Synthesis of the 4-azatricyclo[5.2.2.0(4,8)]undecan-10-one core of daphniphyllum alkaloid calyciphylline A using a Pd-catalyzed enolate alkenylation

[reaction: see text] The ABC ring system of the natural product calyciphylline A has been synthesized. The key steps were a palladium-catalyzed intramolecular coupling of an amino-tethered vinyl bromide with a ketone using potassium phenoxide as the base to generate the C-ring and a hydroxyl-directed hydrogenation of an exocyclic double bond to give the azatricyclic ketone 1.     

Structural Stability of Planar Polynomial Foliations

We discuss natural notions of structural stability of planar polynomial foliations of fixed degree with respect to perturbation within the same restricted set, within the set of all polynomial vector fields of the same degree, and within the set of smooth vector fields. Characterization theorems for structural stability in the latter two settings are obtained as immediate corollaries of known results. We provide sufficient conditions and separate necessary conditions for structural stability of planar polynomial foliations with respect to perturbation within the set of planar polynomial foliations of the same degree.     

Herman Rings and Arnold Disks

For (,a) C* x C, let f_,a be the rational map defined by f_,a(z)= z² (az+1)/(z+a). If R/Z is a Brjuno number, we let D bethe set of parameters (,a) such that f_,a has a fixed Hermanring with rotation number (we consider that (e²ⁱ,0) D). Resultsobtained by McMullen and Sullivan imply that, for any g D, theconnected component of D(C* x (C/{0,1})) that contains g isisomorphic to a punctured disk. We show that there is a holomorphic injection F:DD such thatF(0) = (e²ⁱ ,0) and , where r is the conformal radius at 0 of the Siegel disk of the quadraticpolynomial z e²ⁱ z(1+z). As a consequence, we show that for a (0,1/3), if f_l,a has afixed Herman ring with rotation number and if m_a is the modulusof the Herman ring, then, as a0, we have e m_a=(r/a) + O(a). We finally explain how to adapt the results to the complex standardfamily z e^(a/2)(z-1/z).     

Structural studies of peri-interactions and bond formation between electron-rich atomic centres and N-phenylcarboxamides or nitroalkenyl groups

Structural studies of peri-interactions with dimethylamino groups in naphthalene systems indicate that the N-phenylcarboxamide group has a through-space electron attracting power closer to that of a carboxylic ester than a N,N-dialkylcarboxamide, while 2-nitroalkenyl groups have a lower through-space electron attracting power. However, addition of a benzoyl group to the 2-position of the nitroethenyl group leads to cyclisation to give a zwitterion, in which the carbanion is stabilised by full conjugation with the nitro group and partial conjugation with the carbonyl group. An interesting case where a steric interaction overrides an electrophile/nucleophile attraction is also described. The limitations to the interpretation of short contact distances from crystallographic measurements are discussed.     

A novel nucleophilic approach to 1-alkyladenosines. A two-step synthesis of [1-15N]adenosine from inosine

A novel ANRORC mechanism in the reaction of 1-(2,4-dinitrobenzenesulfonyl)inosines with amines has allowed the preparation of 1-alkyladenosines and [1-15N]adenosines in a straightforward way from inosines.     

Differentiation-on-a-chip: a microfluidic platform for long-term cell culture studies

Here we demonstrate a microfluidic perfusion system suitable for a long-term (>2 week) culture of muscle cells spanning the whole process of differentiation from myoblasts to myotubes. Cell-adhesive surface microdomains alternating with a robust cell-repellent coating mimic in vivo spatial cues for muscle cell assembly and allow for confining the fusion of myoblasts into aligned, isolated multinucleated myotubes. The microfluidic system provides accurate control of the perfusion rates and biochemical composition of the environment surrounding the cells. Comparing muscle cell-specific differentiation markers and the timing of fusion, we observed no differences in differentiation between microfluidic and traditional cultures. All differentiation assays were fully microfluidic, i.e. they were performed by sequentially changing the fluids in the micro-channels. By delivering fluorescent markers using heterogeneous laminar flows, it was possible to confine a membrane receptor labeling assay to a region smaller than a myotube. Our method can serve as an improved in vitro model for studying muscle cell differentiation and for characterizing extracellular molecules and mechanisms involved in neuromuscular differentiation.     

Microscopic dielectric response functions in semiconductor quantum dots

We calculate and model the microscopic dielectric response function for quantum dots using first principle methods. We find that the response is bulklike inside the quantum dots, and the reduction of the macroscopic dielectric constants is a surface effect. We present a model for the microscopic dielectric function which reproduces well the directly calculated results and can be used to solve the Poisson equation in a nanosystem.     

Nonlinear evolution of q=1 triple tearing modes in a tokamak plasma

In magnetic configurations with two or three q=1 (with q being the safety factor) resonant surfaces in a tokamak plasma, resistive magnetohydrodynamic modes with poloidal mode numbers m much larger than 1 are found to be linearly unstable. It is found that these high-m double or triple tearing modes significantly enhance through nonlinear interactions the growth of the m=1 mode. This may account for the sudden onset of the internal resistive kink, i.e., the fast sawtooth trigger. Based on the subsequent reconnection dynamics that can proceed without formation of the m=1 islands, it is proposed that high-m triple tearing modes are a possible mechanism for precursor-free partial collapses during sawtooth oscillations.     

Continuous-wave laser operation of Yb:LuVO4

We report on the room-temperature spectroscopic properties and continuous-wave laser operation of a new Yb:LuVO4 crystal. The peak absorption cross section for the pi-polarization is 8.42 x 10(-20) cm2 at 985 nm, and the stimulated emission cross section at 1020 nm is 1.03 x 10(-20) cm2. An output power of 0.36 W at 1041 nm was obtained with a slope efficiency of 47% by use of Ti:sapphire laser pumping. With diode pumping the output power reached 1.05 W at the highest available incident pump power of 6.8 W.