RMN 13C d'α alcoxy-indenes et d'α alcoxy-styrenes : Topologie electronique du systeme Π et une reflexion sur la relation entre deplacement chimique et reactivite dans les ethers d'enol

¹³C NMR chemical shifts of ethylenic carbon atom C_β of α alkoxy-indenes and α-alkoxy-styrenes are affected by the conformation of the OR group with respect to the double bond and hence the efficiency of p- Π conjugation but, contrary to previous results, δC_α is not affected. The phenyl group exerts a diamagnetic Π- effect on C_α and C_β which is a function of its dihedral angle with the double bond. Although δC_β is especially sensitive to the Π-electron density, the chemical shifts of the ethylenic carbons are best understood by considering the total charge density. The σ and Π contributions to the total charge density are discussed using the preferred conformation of the molecules. This approach strongly suggests that the correlation between the gradual shift of δC_α to low frequency and the gradual shift of δC_β to high frequency (relative to TMS) as R changes from RCH₃ to RtC₄H₉ in certain series of enol-ethers is not due to pΠ conjugation variations. This method of interpreting ¹³C NMR shifts, as opposed to previous methods, is compatible with explanations of other physico-chemical properties of alkyl vinyl ethers. Although it is sometimes possible to correlate the gradual shifts of δC_β with (σ + Π) electron density variations in a homogeneous series, it seems impossible to predict the relation. In all cases, there is no evident correlation between gradual shifts of δC_β(orδC_α) and the reactivity of enol ethers because one cannot consider the role of the out-of-plane conformation of the alkoxy group (which increases from RCH₃ to RtC₄H₉); however, the out of plane conformation does not have an identical effect on δC_β and the reactivity.     

Sylow-metacyclic groups andQ-admissibility

A finite groupG isQ-admissible if there exists a division algebra finite dimensional and central overQ which is a crossed product forG. AQ-admissible group is necessarily Sylow-metacyclic (all its Sylow subgroups are metacyclic). By means of an investigation into the structure of Sylow-metacyclic groups, the inverse problem (is every Sylow-metacyclic groupQ-admissible?) is essentially reduced to groups of order 2 ^a 3 ^b and to a list of known “almost simple” groups.     

Level-to-level vibrational energy transfer studies: energy dependence and observation of product species for azulenes(S0, Evib) + CO2

V—V energy transfer from a large molecule excited to vibrational energies of chemical interest has been demonstrated by detection of ≈ 1.5% yield of CO₂(001) due to energy transfer from azulene (E_vib ≈ 30600 cm^?1. Also, the average enery lost per collision by azulene was measured as a function of E_vib, and the rate constant for CO₂(001) deactivation by azulene was determined.     

Reversible Electrochemical Modulation of a Catalytic Nanosystem

A catalytic system based on monolayer‐functionalized gold nanoparticles (Au NPs) that can be electrochemically modulated and reversibly activated is reported. The catalytic activity relies on the presence of metal ions (Cd²⁺ and Cu²⁺), which can be complexed by the nanoparticle‐bound monolayer. This activates the system towards the catalytic cleavage of 2‐hydroxypropyl‐p‐nitrophenyl phosphate (HPNPP), which can be monitored by UV/Vis spectroscopy. It is shown that Cu²⁺ metal ions can be delivered to the system by applying an oxidative potential to an electrode on which Cu⁰ was deposited. By exploiting the different affinity of Cd²⁺ and Cu²⁺ ions for the monolayer, it was also possible to upregulate the catalytic activity after releasing Cu²⁺ from an electrode into a solution containing Cd²⁺. Finally, it is shown that the activity of this supramolecular nanosystem can be reversibly switched on or off by oxidizing/reducing Cu/Cu²⁺ ions under controlled conditions.     

MoS2/WS2‐Graphene Composites through Thermal Decomposition of Tetrathiomolybdate/Tetrathiotungstate for Proton/Oxygen Electroreduction

MoS₂ and WS₂ have been prepared on a conductive graphene support by thermal reduction of tetrathiotungstate/tetrathiomolybdate and graphite oxide. Whereas the catalytic properties towards hydrogen evolution are strongly influenced by the Magnéli phases formed as a byproduct during the synthesis, the catalytic activity towards oxygen reduction of these composite materials is not affected by this phenomenon and these materials exhibit high catalytic activity towards this industrially important reaction.     

A new FeII quaterpyridyl M4L6 tetrahedron exhibiting selective anion binding

A rigid linear bis-bidentate quaterpyridine undergoes metal directed self-assembly with iron(ii) salts yielding M(4)L(6) host-guest complexes; selective anion binding for PF(6)(-) over BF(4)(-) is observed.     

Experimental determination of the gas phase proton affinities of the conjugate base anions of 2-iodoxybenzoic acid (IBX) and 2-iodosobenzoic acid (IBA)

The gas phase anion proton affinities of the periodinane anions IBX- and IBA- were examined using mass spectrometry-based experiments, and estimated as 1300 +/- 25 and 1390 +/- 10 kJ mol(-1), respectively. The experimental results were supported by theoretical calculations, which yielded proton affinities of 1336 and 1392 kJ mol(-1) for IBX- and IBA- respectively, at the B3LYP/aug-cc-PVDZ level of theory.     

Parametrization, molecular dynamics simulation, and calculation of electron spin resonance spectra of a nitroxide spin label on a polyalanine alpha-helix

The nitroxide spin label 1-oxyl-2,2,5,5-tetramethylpyrroline-3-methyl-methanethiosulfonate (MTSSL), commonly used in site-directed spin labeling of proteins, is studied with molecular dynamics (MD) simulations. After developing force field parameters for the nitroxide moiety and the spin label linker, we simulate MTSSL attached to a polyalanine alpha-helix in explicit solvent to elucidate the factors affecting its conformational dynamics. Electron spin resonance spectra at 9 and 250 GHz are simulated in the time domain using the MD trajectories and including global rotational diffusion appropriate for the tumbling of T4 Lysozyme in solution. Analysis of the MD simulations reveals the presence of significant hydrophobic interactions of the spin label with the alanine side chains.     

Chromatic capacity and graph operations

The chromatic capacityχ_cap(G) of a graph G is the largest k for which there exists a k-coloring of the edges of G such that, for every coloring of the vertices of G with the same colors, some edge is colored the same as both its vertices. We prove that there is an unbounded function f:N→N such that χ_cap(G)?f(χ(G)) for almost every graph G, where χ denotes the chromatic number. We show that for any positive integers n and k with k?n/2 there exists a graph G with χ(G)=n and χ_cap(G)=n-k, extending a result of Greene. We obtain bounds on that are tight as r→∞, where is the complete n-partite graph with r vertices in each part. Finally, for any positive integers p and q we construct a graph G with χ_cap(G)+1=χ(G)=p that contains no odd cycles of length less than q.