Acyclic Stereocontrol in the Additions of Nucleophilic Alkenes to α-Chiral N-Sulfonyl Imines

Diastereoselective Lewis acid-mediated additions of nucleophilic alkenes to N-sulfonyl imines are reported. The canonical polar Felkin–Anh model describing additions to carbonyls does not adequately describe analogous additions to N-sulfonyl imines. Herein, we describe the development of conditions to produce both syn and anti products with high diastereoselectivity and good yields. A stereoelectronic model consistent with experimental outcomes is also proposed.     

Chemical Constituents of the Leaves of Polyscias fruticosa

Chemistry of Natural Compounds -     

Chemical Constituents of the Endophytic Fungus Bipolaris maydis Derived from the Kandelia candel

Chemistry of Natural Compounds -     

On the scaling limit of a singular integral operator

The scaling limit and Schauder bounds are derived for a singular integral operator arising from a difference equation approach to monodromy problems. Research supported in part by National Science Foundation grants DMS-02-45371 and DMS-04-05519.     

Deformation change in light iridium nuclei from laser spectroscopy

Laser spectroscopy measurements have been performed on neutron-deficient and stable Ir isotopes using the COMPLIS experimental setup installed at ISOLDE-CERN. The radioactive Ir atoms were obtained from successive decays of a mass-separated Hg beam deposited onto a carbon substrate after deceleration to 1kV and subsequently laser desorbed. A three-color, two-step resonant scheme was used to selectively ionize the desorbed Ir atoms. The hyperfine structure (HFS) and isotope shift (IS) of the first transition of the ionization path 5d ⁷6s ²⁴ F _9/2 → 5d ⁷6s6p ⁶ F _11/2 at 351.5nm were measured for ^182-189Ir, ¹⁸⁶Ir ^m and the stable ^{191, 193}Ir. The nuclear magnetic moments μ_I and the spectroscopic quadrupole moments Q_s were obtained from the HFS spectra and the change of the mean square charge radii from the IS measurements. The sign of μ_I was experimentally determined for the first time for the masses 182≤A≤189 and the isomeric state ¹⁸⁶Ir ^m . The spectroscopic quadrupole moments of ¹⁸²Ir and ¹⁸³Ir were measured also for the first time. A large mean square charge radius change between ¹⁸⁷Ir and ¹⁸⁶Ir ^g and between ¹⁸⁶Ir ^m and ¹⁸⁶Ir ^g was observed corresponding to a sudden increase in deformation: from β₂ ≃ + 0.16 for the heavier group A = 193, 191, 189, 187 and 186m to β₂≥ + 0.2 for the lighter group A = 186g, 185, 184, 183 and 182. These results were analyzed in the framework of a microscopic treatment of an axial rotor plus one or two quasiparticle(s). This sudden deformation change is associated with a change in the proton state that describes the odd-nuclei ground state or that participates in the coupling with the neutron in the odd-odd nuclei. This state is identified with the π3/2⁺[402] orbital for the heavier group and with the π1/2^-[541] orbital stemming from the 1h _9/2 spherical subshell for the lighter group. That last state seems to affect strongly the observed values of the nuclear moments.     

An example of a chaotic group action on Euclidean space by compactly supported homeomorphisms

We give an example of a group action on Euclidean space for which each map in the action is compactly supported, and such that the action is chaotic in the sense that it is topologically transitive and the set of points with finite orbit is dense. This resolves a conjecture of Naolekar and Sankaran.     

Graphs with Prescribed Mean Curvature on Poincare Disk

We establish the existence and uniqueness of a solution of aquasilinear elliptic equation in the unit disk of R². Usingthis result, we obtain the existence of graphs with prescribedcurvature on the Poincaré disk.     

pH-Dependent self-assembly of water-soluble sulfonate-tetraphenylethylene with aggregation-induced emission

The fabrication of well-defined nanostructures with luminescent properties in the solid or aggregated state is of intense interest due to their applications in nano- and biotechnology. We report the synthesis of water-soluble tetraphenylethylene bearing four sulfonate groups as a sodium salt (Su-TPE), and investigations concerning its AIE characteristics by the addition of organic solvent into the aqueous solution, which is the reverse procedure to conventional AIE-active TPE derivatives. The resultant compound is weakly emissive in pure water, however, emits strongly upon addition of THF solvent (with THF fraction > 60%). The emission properties and the morphologies of the aggregates were greatly dependent upon the solution pH. Su-TPE self-assembled into variety of structures in water/THF mixture with pH control, for the first time. Well-defined uniform nanorods with a width of about 200 nm and a length of up to 10 μm were obtained at solution pH of 1. The Su-TPE showed very good mechanochromic properties were observed during the process of grounding and fuming.