Liaison hydrogène O-H-O symétrique : II. Spectres de vibration des oxalates acides de lithium hydratés et anhydres

Infrared and Raman spectra of polycrystalline LiHC₂O₄, LiHC₂O₄, · H₂O and their D and ⁶Li containing isotopic derivatives have been investigated at 300 and 90 K in the 4000–50 cm⁻¹ region. All the internal and external optically active modes of lithium hydrogen oxalate monohydrate have been identified and an assignment is given. The spectroscopic data are consistent with X-ray data showing an asymmetric short hydrogen bond with a positive deuterium isotope effect. The dehydration of LiHC₂O₄, · H₂O changes the type of hydrogen bond which becomes symmetric of the double minimum type. The deuteration of LiHC₂O₄, on the other hand. weakens the hydrogen bond and makes it asymmetric again. The asymmetry appears more pronounced at low temperature.     

Competition between supernucleation and plasticization in the crystallization and rheological behavior of PCL/CNT‐based nanocomposites and nanohybrids

PCL was blended with pristine multiwalled carbon nanotubes (MWCNT) and with a nanohybrid obtained from the same MWCNT but grafted with low molecular weight PCL, employing concentrations of 0.25 to 5 wt % of MWCNT and MWCNT‐g‐PCL. Excellent CNT dispersion was found in all samples leading to supernucleation of both nanofiller types. Nanohybrids with 1 wt % or less MWCNTs crystallize faster than nanocomposites (due to supernucleation), while the trend eventually reverses at higher nanotubes content (because of plasticization). Rheological results show that yield‐like behavior develops in both nanocomposites, even for the minimum content of carbon nanotubes. In addition, the MWCNT‐g‐PCL family, when compared with the neat polymer, exhibits lower values of viscosity and modulus in oscillatory shear, and higher compliance in creep. These rheological differences are discussed in terms of the plasticization effect caused by the existence of low molecular weight free and grafted PCL chains in the nanohybrids. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1310–1325     

Séparation des orbites coadjointes d'un groupe exponentiel par leur enveloppe convexe

Looking to the separation of irreducible unitary representations of an exponential Lie group G through the image of their moment map, we propose here a new way: instead to extend the moment map to the universal enveloping algebra of G, we define a non linear mapping Φ from the dual of the Lie algebra g of G to the dual g^+∗ of a larger solvable group G⁺, and we extend the representation from G to G⁺, in such a manner that the corresponding coadjoint orbits in g^+∗ have distinct closed convex hull. This allows us to separate the irreducible unitary representations of G.     

A versatile method for the production of monodisperse spherical particles and hollow particles: templating from binary core-shell structures

Using the porosity of a binary exotemplate, with mesoporous core-shell structure (SiO2@ZrO2), opens a new pathway to produce hybrid core-shell spheres, composite hollow spheres, and porous hollow spheres -- all monodisperse in size.     

Stabilization of G-quadruplex DNA and inhibition of telomerase activity by square-planar nickel(II) complexes

Two new alkylamine-substituted nickel(II)-salphen complexes have been prepared and their interactions with DNA investigated. FRET studies have shown that these complexes have a remarkable ability to stabilize G-quadruplex DNA. Furthermore, TRAP/Taq assays have shown that these complexes inhibit telomerase at low micromolar concentrations.     

Q.U.P. and Paley-Wiener properties of unimodular, especially nilpotent, Lie groups

We give a new proof of a weak Paley-Wiener theorem for nilpotent Lie groups due to Lipsman and Rosenberg and we introduce a general notion of Q.U.P for any unimodular locally compact group.

     

Kontsevich formality and cohomologies for graphs

A formality on a manifold M is a quasi isomorphism between the space of polyvector fields (T _poly(M)) and the space of multidifferential operators (D _poly(M)). In the case M=R ^d , such a mapping was explicitly built by Kontsevich, using graphs drawn in configuration spaces. Looking for such a construction step by step, we have to consider several cohomologies (Hochschild, Chevalley, and Harrison and Chevalley) for mappings defined on T _poly. Restricting ourselves to the case of mappings defined with graphs, we determine the corresponding coboundary operators directly on the spaces of graphs. The last cohomology vanishes.     

Effect of annealing time on the self‐nucleation behavior of semicrystalline polymers

It is widely known that when a polymer is heated just above its melting point and is kept at a given temperature (denoted T_s) for a short time, when it is cooled down its nucleation density increases and its peak crystallization temperature shifts to higher temperatures, as detected for instance by differential scanning calorimetry (DSC). The T_s temperature range where the described process occurs has been named Domain II self‐nucleation (SN) because the selected T_s temperatures are high enough to melt the polymer without causing detectable annealing of any remnant crystals by DSC. Experimental results obtained by DSC, polarized light optical microscopy (PLOM), and rheology indicate that these techniques are unable to detect any remaining crystal fragments in Domain II. Our kinetic results demonstrate that Domain II SN is a transient phenomenon that can even disappear if enough time at T_s is allowed. Results of the study of the time dependence of the SN effect indicates two possibilities: (a) if crystal fragments are present (even if undetected by the employed techniques) their final melting is a very slow process (in the order of hours); (b) if all crystallites have melted in Domain II, then it may be more plausible to reinterpret self‐nuclei as arising from “precursors” whose detail nature has not been the subject of this investigation but that can be regarded as either a residual segmental orientation in the melt (i.e., a melt memory effect) or a mesophase in a preordered state. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1738–1750, 2006