Novel surface-modification techniques for polymer-based separation media. Stimulus-responsive phenomena based on double polymeric selectors

A pair of polymeric selectors potentially responding to stimulation was introduced onto monosized porous polymer particles to be evaluated as a packing material for HPLC. Possible complexes formed between polyacrylamide (PAAm) and poly(methacrylic acid) (PMAA) were utilized as stimulus responsive polymeric selectors. Uniformly sized base polymer particle was prepared by multi-step swelling and polymerization method, while the introduction of PAAm and PMAA was done by newly invented modification technique. In this technique, a solvent in which both acrylamide (AAm) and methacrylic acid (MAA) monomers are soluble, but PAAm and PMAA are insoluble, was utilized as a modification medium. The polymer particle doubly modified with PAAm and PMAA was utilized as packing material for HPLC and the stimulus responses were evaluated by changing temperature or pH to check change of the slope of a Van't Hoff plot. By using water as a mobile phase, the expected inflection point of the Van't Hoff plot was observed at upper critical solution temperature (UCST) of the polymer complexes and the temperature responsive ability was observed. Moreover, pH responsive ability was studied by using buffer of either pH 4 or 10 as mobile phase. Slope of the plot was changed in buffer of pH 4, but no change of slope was observed in the buffer of pH 10.     

Highly enantioselective synthesis of organic compound using right- and left-handed helical silica

Highly enantiomerically enriched (up to 96-97% ee) 5-pyrimidyl alkanol was obtained by the addition of diisopropylzinc to pyrimidine-5-carbaldehyde in the presence of the artificially designed chiral inorganic material, right- and left-handed helical silica.     

Chemical synthesis of 23 kDa glycoprotein by repetitive segment condensation: a synthesis of MUC2 basal motif carrying multiple O-GalNAc moieties

Peptide thioester corresponding to a MUC2 tandem repeat unit, which retains seven GalNAc moieties, was prepared by the Fmoc method followed by the low TfOH treatment to remove benzyl groups at the carbohydrate portions. The glycosylated peptide thioester was then consecutively joined by the activation of a thioester group by silver ions to obtain a MUC2 tandem repeat model composed of 141 amino acids with 42 GalNAc moieties.     

Microwave spectrum of CIS chlorine nitrite,CIONO

The metastable intermediate product, CIONO, which is formed from gaseous CINO and Cl₂O at about 203 K, has been detected by microwave spectroscopy. The rotational constants and the inertial defects for the ³⁵Cl and ³⁷Cl species establish that the observed spectrum is that of planar cis CIONO.     

Spectroelectrochemical responsiveness of a freestanding, boron-doped diamond, optically transparent electrode toward ferrocene

The spectroelectrochemical responsiveness of an optically transparent diamond electrode (OTE) toward ferrocene was investigated. A freestanding, mechanically polished, boron-doped diamond disk (0.38 mm thick and 8 mm in diameter) served as the OTE for UV-Vis transmission spectroelectrochemical measurements. A specially designed, thin-layer spectroelectrochemical cell was constructed for the measurements in which ferrocene was electrooxidized to ferricinium ion via a one-electron redox reaction. The oxidation reaction product was spectroscopically monitored in the ultraviolet (λ=252, 285 nm) region of the electromagnetic spectrum. Well-defined and highly stable spectroelectrochemical responses were observed for this type of diamond OTE. The results indicate that diamond is a useful OTE material for spectroelectrochemically studying nonaqueous redox reactions.     

Synthesis and properties of superconductors prepared from ethylenediaminetetraacetic acid (EDTA)-ethylenediamine (ED) polyamide YBC chelate

Single-phase Y₁Ba₂Cu₃O_7-x has been synthesized by a polymer-metal chelate precursor technique. Ethylenediaminetetraacetic acid (EDTA)-ethylenediamine (ED) polyamide was used as chelating polymer for Y, Ba, and Cu. The titration curves of the polymer in the absence and presence of each metal ion showed the chelate formations. The polymer was dissolved in water and the metal nitrates of Y, Ba, and Cu (1:2:3 in mole ratio) were stoichiometrically added to form a homogeneous molecular complex. The clear polymermetal chealate film was obtained by removal of the solvent without phase separation. This precursor was dried, calcined, and sintered to develop the superconducting (1,2,3) phase. The 1,2,3 phase produced was found to be pure according to x-ray diffraction pattern and it possessed good superconducting properties, i.e., the onset of superconductivity was seen at 90.0 K and the resistance rapidly decreased with decreasing temperature, reaching substantially zero at 88.6 K. Scanning electron microscope (SEM) and face and point analyses by electron probe microanalysis (EPMA) showed that Y, Ba, and Cu elements were uniformly dispersed at least micron order. © 1994 John Wiley & Sons, Inc.     

Synthesis,Characterization, and Applications of Polymers Containing Lanthanide Metals

This paper reviews the author's work on polymers containing lanthanide metals. The discussion focuses on the use of lanthanide-metal-ion probes to investigate the structures of ionomers and the ion-binding properties of polyelectrolytes. Preliminary fluorescence results of europium and terbium in chelating polymers are also discussed.     

Practical and Efficient Method for α-Sialylation with an Azide Sialyl Donor Using a Microreactor

Efficient α-sialylation with a C5 azide sialyl donor was investigated under microfluidic conditions using a microreactor composed of a Comet X-01 micromixer and a tube reactor. Precise temperature control realized excellent α-selectivity, and Siaα(2,6)Gal, Siaα(2,3)Gal, and Siaα(2,9)Sia disaccharides were obtained in moderate to good yields.     

Revisiting the Bromination of CH Bonds with Molecular Bromine by Using a Photo‐Microflow System

The photobromination of C?H bonds by using molecular bromine was reinvestigated under microfluidic conditions. The continuous‐flow method suppressed the production of dibrominated compounds and effectively produced the desired monobrominated products with high selectivity. Rapid bromination of benzylic substrates containing a photoaffinity azide group was achieved without any decomposition.