Reaction of 6‐aryl‐ or styryl‐4‐methylsulfanyl‐2‐oxo‐2H‐pyrans with active methylene compounds and fluorescence properties of the products

New 2‐pyrone derivatives, dialkyl 3‐cyano‐6‐phenyl‐2‐oxo‐2H‐pyran‐4‐ylmalonates and alkyl 3‐cyano‐6‐phenyl‐2‐oxo‐2H‐pyran‐4‐ylacetates, which were easily prepared by the reaction of 6‐aryl‐4‐methyl‐sulfanyl‐2‐oxo‐2H‐pyran‐3‐carbonitriles with active methylene compounds in the presence of potassium carbonate, show fluorescence emission radiation. The light‐emitting region of dimethyl 3‐cyano‐6‐(4‐N,N‐dimethylamino)styryl‐2‐oxo‐2H‐pyran‐4‐ylmalonate ( 7h ) was 620 nm in dichloromethane, making this compound a typical red fluorescent compound. Methyl 8‐hydroxy‐6‐methyl‐1‐oxo‐3‐phenyl‐1H‐pyrano‐[3,4‐c]pyridine‐5‐carboxylate deriv‐atives also showed fluorescence in the solid state. This is the first example of fluorescence in fused 2‐pyrone derivatives.     

Three novel cantharidin-related compounds from the Chinese blister beetle, Mylabris phalerata Pall

Three novel cantharidin analogues were isolated from the Chinese blister beetle, Mylabris phalerata PALL. (Meloidae), which has been used in traditional Chinese medicine for the treatment of cancer. Their structures were determined on the basis of heteronuclear multiple-bond connectivity and nuclear Overhauser effect spectroscopy experiments, and chemical data confirmed them to be so-called cantharimides, in which the anhydride oxygen atoms are replaced by the basic amino acid L-lysine, L-ornithine, and L-arginine moieties.     

The Β decay of the new isotope79Y

The neutron deficient isotope⁷⁹Y has been firstly identified and the decay properties were studied from-decay measurements in the reaction of⁵⁴Fe(²⁸Si,p2n at 92 MeV. Three rays of 152.5, 177.4, and 1106 keV were observed concerning the decay. The half life and Q_EC value were determined to be 14.9 ± 0.6 s and 7.12 ± 0.45 MeV, respectively. The decay scheme including spin-parity is discussed, and 5/2⁺ assignment for the ground state is proposed.We would like to thank to Dr. Y. Maeda for his valuable advice about the electroplating method of iron targets. We also thank to Mr. T. Maeda and Mr. S. Niiya for preparation of hardware for data-taking.     

Delamination of Organically Modified Layered Filler via Solid‐State Processing

Summary: Solid‐state processing for the preparation of poly(p‐phenylenesulfide) (PPS‐) based nano‐composites having finely dispersed layered fillers was conducted. The mixture of PPS and organically modified layered filler (OMLF) (95/5 wt./wt.) was subjected to the processing using thermostated hot‐press at 150 °C, below T_m of PPS (i.e., PPS is still at the solid‐state), and applying pressures of 33 MPa for 30 s. The mixture exhibited disorder and delaminated layer structure with the thickness of 10–20 nm into the PPS matrix. In contrast, a nano‐composite prepared by melt compounding at 300 °C for 3 min showed large stacked silicate layers in the PPS matrix. The processing led to delamination of the silicate layers and attained the discrete dispersion.

TEM bright field image and FFT spectrum of a solid‐state processed PPS nano‐composite.     

Sequence-regulated copolymers via tandem catalysis of living radical polymerization and in situ transesterification

Sequence regulation of monomers is undoubtedly a challenging issue as an ultimate goal in polymer science. To efficiently produce sequence-controlled copolymers, we herein developed the versatile tandem catalysis, which concurrently and/or sequentially involved ruthenium-catalyzed living radical polymerization and in situ transesterification of methacrylates (monomers: RMA) with metal alkoxides (catalysts) and alcohols (ROH). Typically, gradient copolymers were directly obtained from the synchronization of the two reactions: the instantaneous monomer composition in feed gradually changed via the transesterification of R(1)MA into R(2)MA in the presence of R(2)OH during living polymerization to give R(1)MA/R(2)MA gradient copolymers. The gradient sequence of monomers along a chain was catalytically controlled by the reaction conditions such as temperature, concentration and/or species of catalysts, alcohols, and monomers. The sequence regulation of multimonomer units was also successfully achieved in one-pot by monomer-selective transesterification in concurrent tandem catalysis and iterative tandem catalysis, providing random-gradient copolymers and gradient-block counterparts, respectively. In contrast, sequential tandem catalysis via the variable initiation of either polymerization or in situ transesterification led to random or block copolymers. Due to the versatile adaptability of common and commercially available reagents (monomers, alcohols, catalysts), this tandem catalysis is one of the most efficient, convenient, and powerful tools to design tailor-made sequence-regulated copolymers.     

Effect of NiAl underlayer and spacer on magnetoresistance of current-perpendicular-to-plane spin valves using Co2Mn(Ga0.5Sn0.5) Heusler alloy

We investigated the effect of a NiAl underlayer and spacer on magnetoresistive (MR) properties in current-perpendicular-to-plane spin valves (CPP-SVs) using Co₂Mn(Ga_0.5Sn_0.5) (CMGS) Heusler alloy ferromagnetic layers. The usage of a NiAl underlayer allowed a high temperature annealing for the L2₁ ordering of the bottom CMGS layer, giving rise to a MR ratio of 10.2% at room temperature. We found that the usage of a NiAl spacer layer also improved the tolerance of the multilayer structure against thermal delamination, which allowed annealing to induce the L2₁ structure in both the bottom and top CMGS layers. However, the short spin diffusion length of NiAl resulted in a lower MR ratio compared to that obtained using a Ag spacer. Transmission electron microscopy of the multilayer structure of CPP-SVs showed that the atomically flat layered structure was maintained after the annealing.