Photo-responsive hole formation in the monolayer membrane wall of a supramolecular nanotube for quick recovery of encapsulated protein.

Nanotubes with a single monolayer membrane wall comprised of a synthetic glycolipid and one of two synthetic azobenzene derivatives were assembled. X-ray diffraction, infrared, UV-visible, and circular dichroism spectroscopy clarified the embedding style of the azobenzene derivatives in the membrane wall, revealing that, depending on their different intermolecular hydrogen bond strengths, one azobenzene derivative was individually dispersed whereas the other formed a J-type aggregate. The non-aggregated derivative was insensitive to UV irradiation due to tight fixation by the surrounding glycolipid. In contrast, the aggregated derivative was sensitive to UV irradiation, which induced trans-to-cis isomerization of the derivative and disassembly of the J-type aggregate. Subsequent dissociation of the derivative into the bulk solution resulted in the formation of many nanometer-scale holes in the membrane wall. Although a model protein encapsulated within the nanotubes was slowly released over time from the two open ends of the nanotubes without UV irradiation, exposure to UV irradiation resulted in faster, preferential release of the protein through the holes in the membrane wall. The present findings are expected to facilitate the development not only of efficient means of recovering guest compounds stored within nanotubes but also the development of novel stimuli-responsive capsules in biological and medical fields.

Stacking of nanorings to generate nanotubes for acceleration of protein refolding.

Self-assembly and photoisomerization of azobenzene-based amphiphilic molecules produced nanorings with an inner diameter of 25 nm and lengths of <40 nm. The nanorings, which consisted of a single bilayer membrane of the amphiphiles, retained their morphology in the presence of a stacking inhibitor; whereas in the absence of the inhibitor, the nanorings stacked into short nanotubes (<500 nm). When subjected to mild heat treatment, these nanotubes joined end-to-end to form nanotubes with lengths of several tens of micrometers. The nanorings and the short and long nanotubes were able to encapsulate proteins and thereby suppress aggregation induced by thermal denaturation. In addition, the nanotubes accelerated refolding of denatured proteins by encapsulating them and then releasing them into the bulk solution; refolding occurred simultaneously with release. In contrast, the nanorings did not accelerate protein refolding. Refolding efficiency increased with increasing nanotube length, indicating that the re-aggregation of the proteins was strictly inhibited by lowering the concentration of the proteins in the bulk solution as the result of the slow release from the longer nanotubes. The migration of the proteins through the long, narrow nanochannels during the release process will also contribute to refolding.

Time-controllable roll-up onset of polythiophene sheets into nanotubes that exhibit circularly polarized luminescence.

Self-assembly of a polythiophene-conjugated glycolipid exclusively produced square sheets a few micrometers on each side. Seventeen hours after the sheets were dispersed in ethanol at 25 °C, they suddenly started to roll up, and eventually they were completely transformed into nanotubes. The onset timing of the roll-up was temperature-dependent. The roll-up involved rearrangement of the molecular packing within the bilayer membranes, which was accompanied by strengthening of the intermolecular hydrogen bonds, alteration of the polythiophene aggregation mode and enhancement of supramolecular chirality due to chiral packing. The nanotubes exhibited not only strong fluorescence derived from J-type aggregation of the polythiophene aromatic moiety but also circularly polarized luminescence (CPL) originating from the left-handed helicity of the polythiophene main chain backbone. Because the CPL onset was concurrent with the sheet roll-up, the CPL onset was also able to be controlled by varying the temperature. Such delayed CPL onset has never been reported in chiral supramolecular structures, in which CPL onset and helicity inversion usually begin immediately upon application of a stimulus and then progress either quickly or gradually. Our findings can be expected to facilitate the development of new stimulus-responsive supramolecular structures that can be used for delayed-action capsules or optical switching devices.

Glycolipid-based nanostructures with thermal-phase transition behavior functioning as solubilizers and refolding accelerators for protein aggregates.

The self-assembly of synthetic glycolipids produced nanostructures such as vesicles and nanotubes consisting of bilayer membranes, which underwent a gel-to-liquid crystalline thermal phase transition. Vesicles formed at temperatures above the thermal phase transition temperatures (Tg-l) could solubilize aggregates of denatured proteins by trapping them in the fluid bilayer membranes. Cooling to temperatures below Tg-l caused a morphological transformation into nanotubes that accompanied the thermal phase transition from the fluid to the solid state. This phenomenon allowed the trapped proteins to be quickly released into the bulk solution and simultaneously facilitated the refolding of the proteins. The refolding efficiency strongly depended on the electrostatic attraction between the bilayer membranes of the nanostructures and the proteins. Because of the long shape (>400 nm) of the nanotubes, simple membrane filtration through a pore size of 200 nm led to complete separation and recovery of the refolded proteins (3-9 nm sizes).

Synergistic effect of tris(4-isopropyltropolonato)cobalt(III) on the extraction of lanthanoid(III) with 2-thenoyltrifluoroacetone.

Synergistic enhancement of the extraction of lanthanoid(III) (Ln) with 2-thenoyltrifluoroacetone (Htta) in benzene has been found by the addition of tris(4-isopropyltropolonato)cobalt(III) (Co(ipt)3). The synergistic effect of Co(ipt)3 was ascribed to the formation of a 1:1 adduct of Ln(tta)3 with Co(ipt)3, i.e., a binuclear complex, in the organic phase. The adduct formation constant (beta s,1) determined by the extraction equilibrium analysis was reasonably consistent with that determined by spectrophotometry. The beta s,1 values decreased with increase in the atomic number of Ln and showed a large difference between light and heavy Ln. Spectroscopic studies were performed to explain the difference in the beta s,1 values. Electronic absorption spectra showed that the change in the structure of Co(ipt)3 complexed with the light Ln chelate is larger than that with the heavy Ln. The IR spectra showed the displacement of the coordinated water molecules of the light Ln chelates with Co(ipt)3. On the other hand, the adduct formation of heavy Ln was caused by the hydrogen bonding between Co(ipt)3 and the coordinated water of the Ln chelate.