Enhanced photochemical [6π] electrocyclization within the lipophilic protein binding site

Photocyclization of N-methyldiphenylamine to N-methylcarbazole is achieved within the microenvironment provided by site I of serum albumins. Quantum yield determinations, combined with transient absorption spectroscopic detection of the dihydrocarbazole intermediate, demonstrate that protein encapsulation provides a subtle control of the kinetic parameters, leading to optimized efficiencies.     

Suzuki coupling of potassium cyclopropyl- and alkoxymethyltrifluoroborates with benzyl chlorides

Efficient Csp(3)-Csp(3) Suzuki couplings have been developed with both potassium cyclopropyl- and alkoxymethyltrifluoroborates. Moderate to good yields have been achieved in the cross-coupling of potassium cyclopropyltrifluoroborate with benzyl chlorides possessing electron-donating or electron-withdrawing substituents. Benzyl chloride was also successfully cross-coupled to potassium alkoxymethyltrifluoroborates derived from primary, secondary, and tertiary alcohols.     

Asymptotics for the Low-Lying Eigenstates of the Schrödinger Operator with Magnetic Field near Corners

The Neumann realization for the Schr?dinger operator with magnetic field is considered in a bounded two-dimensional domain with corners. This operator is associated with a small semi-classical parameter h or, equivalently, with a large magnetic field.We investigate the behavior of its eigenpairs as h tends to zero, like in a semi-classical limit. We prove, in the situation where the domain is a polygon and the magnetic field is constant, that the lowest eigenvalues are exponentially close to those of model problems associated with the corners. We approximate the corresponding eigenvectors by linear combinations of functions concentrated in corners at the scale If the domain has curved sides and the magnetic field is smoothly varying, we exhibit a full asymptotics for eigenpairs in powers of Communicated by Christian Gérard Submitted: October 13, 2005 Accepted: December 19, 2005     

Stokes equations under nonlinear slip boundary conditions coupled with the heat equation: A priori error analysis

In this work, we consider the heat equation coupled with Stokes equations under threshold type boundary condition. The conditions for existence and uniqueness of the weak solution are made clear. Next we formulate the finite element problem, recall the conditions of its solvability, and study its convergence by making use of Babuska–Brezzi's conditions for mixed problems. Third we formulate an Uzawa's type iterative algorithm that separates the fluid from heat conduction, study its feasibility, and convergence. Finally the theoretical findings are validated by numerical simulations.     

Closed time-like curves in flat Lorentz space–times

We consider the region of closed time-like curves (CTCs) in three-dimensional flat Lorentz space–times. The interest in this global geometrical feature goes beyond the purely mathematical one. Such space–times are lower-dimensional toy models of sourceless Einstein gravity or cosmology. In three dimensions all such space–times are known: they are quotients of Minkowski space by a suitable group of Poincaré isometries. The presence of CTCs would indicate the possibility of “time machines”, a region of space–time where an object can travel along in time and revisit the same event. Such space–times also provide a testbed for the chronology protection conjecture, which suggests that quantum back reaction would eliminate CTCs. In particular, our interest in this note will be to find the set free of CTCs for , where is modeled on Minkowski space and γ is a Poincaré transformation. We describe the set free of CTCs where γ is hyperbolic, parabolic, and elliptic.     

Thermal-, pressure-, and light-induced spin transition in novel cyanide-bridged FeII-AgI bimetallic compounds with three-dimensional interpenetrating double structures (FeIILx[Ag(CN)2]2).G

Low-spin, high-spin and spin-transition behaviours have been observed for the doubly interpenetrating three-dimensional bimetallic compounds (FeII(pz)[Ag(CN)2]2).pz (pz = pyrazine), (FeII(4,4'-bipy)2[Ag(CN)2]2) (4,4'-bipy = 4,4'-bipyridine), and (FeII(bpe)2[Ag(CN)2]2) (bpe = bispyridylethylene), respectively. The single crystals of the bpe derivative undergo a spin transition with a large hysteresis loop at about 95 K. After several warming and cooling cycles, the single crystals become a microcrystalline powder with 50% spin transition. Influence of pressure--as well as light-induced excited spin-state trapping (LIESST) on the thermal 50% spin transition of the microcrystalline sample has also been investigated. Thermal spin-transition behaviour has also been induced at pressures higher than 1 bar for the 4,4'-bipy derivative. Both the 4,4'-bipy and bpe derivatives show strong pressure dependence of the spin state at 300 K.     

Theoretical study of 31P, 31P coupling constants in cyclotriphosphazenes

Several scalar coupling constants (mainly 31P, 31P) were calculated for 10 cyclotriphosphazenes and compared with experimental results when available. Although the experimental values cannot be reproduced, the calculated values are proportional to the experimental values. Some difficult cases, such as 19F, 19F couplings, are discussed.     

NMR Studies on Hydrolysis and Condensation Reactions of Alkoxysilanes Containing Si—H Bonds

Hydrolysis and condensation reactions of four organically modified alkoxides, used for the preparation of silicon oxycarbide gel precursors, have been followed by 29Si NMR. Triethoxysilane (HSi(OEt)3) and methyldiethoxysilane (MeHSi(OEt)2) react extremely fast compared to methyltriethoxysilane (MeSi(OEt)3) and tetraethoxysilane (Si(OEt)4). Co-hydrolysis reactions between different pairs of precursors—MeSi(OEt)3/Si(OEt)4; MeSi(OEt)3/HSi(OEt)3; MeHSi(OEt)2/Si(OEt)4; and MeHSi(OEt)2/HSi(OEt)3—were investigated by solution state 29Si and 17O NMR. Despite significantly different reactivities between precursors, evidence for co-condensation reactions has been found for each system. Finally, two-dimensional 29Si-1H heteronuclear correlation MAS-NMR spectroscopy was used to probe the local environments of the various Si sites in the product hybrid networks.     

Chemical Variability and In Vitro Anti-Inflammatory Activity of Leaf Essential Oil from Ivorian Isolona dewevrei (De Wild. & T. Durand) Engl. & Diels

The chemical variability and the in vitro anti-inflammatory activity of the leaf essential oil from Ivorian Isolona dewevrei were investigated for the first time. Forty-seven oil samples were analyzed using a combination of CC, GC(RI), GC-MS and ¹³C-NMR, thus leading to the identification of 113 constituents (90.8–98.9%). As the main components varied drastically from sample to sample, the 47 oil compositions were submitted to hierarchical cluster and principal components analyses. Three distinct groups, each divided into two subgroups, were evidenced. Subgroup I−A was dominated by (Z)-β-ocimene, β-eudesmol, germacrene D and (E)-β-ocimene, while (10βH)-1β,8β-oxido-cadina-4-ene, santalenone, trans-α-bergamotene and trans-β-bergamotene were the main compounds of Subgroup I−B. The prevalent constituents of Subgroup II−A were germacrene B, (E)-β-caryophyllene, (5αH,10βMe)-6,12-oxido-elema-1,3,6,11(12)-tetraene and γ-elemene. Subgroup II−B displayed germacrene B, germacrene D and (Z)-β-ocimene as the majority compounds. Germacrene D was the most abundant constituent of Group III, followed in Subgroup III−A by (E)-β-caryophyllene, (10βH)-1β,8β-oxido-cadina-4-ene, germacrene D-8-one, and then in Subgroup III−B by (Z)-β-ocimene and (E)-β-ocimene. The observed qualitative and quantitative chemical variability was probably due to combined factors, mostly phenology and season, then harvest site to a lesser extent. The lipoxygenase inhibition by a leaf oil sample was also evaluated. The oil IC₅₀ (0.020 ± 0.005 mg/mL) was slightly higher than the non-competitive lipoxygenase inhibitor NDGA IC₅₀ (0.013 ± 0.003 mg/mL), suggesting a significant in vitro anti-inflammatory potential.