Articles in 2023

This focus review described recent research on cinnamate-based polymers. Polyesters derived from hydroxycinnamic acid showed characteristic ultraviolet response behavior. The mechanism of photodeformability and found that polyesters derived from 3-hydroxycinnamic acid are deformed by photoexpansion. By using dimers of bioproduced cinnamates, polyimides and polyamides were synthesized. The biobased polyimides and polyamides were found to exhibit high transparency, mechanical strength, and good chemical modification properties due to the cyclobutane main chain and carboxylic acid side chains, which are not present in other high-performance polymers.

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.

Atomic molecular dynamics simulations of the complexation of plasmid DNA in the presence of two types of cationic peptides clear the mechanism of plasmid DNA condensation for gene delivery systems.

Inspired by mussel adhesion, polydopamine ultrathin films were formed at silicone oil/water interfaces even in neutral solutions. The MCF-7 cells successfully adhered to the oil/water interface without aggregation during cell growth. The interfacial wrinkles were induced by changes in the oil volume and the compressive stress, and the MCF-7 cells adhered to the oil/water interface and were arranged along the wrinkles. The polydopamine interfacial films provide new opportunities to investigate the relationships between toughness and patterns for tissue engineering and regenerative medicine.

Polymer gels containing an iridium complex in their compartmentalized nanodomain structures were designed. Novel Ir-containing vinyl monomers were first synthesized and then incorporated into homogeneously dispersed thermoresponsive nanodomains via living radical polymerization. The product gels exhibited immediate color change by sensing ammonia in a thermoresponsive manner, and catalyzed the N-alkylation reaction. These findings strongly supported the importance of the incorporation of organometallic complexes into the nanodomain of hydrogels for the further development of a novel soft material exhibiting selective molecular recognition abilities and catalytic reactions.

We have developed innovative new phosgenation reactions and their special reaction systems with the key objective of “safe application” to organic synthesis. This focus review summarizes our recent studies on in situ photo-on-demand phosgenation reactions of alcohols and amines for synthesizing polycarbonates, polyurethanes, and their precursors such as chloroformates, carbonate esters, and diisocyanates, in batch reaction systems, which are preferable for laboratory or small-scale industrial syntheses.

The transparent and flexible photocatalytic films composed of titanium oxide, organophosphonate-modified polysilsesquioxane, and poly(bisphenol A-co-epichlorohydrin) were prepared. The effects of hydroxy group ratio and organic substituent on phosphorus atoms in these films were evaluated by appearance and photocatalytic ability. Film using anchoring layer with APPS-low was formed large cracks, while films with other anchoring layers were formed no cracks. However, all films were formed small cracks after a 10-day durability test. All films showed photodegradation ability of methylene blue, photoinduced hydrophilicity, and photocatalytic bactericidal effects on Escherichia coli.

Two-dimensional sheet-shaped poly(methyl methacrylate) (2d-PMMA) with crosslinking only in the two-dimensional direction was synthesized via planar polymerization of MMA monomer in montmorillonite (MMT) nanolayers by using γ-ray irradiation, and the samples obtained were characterized by size-exclusion chromatography with a multiangle light scattering (SEC-MALS) and atomic force microscopy (AFM). Our results provided experimental proof that the desired sheet-like polymer was attained and the obtained samples were appropriately characterized, augmenting the previous reports.

Atomic force microscopy (AFM)-based nanomechanical characterization techniques have been extensively used to investigate the mechanical properties and mechanisms of polymeric materials. This technique enables direct visualization of the micromechanical properties of material surfaces and is referred to as the AFM nanomechanics technique. This review article discusses the application of this technique to studying polymer composites with a specific focus on the significant advances made in tracking the microscopic deformation behavior and visualizing the microscopic stress distribution of materials.

Statistical structural analysis was conducted for ternary blends of copolymers composed of two monomers chosen from acrylonitrile, α-methylstyrene, and styrene. Blending parameters, such as the composition and blending fraction of the component copolymer, were predicted by regularized regression analysis of ¹H NMR data. Regression models were constructed with the dataset for copolymers and binary blends to predict the blending parameters for ternary blends. The composition and blending fraction were predicted with high accuracies

We propose a method for analyzing the morphology of polymer blends with nanometric resolution using scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopic imaging in the low energy-loss region (5–30 eV). Furthermore, we employed medium-voltage (200 kV) and high-voltage (1000 kV) STEMs at different temperatures to compare the extent of electron-beam damage. This comparison highlighted the utility of the ultra-high voltage electron microscope for suppressing thermal damage and analyzing thicker samples.

The recent studies on the development of polymeric core crosslinked particles for drug delivery system are reviewed. The first part of this article describes synthesis of polymeric core crosslinked particles via the formation of nanoemulsion, characterization of the particle structure using small angle scattering techniques, and effect of polymer chain conformation on the particle pharmacokinetics and pharmacodynamics. The second part introduces zwitterionic amino acid polymer (ZAP)-based core crosslinked particles and discusses some advantages of using ZAPs as a pilot macromolecule for cancer-targeting chemotherapy.

Anionic initiator systems for styrene polymerization were prepared via desilylation of benzylsilanes with metal alkoxides. Benzyltrimethylsilyl anions as the anionic polymerization initiators were obtained from benzylsilanes and potassium tert-butoxide at 70 °C in the absence of 18-crown-6. On the other hand, in the presence of 18-crown-6, benzyl anions were obtained at −78 °C. Subsequent addition of the styrene monomer to these initiators yielded polystyrenes. With the addition of 1,1-diphenylethylene (DPE) to the initiator system containing 18-crown-6, the corresponding DPE adduct was obtained.

A novel polymer material PEDOT:DBSA was prepared using oxidative polymerization and was modified by cross-linker GOPS and H₂SO₄-posttreatment. This material exhibits biocompatibility toward cell culture comparable to the glass substrate. The cross-linking process resulted in complete stabilization of PEDOT:DBSA thin film in an aqueous environment, whereas such stabilization was achieved even without high-temperature treatment. The model OECT device proved that the proposed material possesses electrical properties comparable to or even better than other organic mixed conductors used for transistors. This all shows a great potential of PEDOT:DBSA for bioelectronics applications.

Photoresponsive molecular amphiphiles have been incorporated into distinct soft materials to control properties in high temporal and high spatial manners. We demonstrate molecular azobenzene amphiphiles for construction of chiral supramolecular assemblies with excellent photoresponsibility and a high capacity for supramolecular transformation in aqueous media. Supramolecular chiral structures of azobenzene amphiphiles can assemble from microscopic to macroscopic length scales

Quantifying the interfacial energy of a polymer–liquid interface is challenging. We previously succeeded in analyzing the interfacial energy of a dynamic polymer brush interface by measuring the deformation of an ultrathin elastomer film floating on water. However, the quantitativity remains debatable because the bulk modulus was used. In this study, we reanalyze the interfacial energy using the ultrathin-film modulus. Large negative interfacial energy was observed for the system of high-density stretched brushes. The free energy balance for the system floating on water was calculated, validating the negative interfacial energy.

In our study, a continuous change of tensile strength (26.9–49.5 MPa) and impact strength (4.7–23.2 KJ/m²) of iPP samples is successfully accomplished without the specific catalysts. The high content of γ-crystal with thin lamellar thickness related to the ductility property is also experimentally confirmed. A morphology of the diagram is proposed based on the composition and molded technology.

Here, we introduce a candidate material, water-soluble guanidinylated chitosan (WGCS), for a protein delivery system. WGCS composed of 48.2% guanidinylated chitosan, 20.6% chitosan, and 31.2% chitin units was prepared from low-molecular-weight chitosan (CS). WGCS showed ca. 2.5-fold higher internalization into HeLa cells than CS does. Moreover, we found that WGCS significantly enhanced the internalization of bovine serum albumin in transport medium at pH 7.4.

While the physical properties of polymer solution have been extensively investigated, less is explored at the vicinity of vitrification due to the experimental difficulty. In this study, we analyzed polymerization-induced vitrification during bulk polymerization of methyl methacrylate. Dielectric spectroscopy captured vitrification caused by the change of polymer concentration at a constant temperature. Our study shows that the polymerization solution becomes heterogeneous at the vicinity of vitrification. In addition, this heterogenization coincides with the reaction acceleration classically known as the Trommsdorff effect.