Topology-transformable block copolymers based on a rotaxane structure: change in bulk properties with same composition.

The topology of polymers affects their characteristic features, i.e., their microscopic structure and macroscopic properties. However, the topology of a polymer is usually fixed during the construction of the polymer chain and cannot be transformed after its determination during the synthesis. In this study, topology-transformable block copolymers that are connected via rotaxane linkages are introduced. We will present systems in which the topology transformation of block copolymers changes their 1) microphase-separated structures and 2) macroscopic mechanical properties. The combination of a rotaxane structure at the junction point and block copolymers that spontaneously form microphase-separated structures in the bulk provides access to systems that cannot be attained using conventional covalent bonds.

Temperature-Directed Assembly of Crystalline Cellulose Oligomers into Kinetically Trapped Structures during Biocatalytic Synthesis.

Crystalline polysaccharides, such as cellulose and chitin, can form superior assemblies in terms of physicochemical stability and mechanical properties. However, their use as molecular building blocks for self-assembled materials is rare, possibly because each crystalline polysaccharide has its own unique monomer unit, preventing molecular design for controlling the self-assembly. Herein, we demonstrate the temperature-directed assembly of crystalline cellulose oligomers into kinetically trapped structures, namely, precipitated nanosheets, nanoribbon network hydrogels, and dispersed nanosheets (in descending order of temperature). It was found that enzymatically synthesized cellulose oligomers self-assembled in situ into those structures depending on the synthetic temperatures. Mechanistic studies suggested that the formation of the nanoribbon networks and the dispersed nanosheets at lower temperatures were driven by synergy between the decreased hydrophobic effect and the simultaneously induced self-crowding effect. Furthermore, nanoribbon network formation was exploited for the construction of cellulose oligomer-based hybrid gels with colloidal particles. Our findings promote the development of robust self-assembled materials composed of crystalline polysaccharides with highly ordered nano-to-macroscale structures.

High Thermal Diffusivity in Thermally Treated Filamentous Virus-Based Assemblies with a Smectic Liquid Crystalline Orientation.

Polymers are generally considered thermal insulators because the amorphous arrangement of the polymeric chains reduces the mean free path of heat-conducting phonons. Recent studies reveal that individual chains of polymers with oriented structures could have high thermal conductivity, because such stretched polymeric chains effectively conduct phonons through polymeric covalent bonds. Previously, we have found that the liquid crystalline assembly composed of one of the filamentous viruses, M13 bacteriophages (M13 phages), shows high thermal diffusivity even though the assembly is based on non-covalent bonds. Despite such potential applicability of biopolymeric assemblies as thermal conductive materials, stability against heating has rarely been investigated. Herein, we demonstrate the maintenance of high thermal diffusivity in smectic liquid crystalline-oriented M13 phage-based assemblies after high temperature (150 °C) treatment. The liquid crystalline orientation of the M13 phage assemblies plays an important role in the stability against heating processes. Our results provide insight into the future use of biomolecular assemblies for reliable thermal conductive materials.

Filamentous Virus-based Assembly: Their Oriented Structures and Thermal Diffusivity.

Organic polymers are generally regarded as thermal insulators because amorphous arrangement of molecular chains reduces the mean free path of heat-conducting phonons. However, recent studies indicated that single chains of polymers with highly oriented structures could have high thermal conductivity than bulk polymers because stretched polymer chains effectively conduct phonons through polymeric covalent bonds. Here, we demonstrated the possibility of non-covalent virus assembly prepared by simple flow-induced methods toward high thermal conductive polymeric materials. Films with high thermal diffusivity composed of non-covalent bond-based assemblies of liquid crystalline filamentous viruses were prepared using a simple flow-induced orientation method. Structural and thermal characterization demonstrated that highly oriented structures of the viruses in the film were attributed to the high thermal diffusivity. Our results will open attractive opportunities for biomolecular-based thermally conductive soft materials even though the assemblies are based on non-covalent bonds.

Effect of Component Mobility on the Properties of Macromolecular [2]Rotaxanes.

Macromolecular [2]rotaxanes comprising a polymer axle and crown ether wheel were synthesized to evaluate the effect of component mobility on the properties of the axle polymer, especially its crystallinity. Living ring-opening polymerization of δ-valerolactone with a pseudorotaxane initiator with a hydroxy group at the axle terminus was followed by end-capping with a bulky isocyanate. This yielded macromolecular [2]rotaxanes (M2Rs) possessing polyester axles of varying molecular weights. The crystallinity of the axle polymers of two series of M2Rs, with either fixed and movable components, was evaluated by differential scanning calorimetry. The results revealed that the effect of component mobility was significant in the fixed and movable M2Rs with a certain axle length, thus suggesting that the properties of the axle polymer depend on the mobility of the polyrotaxane components.

Number density of liquid inclusions formed in frozen aqueous electrolyte.

Frozen aqueous chlorides (≤50 mM) are characterized by using confocal fluorescence microscopy and small angel X-ray scattering (SAXS). The former method allows us to determine the size of a liquid inclusion formed in the ice matrix at temperatures above the eutectic point of the system (t(eu)). Isolated liquid inclusions of a uniform size are formed when the temperature of a frozen electrolyte increases past t(eu). The size of the liquid inclusions depends on the observation temperature as well as on the concentration (c(salt)) and type of salt dissolved in the original unfrozen solution. However, the number density of liquid inclusions is almost constant and independent of these experimental parameters, particularly when an electrolyte is frozen in liquid nitrogen. Salt accumulation can then occur at the imperfections of the ice crystals. The occurrence probability of the imperfections is independent of the nature of an incorporated salt. The amount of a salt confined in each inclusion ranges from 7 to 240 fmol, depending on c(salt). SAXS measurements provide information on the size of individual salt crystals formed at temperatures below t(eu). The radius of gyration of a salt crystal ranges from 2 to 2.8 nm, and does not depend significantly on c(salt). Thus, each inclusion is formed from 10(6)-10(9) nanocrystals, which can act as seeds. When doped ice is prepared at higher temperatures, for example -16 °C, the isolation of liquid inclusions is not sufficient and coalescence occurs more easily upon an increase in temperature or cs(alt). However, when c(salt) is lower than 10 mM, the number density of liquid inclusions is almost constant, irrespective of the freezing temperature.