On the Landau-Levich transition

We discuss here the nature of the Landau-Levich transition, that is, the dynamical transition that occurs when drawing a solid out of a bath of a liquid that partially wets this solid. Above a threshold velocity, a film is entrained by the solid. We measure the macroscopic contact angle between the liquid and the solid by different methods, and conclude that this angle might be discontinuous at the transition. We also present a model to understand this fact and the shape of the meniscus as drawing the solid.     

Determination of added sulfites in dried garlic with a modified version of the optimized Monier-Williams method

The optimized Monier-Williams method is slightly modified so that it could be applied for determining sulfite content in dried garlic. Dried garlic sample is directly acidified in a reactor at a pH below 3. At this pH level, the alliinase enzyme activity is irreversibly blocked, and the sulfur-containing amino acids such as alliin (the most abundant) present in dried garlic cannot be transformed into corresponding thiosulfinates such as allicin, which is absent in dried garlic. This prevents allicin from reacting with added sulfites and being probably converted to S-allyl thiosulfate, which is not volatile and has no taste. It is found that at a pH below 2.4 and at boiling water temperature, allicin produces sulfur dioxide in adequate quantity to explain the false-positive results when utilizing the optimized Monier-Williams method with allicin suppression for unsulfited dried garlic samples. Finally, when garlic samples are stabilized in a phosphoric acid buffer at a final pH around 2.4, no sulfite is produced during the Monier-Williams distillation, which is further proof there are no naturally occurring sulfites in unsulfited dried garlic under these mild conditions.     

Composition and major odorous compounds of the essential oil of Bifora radians,an aldehyde-producing weed

The composition of the essential oil of Bifora radians, an aldehyde-producing weed, has been investigated by capillary gas chromatography, coupled gas chromatography – mass spectrometry, on-line catalytic hydrogenation and coupled gas chromatography – infrared spectrometry. The nineteen compounds identified included eighteen aldehydes: seven alkanals (C6, C9, C10, C11, C12, C13, and C14), ten alkenals, including five (E)-2-alkenals (C12, C13, C14, C15, and C16), and one (E,E)-2,4-alkadienal (C13). Typical Bifora odors were attributed to three major (E)-2-alkenals, C12, C13, and C14.     

Synthesis of Gels in the System Na2O-ZrO2-SiO2

Gels have been synthesized in the SiO₂-Na₂O-ZrO₂ system and calcined at various temperatures up to 700°C. They have been studied by infrared absorption spectroscopy. The position of the asymmetric stretching frequency of the SiO₄ unit is used as a tracer of the homogeneity. It is shown that sodium increases the solubility of zirconium in the silica matrix as already observed in fused glasses.     

Templated Synthesis and Assembly of Two-, Three- and Six-Patch Silica Nanoparticles with a Controlled Patch-to-Particle Size Ratio

We report a fabrication route of silica nanoparticles with two, three or six patches with an easily tunable patch-to-particle size ratio. The synthetic pathway includes two main stages: the synthesis of silica/polystyrene multipod-like templates and the selective growth of their silica core through an iterative approach. Electron microscopy of the dimpled nanoparticles obtained after dissolution of the polystyrene nodules of the multipod-like nanoparticles provides evidence of the conformational growth of the silica core. Thanks to the presence of some polymer chains, which remained grafted at the bottom of the dimples after the dissolution of the PS nodules, the solvent-induced assembly of the patchy nanoparticles is performed. Chains, hexagonal suprastructures and cubic lattices are obtained from the assembly of two-, three- and six-patch silica nanoparticles, respectively. Our study can guide future work in both patchy nanoparticle synthesis and self-assembly. It also opens new routes towards the fabrication of specific classes of one-, two- and three-dimensional colloidal lattices, including complex tilings.     

Etude structurale des sulfotellurures de terres rares (LS)2Te1+x (L = Tb,Dy, Ho,Er, Tm et Y). I. Sous-structure de la phase ordonnée de (HoS)2Te1,34. Structure de la phase desordonnée de (TbS)2Te

The lanthanide sulfotellurides (LS)₂Te_1+x (0 ≤ x < 0.50) show order-disorder phenomena. Above 450°C, they crystallize in a partially disordered structure, orthorhombic with cell parameters a, b, and c close to 4.1, 5.2, and 13.6 Å, respectively. This structure is determined from diffractometer data on a (HoS)₂Te_1.34 crystal (R = 0.061). It is built up along the c axis from (L₄S) tetrahedra layers, separated by Te planes. Disorder and nonstoichiometry are related to the two vacant Te sites.     

Stereo- and Regiochemical Effect of N,N-Dialkylamide Extractants on the Speciation of Pu Complexes

The relationship between extractant stereochemistry and their extraction performance has only poorly been established. In order to address a part of this concern, we investigated the Pu(IV) liquid-liquid extraction (LLE) by using the N,N-di-(2-ethylhexyl)butyramide (DEHBA), as well as those of its position isomers. DEHBA (ββ-isomer) and N-(2-ethylhexyl)-N-(oct-3-yl)butyramide (EHOBA or αβ-isomer) were synthesized as a mixture of stereoisomer or stereoenriched (R,S)- and (S,S)-diastereoisomers, and were all assessed for Pu^IV LLE. The results showed that both the position and the stereoisomerism of the aliphatic substituents affect Pu^IV complexation and extraction. We found that Pu extraction is lowered by factor 2 to 4 when the ethyl branching group is closer to the complexing site. UV-vis spectroscopy showed that this extraction decrease was affected by steric hindrance inducing a deprivation of Pu inner sphere complex. Effect of stereoisomerism is highlighted for branching closer to the complexing site (α-position). Enantiopure DEHBA stereoisomers provided similar Pu extraction, whereas a slight decrease could be noticed for the more cluttered stereoenriched (αβ)-isomers, which was also concomitant with a smaller population of inner sphere complex. In contrast, the stereoisomers mixture led to a strong decrease of Pu extraction because of an antagonistic association in the mixed complexes.     

Inverse Polyamidoamine (i-PAMAM) Dendrimer Antimicrobials

Here we redesigned the branches of polyamidoamine (PAMAM) dendrimers by moving the amide carbonyl group on the other side of the amide nitrogen atom, transforming the β-alaninyl-amidoethylamine branch, which easily undergoes retro-Michael reactions and renders PAMAMs intrinsically unstable, into a more stable glycyl-amidopropylamine branch. The resulting inverse PAMAM (i-PAMAM) dendrimers have the same carbon framework as PAMAMs and only differ by the position of the carbonyl group. In contrast to PAMAMs which are prepared in solution and are difficult to purify, we synthesize i-PAMAMs using high-temperature solid-phase peptide synthesis by iterative coupling and deprotection of the commercially available N,N-bis(N′-Fmoc-3-aminopropyl)glycine and purify them preparative reverse phase HPLC. Our i-PAMAM dendrimers show no detectable degradation over time. We demonstrate this new class of dendrimers with the synthesis of antimicrobial dendrimers with potent yet non-membrane disruptive activities against both Gram-negative and Gram-positive bacteria.     

The small quantum cohomology of a weighted projective space, a mirror D-module and their classical limits

We first describe a mirror partner (B-model) of the small quantum orbifold cohomology of weighted projective spaces (A-model) in the framework of differential equations: we attach to the A-model (resp. B-model) a quantum differential system (that is a trivial bundle equipped with a suitable flat meromorphic connection and a flat bilinear form) and we give an explicit isomorphism between these two quantum differential systems. On the A-side (resp. on the B-side), the quantum differential system alluded to is naturally produced by the small quantum cohomology (resp. a solution of the Birkhoff problem for the Brieskorn lattice of a Landau–Ginzburg model). Then we study the degenerations of these quantum differential systems and we apply our results to the construction of (classical, limit, logarithmic) Frobenius manifolds.     

Entropy-stable and entropy-dissipative approximations of a fourth-order quantum diffusion equation

Structure-preserving numerical schemes for a nonlinear parabolic fourth-order equation, modeling the electron transport in quantum semiconductors, with periodic boundary conditions are analyzed. First, a two-step backward differentiation formula (BDF) semi-discretization in time is investigated. The scheme preserves the nonnegativity of the solution, is entropy stable and dissipates a modified entropy functional. The existence of a weak semi-discrete solution and, in a particular case, its temporal second-order convergence to the continuous solution is proved. The proofs employ an algebraic relation which implies the G-stability of the two-step BDF. Second, an implicit Euler and $q$ -step BDF discrete variational derivative method are considered. This scheme, which exploits the variational structure of the equation, dissipates the discrete Fisher information (or energy). Numerical experiments show that the discrete (relative) entropies and Fisher information decay even exponentially fast to zero.