Research articles

We explored the feasibility of Tetra-PEG gel, a controllable hydrogel, as a new biomaterial to develop a coating agent for post-ESD ulcers. We examined the optimal conditions for hydrogel application and developed a specialized catheter, then investigated its properties. Ultimately, we successfully used the optimized hydrogel and device to cover post-ESD ulcers in the porcine stomach. Further optimization of the hydrogel and ongoing research through animal experiments are expected to deepen our understanding of the material’s effects on ulcer healing and contribute to its clinical applications.

The effects of an organic monoglyceride (OMG) plasticizer on the crystallization of the PLLA/PDLA (50/50) blend were investigated by examining the isothermal crystallization of the blend with different contents of OMG (1–5 wt%) using POM, DSC, and time-resolved WAXD. It was found that the increase of the OMG content promoted the exclusive formation of stereocomplex crystallites and enhanced its crystallinity while suppressing the formation of homocrystals.

The thiol-Michael polyaddition of three dialkynyl monomers with several dithiols proceeded using triethylamine as the catalyst to give unsaturated poly(ester-thioether)s with the expected structures (M_n, 2.4 × 10³ to 22.6 × 10³; molecular dispersity index [M_w/M_n], 1.26–2.00). All of the poly(ester-thioester)s had single glass-transition temperature values between −27 and 49 °C. While the rigid main chains improved the glass transition temperature, all of the poly(ester-thioester)s showed apparent enzymatic hydrolysis by lipase but low biodegradability in biodegradation tests using activated sludge.

Three cyclic oxoester-thioester hybrid monomers were studied for anionic and cationic ring-opening polymerizations. Anionic polymerizations using thiol with 2,6-lutidine were successful for the chemoselective cleavage of the thioester with the thiol propagating end, exhibiting the living character to some extent. The polymerization in 2,6-lutidine without an initiator produced macrocyclic polymers. The cationic polymerizations occurred with the aid of CF₃SO₃H and benzyl alcohol but involved side reactions with low chemoselective ring cleavage. The thioester unit caused the polymers to exhibit a lower T_g with greater thermal and photo degradability.

Doping lanthanides into lamellar crystals of diacetylene derivatives with terminal carboxylic acids reorganized the lamellar structure and dramatically changed the crystal morphology. Detailed investigation of the crystal growth process revealed that the complexes of lanthanide and diacetylene derivatives, which are slightly formed in the solution phase during lanthanide doping, may act as a pseudonuclear agent and change the morphology of the lamellar crystals. Furthermore, the morphology changes of the lamellar crystal films significantly altered surface properties such as film appearance and water repellency.

Simple control of the thermoresponsive properties of polymers in water over a broad range is achieved by using a designed urethane-containing acrylamide monomer in combination with a hydroxy-containing precursor monomer, which forms a statistical sequence due to its similar backbone. The copolymers exhibited a lower critical solution temperature-type responsive behavior in water, and the effects of structural factors such as composition, molecular weight, end groups and side-chain structure in urethane monomers were systematically evaluated.

Schematic illustrations of the alignment behavior induced by SWaP. Photopolymerization was conducted with a scanned UV slit light. Uniaxial molecular alignment was induced when the polymer concentration in the exposure area was high, while it was random when the polymer concentration was low.

Natural rubber exhibits the strain-induced crystallization (SIC). By using WAXD, the orientation of NR crystal formed by SIC under planar elongation was revisited. We found that the orientational state of the crystal lattice possesses a continuous margin of the orientation angle between 6.4 and 19.6° for the ac plane with respect to the surface of the specimen sheet in the real NR specimen. This orientational state could be accomplished as a result of balancing the preferential parallel orientation of (120) planes (the slip planes) and C = C planes with respect to the surface of the specimen sheet.

We synthesized a new benzobisthiazole (BBTz) containing building unit in which two alkoxythiophenes were attached to the BBTz moiety so as to induce oxygen–sulfur noncovalent intramolecular interactions and thereby interlock the linkage. As a result, the π-conjugated polymer incorporating the new building unit, PDBTz2, had a more coplanar and rigid backbone than the alkyl counterpart, PDBTz1. Interestingly, the backbone orientation was completely altered from the edge-on orientation (PDBTz1) to the face-on orientation (PDBTz2), which is preferable for organic photovoltaics. Accordingly, PDBTz2 showed a much higher photovoltaic performance than PDBTz1.

Developing fluorescence anion sensors is important because anions play a significant role in various biological phenomena. Herein, we evaluated the anion binding properties of a polyhedral oligomeric silsesquioxane (POSS) derivative with eight urea groups and a 3D structure. The results revealed that the POSS derivative with urea groups can bind to sulfate ions and exhibits a greater binding ability than that of the model compound because multiple urea groups exhibit cooperative effects. Through the introduction of naphthyl urea groups, the POSS derivative can be used as a fluorescence sensor for quantifying sulfate ions.

a Column separation under black light illumination. b Calculated overlap of dπ-pπ orbitals demonstrating conjugation

The in situ wide-angle (WAXD) and small-angle X-ray scattering (SAXS) measurements have been performed using a synchrotron microbeam technique for the melt-isothermally-growing iPP spherulites. The thus-collected data were found to be classified into three sets of totally different WAXD/SAXS patterns, from which the three different orientation modes of the stacked lamellae and related crystallographic axes were deduced. These structural information allowed us to discuss the growth mechanism of stacked lamellae in the iPP spherulites from the microscopic point of view.

Water-insoluble micropatterned films were prepared from poly(vinyl alcohol) (PVA) (or ethylene-vinyl alcohol copolymer (EVOH)) and poly(methacrylic acid) (poly(MAAc)). The carboxy groups in poly(MAAc) underwent dehydration reactions with the hydroxy groups in the vinyl alcohol units during heating at 135 °C, which resulted in the introduction of a crosslinked structure with ester bonds into the polymeric network of the micropatterned films. The micropatterns could be peeled off from the films after decomposition and maintained their patterned shapes.

Side-chain typed POSS-based polynorbornenes connecting with a short spacer exhibiting optical transparency owing to prevention of POSS crystallization to provide amorphous character. In addition, the resulting amorphous polymers exhibited excellent thermal stability.

This study explores the effects of long-term degradation on the viscoelastic properties of viscoelastic liquids using tetra-armed polyethylene glycol (Tetra-PEG) slimes as model material. It aims to enhance control over the viscoelasticity of biomedical materials, like sodium hyaluronate, by introducing specific cleavage sites into the Tetra-PEG slimes to simulate degradation. The study reveals that despite degradation, the slimes maintain a single relaxation mode, offering a method to design viscoelastic liquids with predictable and controllable degradation for biomedical applications.

A new peptide carrier that mimics the basic leucine zipper domain (bZIP) of DNA-binding proteins was designed, in which (LU)₄ is the leucine zipper motif and (KUA)₃ is the basic DNA-binding motif (U = α-aminoisobutyric acid). When mixed with pDNA, (KUA)₃-(LU)₄ peptide condensed DNA molecules to form nanoparticles. Furthermore, when complexes of the (KUA)₃-(LU)₄ peptide and pDNA were introduced into the leaves of Arabidopsis thaliana (A. thaliana), the reporter protein was expressed in plant cells. Thus, (KUA)₃-(LU)₄ is an efficient carrier of pDNA with high dissociation efficiency.

In this study, the effects of the polyrotaxane cross-linker concentration and solvent content on elastomer preparation were investigated to obtain elastomers with high toughnesses due to the properties of the polyrotaxane cross-linking agent. If elastomers were prepared in a state in which the slide-ring effect of the polyrotaxane was easily expressed by the concentration of the polyrotaxane cross-linker and the amount of solvent, the elastomers obtained elongated more and were tougher than elastomers made from conventional cross-linkers.

Postpolymerization modifications of poly(2-methoxyethoxycarbonylmethylene) and poly(2-phenoxyethoxycarbonylmethylene) with mixtures of Me₃SiCl and LDA efficiently transformed the alkoxycarbonylmethylene repeating units to ketene silyl acetals to yield a product with up to 93 mol% composition of the latter unit. TBAF-mediated benzylation of the highly silylated polymer with benzyl bromide yielded a polymer containing side chain O (major)- and main chain C (minor)-benzylated units along with the unreacted ketene silyl acetal unit.

This study reports a method that significantly improved the stretchability and damping properties of hydrogels. The innovation is the replacement of traditional short-chain crosslinkers, such as N,N-methylenebis(acrylamide) (MBA), with long-chain crosslinkers. As a result, the molecular chains of the network could slide when stretched, which greatly increased the mechanical elongation and enabled damping by the hydrogel (up to 85%). The maximum elongation reached 21800%, with a toughness of 11.32 MJ m⁻³. This study provides a new approach for the development of highly stretchable and damping hydrogels.

Structural changes induced by thermal denaturation and renaturation of a double-helical polysaccharide xanthan in acidic and basic solutions were investigated mainly by light scattering measurements and circular dichroism spectroscopy. In acidic solution, the renatured components were almost the same as those in native components, while small amounts of aggregates and a hairpin structure were produced via denaturation and renaturation processes. In basic solution, the double helices were dissociated upon heating into the single coils, and high molar mass sample produced a hairpin structure after subsequent renaturation.