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.     

Composition, structure and solution properties of polysaccharides extracted from leaves of Mesembryanthenum crystallinum

Water and Chelator-soluble polymers were independently isolated from the alcoholic-insoluble substance (AIS) of Mesembryanthenum crystallinum leaves. After precipitation in ethanol and ultrafiltration (40 kD cut-off) of recovered solids dissolved in water, the yield relative of the so-call Lw and LCh polymers to the AIS dry matter was 2.5 ± 0.2 and 7 ± 0.5%. The galacturonic acid contents were 67 ± 3% and 63 ± 5%. The degrees of methylesterification of ca. 45 ± 3% and 50 ± 3%, showed that Lw and LCh belonged to the fairly methylesterified pectin class. From sugar analysis, LCh was shown to contain at least two types of pectic blocks, homogalacturonan (HG: 58%) and rhamnogalacturonan-I (RG-I: 34%). Their structure were deduced after saponification, polygalacturonase treatments, size exclusion chromatography (SEC) onto Sephacryl S-200 and then sugar composition of the collected fractions. The main polymers were methylesterified HG (32%), some of them being linked to non-methylesterified HG (10%), and to polygalacturonase-resistant HG (17%). In addition, there were (1) a highly soluble RG-I with long galactan side chains (RG-I-gal accounting for 9%) and (2) a RG-I with short arabino-galactan side chains (25%), named RG-I-ara/gal that was almost totally lost during SEC analysis, due to its low solubility at room temperature and in absence of chelators.SEC coupled with differential refractive index and light scattering showed that highly methylesterified HG chains exhibited aggregate structures in solution due to intermolecular hydrophobic interactions. These interactions formed hydrophobic clusters, which have been characterized by surface tension measurements and with a polarity probe, the Coomassie Brilliant Blue dye. After alkaline treatment of LCh, the self-assembly of HG disappeared.     

Modelling of unsteady 2D cavity flows using the Logvinovich independence principleModélisation des écoulements cavitants bidimensionnels basée sur le principe d'indépendance de Logvinovich.

A simple model for two-dimensional cavity flows is presented. It is based upon the Logvinovich independence principle. Each section of the cavity is assumed to behave independently of the neighbouring ones. The equation of evolution of the cavity interface is derived. It mainly takes into account an added mass effect and is similar to the well-known Rayleigh–Plesset equation relative to spherical bubbles. The dynamics of the 2D cavity is controlled by the pressure difference between infinity and the cavity. The model proves to be in good agreement with Tulin's solution for a steady cavity flow and easily applicable to unsteady cavity flows. To cite this article: C. Pellone et al., C. R. Mecanique 332 (2004).     

Miscibility maps for polymer blends: Effects of temperature,pressure, and molecular weight

We study a Gibbs free energy model for describing the thermodynamics of compressible polymer blends in the case of nonpolar polymers. This model is a mean field model equivalent to the cell model of Prigogine et al. and close also to the model by Flory‐Orvoll and Vrij. The model is expressed as a function of the interaction energies between monomer pairs (a, b, and c), the degrees of polymerization (X_A and X_B), a close packing parameter ρ₀, the temperature, and the pressure. We derive an analytical expression regarding blend miscibility. All the already observed phase behaviors are recovered: the occurrence of two kinds of upper critical solution transition (UCST): case‐I and case‐II UCST for which the pressure has a destabilizing or stabilizing effect, respectively, and lower critical solution transition; cases where the pressure have a non‐monotonous effect on the UCST temperature; cases where the spinodal lines close up under high pressures; and the so‐called hour‐glass transition. The model allows for making explicit the effect of the different physical parameters on phase behavior. We calculate complete miscibility maps regarding the occurrence of the various possible kinds of transitions in the 2D space b/a and X_A, for different values of , applied pressure P, and chain length ratios. This approach may come as a complement to already existing, more quantitative and elaborated approaches. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 419–443     

Tris‐cyclometalated Iridium(III) Complexes with Three Different Ligands: a New Example with 2‐(2,4‐Difluorophenyl)pyridine‐Based Complex

An iridium(III) complex comprising three different cyclometalated phenylpyridine‐based ligands was designed and synthesized. Interestingly, mixed‐ligand complexes could be obtained by using a simple and straightforward procedure. A tris(heteroleptic) Ir^III complex was obtained as a mixture of stereoisomers that could not be separated. Photophysical properties of the tris(heteroleptic) complex was investigated by UV/VIS absorption and luminescence spectroscopy, and compared with those of the parent homoleptic complexes. Modelling by time‐dependent density functional theory (TD‐DFT) was also performed to elucidate the nature and the location of the excited state, and to support the experimental results.     

Concerning restricted rotations in pyridinyl anisoles and pyridinyl phenols bearing saturated handles,and their solid state structures

The variable-temperature («dynamic») NMR measurements of series of pyridinyl anisoles and pyridinyl phenols each of them bearing ortho, ortho′ handles of various lengths at oxygenated ring lead to the following results: (i) at room temperature, a restricted rotation around the intercyclic bond of pyridinyl anisoles and pyridinyl phenol bearing short handles formed by 9–10 atoms is underscored, (ii) all handles at the former derivatives are blocked on one side of the oxygenated ring face, and (iii) handles of 11–12 atoms long at phenol rings are able to move freely. The solid-state packing indicates that all saturated chains are substantially perpendicular to the oxygenated ring.     

Synthesis and Spin‐Trapping Properties of a Trifluoromethyl Analogue of DMPO: 5‐Methyl‐5‐trifluoromethyl‐1‐pyrroline N‐Oxide (5‐TFDMPO)

The 5‐diethoxyphosphonyl‐5‐methyl‐1‐pyrroline N‐oxide superoxide spin adduct (DEPMPO?OOH) is much more persistent (about 15 times) than the 5,5‐dimethyl‐1‐pyrroline N‐oxide superoxide spin adduct (DMPO?OOH). The diethoxyphosphonyl group is bulkier than the methyl group and its electron‐withdrawing effect is much stronger. These two factors could play a role in explaining the different half‐lifetimes of DMPO?OOH and DEPMPO?OOH. The trifluoromethyl and the diethoxyphosphonyl groups show similar electron‐withdrawing effects but have different sizes. We have thus synthesized and studied 5‐methyl‐5‐trifluoromethyl‐1‐pyrroline N‐oxide (5‐TFDMPO), a new trifluoromethyl analogue of DMPO, to compare its spin‐trapping performance with those of DMPO and DEPMPO. 5‐TFDMPO was prepared in a five‐step sequence by means of the Zn/AcOH reductive cyclization of 5,5,5‐trifluoro‐4‐methyl‐4‐nitropentanal, and the geometry of the molecule was estimated by using DFT calculations. The spin‐trapping properties were investigated both in toluene and in aqueous buffer solutions for oxygen‐, sulfur‐, and carbon‐centered radicals. All the spin adducts exhibit slightly different fluorine hyperfine coupling constants, thereby suggesting a hindered rotation of the trifluoromethyl group, which was confirmed by variable‐temperature EPR studies and DFT calculations. In phosphate buffer at pH 7.4, the half‐life of 5‐TFDMPO?OOH is about three times shorter than for DEPMPO?OOH and five times longer than for DMPO?OOH. Our results suggest that the stabilization of the superoxide adducts comes from a delicate balance between steric, electronic, and hydrogen‐bonding effects that involve the β group, the hydroperoxyl moiety, and the nitroxide.     

Multifunctional Redox Polymers: Electrochrome,Polyelectrolyte, Sensor,Electrode Modifier,Nanoparticle Stabilizer,and Catalyst Template

Simple “click” polycondensation metallopolymers of redox‐robust bis(ethynyl)biferrocene (biFc) and di(azido) poly(ethylene glycol) (PEG400 and PEG1000) were designed for multiple functions including improvement of water solubility and biocompatibility, the introduction of mixed valency and sensing capabilities, and as nanoparticle stabilizers for catalysis.     

Monitoring the extraction of additives and additive degradation products from polymer packaging into solutions by multi-residue method including solid phase extraction and ultra-high performance liquid chromatography-tandem mass spectrometry analysis

The use of polymer materials in industry for product packaging is increasing. The presence of additives in the polymer matrix enables the modification or improvement of the properties and performance of the polymer, but these industries are concerned regarding the extractability of these additives. The quantification of these additives is particularly challenging because of the presence of these substances as contaminants in all the analytical equipment and the diversity of their physicochemical properties. In this context, a multi-residue analytical method was developed for the trace analysis of the twenty main additives (and their degradation products) authorized in plastic products such as pharmaceutical packaging (e.g., antioxidants, release agents, and light absorbers). This analytical method consisted of a solid phase extraction (SPE) followed by an analysis using ultra-high performance liquid chromatography coupled to a tandem mass spectrometer (UHPLC-MS/MS). A comparison of two ionization interfaces and the optimization of the extraction procedure were discussed. The influence of the quality of the solvent type (distilled versus not distilled) and the nature of the SPE cartridges (Polypropylene versus Teflon^®) were demonstrated. The optimized method exhibited a quantification limit lower than 20 ng mL^?1 and recoveries between 70 % and 120 % for all compounds. Finally, the method was validated according to the ICH directive and was subsequently applied to the extraction of polymers under different pH conditions and storage temperatures. To the best of our knowledge, this study presents the first methodology allowing the simultaneous quantification of 24 additives at low ng mL^?1.