Rintaro Takahashi

Growth Kinetics of Polyelectrolyte Complexes Formed from Oppositely-Charged Homopolymers Studied by Time-Resolved Ultra-Small-Angle X-ray Scattering

We have monitored the kinetic process of polyelectrolyte complex formation between sodium polyacrylate (SPA) and polyallylamine hydrochrolide (PAH) in aqueous NaCl solution by time-resolved ultra-small-angle X-ray scattering (TR-USAXS) combined with rapid mixing. SPA and PAH with different NaCl concentrations from 0 to 1 M were rapidly mixed in equimolar concentration of the monomer units using a stopped-flow apparatus with a dead time of about 2.5 ms. Within the dead time, percolated aggregate-like structures were observed suggesting that the initially formed small charge neutral aggregates further assembled to form higher order agglomerates. The early stage time evolution of the molar mass of the global structure in the presence of NaCl was found to be comparable to the Brownian-coagulation rate.

Glutamic Acids Bearing Calix[4]arene Micelles: pH-Controllable Aggregation Number Corresponding to Regular Polyhedra

We have prepared a new calix[4]arene-based lipid containing glutamic acid as the hydrophilic group. The α-amine and the γ-carboxylic acid groups of the glutamic acid moiety allowed a continuous change in the state of the headgroup from cationic to zwitterionic and then to anionic with increasing pH. Accompanying this headgroup change, micelles of the lipid underwent a morphological transformation from spherical to cylindrical and again to spherical. The morphological transition was ascribed to the change in the lipid conformation corresponding to the pH conditions. Interestingly, at acidic and basic pH, the spherical micelles demonstrated monodispersity in terms of the aggregation number, which agreed with the vertex numbers of Platonic solids, indicating the formation of Platonic micelles. At acidic and basic pH, the lipid conformations were almost identical, but there was a slight difference in the hydrophilic volume, which might affect the packing behavior of the lipid in micelles and account for the difference in the aggregation number. This study clearly demonstrates the precise pH-controllable aggregation number of micelles, which belong to the Platonic micelle systems.

Rediscovering the Monodispersity of Sulfonatocalix[4]arene-Based Micelles

When the micellar aggregation number ( Nagg) is small enough (<30), the Nagg matches the value of vertexes of a regular polyhedron: Platonic solids, and demonstrates perfect monodispersity. These micelles are named Platonic micelles and are particularly found in the system of calix[4]arene-based micelles due to the rigid structure of the backbone molecule. Although sulfonatocalix[4]arene-based micelles are among the most studied host molecules in supramolecular chemistry, their micellar properties as Platonic micelles have thus far been overlooked. In this study, we prepared various sulfonatocalix[4]arene-based amphiphiles bearing alkyl chains with different lengths and investigated their aggregation behavior. When the amphiphiles formed spherical micelles, they demonstrated monodispersity in terms of Nagg, whose value changed from 4 to 17, and then to 24, upon increasing the carbon number in each alkyl chain from C5 to C6, and then to C7, respectively. Although the numbers 17 and 24 do not match the vertices of regular polyhedra, these values can be reasonably explained by the Thomson problem, which considers the Coulomb potential for calculating the best packing on a sphere with multiple identical spherical caps. This study describes rediscovery of the monodispersity of sulfonatocalix[4]arene-based micelles, which is consistent with the idea of Platonic micelles.

Dual and multiple stimuli-responsive platonic micelles bearing disaccharides

We recently identified completely monodisperse micelles whose aggregation number (Nagg) coincides with the vertex number of regular polyhedra, named Platonic micelles. The combination of both the micellar properties and controlling their structures by external stimuli could be promising for producing precisely controlled self-assembled structures. From this perspective, we newly synthesized a calix[4]arene-based amphiphile bearing disaccharides, cellobioses. The crowded and bulky structure in the hydrophilic group could provide a novel stimuli-responsiveness of disaccharides in amphiphiles. The aggregation behavior such as the morphologies and the aggregation number of the calix[4]arene-based micelle was characterized using small angle scattering techniques and analytical ultracentrifugation measurements. Owing to hydrogen bonding among the disaccharide, the head volume became smaller than expected, resulting in the formation of cylindrical ones. However, cleaving the hydrogen bond by controlling temperature or pH induced morphological transition of the micellar structure from cylindrical to spherical. The dual-stimuli (temperature and pH) generated smaller micelles with Nagg of 12. Interestingly, when the amphiphile formed spherical micelles at various conditions, the Nagg matched the Platonic number, and the change of Nagg in response to the external stimuli was non-continuous, which is consistent with the concept of Platonic micelles.

Core–Shell–Corona Micelles from a Polyether-Based Triblock Terpolymer: Investigation of the pH-Dependent Micellar Structure

Core-shell-corona micelles featuring a pH-responsive shell have been characterized in dilute aqueous solution at different pH values (4-8) by using dynamic light scattering (DLS), field-flow fractionation coupled with multiangle light scattering detector (FFF-MALS), steady-state fluorescence, small-angle X-ray scattering (SAXS), and cryogenic transmission electron microscopy (cryo-TEM). The micelles are formed by self-assembly of a polyether-based triblock terpolymer consisting of a hydrophobic poly( tert-butyl glycidyl ether) block (P tBGE), a pH-responsive modified poly(allyl glycidyl ether) segment (PAGECOOH), and a neutral hydrophilic poly(ethylene oxide) block (PEO). Because of the side-chain carboxylic acids in the middle block, the micellar structure and size depends on the solution pH. Hereby, we show that an increase in pH induces a decrease in the aggregation number ( Nagg). In addition, the combination of the above measurements revealed an unexpected morphological change from spherical to ellipsoidal micelles by increasing pH.