Nobuhiko Hosono

We herein report the synthesis and characterization of ABA triblock copolymers that contain two complementary association motifs and fold into single-chain polymeric nanoparticles (SCPNs) via orthogonal self-assembly. The copolymers were prepared using atom-transfer radical polymerization (ATRP) and possess different pendant functional groups in the A and B blocks (alcohols in the A block and acetylenes in the B block). After postfunctionalization, the A block contains o-nitrobenzyl-protected 2-

Metal-organic frameworks (MOFs) and porous coordination polymers (PCPs) have been well-recognized as emerging porous materials that afford highly tailorable and well-defined nanoporous structures with three-dimensional lattices. Because of their microporous nature, MOFs can accommodate small molecules in their lattice structure, thus discriminating them on the basis of their size and physical properties and enabling their separation even in the gas phase. Such characteristics of MOFs have attrac

Rational molecular design and processing, enabling large-area molecular ordering, are important for creating high-performance organic materials and devices. We show that, upon one-step hot-pressing with uniaxially stretched Teflon sheets, a polymer brush carrying azobenzene-containing mesogenic side chains self-assembles into a freestanding film, where the polymer backbone aligns homeotropically to the film plane and the side chains align horizontally. Such an ordered structure forms through tra

We herein report the divergent and convergent synthesis of coordination star polymers (CSP) by using metal-organic polyhedrons (MOPs) as a multifunctional core. For the divergent route, copper-based great rhombicuboctahedral MOPs decorated with dithiobenzoate or trithioester chain transfer groups at the periphery were designed. Subsequent reversible addition-fragmentation chain transfer (RAFT) polymerization of monomers mediated by the MOPs gave star polymers, in which 24 polymeric arms were gra

Atomic force microscopy (AFM)-based single-molecule force spectroscopy (SMFS) is applied to single-chain polymeric nanoparticles (SCPNs) to acquire information about the internal folding structure of SCPNs and inherent kinetic parameters of supramolecular self-assembling motifs embedded into the SCPNs. The SCPNs used here are polyacrylate-based polymers carrying 2-ureido-4-[1H]-pyrimidinone (UPy) or benzene-1,3,5-tricarboxamide (BTA) pendants that induce an intramolecular chain collapse into nan

Molecular recognition is of paramount importance for modern chemical processes and has now been achieved for small molecules using well-established host-guest chemistry and adsorption-science principles. In contrast, technologies for recognizing polymer structure are relatively undeveloped. Conventional polymer separation methods, which are mostly limited in practice to size-exclusion chromatography and reprecipitation, find it difficult to recognize minute structural differences in polymer stru

Photoresponsive poly(amide acid) (PAA) gels containing multiple azobenzene units in a rigid aromatic backbone were synthesized. A centimeter-long cantilever made up of the photoresponsive PAA gel exhibited reversible bending motions upon blue (442 nm) and visible light (>490 nm) irradiation. The network structure in the PAA gels during alternating photoirradiation of blue and visible light was characterized using in situ scanning microscopic dynamic light scattering (SMILS), which revealed rever

The purification step in the manufacturing of cyclic polymers is difficult as complete fractionation to eliminate linear impurities requires considerable effort. Here, we report a new polymer separation methodology that uses metal-organic frameworks (MOFs) to discriminate between linear and cyclic polyethylene glycols (PEGs) via selective polymer insertion into the MOF nanopores. Preparation of a MOF-packed column allowed analytical and preparative chromatographic separation of these topological

Adsorption of polymers from the solution phase has been extensively studied to cope with many demands not only for separation technologies, but also for the development of coatings, adhesives, and biocompatible materials. Most studies hitherto focus on adsorption on flat surfaces and mesoporous adsorbents with open frameworks, plausibly because of the preconceived notion that it is unlikely for polymers to enter a pore with a diameter that is smaller than the gyration diameter of the polymer in

Polymers with two-dimensional (2D) network topologies are currently gaining significant attention due to their unique properties that originate from their regulated conformations. However, in contrast to conventional 1D- and 3D-networked macromolecules, the synthesis of such 2D networks provides challenges for polymer chemists because of the nature of the networking polymerisation reaction, which occurs in a spatially random fashion when conventional solution-phase synthesis is performed. Here w

Strategic design of the stationary phase in liquid chromatography (LC) is crucial for modern separation science. Herein, a design approach using mixed metal-organic frameworks (MOFs) as tunable LC stationary phases is proposed. Three MOFs with an isostructural pillared-layer structure are employed, with pore sizes tuned by the systematic design of the constituent ligands, using 1,4-benzenedicarboxylate (bdc), 1,4-naphthalenedicarboxylate (ndc), and 9,10-anthracenedicarboxylate (adc). Packed colu

Abstract Incorporating soft and dynamic elements into crystalline porous materials with hard and static structures can be of immense utility. To this end, herein, the design of functional porous materials and their dynamic properties are described. Dynamic molecular elements were incorporated in porous coordination polymers (PCPs)/metal-organic frameworks (MOFs) to realize responsive and high-performance porous systems. The dynamic nature of the PCPs/MOFs was directly visualized in real-time via

"Soldiers-Sergeant-Soldiers" experiments performed on single-chain polymeric nanoparticles (SCPNs) with an ABA-type triblock architecture carrying chiral and achiral benzene-1,3,5-tricarboxamides (BTAs) in different blocks reveal that the BTAs form segregated, multiple stacks in a single SCPN.