Review

Photoinduced transitions between the solid, glass, and liquid states based on molecular photoswitches promise an enormous variety of applications, such as photoswitchable adhesives, which contribute to material recycling for a sustainable future in the era of composite materials. In this review, we highlight recent progress in the photoinduced transitions of small molecules and polymers and systematically discuss the molecular designs, mechanisms, applications, merits and demerits, and future challenges in each photoswitch and the whole field.

Mechanochemistry is a promising technology to tackle current and future polymer waste streams for a sustainable future. With this review, we take into account synthetic, computational, technical, and engineering perspectives to converge trituration and polymer mechanochemistry with a particular focus on the fate of commodity polymers and potential technologies to monitor mechanochemical reactions while they occur. We highlight the need for future transdisciplinary research to tackle the high-leverage parameters governing an eventually successful mechanochemical polymer degradation approach for a circular economy.

In this review, we show that reversibility of charge storage occurs in polymers with bistable redox-active groups populated in the repeat units of a nonconjugated backbone, especially when an electron self-exchange reaction spreads throughout the polymer. We will also show that extending the idea of electron exchange to electron/proton exchange leads to reversible hydrogen storage based on the bistability of hydrogenated and dehydrogenated states and the equilibrium for hydrogenation.

In this review article, an overview of recent studies on heat-responsive and photoresponsive adhesive materials and the characteristics of other external stimuli used for dismantlable adhesive systems are described. Then, research on dismantlable adhesive materials using polyperoxides is introduced as an example of early material design. Next, the development of a dual-stimuli responsive dismantlable adhesive material is interpreted as a material design for achieving stability during use and degradability during dismantling. Finally, recent studies on heat-responsive, dismantlable adhesive materials, which are thermally stable during use while responding quickly during disassembly by heating, are described.

Crystalline porous molecular frameworks formed through intermolecular hydrogen bonding calling hydrogen-bonded organic frameworks (HOFs) have recently been investigated as a new family of functional porous materials. In this review, HOFs composed of tritopic, tetratopic, and hexatopic carboxylic acid derivatives, which form H-bonded network such as those with hcb, sql, and hxl topologies depending on the numbers, positions, and orientations of the carboxy groups and conformational flexibility of the molecular skeletons, are reviewed by considering structural aspects such as isostructurality.

A newly discovered nanostructure (island-nanomatrix structure) is introduced based on previous studies on the structure of natural rubber. Effects of the proteins and phospholipids that form the nanomatrix on the mechanical properties of natural rubber are described using a model island-nanomatrix structure of natural rubber. Furthermore, a synthetic cis-1,4-polyisoprene with island-nanomatrix structure is prepared; its mechanical properties are similar to those of natural rubber.

With recent advancements in the Internet of Things (IoT), indoor organic photovoltaic devices (iOPVs) have attracted increasing attention because of their potential utility as self-sustainable, eco-friendly power sources. This review highlights emerging iOPV technologies based on π-conjugated polymers and oligomeric materials and outlines their fundamental principles and characterization techniques.

Chemical design strategies developed in the last decade for conjugated polymer binders in lithium-ion batteries (LIBs) are reviewed here. The first part of this review discusses the mechanism of operation and role of binders in LIBs, and the importance of conductivity in advanced binder systems. The second part of this review gives an account of various conducting polymer binders developed for cathodes and anodes of LIBs. The review concludes with an emphasis on sustainable synthetic design strategies for next-generation conducting polymer binders for greener electrochemical energy storage systems.

This review is focused on evolutions of precision radical polymerizations in various directions from metal-catalyzed Kharasch addition or atom transfer radical addition (ATRA). The developments include metal-catalyzed living radical polymerizations via reversible activation of carbon-halogen bonds, metal-catalyzed step-growth radical polymerizations of designed monomers having an unconjugated vinyl group and a reactive carbon-halogen bond, simultaneous metal-catalyzed chain- and step-growth radical polymerization for producing degradable vinyl copolymers with main-chain ester units, and vinyl monomer sequence control via combinations of iterative ATRAs and various controlled polymerizations.

Academia and industry are interested in using autotrophic microorganisms as a sustainable/green production platform to produce biochemical products and commercially relevant commodities, including biopolymers. Unlike heterotrophs that require carbohydrates and amino acids for growth, autotrophs have evolved to fix carbon dioxide and drive metabolic processes utilizing either light (photoautotrophs) or chemical compounds (chemolithotrophs) as energy sources. Here, we review the current state-of-the-art in the construction of autotrophic microbial cell factories for efficient biopolymer production and recent breakthroughs in natural autotrophs focusing on biopolymer production.

In 1996, the author reported “self-oscillating” polymer gels that spontaneously repeat swelling–deswelling changes in a closed solution without any on–off switching by external stimuli, such as with heart muscle. The gel has an energy converting system provided by an oscillatory chemical reaction called the Belousov–Zhabotinsky (BZ) reaction, which induces periodic mechanical motion of the polymer chain. The author systematically developed self-oscillating polymer gels with approaches ranging from demonstrating fundamental behaviors to constructing material systems for potential applications in biomimetic materials such as autonomous soft actuators, automatic transport systems, and functional fluids causing autonomous sol-gel oscillations, as seen with amebas. In this review, these research developments and recent progress from the author’s group are summarized.

In this review, we overview the recent advances associated with seminal findings in the development of nucleic acid-based fluorescent sensor systems aimed at application for exploring intracellular phenomena. We described the fluorescence signal generation mechanisms of each nucleic acid-based fluorescent sensor, including molecular beacon and quencher-free linear probes, as well as aptamer or DNAzyme-based systems. In addition, cascade hybridization chain reaction and catalyzed hairpin assembly are introduced as methods for amplifying fluorescence signals under isothermal conditions.

Research advances in the extraction, structural and conformational characteristics, and biological activities (antitumor, anti-inflammation, immunomodulatory, hypoglycemic activity) of β-glucans from three fungi, Auricularia auricula judae, Lentinus edodes and yeast, as typical representatives, were reviewed, as well as the potential mechanism and the structure-function relationship. Additionally, as-fabricated β-glucan-derived nanocomposite biomaterials as carriers for delivering drugs, genes, nanoparticles, and fluorescence probes were addressed.

The present review focuses on the enzymatic synthesis of unnatural oligosaccharides and polysaccharides linked through strictly controlled α(1→4)-glycosidic linkages by glucan phosphorylase (GP) catalysis. In particular, the recent progress of the enzymatic synthesis of unnatural polysaccharides by GP (isolated from thermophilic bacteria, Aquifex aeolicus VF5)-catalyzed polymerization and related reactions is overviewed. The unnatural substrates have high applicability as practical functional materials in pharmaceutical, medicinal, and biological research fields.

Hydrophobically modified polysaccharides have attracted considerable attention in the biomedical field because of their biocompatibility, biodegradability, and nontoxicity. This article reviews previous studies on micellar structures formed by hydrophobically modified polysaccharides (pullulan and amylose) in aqueous solutions by static and dynamic light scattering, small angle X-ray and neutron scattering, and fluorescence from pyrene solubilized in the polymer solution. Depending on the degree of substitution, the hydrophobically modified polysaccharides exist in aqueous solution as full or loose flower necklaces or as nanogels made up of randomly branched polymers.

TEMPO-catalyzed oxidation enables efficient and position-selective conversion of primary hydroxy groups in water-soluble and -insoluble polysaccharides to sodium carboxylate groups. TEMPO/NaBr/NaClO in water at pH 10 is an advantageous system in terms of the degrees of oxidation and reaction rates. Various new water-soluble TEMPO-oxidized polysaccharides have been prepared by TEMPO-catalyzed oxidation, and they have unique properties and functionalities. When crystalline native cellulose and chitin are oxidized by the TEMPO/NaBr/NaClO system under suitable conditions, the obtained water-insoluble oxidized products can be converted to characteristic nanomaterials by mechanical disintegration in water.

“Breath figure formation” during the casting process of polymer solutions under high atmospheric humidity provides honeycomb-patterned polymer films (honeycomb films) with regularly arranged micropores. The development of production technology for large-area honeycomb films is indispensable for their various applications. Manufacturing equipment consisting of three zones (for casting, humidification, and drying of polymer solutions) for successive formation of large-area honeycomb films was newly designed and constructed. By using this equipment, physicochemical experimental parameters, e.g., the surface temperature of polymer solutions, dew point of the humidification zone, humidification time, and interfacial tension between water and the polymer solution, were effectively changed to optimize the density and size of condensed water droplets. Large-area honeycomb films were formed by a roll-to-roll process. Herein, recent developments in biomedical applications of honeycomb films are described.

Our recent progress on the phenylazomethine dendrimers to afford advanced functionalities due to the π-conjugated azomethine structure and electronic state are reviewed. The functions include luminous dendrimers by bismuth assembly, Y-shape recognition using porphyrin core, and atomicity-controlled template of metal salts on imine parts. The precisely controlled template ability developed synthesis of multimetallic subnanoparticles and superatoms that can mimic the properties of elemental atoms.

Block copolymers are used as nano-tools for delivering hydrophobic drugs. Their formulation requires robust characterization and clarification of the critical quality attributes correlating with the safety and efficacy. Static solution scattering from block copolymers is one such technique. This paper outlines the theoretical background and current models for analyzing this scattering and then presents an overview of our recent studies on block copolymers.

Recent developments in the one-step synthesis of structurally controlled hyperbranched polymers (HBPs) in terms of molecular weight, dispersity, number of branching points, branching density, and number of chain-end groups by radical polymerization are summarized. Copolymerization of conventional vinyl monomers and a vinyl telluride, which induces the branching structure, under organotellurium-mediated radical polymerization (TERP) affords HBPs with dendrimer and dendron structures. The same synthetic strategy under atom transfer radical polymerization is also discussed.