An Unusual Skeletal Rearrangement in the Biosynthesis of the Sesquiterpene Trichobrasilenol from Trichoderma

The skeletons of some classes of terpenoids are unusual in that they contain a larger number of Me groups (or their biosynthetic equivalents such as olefinic methylene groups, hydroxymethyl groups, aldehydes, or carboxylic acids and their derivatives) than provided by their oligoprenyl diphosphate precursor. This is sometimes the result of an oxidative ring‐opening reaction at a terpene‐cyclase‐derived molecule containing the regular number of Me group equivalents, as observed for picrotoxan sesquiterpenes. In this study a sesquiterpene cyclase from Trichoderma spp. is described that can convert farnesyl diphosphate (FPP) directly via a remarkable skeletal rearrangement into trichobrasilenol, a new brasilane sesquiterpene with one additional Me group equivalent compared to FPP. A mechanistic hypothesis for the formation of the brasilane skeleton is supported by extensive isotopic labelling studies.     

CO2 Conversion with Alcohols and Amines into Carbonates,Ureas, and Carbamates over CeO2 Catalyst in the Presence and Absence of 2‐Cyanopyridine

Recent progress on the CeO₂ catalyzed synthesis of organic carbonates, ureas, and carbamates from CO₂+alcohols, CO₂+amines, and CO₂+alcohols+amines, respectively, is reviewed. The reactions of CO₂ with alcohols and amines are reversible ones and the degree of the equilibrium limitation of the synthesis reactions is strongly dependent on the properties of alcohols and amines as the substrates. When the equilibrium limitation of the reaction is serious, the equilibrium conversion of the substrate and the yield of the target product is very low, therefore, the shift of the equilibrium reaction to the product side by the removal of H₂O is essential in order to get the target product in high yield. One of the effective method of the H₂O removal from the related reaction systems is the combination with the hydration of 2‐cyanopyridine to 2‐picolinamide, which is also catalyzed by CeO₂.     

Coherent transfer of light polarization to electron spins in a semiconductor

We demonstrate that the superposition of light polarization states is coherently transferred to electron spins in a semiconductor quantum well. By using time-resolved Kerr rotation, we observe the initial phase of Larmor precession of electron spins whose coherence is transferred from light. To break the electron-hole spin entanglement, we utilized the big discrepancy between the transverse g factors of electrons and light-holes. The result encourages us to make a quantum media converter between flying photon qubits and stationary electron-spin qubits in semiconductors.     

Thermodynamic evidence for nanoscale bose-einstein condensation in (4)He confined in nanoporous media

We report the measurements of the heat capacity of (4)He confined in nanoporous Gelsil glass that has nanopores of 2.5-nm diameter at pressures up to 5.3 MPa. The heat capacity has a broad peak at a temperature much higher than the superfluid transition temperature obtained using the torsional oscillator technique. The peak provides definite thermodynamic evidence for the formation of localized Bose-Einstein condensates on nanometer length scales. The temperature dependence of the heat capacity is described well by the excitations of phonons and rotons, supporting the existence of localized Bose-Einstein condensates.     

Recyclable carbon fiber‐reinforced plastics (CFRP) containing degradable acetal linkages: Synthesis,properties, and chemical recycling

Two epoxy resins containing degradable acetal linkages were synthesized by the reaction of cresol novolak‐type phenolic resin (CN) with vinyl ethers containing a glycidyl group [cyclohexane dimethanol vinyl glycidyl ether (CHDMVG) and 4‐vinyloxybutyl glycidyl ether (VBGE). Carbon fiber‐reinforced plastics (CFRPs) were prepared by heating laminated prepreg sheets with CN‐CHDMVG resin (derived from CN and CHDMVG) and CN‐VBGE resin (derived from CN and VBGE), in which carbon fibers are impregnated with epoxy resins containing curing agents [dicyandiamide (DICY)] and curing accelerator [3‐(3,4‐dichlorophenyl)‐1,1‐dimethylurea (DCMU)]. CN‐CHDMVG‐based CFRPs and CN‐VBGE‐based CFRPs exhibited almost the same tensile strength as the conventional bisphenol‐A‐based CFRPs. CN‐CHDMVG‐based CFRPs and CN‐VBGE‐based CFRPs underwent smooth breakdown with the treatment of hydrochloric acid in tetrahydrofuran at room temperature for 24 h to regenerate strands of carbon fibers. The surface conditions of the recovered carbon fibers had little changes during degradation and recovery processes on the basis of scanning electron microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS). The recovered carbon fibers exhibited almost the same tensile strength as virgin carbon fibers and hence would be reused for the production of CFRPs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1052–1059     

On the Fourier coefficients of Siegel–Eisenstein series of degree 2 for odd level

The Ramanujan Journal - We calculate the Fourier coefficients of the Siegel–Eisenstein series of degree 2, level $$p^n$$ with trivial character. The main result is to compute the Siegel...     

Synthesis of C12-Keto Saxitoxin Derivatives with Unusual Inhibitory Activity Against Voltage-Gated Sodium Channels

A novel series of C12-keto-type saxitoxin (STX) derivatives bearing an unusual nonhydrated form of the ketone at C12 has been synthesized, and their Na_V-inhibitory activity has been evaluated in a cell-based assay as well as whole-cell patch-clamp recording. Among these compounds, 11-benzylidene STX ( 3 a ) showed potent inhibitory activity against neuroblastoma Neuro 2A in both cell-based and electrophysiological analyses, with EC₅₀ and IC₅₀ values of 8.5 and 30.7 nm , respectively. Interestingly, the compound showed potent inhibitory activity against tetrodotoxin-resistant subtype of Na_V1.5, with an IC₅₀ value of 94.1 nm . Derivatives 3 a – d and 3 f showed low recovery rates from Na_V1.2 subtype (ca 45–79 %) compared to natural dcSTX ( 2 ), strongly suggesting an irreversible mode of interaction. We propose an interaction model for the C12-keto derivatives with Na_V in which the enone moiety in the STX derivatives 3 works as Michael acceptor for the carboxylate of Asp¹⁷¹⁷.