High‐performance liquid chromatography separation of unsaturated organic compounds by a monolithic silica column embedded with silver nanoparticles

The optimization of a porous structure to ensure good separation performances is always a significant issue in high‐performance liquid chromatography column design. Recently we reported the homogeneous embedment of Ag nanoparticles in periodic mesoporous silica monolith and the application of such Ag nanoparticles embedded silica monolith for the high‐performance liquid chromatography separation of polyaromatic hydrocarbons. However, the separation performance remains to be improved and the retention mechanism as compared with the Ag ion high‐performance liquid chromatography technique still needs to be clarified. In this research, Ag nanoparticles were introduced into a macro/mesoporous silica monolith with optimized pore parameters for high‐performance liquid chromatography separations. Baseline separation of benzene, naphthalene, anthracene, and pyrene was achieved with the theoretical plate number for analyte naphthalene as 36 000 m^?1. Its separation function was further extended to cis/trans isomers of aromatic compounds where cis/trans stilbenes were chosen as a benchmark. Good separation of cis/trans‐stilbene with separation factor as 7 and theoretical plate number as 76 000 m^?1 for cis‐stilbene was obtained. The trans isomer, however, is retained more strongly, which contradicts the long‐ established retention rule of Ag ion chromatography. Such behavior of Ag nanoparticles embedded in a silica column can be attributed to the differences in the molecular geometric configuration of cis/trans stilbenes.     

Hydroxyapatite-supported copper(II)-catalyzed azide-alkyne [3+2] cycloaddition with neither reducing agents nor bases in water

Copper(II)-exchanged hydroxyapatite, prepared by ion-exchanging of Ca(II) in calcium hydroxyapatite [Ca₁₀(PO₄)₆(OH)₂] with Cu(NO₃)₂ at 70 °C in water, functions as a reusable heterogeneous catalyst with neither reducing agents nor bases for azide-alkyne [3+2] cycloaddition at 50 °C in water under air.     

Evaluation of the abilities of ��-cyclodextrin to form complexes by surface plasmon resonance with a Biacore? system

Although phase-solubility studies have often been used to evaluate the interaction of cyclodextrins (CDs) with various drugs, hundreds of milligrams of both CD and drug are required to prepare a phase diagram. A method that would require considerably less material for evaluating complex formation between a CD and guest compound is therefore needed. We previously reported the detection of the interactions between ??-CD and various drugs using a Biacore^® system. In this study, we succeeded in immobilizing 6-monodeoxy-6-monoamino-??-CD on the gold surface of a sensor chip and in detecting the interactions between the immobilized ??-CD and various drugs. The interaction processes were kinetically analyzed using Biacore^®. The surface plasmon resonance sensorgrams indicated that the association and dissociation rates of the interactions between ??-CD and drugs were faster than those between ??-CD and drugs. Although the association constants calculated from the sensorgrams were smaller than those calculated from phase-solubility studies, good correlation was shown between these data.     

Direct conversion of acetals to esters with high regioselectivity via O,P-acetals

A new direct conversion of O,O-acetals to esters via O,P-acetal intermediates was developed. The regioselective cleavage of unsymmetrical cyclic acetals occurred to give the more crowded esters as single isomers.     

A tertiary amine as a hydride donor: trichlorosilyl triflate-mediated conjugate reduction of unsaturated ketones

Bulky tertiary amines, especially dicyclohexylisobutylamine, smoothly reduced α,β-unsaturated ketones in the presence of trichlorosilyl triflate to give the corresponding saturated ketones in excellent yields. Isotope-labeling studies revealed that an α-hydrogen of the amine was transferred to the enones during reduction.     

Electrochemically controllable emission and coloration by using europium(III) complex and viologen derivatives

We have demonstrated electroswitchable emission and coloration using a novel composite material containing luminescent europium(III) complex Eu(hfa)(3)(H(2)O)(2) and diheptyl viologen HV(2+). The photoluminescence of the Eu(III) complex was controlled by the electrochemical coloration of HV(2+)via intermolecular energy transfer mechanisms.     

Optical Storage Media with Dye-Doped Minute Spheres on Polymer Films

We have fabricated a new optical storage media using minute spheres arranged on a surface relief grating (SRG). Using minute spheres as recording bits, we can limit recordable regions by sphere size, and can realize high resolution reproduction in the plane direction. Surface relief structures were made on a polymer thin film on which we performed diffusion arrangement and adsorptive fixation of minute spheres. The stability of the arranged spheres was confirmed for heating and washing. Furthermore, we used a dipping method for a more simple arrangement of minute spheres on a large area of the substrate and made a monolayer sample of the spheres. We were able to realize a highly sensitive reconstruction of the medium using a confocal optical system as a record and readout system.