ESR study on the reactivity of two isomers of LaC82 with disilirane

We observed photochemical and thermal addition of disilirane to the LaC₈₂-A isomer, which give new ESR active species. Both ESR spectra of the adducts in photo- and thermal reactions are well simulated by at least six octet components, and the isotropic La coupling constants and g-factors of the six octet components are determined. On the other hand, the reaction of the LaC₈₂-B isomer with disilirane gives no ESR active species. This fact is also verified by mass spectroscopic measurements. The different reactivities with disilirane of the two isomers are not interpreted by a popular view that the two isomers have a different C₈₂ cage structure, but we rather suggest that the origin of the isomers of metallofullerenes should be re-examined.     

Angle-resolved photoemission study of CoSi2 nanofilms grown on Si(111) substrates

We have carried out an angle-resolved photoemission study for CoSi₂ nanofilms grown on the Si(111)-7×7 substrates. The surface of CoSi₂(111) nanofilm changes from the bulk-truncated surface to the surface with additional Si-bilayer by annealing at higher temperature above 825 K. The angle-resolved photoemission spectra of the CoSi₂ nanofilm annealed at 853 K show the spectral features originated from the surface resonance state on the CoSi₂ surface terminated by Si-bilayer. From the detailed photoemission study, we discuss the surface electronic structure in CoSi₂(111) nanofilms grown on Si(111) substrates.     

Whittaker Vector of Deformed Virasoro Algebra and Macdonald Symmetric Functions

We give a proof of Awata and Yamada’s conjecture for the explicit formula of Whittaker vector of the deformed Virasoro algebra realized in the Fock space. The formula is expressed as a summation over Macdonald symmetric functions with factored coefficients. In the proof, we fully use currents appearing in the Fock representation of Ding–Iohara–Miki quantum algebra.     

Synthesis of perfluorobicyclic ethers

The electrochemical fluorination of cycloalkyl-substituted acetic and propionic acids were conducted to obtain several kinds of perfluorobicyclic ethers [reaction conditions: Anodic current density: 3.5 A/dm², Volt: 5～8V, Temp: 5～6 °C] . For example, from cyclopentyl-substituted acetic acids, perfluoro(4-alkyl-2-oxabicyclo[3.3.0]octane)s (I) were formed as the cyclization products in yields of 10～19% together with the corresponding perflouroalkanoyl flourides (II) (Y=3～13%).

While, perfluorospiro-ethers were obtained from the fluorination of 3-cycloalkyl-substituted propionic acids. The characterization of these perfluorobicyclic ethers which consists of the reaction with anhydrous aluminum chloride will be reported also.     

Asymmetric synthesis of permethric acid. stereochemistry of chiral copper carbenoid reaction

The most effective optical isomer (1$\text{R}$-$\text{cis}$) of permethric acid ($\text{2}$, R = H), a potent intermediate in the production of synthetic pyrethroid, was enantioselectively prepared.     

Quantum Chemical Insight of the Dimetallic Sulfide Endohedral Fullerene Sc2S@C70: Does It Possess the Conventional D5h Cage?

Like C₆₀, C₇₀ is one of the most representative fullerenes in fullerene science. Even though there are 8149 C₇₀ isomers, only two of them have been found before: the conventional D_5h and an isolated pentagon rule (IPR)‐violating C_2v(7854). Through the use of quantum chemical methods, we report a new unconventional C₇₀ isomer, C₂(7892), which survives in the form of dimetallic sulfide endohedral fullerene Sc₂S@C₇₀. Compared with the IPR‐obeying C₇₀ and the C_2v(7854) fullerene with three pairs of pentagon adjacencies, the C₂(7892) cage violates the isolated pentagon rule and has two pairs of pentagon adjacencies. In Sc₂S@C₂(7892)‐C₇₀, two scandium atoms coordinate with two pentalene motifs, respectively, presenting two equivalent Sc? S bonds. The strong coordination interaction, along with the electron transfer from the Sc₂S cluster to the fullerene cage, results in the stabilization of the non‐IPR endohedral fullerene. The electronic structure of Sc₂S@C₇₀ can be formally described as [Sc₂S]⁴⁺@[C₇₀]^4?; however, a substantial overlap between the metallic orbitals and cage orbitals has also been found. Electrochemical properties and electronic absorption, infrared, and ¹³C NMR spectra of Sc₂S@C₇₀ have been calculated theoretically.     

Synthesis and properties of PI polyamide-SAHA conjugate

We have designed and synthesized new types of pyrrole (P)-imidazole (I) polyamide conjugates 1 and 2 possessing a suberoylanilide hydroxamic acid (SAHA) moiety that is a strong inhibitor of histone deacetylase (HDAC). SAHA conjugate 2 was designed to target the promoter region of the p16 tumor suppressor gene. The DNA binding affinity of SAHA conjugate 2 to its target sequence was examined using surface plasmon resonance. HDAC inhibition activity of conjugates 1 and 2 was evaluated using a colorimetric assay. The results demonstrated that even though it possesses the relatively large SAHA moiety, conjugate 2 has high DNA sequence-specific binding properties and moderate HDAC inhibitory activity in vitro. SAHA conjugate 2 was found to cause morphological changes in HeLa cells and to induce selective Histone H3 lysine 9 acetylation.