Stacking of poly(3-alkylthiophene)s P3RThs and poly(4-alkylthiazole)s P4RTzs has been studied. Light scattering analysis indicates that head-to-tail (HT) type HT-P3HexTh (R = n-C6H13) gives a degree of depolarization (ρv) of 0.26 in CHCl3, which reveals that HT-P3HexTh takes a stiff structure even in the good solvent. Addition of CH3OH to CHCl3 solutions of HT-P3HexTh and head-to-head (HH) type HH-P4HepTz (R = n-C7H15) leads to π-stacking of the polymer molecules to form stable colloidal particles. The light scattering analysis of the colloidal solution of HT-P3HexTh in a 2:1 solution of CHCl3 and CH3OH reveals that HT-P3HexTh is aggregated in a parallel style. Results of filtration experiments using membranes with 0.20 and 0.02 μm pores agree with the degree of the aggregation. P3HexThs with irregular structures (P3HexTh (Fe) and P3HexTh (Ni) with HT/HH ratios of about 7/3 and 1/2, respectively) show a weaker trend to aggregate; however, P3HexTh (Fe) is considered to stack in a surface region of a stretched poly(ethylene terephthalate) PET film. A dichroism observed with the stretched PET film indicates that the π−π* absorption as well as photoluminescence of the stacked P3HexTh molecules have a transition moment along the direction of the polymer main chain. X-ray diffraction analysis of HT-P3RThs and HH-P4RTzs reveals that they take a face-to-face stacked structure with an end-to-end packing mode, except for HT-P3MeTh (R = Me). HT-P3MeTh forms a face-centered lattice with an interlayer distance of 3.51 Å. An alternative copolymer of bithiazole and 4,4‘-dibutylbithiazole is packed in an interdigitation mode. At temperatures below 0 °C, the HT-P3HexTh molecules are π-stacked in CHCl3, and the 1H NMR spectrum shows a severe magnetic effect on the thiophene ring. Solid 13C NMR data are also consistent with the π-stacking.

A coated capillary modified with a cationic polymer was developed by using a novel coating procedure, successive multiple ionic-polymer (SMIL) coating. The SMIL coating was achieved by first attaching the cationic polymer to the capillary inner wall, and then the anionic polymer to the cationic polymer layer, and finally the cationic polymer to the anionic polymer layer. The stability of Polybrene (PB)-modified capillary made by SMIL coating was remarkably improved in comparison with a conventional PB-modified capillary. It endured during 600 replicate analyses and also showed strong stability against 1 M NaOH and 0.1 M HCl. The relative standard deviation of the run-to-run, day-to-day, and capillary-to-capillary coating was all below 1%, and good reproducibilities were obtained. The PB-modified capillary made by SMIL coating was applied to the basic protein analyses. It gave good performances for the protein analyses even when the pH of the electrolyte was near the isoelectric point (pI) of the protein. In addition, 0.1 M NaOH rinse prior to the sample injection allowed the reproducible analysis of a highly adsorptive sample such as plasma because the adsorbed sample could be flushed out of the capillary. Besides protein analyses, an efficient analysis of the cationic drugs by capillary electrophoresis/mass spectrometry (CE/MS) was also possible.

Shock due to Gram-negative bacterial sepsis is a consequence of acute inflammatory response to lipopolysaccharide (LPS) or endotoxin released from bacteria. LPS is a major constituent of the outer membrane of Gram-negative bacteria, and its terminal disaccharide phospholipid (lipid A) portion contains the key structural features responsible for toxic activity. Based on the proposed structure of nontoxic Rhodobacter capsulatus lipid A, a fully stabilized endotoxin antagonist E5531 has been synthesized. In vitro, E5531 demonstrated potent antagonism of LPS-mediated cellular activation in a variety of systems. In vivo, E5531 protected mice from LPS-induced lethality and, in cooperation with an antibiotic, protected mice from a lethal infection of viable Escherichia coli.

A stable modification of the inner wall of a fused silica capillary was established by a simple coating procedure, successive multiple ionic-polymer layer (SMIL) coating. An anionic polymer was tightly fixed to the capillary wall by the SMIL coating, in which a cationic polymer was sandwiched between the anionic polymer and the uncoated fused silica capillary by noncovalent bonding. The SMIL-coated capillary showed a long lifetime. The endurance of the SMIL-coated capillary was more than 100 runs, and it was also tolerant to organic solvents, 1 M NaOH, and a surfactant. The coating efficiency did not depend on capillary sources, and the relative standard deviation of capillary-to-capillary reproducibility was less than 1%. In this study, dextran sulfate (DS) was used as the anionic polymer, and Polybrene was used as the cationic polymer for SMIL modification. The DS-modified capillary (SMIL-DS capillary) exhibited a pH-independent electroosmotic flow (EOF) from anode to cathode in the pH range of 2-11. The SMIL-DS capillary showed good performance for acidic protein analyses under physiological conditions (pH 7.4). Also, the presence of EOF under acidic conditions permitted new applications. Simultaneous separations of cationic, anionic, and neutral amino acids were achieved by capillary zone electrophoresis, and separations of cresol isomers were achieved by micellar electrokinetic chromatography under the acidic conditions. The SMIL-DS capillary was also useful for fast and precise determination of the pKa of acidic functional groups.