Use of 1,10-phenanthroline in diiron dithiolate derivatives related to the [Fe-Fe] hydrogenase active site

Treatment of [Fe(2)(micro-pdt)(CO)(6)] (pdt = S(CH(2))(3)S) with 1,10-phenanthroline (phen) in refluxing toluene affords the asymmetric complex [Fe(2)(micro-pdt)(CO)(4)(phen)] (1); the protonation of with HBF(4).OEt(2) in CD(2)Cl(2) at 203 K has been monitored by (1)H NMR.     

Simulation of Electrical and Thermal Behavior of Poly(propylene) / Carbon Filler Conductive Polymer Composites

PP-carbon CPC show interesting thermo-electrical properties, smooth resistivity increase with temperature up to 150°C and consequently high power dissipation on a wide temperature range. The addition of short carbon fibers to PP already formulated with carbon black increases sharply the electrical conductivity of the CPC but does not have much influence on thermal conductivity as it could have been expected from the favorable aspect ratio of the fibers. The simulations of the thermo-electrical behavior of the CPC under tension put into evidence a temperature gradient at high heat flux due to the low thermal conductivity, which may damage the material itself.     

Diastereocontrolled addition of organometallic reagents to S-chiral N-(tert-butanesulfinyl)-α-fluoroenimines

Grignard and organolithium reagents efficiently react with (S)-N-(tert-butanesulfinyl)-α-fluoroenimines to provide chiral allylamines in excellent yields and with diastereomeric ratios of up to 96:4. Acidic removal of the sulfinyl group and simple functional group transformations allow to get enantiopure fluoroolefin dipeptide mimics.     

The marine sponge Plakortis zyggompha: a source of original bioactive polyketides

Three new spiculoic acids 1-3 and two members of a new closely related family of natural products named zyggomphic acids 4 and 5 were isolated from the very little studied marine sponge Plakortis zyggompha. Both families of compounds share a unique trans-hydrindan-2-one skeleton with six stereogenic centers. A total of 15 new metabolites were isolated from this sponge, all are of polyketide origin. The structures were elucidated using LC-MS, 1D, and 2D NMR methods. The absolute stereochemistry was determined by circular dichroism. The large number of close bioactive analogues allowed us to propose preliminary structure-activity relationships as antitumoral and antimycobaterial agents.     

Stability of Plasma Treated Non-vulcanized Polybutadiene Surfaces: Role of Plasma Parameters and Influence of Additives

Surface modification studies of non-vulcanized BR elastomers (butadiene rubber) by low-pressure air plasma treatment and the effect on ageing and adhesion performances are presented in this paper. In particular, the influence of discharge power and distance from the glow discharge, and impact of antioxidant molecules in the BR formulation were examined. To characterize the changes to the BR surface, XPS spectroscopy, contact angle measurements, AFM nanoindentation experiments and tack measurements were utilized. Oxidation and crosslinking were the main mechanisms observed on the polymer chains regardless of the plasma conditions used. Beyond a certain threshold of plasma energy (in our case, discharge power of ~60 W and exposure time of ~30 s), a steady state was reached irrespective of the distance from the glow discharge. The presence of antioxidant molecules considerably reduced crosslinking phenomena while maintaining oxidation processes on polymer chains and increasing the nitrogen content in the near surface region. The mechanisms responsible for these differences have been identified. Interestingly, the COOH/C=O ratio changed according to the balance between oxidation and crosslinking. The hydrophobic recovery rate was mainly driven by temperature-dependent dynamics and varied according to the degree of crosslinking in the surface region. It was found to be lower in air atmosphere in the presence of antioxidant molecules. Finally, the presence of antioxidant molecules in the BR formulation allowed the adhesion performances after plasma exposure to significantly increase.     

Orbitals and the Interpretation of Photoelectron Spectroscopy and (e,2e) Ionization Experiments

Electron momentum spectroscopy, scanning tunneling microscopy, and photoelectron spectroscopy provide unique information about electronic structure, but their interpretation has been controversial. This essay discusses a framework for interpretation. Although this interpretation is not new, we believe it is important to present this framework in light of recent publications. The key point is that these experiments provide information about how the electron distribution changes upon ionization, not how electrons behave in the pre‐ionized state. Therefore, these experiments do not lead to a “selection of the correct orbitals” in chemistry and do not overturn the well‐known conclusion that both delocalized molecular orbitals and localized molecular orbitals are useful for interpreting chemical structure and dynamics. The two types of orbitals can produce identical total molecular electron densities and therefore molecular properties. Different types of orbitals are useful for different purposes.     

Convenient and easy access to 2-hydroxycyclopent-2-enones from acylcyanohydrins

A convenient access to 2-hydroxycyclopentenones was designed from acylcyanohydrins, by using titanacyclopropane complexes as nucleophilic partners and an intramolecular aldol condensation in basic conditions. The development of a one-pot procedure allows a step- and atom-economic process, and the use of Grignard reagents other than ethylmagnesium bromide provided valuable 3,4-disubstituted 2-hydroxycyclopentenones. The utility of the hydroxy group was illustrated by further functionalization of the α-position using palladium-mediated cross-coupling reactions.     

Enantio- and diastereoselective synthesis of (E)-1,5-syn-diols: application to the synthesis of the C(23)-C(40) fragment of tetrafibricin

A highly stereoselective synthesis of (E)-1,5-syn-diols 6 is described. The kinetically controlled hydroboration of allenyltrifluoroborate 8 with Soderquist borane 2 provides the (Z)-allylic trifluoroborate 9, which undergoes sequential allylboration with two different aldehydes to provide (E)-1,5-syn-diols 6 in 72-98% yields with >95% ee and >20:1 dr. Application of this method to the synthesis of the tetrafibricin C(23)-C(40) fragment 19 is described.