Synthesis of self‐healing supramolecular rubbers from fatty acid derivatives,diethylene triamine,and urea

We describe the synthesis of supramolecular self‐healing elastomers from vegetable oil fatty acid derivatives, diethylene triamine, and urea. Our strategy to obtain materials that are self‐healing but do not flow relies on the use of a wide molecular distribution of randomly branched oligomers equipped with self‐complementary and complementary hydrogen bonding groups. We prepared such oligomers with a two steps procedure. In the first step, diethylene triamine was condensed with dimer acids. In the second step, the oligomers obtained were allowed to react with urea. The molecules were characterized by NMR and IR spectroscopies and Monte‐Carlo simulations were used to analyze the molecular size distribution. The sensitivity to small variations of the experimental conditions has been examined and the robustness of the synthetic procedure optimized. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7925–7936, 2008     

Towards the total synthesis of Calyculin C: preparation of the C13-C25 spirocyclic core

A stereoselective synthesis of the C₁₃-C₂₅ of Calyculin C is described. Key steps involve the coupling of a terminal acetylene with a thiol ester and subsequent spirocyclisation using a double intramolecular hetero-Michael addition.     

High magnetic field properties of mixed terbium-yttrium ferrite garnets

Magnetization measurements in d.c. magnetic fields up to 180 kOe have been performed on polycrystalline specimens and on single crystals of mixed terbium-yttrium iron garnets: Tb _x Y_3–x Fe₅O₁₂ in the 4.2–300 K temperature range. On polycrystals (x=2.5; 2; 1; 0.37) the concentration dependence of both compensation point and spontaneous magnetization has been determined. In the single crystals (x=2; 1; 0.37) a strong magnetic anisotropy has been observed with a change of the easy direction of magnetization from [111] to [100] whenx decreases; abrupt field-induced transitions have been observed at low temperatures when the external field is applied along the [100] direction.     

Exclusion process and droplet shape

We use a mathematical isomorphism between the one-dimensional exclusion process and the two-dimensional stochastic Ising model in the low-temperature limit to describe the typical instantaneous shape of a supercritical droplet. We derive, specifically, the exact asymptotic distribution of the boundaries of a (+1) spin region, confined to Z ₊ ² and subjected to a positive magnetic field. In an appropriate scaling, the boundary distribution converges to a deterministic continuum limit.On leave at the EPFL, CH-1015 Lausanne, Switzerland.     

Structure determination of slowly exchanging conformers in solution using high‐resolution NMR,computational modeling and DFT‐GIAO chemical shielding: application to an erythronolide A derivative

We discuss and demonstrate the potential of HSQC‐TOCSY and HSQC‐NOESY experiments to offer solutions for overlap problems in COSY and NOESY spectra, leading to improved signals that can be unambiguously assigned to individual carbons. Direct comparison of experimental ¹H and ¹³C chemical shielding with density functional theory (DFT)‐calculated values are uninformative; in contrast, the relative differences in experimental shielding between pairs of molecules correlates well with the relative differences in DFT‐GIAO shielding for the computed lowest energy conformers. A detailed application of both experimental and theoretical techniques is illustrated for slowly exchanging conformers of an erythronolide A derivative, which demonstrates that structure determination can strongly benefit from the interplay between experiment and theory. Copyright © 2009 John Wiley & Sons, Ltd.     

Reactivity of methacrylates in insertion polymerization

Polymerization of ethylene by complexes [{(P^O)PdMe(L)}] (P^O = κ(2)-(P,O)-2-(2-MeOC(6)H(4))(2)PC(6)H(4)SO(3))) affords homopolyethylene free of any methyl methacrylate (MMA)-derived units, even in the presence of substantial concentrations of MMA. In stoichiometric studies, reactive {(P^O)Pd(Me)L} fragments generated by halide abstraction from [({(P^O)Pd(Me)Cl}μ-Na)(2)] insert MMA in a 1,2- as well as 2,1-mode. The 1,2-insertion product forms a stable five-membered chelate by coordination of the carbonyl group. Thermodynamic parameters for MMA insertion are ΔH(++) = 69.0(3.1) kJ mol(-1) and ΔS(++) = -103(10) J mol(-1) K(-1) (total average for 1,2- and 2,1-insertion), in comparison to ΔH(++) = 48.5(3.0) kJ mol(-1) and ΔS(++) = -138(7) J mol(-1) K(-1) for methyl acrylate (MA) insertion. These data agree with an observed at least 10(2)-fold preference for MA incorporation vs MMA incorporation (not detected) under polymerization conditions. Copolymerization of ethylene with a bifunctional acrylate-methacrylate monomer yields linear polyethylenes with intact methacrylate substituents. Post-polymerization modification of the latter was exemplified by free-radical thiol addition and by cross-metathesis.     

Memory of chirality in cascade rearrangements of enediynes

The cascade rearrangement of chiral enediynes 1c-e, involving successively 1,3-proton shift, Saito-Myers cyclization, 1,5-hydrogen atom transfer, and intramolecular coupling of the resulting biradical, proceeded at 80 °C to form tri- and tetracyclic heterocycles possessing a quaternary stereogenic center with a very high level of memory of chirality.     

Π‐Stacking Functionalization of Carbon Nanotubes through Micelle Swelling

We report on a new, original and efficient method for π‐stacking functionalization of single‐wall carbon nanotubes. This method is applied to the synthesis of a high‐yield light‐harvesting system combining single‐wall carbon nanotubes and porphyrin molecules. We developed a micelle‐swelling technique that leads to controlled and stable complexes presenting an efficient energy transfer. We demonstrate the key role of the organic solvent in the functionalization mechanism. By swelling the micelles, the solvent helps the non‐water‐soluble porphyrins to reach the micelle core and allows a strong enhancement of the interaction between porphyrins and nanotubes. This technique opens new avenues for the functionalization of carbon nanostructures.