Kinetics and scaling in ballistic annihilation

We study the simplest irreversible ballistically controlled reaction, whereby particles having an initial continuous velocity distribution annihilate upon colliding. In the framework of the Boltzmann equation, expressions for the exponents characterizing the density and typical velocity decay are explicitly worked out in arbitrary dimension. These predictions are in excellent agreement with the complementary results of extensive Monte Carlo and molecular dynamics simulations. We finally discuss the definition of universality classes indexed by a continuous parameter for this far from equilibrium dynamics with no conservation laws.     

Interaction of primary amphipathic cell-penetrating peptides with phospholipid-supported monolayers

The mesoscopic organization adopted by two primary amphipathic peptides, P(beta) and P(alpha), in Langmuir-Blodgett (LB) films made of either the pure peptide or peptide-phospholipid mixtures was examined by atomic force microscopy. P(beta), a potent cell-penetrating peptide (CPP), and P(alpha) mainly differ by their conformational states, predominantly a beta-sheet for P(beta) and an alpha-helix for P(alpha), as determined by Fourier transform infrared spectroscopy. LB films of pure peptide, transferred significantly below their collapse pressure, were characterized by the presence of supramolecular structures, globular aggregates for P(beta) and filaments for P(alpha), inserted into the monomolecular film. In mixed peptide-phospholipid films, similar structures could be observed, as a function of the phospholipid headgroup and acyl chain saturation. They often coexisted with a liquid-expanded phase composed of miscible peptide-lipid. These data strongly suggest that primary amphipathic CPP and antimicrobial peptides may share, to some extent, common mechanisms of interaction with membranes.     

Stereoselective synthesis of the ABC ring system of norzoanthamine

[reaction: see text] An efficient synthesis of enone 4, representing the ABC ring motif of norzoanthamine, is presented. The crucial C22 quaternary center was introduced via a stereoselective methylation of enone 8. The trans-anti-trans relative configuration of the ABC framework of 4 was installed via a sequence of reactions that included a hydroboration and a modified Robinson annulation.     

Synthesis of Co2Pt, Co2Pd and MoPd2 mixed-metal clusters with the P–N–P assembling ligands (Ph2P)2NH (dppa) and (Ph2P)2NMe (dppaMe). Crystal structure of [Co2Pt(μ3-CO)(CO)6(μ-dppa)]

Heterometallic triangular platinum–cobalt, palladium–cobalt and palladium–molybdenum clusters stabilized by one or two bridging diphosphine ligands such as Ph₂PNHPPh₂ (dppa) or (Ph₂P)₂NMe (dppaMe) or by mixed ligand sets Ph₂PCH₂PPh₂ (dppm)/dppa have been prepared with the objectives of comparing the stability and properties of the clusters as a function of the short-bite diphosphine ligand used and of the metal carbonyl fragment they contain. Ligand redistribution reactions were observed during the purification of [Co₂Pd(μ₃-CO)(CO)₄(μ-dppa)(μ-dppm)] (4) by column chromatography with the formation of [Co₂Pd(μ₃-CO)(CO)₄(μ-dppm)₂] and the dinuclear complex [(OC)₂ Cl] (5). The latter was independently prepared by reaction of [Pd(dppa-P,P′)₂](BF₄)₂ with Na[Co(CO)₄]. Attempts to directly incorporate the ligand (Ph₂P)₂N(CH₂)₃Si(OMe)₃ (dppaSi) into a cluster or to generate it by N-functionalization of coordinated dppa were unsuccessful, in contrast to results obtained recently with related clusters. The crystal structure of [Co₂Pt(μ₃-CO)(CO)₆(μ-dppa)] (1) has been determined by X-ray diffraction.