An anomalous hydration/dehydration sequence for the mild generation of a nitrile oxide

A nitrile oxide containing a carbamoyl group is readily generated upon the treatment of 2-methyl-4-nitro-3-isoxazolin-5(2H)-one with water under mild reaction conditions, even in the absence of special reagents. The obtained nitrile oxide undergoes cycloaddition with dipolarophiles, alkynes and alkenes, to afford the corresponding isoxazol(in)es, which are useful intermediates in the synthesis of polyfunctionalized compounds. A plausible mechanism underlying the formation of the nitrile oxide is proposed, which involves an anomalous hydration/dehydration sequence. DFT calculations were also performed to support this mechanism.     

Platonic hexahedron composed of six organic faces with an inscribed Au cluster

The structures of nanomaterials determine their individual properties and the suprastructures they can form. Introducing anisotropic shapes and/or interaction sites to isotropic nanoparticles has been proposed to extend the functionality and possible suprastructure motifs. Because of symmetric anisotropy, Platonic solids with regular polygon faces are one of the most promising nanoscale structures. Introduction of Platonic solid anisotropy to isotropic nanomaterials would expand the functionality and range of possible suprastructure motifs. Here, we demonstrate a novel strategy to obtain nano-Platonic solids through the face coordination of square porphyrins on an inscribed Au sphere with adequate size. The face coordination of the multidentate porphyrin derivatives, with four acetylthio groups facing the same direction, on the Au cluster encased the Au cluster in a Platonic hexahedron with six porphyrin faces. Transmission electron microscopy, mass spectrometry, elemental analysis, and scanning tunnelling microscopy were used to confirm the formation of the nano-Platonic hexahedron.     

Effect of Processing Conditions on Heat Seal Strength for Peelable Heat Sealing of Multilayered Polyethylene Films with Different Sealant Layers

The effect of heat sealing temperature on peelable heat seal strength (HSS) before and after the sterilization, often used industrially, was investigated for one of either polyethylene (PE) multilayered films with various inner sealant layers consisting of two high density PEs (HDPEs), a linear low density PE (LLDPE) or low density PE (LDPE). To attain similar HSS, heat sealing at a temperature close to the melting peak temperature (Tm-p) was needed only in the case of LDPE. Heat sealing behavior at higher temperatures, to attain higher HSS, was also investigated for HDPE and LDPE. High HSS, as well as suppressed reduction of HSS after the sterilization, was achieved for HDPE at a heat sealing temperature well below its Tm-p. An Increase of HSS with the increase of dwell time was also observed. On the other hand, for LDPE, high HSS and its stability after the sterilization were achieved only when the heat sealing temperature was increased to the value equivalent to its Tm-p. Improvement of the processing conditions for the shortening of the processing period was also investigated. For HDPE, higher sealing bar temperature was needed to gain similar HSS when the dwell time of the heat sealing was shortened from 4 to 2 s, whereas the attained maximum temperature at the interface was found to be similar. The characteristics of the heat sealed portion, judged from the relation between HSSs before and after the sterilization, were not affected by the dwell time of heat sealing, indicating that the shortening of the processing time by appropriate raising of the sealing bar temperature is possible.     

Smoothing of an atomically rough vicinal surface – STM observation and MC simulation

Smoothing of an atomically rough vicinal surface of SrTiO₃ is studied by scanning tunneling microscope (STM) observation and by Monte Carlo (MC) simulation. A complex step pattern that resembles a two-dimensional phase separation pattern is observed on the surface. Analysis of the step pattern during annealing obtained by the STM in comparison with the MC simulation reveals an asymmetry of the relaxation pattern between islands and holes. The asymmetry is attributed to the difference of the mobility of an adatom and an atomic hole, and the asymmetry is enhanced by the step edge diffusion barrier. Values of an effective bond energy and an effective diffusion barrier as well as the surface diffusion coefficient are deduced from the relaxation pattern.     

An efficient synthetic method for macrocyclic ketones by intramolecular alkylation of protected cyanohydrins,and its application to the syntheses of muscone and exaltone

A simple synthetic method for macrocyclic ketones based on intramolecular alkylation of carbanion, generated from protected cyanohydrin is reported. Subsequent mild treatment with acid and base of the cyclized products leads to macrocyclic ketones in high yields. The reaction is rapid and irreversible, and hence required short reaction time. The method was successfully applied to the syntheses of cyclohexadecanone and trans-2-cyclopentadecenone as a precursor of (±)-muscone and exaltone.     

Formation of molecular glasses and the aggregation in solutions for lanthanum(III), calcium(II), and yttrium(III) complexes of octanoyl-DL-alaninate

Octanoylalaninato-metal (metal = calcium(II), yttrium(III), lanthanum(III), and zinc(II)) complexes were prepared and the first three metal complexes were found to readily form transparent and stable molecular glasses from methanol and chloroform solutions. The process of glass formation from solution was studied in detail. The effect of the central metal ions on the formation of glassy states was remarkable: the lanthanum and calcium complexes assumed glassy or crystalline states depending on the isolation method and the yttrium complex had a large tendency to assume an amorphous state, whereas the zinc complex did not assume a pure and stable glassy-state. The glass transition temperatures were 50 degrees C for the yttrium complex and 70-75 degrees C for the lanthanum and calcium complexes when these complexes are monohydrates prepared by a solvent-cast method, whereas they increase by 10-30 degrees for the hemihydrates which were obtained by an annealing treatment at 110 degrees C. The coordinated water was eliminated from the solid above the glass transition temperature. The glassy state was regarded as a result of the self-aggregation of the metal complex in solution by an entanglement of the methylene chains with one another. SAXS showed the presence of two disordered bilayer structures with 2.2 nm and 4.5 nm periods in the glassy states. The structures of the molecular assemblies in the solid states and solutions were compared by SAXS and NMR studies. EXAFS studies confirmed the coordination numbers of oxygen atoms around the yttrium and lanthanum atoms in the glassy states for the yttrium and lanthanum complexes to be about 7.     

On the robust estimation in poisson processes with periodic intensities

Under some regularity conditions, it is well known that the maximum likelihood estimator (MLE) is asymptotically normal and efficient. However, if the observation is contaminated, the MLE is not always an appropriate estimator. In this paper, we treat M-estimators and study their asymptotic behavior. By choosing estimation equations, robust M-estimators are presented for phase parameters.     

In Vitro Thermal and Ethanol Adaptations to Improve Vinegar Fermentation at High Temperature of Komagataeibacter oboediens MSKU 3

Applied Biochemistry and Biotechnology - High temperature and high ethanol concentrations obviously affect vinegar fermentation. The thermotolerant and ethanol-resistant strains are expected to...