60]fullerenoacetyl chloride as a versatile precursor for fullerene derivatives: efficient ester formation with various alcohols

[reaction: see text] [60]Fullerenoacetyl chloride, one of the reactive derivatives of [60]fullerenoacetic acid, was isolated and identified for the first time. This acid chloride was easily synthesized in good yield from tert-butyl [60]fullerenoacetate through two steps. In the presence of 4-(dimethylamino)pyridine as a base, the acid chloride smoothly reacted with various alcohols under mild conditions to give the corresponding esters including [60]fullerene-biomolecule hybrids in moderate to high yields.     

Peumusolide A, unprecedented NES non-antagonistic inhibitor for nuclear export of MEK

A new polyketide peumusolide A was disclosed as an unprecedented NES non-antagonistic inhibitor for nuclear export of MEK, a promising scaffold for antitumor agents with novel mechanism of action, from Peumus boldus Molina. The absolute stereostructure as well as optical purity was established by use of the two synthesized enantiomeric model lactones. In addition, the Δε values in their CD spectra were demonstrated to be the conclusive index for determination of not only configuration at C-3 but also optical purity of natural congeneric polyketides. Peumusolide A was revealed to show NES non-antagonistic action by the biotinylated probe and to inhibit proliferation of MEK-activated tumor cells selectively.     

Study on response of CR-39 detector to light ions

The response of CR-39 detector has been obtained precisely for protons, deuterons, tritons, alpha-particles and lithiumions with energies of a few MeV/nucleon. The track etch rates were determined from the growth curves of pit radius and summarized as the response functions. The accuracy of this method is high enough to discriminate among hydrogen isotopes under a certain condition. The correlation between the response and LET with various cut-off energies has also been examined. It was found that LET is not an unique parameter describing the response function adequately for different ions by the same expression.     

Analytic non-integrable Hamiltonian systems and irregular singularity

We study a C ^∞-Liouville-integrable and analytic non-integrable Hamiltonian system. We will show that an irregular singular character plays a crucial role in the analytic non-integrability of the system. Partially supported by Grant-in-Aid for Scientific Research (No. 11640183), Ministry of Education, Science and Culture, Japan.     

Unitarity in Dirichlet Higgs model

We show that a five-dimensional Universal Extra Dimension model, compactified on a line segment, is consistently formulated even when the gauge symmetry is broken solely by non-zero Dirichlet boundary conditions on a bulk Higgs field, without any quartic interaction. We find that the longitudinal W ⁺ W ⁻ elastic scattering amplitude, under the absence of the Higgs zero mode, is unitarized by exchange of infinite towers of KK Higgs bosons. Resultant amplitude scales linearly with the scattering energy μ ?s\propto\sqrt{s}, exhibiting five-dimensional nature. A tree-level partial-wave unitarity condition is satisfied up to 6.7 (5.7) TeV for the KK scale m _KK=430 (500) GeV, favored by the electroweak data within 90% CL.     

A concise route to the C2-symmetric tricyclic skeleton of ryanodine

Ryanodine is a potent calcium channel modulator. In this Letter, we report the 10-step synthesis of the highly substituted tricyclic ring system of ryanodine. Diels-Alder reaction via dearomatization of 2,5-dimethylbenzene-1,4-diol and subsequent SmI₂-mediated reductive coupling of eight-membered 1,5-diketone efficiently introduced the four consecutive fully substituted carbons of the tricyclo[3.3.2.0^2,6]decane system.     

A function space model approach to the rational evaluation subgroups

Let f : U → X be a map from a connected nilpotent space U to a connected rational space X. The evaluation subgroup G _*(U, X; f), which is a generalization of the Gottlieb group of X, is investigated. The key device for the study is an explicit Sullivan model for the connected component containing f of the function space of maps from U to X, which is derived from the general theory of such a model due to Brown and Szczarba (Trans Am Math Soc 349, 4931–4951, 1997). In particular, we show that non Gottlieb elements are detected by analyzing a Sullivan model for the map f and by looking at non-triviality of higher order Whitehead products in the homotopy group of X. The Gottlieb triviality of a fibration in the sense of Lupton and Smith (The evaluation subgroup of a fibre inclusion, 2006) is also discussed from the function space model point of view. Moreover, we proceed to consideration of the evaluation subgroup of the fundamental group of a nilpotent space. In consequence, the first Gottlieb group of the total space of each S ¹-bundle over the n-dimensional torus is determined explicitly in the non-rational case.      

Organic high-spin systems: Synthesis,electrochemical and spectroscopic studies of π-extended tetraaryl m-phenylenediamines

Three highly π-extended tetraaryl-1,3-phenylenediamines for charged high-spin molecular systems were successfully synthesized using Suzuki coupling. Their electrochemical and spectroscopic properties were also examined. They showed blue fluorescence. The dications derived from highly π-extended tetraaryl-1,3-phenylenediamines were generated and characterized by electron transfer stopped-flow method.