Resonance paramagnetique electronique du manganese divalent dans ZnAl2O4

The electron paramagnetic resonance spectrum of a single crystal of ZnAl₂O₄ (spinel structure) doped with manganese displays a fine structure characteristic of a purely cubic crystal field. Contrary to MgAl₂O₄: Mn²⁺, where the degree of inversion is sizable, ZnAl₂O₄ therefore is a normal spinel.     

Order-disorder transition in supramolecular polymers

In supramolecular polymers, directional interactions control the constituting units connectivity, but dispersion forces may conspire to make complex organizations. Here we report on the long-range order and order-disorder transition (ODT) of main-chain supramolecular polymers based on poly(propylene oxide) (PPO) spacers functionalized on both ends with thymine. Below the ODT temperature (T(ODT)), these compounds are semicrystalline with a lamellar structure, showing nanophase separation between crystallized thymine planes and amorphous PPO layers. Above T(ODT), they are amorphous and homogeneous even though their X-ray scattering spectrum reveals a peak. This peak is due to correlation hole effect resulting from contrast between end-functional groups and spacer. Macroscopically, the transition is accompanied by dramatic flow and mechanical properties changes.     

Comparative Analysis of Conjugated Alkynyl Chromophore–Triazacyclononane Ligands for Sensitized Emission of Europium and Terbium

A series of europium and terbium complexes based on a functionalized triazacyclononane carboxylate or phosphinate macrocyclic ligand is described. The influence of the anionic group, that is, carboxylate, methylphosphinate, or phenylphosphinate, on the photophysical properties was studied and rationalized on the basis of DFT calculated structures. The nature, number, and position of electron‐donating or electron‐withdrawing aryl substituents were varied systematically within the same phenylethynyl scaffold in order to optimize the brightness of the corresponding europium complexes and investigate their two‐photon absorption properties. Finally, the europium complexes were examined in cell‐imaging applications, and selected terbium complexes were studied as potential oxygen sensors.     

Capillary cohesion and mechanical strength of polydisperse granular materials

We investigate the macroscopic mechanical behaviour of wet polydisperse granular media. Capillary bonding between two grains of unequal diameters is described by a realistic force law implemented in a molecular-dynamics algorithm together with a protocol for the distribution of water in the bulk. Axial-compression tests are simulated for granular samples at different levels of water content, and compared to experiments performed in similar conditions. We find good agreement between numerical and experimental data in terms of the rupture strength as a function of water content. Our results show the importance of the distribution of water for the mechanical behaviour.     

Investigation of passivated silicon detectors for direct measurements of actinides

Although much progress was made by using high purity gemanium detectors for direct measurement of²³⁹Pu in man, the improvement of lung spectroscopy sensitivity remains a challenge. Previous work showed that passivated implanted planar silicon detectors could provide an alternative by combining high-energy resolution at room temperature and planar geometry with large detection arrays. This paper reports on the status of this research based on the characterisation of 3×3 cm² and 6×3 cm² strip silicon detectors. Furthemore, the possibility to apply such detectors towards other monitoring problems for accidental situations such as the direct measurement of small contaminated surfaces was investigated.     

On lifted cover inequalities: A new lifting procedure with unusual properties

Lifted cover inequalities are well-known cutting planes for 0–1 linear programs. We show how one of the earliest lifting procedures, due to Balas, can be significantly improved. The resulting procedure has some unusual properties. For example, (i) it can yield facet-defining inequalities even if the given cover is not minimal, (ii) it can yield facet-defining inequalities that cannot be obtained by standard lifting procedures, and (iii) the associated superadditive lifting function is integer-valued almost everywhere.     

Suppression of mesoscopic order by complementary interactions in supramolecular polymers

We show here that complementary interactions can suppress mesoscopic order and thus lead to a counterintuitive change in material properties. We present results for telechelic supramolecular polymers based on poly(propylene oxide) (PPO), thymine (Thy), and diaminotriazine (DAT). The self-complementary systems based on Thy exhibit lamellar order and 2D crystallization of Thy in the bulk. We show that the microphase segregation is inhibited by addition of DAT: the strong complementary Thy-DAT interaction inhibits crystallization of thymine in microdomains and lamellar structuration. As a result, the supramolecular polymer with only weakly self-complementary stickers is a solid, whereas the supramolecular polymer with strongly complementary stickers is a liquid.     

A powerful approach for the selection of 2-aminopurine substitution sites to investigate RNA folding

A precise tertiary structure must be adopted to allow the function of many RNAs in cells. Accordingly, increasing resources have been devoted to the elucidation of RNA structures and the folding of RNAs. 2-Aminopurine (2AP), a fluorescent nucleobase analogue, can be substituted in strategic positions of DNA or RNA molecules to act as site-specific probe to monitor folding and folding dynamics of nucleic acids. Recent studies further demonstrated the potential of 2AP modifications in the assessment of folding kinetics during ligand-induced secondary and tertiary RNA structure rearrangements. However, an efficient way to unambiguously identify reliable positions for 2AP sensors is as yet unavailable and would represent a major asset, especially in the absence of crystallographic or NMR structural data for a target molecule. We report evidence of a novel and direct correlation between the 2'-OH flexibility of nucleotides, observed by selective 2'-hydroxyl acylation analyzed by primer extension (SHAPE) probing and the fluorescence response following nucleotide substitutions by 2AP. This correlation leads to a straightforward method, using SHAPE probing with benzoyl cyanide, to select appropriate nucleotide sites for 2AP substitution. This clear correlation is presented for three model RNAs of biological significance: the SAM-II, adenine (addA), and preQ(1) class II (preQ(1)cII) riboswitches.