Aziridines N-Non substituées. Détermination des Paramètres Thermodynamiques ΔG°, ΔH°, ΔS° Liés à l'Equilibre Conformationnel à partir de Mesures RMN 1H à Haut Champ

Although nitrogen inversion in unsubstituted aziridines has been shown by ¹H NMR, it was only possible to study quantitatively the distribution of both invertomers and determine the thermodynamic parameters by a systematic high field NMR study (CAMECA 250 MHz). Thermodynamic parameters have been determined for 32 compounds. In C-aryl aziridines, the steric hindrance of the aromatic group and its variation with other aziridine ring substituents can be studied. These observations are in agreement with a conjugation phenomenon between the aromatic system and the aziridine ring.     

EPR study of the surface basicity of calcium oxide. 3. Surface reactivity and nonstoichiometry

High surface area polycrystalline calcium oxide forms ozonide O3- ions upon O2 adsorption and NO3(2-) anions under low pressures of NO. Both radical anions, detected by electron paramagnetic resonance (EPR), are not observed in the case of the homologous magnesium oxide. This behavior reveals the presence, in CaO, of anomalies with respect to the ideal composition of an ionic oxide which are identified in terms of two main types of defects. The first type consists of positive holes dispersed in the bulk and originated by the unavoidable presence of Na+ ions in the composition of the solid. The decomposition of the surface ozonide shows the formation of a transient surface stabilized O- (the chemical notation of a positive hole associated to an oxide ion) which is for the first time reported at the surface of CaO. The second type of defect consists of surface peroxide groups (present at particular surface sites where they are formed by pairing of two distinct O-) which react with nitric oxide (NO) yielding NO3(2-) radical anions. The presence of peroxide is not related to the presence of impurities but, rather, to a certain propensity of the solid to form such ions at the surface along the dehydration process.     

The Conjugacy Problem is Solvable in Free-By-Cyclic Groups

We show that the conjugacy problem is solvable in [finitelygenerated free]-by-cyclic groups, by using a result of O. Maslakovathat one can algorithmically find generating sets for the fixedsubgroups of free group automorphisms, and one of P. Brinkmannthat one can determine whether two cyclic words in a free groupare mapped to each other by some power of a given automorphism.We also solve the power conjugacy problem, and give an algorithmto recognize whether two given elements of a finitely generatedfree group are twisted conjugated to each other with respectto a given automorphism. 2000 Mathematics Subject Classification20F10, 20E05.     

Pulse-width modulation in defocused three-dimensional fringe projection

Shape measurements by fringe projection methods require high-quality sinusoidal fringes. We present a sinusoidal fringe generation technique that utilizes slightly defocused binary fringe projection. The proposed method is a spatial version of the well-known pulse-width modulation (PWM) technique of electrical engineering. PWM is easy to implement using off-the-shelf projectors, and it allows us to overcome the gamma problem (i.e., the nonlinear projector response) in the output light intensity. We will demonstrate that, with a small defocusing level--lower than with other techniques proposed in the literature--a high-quality sinusoidal pattern is obtained. Validation experiments using a commercial video projector are presented.     

Nonlinear magnetotransport in interacting chiral nanotubes

Nonlinear transport through interacting single-wall nanotubes containing a few impurities is studied theoretically. Extending the Luttinger liquid theory to incorporate trigonal warping and chirality effects, we derive the current contribution Ie even in the applied voltage V and odd in an orbital magnetic field B, which is nonzero only for chiral tubes and in the presence of interactions.     

Statistical properties of subgroups of free groups

The usual way to investigate the statistical properties of finitely generated subgroups of free groups, and of finite presentations of groups, is based on the so‐called word‐based distribution: subgroups are generated (finite presentations are determined) by randomly chosen k ‐tuples of reduced words, whose maximal length is allowed to tend to infinity. In this paper we adopt a different, though equally natural point of view: we investigate the statistical properties of the same objects, but with respect to the so‐called graph‐based distribution, recently introduced by Bassino, Nicaud and Weil. Here, subgroups (and finite presentations) are determined by randomly chosen Stallings graphs whose number of vertices tends to infinity. Our results show that these two distributions behave quite differently from each other, shedding a new light on which properties of finitely generated subgroups can be considered frequent or rare. For example, we show that malnormal subgroups of a free group are negligible in the graph‐based distribution, while they are exponentially generic in the word‐based distribution. Quite surprisingly, a random finite presentation generically presents the trivial group in this new distribution, while in the classical one it is known to generically present an infinite hyperbolic group. © 2012 Wiley Periodicals, Inc. Random Struct. Alg., 2013     

Homology computation for a class of contact structures on T^3

We consider a family of tight contact forms on the three-dimensional torus and we compute the relative Contact Homology by using the variational theory of critical points at infinity. We will also show local stability.     

Discovery of novel cathepsin S inhibitors by pharmacophore-based virtual high-throughput screening

The cysteine protease cathepsin S (CatS) is involved in the pathogenesis of autoimmune disorders, atherosclerosis, and obesity. Therefore, it represents a promising pharmacological target for drug development. We generated ligand-based and structure-based pharmacophore models for noncovalent and covalent CatS inhibitors to perform virtual high-throughput screening of chemical databases in order to discover novel scaffolds for CatS inhibitors. An in vitro evaluation of the resulting 15 structures revealed seven CatS inhibitors with kinetic constants in the low micromolar range. These compounds can be subjected to further chemical modifications to obtain drugs for the treatment of autoimmune disorders and atherosclerosis.     

Ge-O coordination in cesium germanate glasses

Neutron diffraction data with high real-space resolution are reported for an extensive series of cesium germanate glasses with 2, 5, 10, 15, 18, 21, 25, and 30 mol % Cs(2)O, and also for pure GeO(2) in its vitreous, quartz, and rutile forms. The results for pure GeO(2) show that neutron diffraction can clearly identify an increase in the Ge-O coordination number above the tetrahedral value of four. The results for cesium germanate glasses give strong evidence that the Ge-O coordination number rises to a maximum of 4.36 +/- 0.03 for 18 mol % Cs(2)O and then declines. This behavior may be associated with the germanate anomaly in the thermophysical properties. A model is developed for the composition-dependence of the Ge-O coordination number, and according to this model the rise in the coordination number involves the formation of mostly GeO(5) units, rather than GeO(6) units. Our results also show that the low alkali anomaly is a longer range phenomenon, and is not associated with a preference for the formation of nonbridging oxygens for very low alkali oxide content.     

Structural and thermodynamic studies of the interaction of distamycin A with the parallel quadruplex structure [d(TGGGGT)]4

The complex between distamycin A and the parallel DNA quadruplex [d(TGGGGT)]4 has been studied by 1H NMR spectroscopy and isothermal titration calorimetry (ITC). To unambiguously assert that distamycin A interacts with the grooves of the quadruplex [d(TGGGGT)]4, we have analyzed the NMR titration profile of a modified quadruplex, namely [d(TGGMeGGT)]4, and we have applied the recently developed differential frequency-saturation transfer difference (DF-STD) method, for assessing the ligand-DNA binding mode. The three-dimensional structure of the 4:1 distamycin A/[d(TGGGGT)]4 complex has been determined by an in-depth NMR study followed by dynamics and mechanics calculations. All results unequivocally indicate that distamycin molecules interact with [d(TGGGGT)]4 in a 4:1 binding mode, with two antiparallel distamycin dimers that bind simultaneously two opposite grooves of the quadruplex. The affinity between distamycin A and [d(TGGGGT)]4 enhances ( approximately 10-fold) when the ratio of distamycin A to the quadruplex is increased. In this paper we report the first three-dimensional structure of a groove-binder molecule complexed to a DNA quadruplex structure.