Crosslinking network of bio‐based bis‐functional epoxides derived from trans‐limonene oxide

The thiol‐ene reaction between trans‐limonene oxide (trans‐LO) and ethane‐1,2‐dithiol in the presence of triethylborane affords a bio‐based bis‐functional epoxide (bis‐trans‐LO). The crosslinking reaction of bis‐trans‐LO with branched polyethyleneimine (BPEI; M_n = 600; BPEI₆₀₀) at a feed ratio of bis‐trans‐LO/BPEI₆₀₀ = 57/43 (wt/wt) yields the corresponding network polymer with T_d10 (10% thermal decomposition temperature) of 304.7 °C in 98% yield. In contrast, negligible amounts of network polymer are obtained by the reaction of bis‐LO (bis‐functional epoxide derived from cis and trans‐LO) and BPEI₆₀₀ regardless of the feed ratio. The mechanical strengths as measured by direct tensile tests of the network polymers derived from bis‐trans‐LO and BPEI_600,1800 (M_n = 600 and 1800) were approximately 16 and 11 times higher than that of bis‐LO and BPEI₁₈₀₀, respectively. The tensile shear strengths of the metal‐to‐metal adhesive bonds induced by bis‐trans‐LO and BPEI_600,1800 were 9.5 and 14.1 MPa, respectively. DMA revealed that the storage modulus of the network polymer derived from bis‐trans‐LO and BPEI₁₈₀₀ in the rubber region was higher than that of the material prepared from bis‐LO and BPEI₁₈₀₀, indicating higher crosslink density of the bis‐trans‐LO/BPEI₁₈₀₀ system. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2466–2473     

Interfacial adsorption state of protonated lipophilic porphyrins in a liquid-liquid system by using reflection spectrometry.

Analysis by reflection spectrometry was performed to clarify the interfacial adsorption of protonated lipophilic tetraphenylporphyrin derivatives in a dodecane-aqueous sulfuric acid system, and to confirm the utility of partial reflection spectroscopy. Interfacial adsorption was not observed for porphyrins substituted at the 2,6 positions of meso-phenyl groups, suggesting that the substituents prevent porphyrins from forming aggregates by steric hindrance. Polymorphous J-aggregates of acid dications were produced by tetra-p-tolylporphyrin with a saturated interfacial molecular density of 1.0 x 10(-10) mol cm(-2), which could yield 48 degrees as a mean tilting angle of the pyrrole ring plane from the interface normal. Partial-reflection spectrometry can provide sensitive detection and molecular orientation analysis of interfacial adsorbates.     

Hetergeneous-nucleation synthesis of monodisperse ε-cobalt nanoparticles using palladium seeds

Monodisperse bimetallic Pd–Co nanoparticles were prepared via a thermal decomposition of cobalt carbonyl using palladium seeds at the Pd/Co molar ratios 0.5%, 1%, and 5%. The heterogeneously nucleated nanoparticles without any size-selective precipitation are sufficiently uniform to self-assemble into ordered arrays. The as-synthesized nanoparticles are each a single crystal with a complex cubic structure called ε-Co. The presence of Pd seeds seems to improve the stability of Co nanoparticles against oxidation based on the results from time-dependent magnetization measurement.     

Bioavailability study of commercial sustained-release preparations of diclofenac sodium in gastrointestinal physiology regulated-dogs.

The gastrointestinal (GI) physiology of beagle dogs was regulated with a combined-treatment of intramuscular pentagastrin (10 micrograms/kg x 2) and intravenous atropine sulfate (0.02 mg/kg x 1). Here, the gastric acidity, the gastric emptying time and the small intestinal transit time in the regulated-dogs were respectively around pH 2, 0.7h and 4h, approximating those in healthy humans. The superiority of the regulated-dogs over the intact dogs was confirmed in comparative bioavailability studies by using two classes of commercial preparations. Both the conventional tablet and the sustained-release capsule of diclofenac sodium exhibited simple and similar average plasma concentration-time curves of free diclofenac in the intact dogs, while the latter preparation is reported to reveal a bimodal plasma curve of the drug in healthy humans. The regulated-dogs, however, permitted a bimodal average plasma pattern of the drug for the capsules due to an approximation of the GI physiology between humans and these classes of the dogs. The combined-treatment of beagle dogs with pentagastrin and atropine sulfate seems to supply a useful animal model in predicting the absorption characteristics of the sustained-release preparations and poor water-soluble drugs.     

Synthesis of 3-hydroxyindolin-2-one alkaloids, (±)-donaxaridine and (±)-convolutamydines A and E, through enolization-Claisen rearrangement of 2-allyloxyindolin-3-ones

Claisen rearrangement triggered by enolization of 2-allyloxyindolin-3-ones with DBU was performed in order to prepare 3-allyl-3-hydroxyindolin-2-ones. Total synthesis of 3-hydroxyindolin-2-one alkaloids, (±)-donaxaridine, as well as (±)-convolutamydines A and E, was achieved by transformation of the allyl moiety of 3-allyl-3-hydroxyindolin-2-ones.     

Temperature dependence of aluminum nitride reflectance spectra in vacuum ultraviolet region

Temperature dependence of optical reflectance spectra in vacuum ultraviolet region for aluminum nitride has been measured on high-quality single crystal with synchrotron radiation. The dominant structure due to the interband transition is observed at photon energy around 7.7 eV. With decreasing temperature, the energy position of the dominant structure in the reflectance spectra shifts towards higher energy. The experimental data has been fitted to the Bose-Einstein expression and the obtained parameter related to the strength of the electron-phonon interactions is much smaller than that for the peak at 6.2 eV, suggesting that the higher-lying interband transition energy decreases more slowly with increasing temperature in aluminum nitride (AlN).     

Recoil distance half-life measurements of the excited states in 145Sm

A recoil distance method was used to measure half-lives of the excited states of ₁₄₅Sm. The reaction used was ₁₃₉La(₁₀B, 4n)₁₄₅Sm. A plunger system was used. Half-lives were determined for two excited states for the first time. The yrast 27/2₊ state was found to have a half-life of 1.1 ± 0.2 ns corresponding to the retardation of 3.1 × 10₋₄ comparing with the single particle estimate of M1. The excitation energy of this state was well reproduced by the shell model calculation having a mixed configuration of [π{h^11/2(g^7/2)₋₂ (d^5/2)₋₁}¹⁰⁻, νf^7/2] + [π{h^11/2(g^7/2)₋₁}⁹⁻,νh^9/2]. Another retarded E1 transition was also found in a decay of a 21/2₊ state. Its retardation was 1.6 × 10₋₄ comparing with the single particle value. Received: 9 September 1997 / Revised version: 12 June 1998