Preparation of polypseudorotaxane consisting of fluorescent molecule-modified β-cyclodextrins and biotin-terminated poly(propylene glycol) with high yield

A polypseudorotaxane was prepared using 4-(N,N-dimethylamino) benzoyl modified β-cyclodextrin (DMAB-β-CD) and biotin-terminated poly(propylene glycol) (biotin-terminated PPG) in water for 7 days. When the biotin-terminated PPG was added to a saturated solution of DMAB-β-CD at room temperature, the polypseudorotaxane was not obtained. However, with increasing temperature to 60 °C, precipitation was observed. The ¹H-NMR spectrum indicated that the obtained precipitate was the polypseudorotaxane. The final yield was 54%, which was higher than that previously reported for polypseudorotaxane formation using chemically modified β-CD. The polypseudorotaxane can be useful to make a polyrotaxane via avidin–biotin molecular recognition using the terminal biotin group.     

Design and synthesis of a novel water-soluble Aβ1-42 isopeptide: an efficient strategy for the preparation of Alzheimer's disease-related peptide, Aβ1-42, via O-N intramolecular acyl migration reaction

A novel water-soluble isopeptide of Alzheimer's disease-related peptide Aβ1-42, `26-O-acyl isoAβ1-42', which could efficiently convert to intact Aβ1-42 under physiological conditions via O-N intramolecular acyl migration, was synthesized providing a new system useful for investigation of biological function of Aβ1-42.     

Chemical speciation of chromium in sea water: Part 3. The determination of chromium species

A method for the determination of chromium(III), chromium(VI) and organicallybound chromium in sea water is reported. It is confirmed that sea water contains about 9 × 10^-9 M dissolved chromium. This is shown to be divided as ca. 15% inorganic Cr(III), ca. 25% inorganic Cr(VI) and ca. 60% organically-bound chromium. It is suggested that the inconsistency of earlier results on the dominant chromium species and its concentration in sea water is largely due to the fact that organically bound chromium species were not considered.     

pH- and thermosensitive supramolecular assembling system: rapidly responsive properties of beta-cyclodextrin-conjugated poly(epsilon-lysine)

beta-Cyclodextrin-conjugated poly(epsilon-lysine) (beta-CDPL) was synthesized as a novel polymeric host for constructing a smart supramolecular assembling system. Systematic studies on the inclusion complexation between the polymeric host with an alpha- or beta-CD cavity and a model guest molecule provided evidence that dual cooperative interactions, specific host-guest interaction and intermolecular ionic interaction, played a dominant role in leading to a fast aggregation phenomenon. In addition, a rapid phase transition induced by the supramolecular assembly was observed reversibly in response to a small change in pH or temperature.     

Synthesis of poly(epsilon-lysine)-grafted dextrans and their pH- and thermosensitive hydrogelation with cyclodextrins.

To give pH sensitivity to a thermoreversible supramolecular-structured hydrogel system, poly(epsilon-lysine) (PL), as a cationic polymer, was grafted to dextran and used for inclusion complexation with alpha-cyclodextrins (alpha-CDs). The synthesized graft copolymer was characterized by 1H NMR spectroscopy, and the hydrogel formation was confirmed by X-ray diffraction and solid-state 13C NMR analysis. The hydrogelation was induced from a phase-separated structure of hydrated dextrans and hydrophobically aggregated inclusion complexes in buffer solution at pH 10.0. The prepared hydrogels showed thermoreversible gel-sol transitions as well as pH-sensitive phase transitions, which were recorded by the changes in UV/Vis transmittance. A rapid phase transition from gel to sol was observed upon decreasing the pH value to 4.0, which resulted from the dissociation process between the protonated guest polymer and alpha-CDs. The stimuli-responsive physical properties of the hydrogels were improved by modulating the degree of substitution of the grafted PL and the combination with alpha-CDs.     

Confirmation of the crystal structure of poly(p‐phenylene benzobisoxazole) by the X‐ray structure analysis of model compounds and the energy calculation

To check the previously proposed crystal structure of poly(p‐phenylene benzobisoxazole) [PBO], we performed an X‐ray structure analysis for single crystals of low molecular weight model compounds with the following chemical formulas: Both of these two model compounds show essentially the same molecular and subcell structures as those of PBO: the molecular chains take an almost perfect planar conformation and are packed together with a relative height between the adjacent chains of about 3 Å along the chain axis, although for the polymer the chains are shifted by the same value but in a disordered mode with respect to the direction of the shift (upward or downward), different from the regular packing in model compounds. These structural features are reproduced well with energy calculations. Structural ordering in PBO fibers caused by heat treatment at high temperatures, as clarified by X‐ray diffraction measurement, are interpreted on the basis of the energy calculations. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1296–1311, 2001     

"Click peptide" based on the "o-acyl isopeptide method": control of A beta1-42 production from a photo-triggered A beta1-42 analogue

A clear understanding of the dynamic events of amyloid beta peptide (Abeta) 1-42, such as the folding, self-assembly, and aggregation processes, would be of great significance in Alzheimer's disease (AD) research. However, elucidation of these Abeta1-42 dynamic events is a difficult issue due to uncontrolled polymerization, which also poses a significant obstacle for establishing an experimental system that clarifies the pathological function of Abeta1-42. On the basis of the O-acyl isopeptide method, we herein developed a novel photo-triggered "click peptide" of Abeta1-42, for example, 26-N-Nvoc-26-AIAbeta42, in which the photocleavable 6-nitroveratryloxycarbonyl (Nvoc) group was introduced at the alpha-amino group of Ser26 in 26-O-acyl isoAbeta1-42 (26-AIAbeta42). From the results, (1) the click peptide did not exhibit the self-assembling nature under physiological conditions due to one single modified ester; (2) photoirradiation of the click peptide and subsequent O-N intramolecular acyl migration afforded the intact Abeta1-42 with a quick and one-way conversion reaction (so-called "click"), while the click peptide was stable under nonphotolytic or storage conditions. In addition, it is advantageous that no additional fibril inhibitory auxiliaries were released during conversion to Abeta1-42. This method provides a novel system useful for investigating the dynamic biological functions of Abeta1-42 in AD by inducible activation of Abeta1-42 self-assembly.     

Effects of Thermal History in the Fiber Production on Preferential Orientations of Molecular Planes of Rigid-Rod Polymers along the Radial Direction Normal to the Fiber Axis

The research described in this article was primarily concerned with the preferential orientations of crystal planes along the radial direction normal to the fiber axis, using fibers of poly-p-phenylenebenzobisoxasole as an example. The focus is placed on the formation of the preferential orientation during the dry-jet wet spinning fiber production process for rigid-rod polymers in which, after coagulation, the fibers are washed and dried at low temperatures. It is suggested that the formation of the radial or random preferential orientation was determined in the coagulation and washing processes, based on an analysis of micro-focus X-ray diffraction intensities in a synchrotron radiation facility.