Total synthesis of 10-isocyano-4-cadinene and its stereoisomers and evaluations of antifouling activities

The first enantioselective total synthesis of 10-isocyano-4-cadinene, a marine sesquiterpene isolated from nudibranchs of the family Phyllidiidae, and determination of its absolute stereochemistry were achieved. 10-Isocyano-4-cadinene is expected to be a novel nontoxic antifouling agent. In the synthesis, intermolecular Diels-Alder reaction and samarium diiodide induced Barbier-type cyclization were employed as key steps. The absolute configuration of 10-isocyano-4-cadinene was determined as (1S,6S,7R,10S) by comparison of the optical rotations between natural and synthetic samples. In addition, the authors successfully synthesized 10-epi- and di-1,6-epi-10-isocyano-4-cadinene through the same synthetic pathway. Antifouling activities against Balanus amphitrite with the cadinenes were also evaluated.     

Formation and Stability of Binary Complexes of Divalent Ecotoxic Ions (Ni, Cu, Zn, Cd, Pb) with Biodegradable Aminopolycarboxylate Chelants (dl-2-(2-Carboxymethyl)Nitrilotriacetic Acid, GLDA, and 3-Hydroxy-2,2′-Iminodisuccinic Acid, HIDS) in Aqueous Solutions

The protonation and complex formation equilibria of two biodegradable aminopolycarboxylate chelants {dl-2-(2-carboxymethyl)nitrilotriacetic acid (GLDA) and 3-hydroxy-2,2??-iminodisuccinic acid (HIDS)} with Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺ and Pb²⁺ ions were investigated using the potentiometric method at a constant ionic strength of I?=?0.10?mol·dm^?3 (KCl) in aqueous solutions at 25?±?0.1?°C. The stability constants of the proton?Cchelant and metal?Cchelant species for each metal ion were determined, and the concentration distributions of various complex species in solution were evaluated for each ion. The stability constants (log₁₀ K _ML) of the complexes containing Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺ and Pb²⁺ ions followed the identical order of log₁₀ K _CuL?>?log₁₀ K _NiL?>?log₁₀ K _PbL?>?log₁₀ K _ZnL?>?log₁₀ K _CdL for either GLDA (13.03?>?12.74?>?11.60?>?11.52?>?10.31) or HIDS (12.63?>?11.30?>?10.21?>?9.76?>?7.58). In each case, the constants obtained for metal?CGLDA complexes were larger than the corresponding constants for metal?CHIDS complexes. The conditional stability constants (log₁₀ $ K_{\text{ML}}^{'} $ ) of the metal?Cchelant complexes containing GLDA and HIDS were calculated in terms of pH, and compared with the stability constants for EDTA and other biodegradable chelants.     

Azetidine iminosugars from the cyclization of 3,5-di-O-triflates of α-furanosides and of 2,4-di-O-triflates of β-pyranosides derived from glucose

Primary amines with either 3,5-di-O-ditriflates of α-furanosides or 2,4-di-O-triflates of β-pyranosides form bicyclic azetidines in high yield.     

Four types of nonlinear scalarizations and some applications in set optimization

There are two types of criteria of solutions for the set-valued optimization problem, the vectorial criterion and set optimization criterion. The first criterion consists of looking for efficient points of set valued map and is called set-valued vector optimization problem. On the other hand, Kuroiwa–Tanaka–Ha started developing a new approach to set-valued optimization which is based on comparison among values of the set-valued map. In this paper, we treat the second type criterion and call set optimization problem. The aim of this paper is to investigate four types of nonlinear scalarizing functions for set valued maps and their relationships. These scalarizing functions are generalization of Tammer–Weidner’s scalarizing functions for vectors. As applications of the scalarizing functions for sets, we present nonconvex separation type theorems, Gordan’s type alternative theorems for set-valued map, optimality conditions for set optimization problem and Takahashi’s minimization theorems for set-valued map.     

Photophysical properties of phenanthro[9,10-d]imidazole-type fluorescent hosts upon inclusion of organic solvent molecules

The crystal of phenanthro[9,10-d]imidazole-type fluorescent clathrate host (1) exhibits fluorescence enhancement behavior with a blue-shift of the emission maximum upon enclathration of organic solvent molecules such as 1-butanol and morpholine, whereas the crystal of 1 exhibits fluorescence enhancement behavior with a red-shift of the emission maximum upon enclathration of carboxylic acid such as acetic acid and propionic acid. The crystal structures of the guest-free and the guest-inclusion compounds of 1 have been determined by X-ray analysis. On the bases of the spectral data and the crystal structures, the effects of the enclathrated guest molecule on the solid-state photophysical properties of the guest-inclusion compounds are discussed.     

First Principles Calculations Toward Understanding SERS of 2,2′-Bipyridyl Adsorbed on Au,Ag, and Au–Ag Nanoalloy

First principles electrodyanmics and quantum chemical simulations are performed to gain insights into the underlying mechanisms of the surface enhanced Raman spectra of 22BPY adsorbed on pure Au and Ag as well as on Au–Ag alloy nanodiscs. Experimental SERS spectra from Au and Ag nanodiscs show similar peaks, whereas those from Au–Ag alloy reveal new spectral features. The physical enhancement factors due to surface nano-texture were considered by numerical FDTD simulations of light intensity distribution for the nano-textured Au, Ag, and Au–Ag alloy and compared with experimental results. For the chemical insights of the enhancement, the DFT calculations with the dispersion interaction were performed using Au₂₀, Ag₂₀, and Au₁₀Ag₁₀ clusters of a pyramidal structure for SERS modeling. Binding of 22BPY to the clusters was simulated by considering possible arrangements of vertex and planar physical as well as chemical adsorption models. The DFT results indicate that 22BPY prefers a coplanar adsorption on a (111) face with trans-conformation having close energy difference to cis-conformation. Binding to pure Au cluster is stronger than to pure Ag or Au–Ag alloy clusters and adsorption onto the alloy surface can deform the surface. The computed Raman spectra are compared with experimental data and assignments for pure Au and Ag models are well matching, indicating the need of dispersion interaction to reproduce strong Raman signal at around 800 cm^–1. This work provides insight into 3D character of SERS on nanorough surfaces due to different binding energies and bond length of nanoalloys. © 2018 Wiley Periodicals, Inc.     

Importance of punching and workability in non-oriented electrical steel sheets

In order to reduce energy loss in motors, the use of high-efficiency non-oriented electrical steel sheets and an optimal motor core design are important. It is also crucial to minimize the deterioration of magnetic properties during the motor core manufacturing process. Accordingly, this report evaluates the effects of cutting and clamping methods on the deterioration factors of motor cores. Magnetic properties are largely influenced by both cutting and clamping methods. While it is difficult to avoid cutting and clamping altogether, it is necessary to adopt suitable production conditions and minimize the deterioration involved.     

Creep behavior of epoxy resin during irradiation at cryogenic temperature

Creep tests of an epoxy resin during bending and irradiation have been carried out to investigate the synergistic effects of radiation and stress on mechanical properties of the resin. Simultaneous application of stress and irradiation on the epoxy resin enhanced creep rates in comparison with the application of stress on an irradiated sample. In order to clarify the mechanism of the radiation-induced creep, measurements of solvent swelling of specimens have been performed. The swelling increased with the dose and the increase of the swelling corresponds to the increase of the chain scission. The mechanism of increased deformation of the resin during irradiation is proposed to be caused by increased chain scission following the release of the local strain energy.