorescence decay studies confirm this interpretation.     

Internal mobilities and diffusion in an ionic liquid mixture

The internal mobility gives the rate at which one ionic species moves relative to the other species present in an ionic mixture, it mirrors the differential strength of the interactions between different ionic species. In this work we examine the dependence of the internal mobilities of the Li(+) and K(+) ions on the composition in molten mixtures of LiF and KF. We compare them to the behaviour of the individual diffusion coefficients and the self-exchange velocities, which measure the rate at which an ion separates from its nearest-neighbour coordination shell. The examination is made using molecular dynamics simulations with polarizable, first-principles parameterised interaction potentials which are shown to reproduce the limited available experimental data on the transport properties of these mixtures extremely well. The results confirm that the composition-dependence of the internal mobilities in LiF/KF follows the unusual type-II behaviour, which is not reflected in that of the diffusion coefficients or the self-exchange velocities.