Three new types of indoloditerpenes, emindole PA-PC, from Emericella purpurea. Revision of the structure of emindole PA

Three new type indoloditerpenes, emindoles PA (1), PB (2), and PC (3), were isolated from the mycelium of Emericella purpurea along with the sesterterpenes variecolol and variecolactone, and the dicyanide derivatives epurpurins A to C. The structures of 1-3 were confirmed by the spectroscopic investigation. The structure of emindoles PA (1) was revised from our preliminary report. Emindoles PA (1), PB (2), and PC (3) are the indoloditerpenes having a new type of carbon skeleton.     

Efficient C-N bond formations catalyzed by a proton-exchanged montmorillonite as a heterogeneous Brønsted acid

Nucleophilic addition of sulfonamides and carboxamides to simple alkenes proceeded smoothly using a proton-exchanged montmorillonite catalyst. The spent catalyst was recovered easily from the reaction mixture and was reusable at least five times without any loss of activity. The unique acidity of the proton-exchanged montmorillonite (H-mont) catalyst was found to be applicable to additional reactions: substitution of hydroxyl groups of alcohols with amides and anilines.     

Simulation of sound field in a tissue medium generated by a concave spherically annular transducer

The concave spherically annular transducer is regarded as a negative and a positive concave spherical transducer, and the spheroidal beam equation is used to simulate the linear and nonlinear sound field in a tissue medium generated by this transducer. It is found that the acoustic focus of the ring does not coincide with the acoustic focus of its central part. If the width of the ring increases, its acoustic focus will move toward the geometric focus and the amplitudes of nonlinear harmonics will increase obviously. If there are several coaxial rings placed on the concave spherical surface, more than one peak will appear along the axial direction for the fundamental, and high harmonics focus better. The distribution of sound field will change with the number and the excited signals of rings, so it maybe is a potential approach to treat locally big tumors.     

A novel montmorillonite-enwrapped scandium as a heterogeneous catalyst for Michael reaction

Treatment of a Na+-exchanged montmorillonite with an aqueous Sc(OTf)3 solution afforded a robust Sc3+ aqua complex enwrapped by the silicate layers of the montmorillonites (Sc3+-mont). The resulting Sc3+-mont showed outstanding catalytic activities for the Michael reaction of 1,3-dicarbonyls under aqueous and solvent-free conditions. Moreover, this heterogeneous catalyst had an advantage of a strikingly simple workup procedure over the Lewis acids reported to date and was reusable without any appreciable losses in its activity and selectivity.     

Structural and thermodynamic behavior of eukaryotic initiation factor 4E in supramolecular formation with 4E-binding protein 1 and mRNA cap analogue, studied by spectroscopic methods

The structural and thermodynamic behavior of the complex formation of eIF4E with either or both mRNA cap analogue (m7GTP, m7GpppA, or m7GpppG) and 4EBP1 has been investigated by spectroscopic measurements. Although the circular dichroism (CD) spectrum of eIF4E was little affected by the association with any cap analogue, the association constant of eIF4E with m7GpppA/G, estimated from the fluorescence quenching, was about 10 times larger than that with m7GTP. The van't Hoff analyses showed that the m7GpppA/G binding is enthalpy-driven with a large negative deltaH(o), and this is in contrast with the entropy-driven binding of m7GTP, where the positive deltaS(o) is large enough to overcome an increase of deltaH(o). This different behavior obviously originates in the interaction of the second nucleotide in m7GpppA with eIF4E, suggesting the importance of the nucleotide sequence linked to the m7Gppp terminal moiety, in addition to the specific interaction with the m7G base, for the recognition of mRNA cap structure by eIF4E. On the other hand, the CD spectra indicated that the binding of 4EBP1, an endogenous eIF4E-regulatory protein without having any defined secondary structure, shifted the m7GTP- or m7GpppA/G-bound eIF4E to an irregular structure, although such a structural change was not observed for eIF4E alone. The association constant of 4EBP1 with m7GTP- or m7GpppA/G-bound eIF4E was by two orders of magnitude larger than that with eIF4E alone. These results suggest the close interrelation in the supramolecular formation of 4EBP-eIF4E-mRNA cap structure.     

Design of hydroxyapatite-bound transition metal catalysts for environmentally-benign organic syntheses

Novel heterogeneous catalysts, which were designed with atomic precision, easy to prepare, and recyclable, have been developed using a unique inorganic support hydroxyapatite, Ca₁₀(PO₄)₆(OH)₂. The introduction of a Ru cation into the apatite framework can generate a stable monomeric phosphate complex, which exhibits prominent catalytic performances for various oxidation reactions using molecular oxygen as a primary oxidant. Treatment of the RuHAP with an aqueous solution of AgX affords cationic Ru phosphate complexes as Lewis acid catalysts, promoting Diels–Alder and aldol reactions under mild and neutral conditions. Furthermore, two classes of heterogeneous Pd catalysts were synthesized with both stoichiometric and Ca-deficient hydroxyapatites, which show specific functions for aerobic oxidation of alcohols and carbon–carbon bond-forming reactions with extremely high turnover numbers. The catalytic systems described here are simple, efficient, and general for practical organic syntheses; thus meeting the increasing demands for environmentally-benign chemical processes.