Synthesis of green organogelators with a sulfide linkage via solvent-free Michael addition: soft templates for the preparation of size-controlled gold nanoparticles

Green organogelators with a sulfide linkage and free amino groups were synthesized via phase transfer catalysis using a N-benzylcinchonidinium bromide catalyst. Their self-assemblies in various common solvents were examined. These compounds exhibit high gelation ability especially in aromatic and highly polar solvents with a low critical gelation of 0.1 wt %. The organogels were analyzed by ¹H nuclear magnetic resonance (¹H NMR) and Fourier transfer-infrared spectroscopies (FT-IR), and their phase transition temperatures were determined by differential scanning calorimetry. The homogeneity of the gel networks was examined by field emission scanning electron microscopy and transmission electron microscopy (TEM). A lamellar structure was also confirmed by X-ray diffraction analysis. The organogels were employed as soft-templates for the in situ generation of stable gold nanoparticles dispersed in the gel matrix, and the resulting GNP dispersions were studied by ¹H NMR and UV–vis absorption. Transmission electron microscopy showed that GNPs assemble into a thin membrane-like structure.     

Synthesis and characterization of 9,9‐bis(4‐hydroxyphenyl and 4‐aminophenyl)dibenzofluorenes: Novel fluorene‐based monomers

Two novel 9,9‐difunctionalized fluorene‐type monomers, 9,9‐bis(4‐hydroxyphenyl‐ and 4‐aminophenyl)‐2,3:6,7‐dibenzofluorenes, are synthesized by the reaction of dibenzenzofluorenone with phenol and aniline. These monomers are used for the preparation of polyester and polyimide as the typical polymers to evaluate the property change such as thermal stability caused by the benzene rings fused to the fluorene skeleton with keeping good solubility, in comparison with the polymers derived from simple fluorenone. In fact, these two new polymers have the fairly enhanced thermal stability and refractive index value along with satisfactory solubility in organic solvents, enough to emphasize the fusion effect. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2602–2605     

Chiral Dinuclear EuIII,TbIII, and YIII Complexes Supported by P-Stereogenic Linear Tetraphosphine Tetraoxide

A P-stereogenic linear tetraphosphine tetraoxide, (R,R)- or (S,S)-dpmppm(=O)₄, was synthesized to prepare C₂ dinuclear M(hfa)₃ complexes (M=Eu, Tb, Y) as the first example of lanthanide(III) complexes with P-chiral multidentate phosphine oxides. The mononuclear M(hfa)₃ complexes (M=Eu, Y) with a P-chiral diphosphine dioxide, tpdpb(=O)₂, were also prepared, and comparison of their photophysical properties for the Eu^III complexes revealed that significant chiral induction from the P-chiral centers arises on the achiral M(hfa)₃ units through intramolecular π-π stacking constraint in the dinuclear system.     

Aryl-β-C-glucosidation using glucal boronate: application to the synthesis of tri-O-methylnorbergenin

Novel aryl-β-C-glucosidation method using glucal boronate was developed. This protocol can offer several advantages including use of non-toxic, easily handling glucal boronate as a crystalline solid and storable at room temperature for several months. Tri-O-methylnorbergenin (8,10-di-O-methylbergenin), an anti-HIV active bergenin derivative, was concisely synthesized by application of the aryl-β-C-glucosidation method.     

pH-Responsive Phase Transition of Supramolecular Hydrogel Consisting of Glycosylated Amino Acetate and Carboxylic Acid Derivative

By addition of a carboxylated amino acetate (2) to a low-molecular-weight hydrogel (1) which has a unique thermally induced volume-phase transition character, a macroscopic pH-responsive feature is newly conferred on the supramolecular hydrogel. The direct observation of temperature-dependent behavior of the mixed hydrogel clearly showed that the thermally induced swelling-shrinkage type of the volume phase transition at pH 4 is shifted to the gel–sol transition at pH 7 by 10?mol% addition of 2 to the hydrogel 1. On the basis of the measurements by TEM, SEM, XRD and FT-IR, it is conceivable that incorporation of the anionic carboxylate of 2 slightly disturbs the packing of the hydrogen bond belt of the mixed hydrogel. Such a slight disturbance greatly leads to the sol–gel transition by elevating temperature, instead of the volume-phase transition. Introduction of dynamic characteristics to supramolecular systems in a macroscopic level may extend the potential of these materials in various fields.     

Novel synthesis of zerumbone-pendant derivatives and their biological activity

Zerumbone 1, having powerful latent reactivity and containing two conjugated double bonds and a double conjugated carbonyl group is the major component of the essential oil of wild ginger, Zingiber zerumbet Smith. The conjugation system plays an important role in the expression of biological activity. N-Bromosuccinimide (NBS) reaction of 1 gave high reactive intermediate 2 with an exo-methylene group, which was obtained from 1 quantitatively. Treatment of 2 with nucleophiles gave various zerumbone-pendant derivatives, including C–H, C–O, C–N, and C–C bond formation, maintaining the conjugation system through S_N2′-type reaction. Almost all zerumbone-pendant derivatives showed a good value of IC₅₀ against the suppressive effect of NO generation. Among them, amine derivative 5, binding with 2 mol of zerumbone, showed the strongest activity (IC₅₀: 0.24 μM).