Unprecedented substoichiometric use of hazardous aryl diazonium salts in the Heck-Matsuda reaction via a double catalytic cycle

The first Heck-Matsuda reaction using a catalytic amount of diazonium salts has been discovered. The reaction proceeds through an unprecedented double catalytic cycle in which the electrophile is in situ generated through the reaction advancement. This concept features mild and safe conditions as hazardous aryl diazonium salts are not isolated anymore. Importantly, this sustainable procedure generates only environmentally friendly byproduct such as t-BuOH, H(2)O, and N(2).     

Use of Doubly Charged Precursors to Validate Dissociation Mechanisms of Singly Charged Poly(Dimethylsiloxane) Oligomers

Collision-induced dissociation of doubly charged poly(dimethylsiloxane) (PDMS) molecules was investigated to provide experimental evidence for fragmentation reactions proposed to occur upon activation of singly charged oligomers. This study focuses on two PDMS species holding trimethylsilyl or methoxy end-groups and cationized with ammonium. In both cases, introduction of the additional charge did not induce significant differences in dissociation behavior, and the use of doubly charged precursors enabled the occurrence of charge-separation reactions, allowing molecules always eliminated as neutrals upon activation of singly charged oligomers to be detected as cationized species. In the case of trimethylsilyl-terminated oligomers, random location of the adducted charge combined with rapid consecutive reactions proposed to occur from singly charged precursors could be validated based on MS/MS data of doubly charged oligomers. In the case of methoxy-terminated PDMS, favored interaction of the adducted ammonium with both end-groups, proposed to rationalize the dissociation behavior of singly charged molecules, was also supported by MS/MS data obtained for molecules adducted with two ammonium cations.

Isolation,characterization, and determination of a new compound in red wine

Chromatographic separation using fluorescence as a detection mode revealed, besides a series of flavan-3-ols, the recurrent presence of an undefined compound in Bordeaux red wine. Its isolation and structure characterization by complementary means (high-resolution mass spectrometry, nuclear magnetic resonance, and chemical synthesis) has permitted us to identify it as the nitrogen-containing glycoconjugate 3-indolyl-(2R)-O-β-d-glucosyl-lactic acid. Its quantification was performed for different wines of different vine varieties and terroirs with the aim to assess whether this compound may be used as a terroir, variety, or wine process tag.     

A 3D structural and conformational study of procyanidin dimers in water and hydro-alcoholic media as viewed by NMR and molecular modeling

The three-dimensional structures of 5 procyanidin dimers have been determined in a hydro-alcoholic medium and in water using 2D NMR and molecular mechanics. They are made from monomers of catechin (CAT) and epicatechin (EPI)-B1: EPI-CAT, B2: EPI-EPI, B3: CAT-CAT, B4: CAT-EPI and B2g: EPI-EPI-3-O-gallate. These tannins exist in two conformations that are in slow exchange in the NMR timescale (s), one is compact and the other extended. The compact form is found to dominate (76-98%) when the dimer is made of at least one CAT monomer (B1, B3, B4). Both forms are found in even proportions only in the case of procyanidin B2. The latter tannin can be converted into a dominant compact form when the lower EPI unit is galloylated. The finding of a predominant compact form for procyanidin dimers is discussed in relation with tannin-saliva protein interactions that are of importance for the wine-tasting/making processes.     

Methyl transfer reaction from monomethyltin reagent under palladium(0) catalysis: a versatile method for labelling with carbon-11

The 11C-monomethylstannate prepared from [11C]-methyl iodide and Lappert's stannylene, was subject to a palladium-mediated cross-coupling reaction with an aryl halide under ligand-free conditions, to afford easily purified 11C-methyl(hetero)arenes in high radiochemical yields.     

On Compatible Normal Odd Partitions in Cubic Graphs

A normal odd partition of the edges of a cubic graph is a partition into trails of odd length (no repeated edge) such that each vertex is the end vertex of exactly one trail of the partition and internal in some trail. For each vertex v, we can distinguish the edge for which this vertex is pending. Three normal odd partitions are compatible whenever these distinguished edges are distinct for each vertex. We examine this notion and show that a cubic 3‐edge‐colorable graph can always be provided with three compatible normal odd partitions. The Petersen graph has this property and we can construct other cubic graphs with chromatic index four with the same property. Finally, we propose a new conjecture which, if true, would imply the well‐known Fan and Raspaud Conjecture.     

Hidden magnetic frustration by quantum relaxation in anisotropic Nd langasite

The static and dynamic magnetic properties of the Nd(3)Ga(5)SiO(14) compound, which appears as the first materialization of a rare-earth kagome-type lattice, were reexamined, owing to contradictory results in the previous studies. Neutron scattering, magnetization, and specific heat measurements were performed and analyzed, in particular, by fully taking account of the crystal electric field effects on the Nd(3+) ions. One of the novel findings is that the peculiar temperature independent spin dynamics observed below 10 K expresses single-ion quantum processes. This would short-circuit the frustration induced cooperative dynamics, which would emerge only at very low temperature.     

Increase of the backward Raman reflectivity caused by the langmuir decay instability in an inhomogeneous plasma: the loss of gradient stabilization

We investigate the nonlinear evolution of the backward stimulated Raman scattering (BSRS) in the regime where the nonlinear saturation mechanism is the Langmuir decay instability resulting from the coupling of the BSRS-generated Langmuir wave with the ion acoustic waves. We present numerical results obtained with a fluid-type code in one- and two-dimensional spatial dimensions, in the case of an inhomogeneous plasma. The plasma density is under quarter-critical and depends linearly on the longitudinal spatial coordinate, in the regime where the Rosenbluth gain factor for the amplitude, denoted as G(Ros), is in the range pi/2< or =G_(Ros)< or =6. We observe that the Langmuir decay instability is able to suppress the gradient stabilization and restore the absolute nature of BSRS, thus leading to a significantly increased BSRS reflectivity.