Nanoarchitectonics of a Smectite with 4,4'-Diammonium-α-truxillic Acid and Its Methyl Ester for the Removal of o-Phenylphenol and Biphenyl from Water.

Adsorbents with hydrophilic and hydrophobic natures were designed by intercalating a bioderived molecule; 4,4'-diammonium-α-truxillic acid (4ATA) and 4,4'-diammonium-α-truxillic acid dimethyl ester (E4ATA), which both are bioderived molecules, into a smectite (purified bentonite) to concentrate o-phenylphenol and biphenyl, respectively, from water. The adsorption isotherm showed high affinity between the 4ATA-smectite hybrid and o-phenylphenol with a high Langmuir constant (0.98 L mg-1). Meanwhile, the E4ATA-smectite hybrid adsorbed biphenyl with a high Langmuir constant (3.61 L mg-1). The adsorption properties of 4ATA- and E4ATA-smectite hybrid were contributed by the chemical characteristics of 4ATA and E4ATA in the interlayer space of the smectite.

Regulating Electrostatic Interactions toward Thermoresponsive Hydrogels with Low Critical Solution Temperature.

Low critical solution temperature (LCST) of commonly used thermoresponsive polymers in water is basically dominated by hydrophobic interactions. Herein, a novel thermoresponsive system based on electrostatic interactions is reported. By simply loading aluminum chloride (AlCl3 ) into non-responsive poly(2-hydroxyethyl acrylate) (PHEA) hydrogels, PHEA-Al gels turn to have reversible thermoresponsive behavior between transparent and opaque without any volume change. Further investigations by changing metal ion-polymer compositions unravel the necessity of specific electrostatic interactions, namely, cation-dipole bonding interactions between hydroxy groups and trivalent metal ions. The thermoresponsive hydrogel demonstrates high transparency (≈95%), excellent luminous modulation capability (>98%), and cyclic reliability, suggesting great potential as an energy-saving material. Although LCST control by salt addition is widely known, salt-induced expression of thermoresponsiveness has barely been discussed before. This design provides a new approach of easy fabrication, low cost, and scalability to develop stimuli-responsive materials.

Incorporation of Aramids into Polybenzimidazoles to Achieve Ultra-High Thermoresistance and Toughening Effects.

Polybenzimidazoles (PBIs) are recognized for their remarkable thermal stability due to their unique molecular structure, which is characterized by aromaticity and rigidity. Despite their remarkable thermal attributes, their tensile properties limit their application. To improve the mechanical performance of PBIs, we made a vital modification to their molecular backbone to improve their structural flexibility. Non-π-conjugated components were introduced into PBIs by grafting meta-polyamide (MA) and para-polyamide (PA) onto PBI backbones to form the copolymers PBI-co-MA and PBI-co-PA. The results indicated that the cooperation between MA and PA significantly enhanced mechanical strain and overall toughness. Furthermore, the appropriate incorporation of aromatic polyamide components (20 mol% for MA and 15% for PA) improved thermal degradation temperatures by more than 30 °C. By investigating the copolymerization of PBIs with MA and PA, we unraveled the intricate relationships between composition, molecular structure, and material performance. These findings advance copolymer design strategies and deepen the understanding of polymer materials, offering tailored solutions that address thermal and mechanical demands across applications.

Cyanobacterial supra-polysaccharide: Self-similar hierarchy, diverse morphology, and application prospects of sacran fibers.

The biological functions of polysaccharides are influenced by their chemistry and chain conformation, which have resulted in various functional applications and new uses for polysaccharides in recent years. Sacran is an intriguing ampholytic polysaccharide with several key properties such as metal adsorption, anti-inflammatory nature, and transdermal drug-carrying capacity. It has an extremely high molecular weight over 107 g/mol, which is much higher than those of the previously reported microbial polysaccharides. In particular, it has a remarkable self-orienting characteristic over a large length scale, which could produce a bundle with twisted morphologies from the nanoscale to the microscale with diameters of ~1 µm and lengths of >800 µm. In this review, morphological variations, as well as novel self-organization and hierarchical self-assembly are comprehensively discussed. Sacran fibers deform into various forms, such as two- and three-dimensional flexible fibers and micro-nano fragments, during their evaporation. The self-assembly and disassembly of the sacran are explained in terms of the preparation process and factors that influence the morphology. This review will pave the way for the development of novel modules such as humidity-sensitive actuators, micro-patterned cell scaffolds, and uniaxially oriented membranes.

Self-Standing Nanomembranes of Super-Tough Plastics.

Nanomembranes are effective coating materials for protecting substrates from external stimuli; however, they are generally not self-standing owing to their low mechanical toughness. Self-standing nanomembranes would be an innovative development in the field of nanotechnology including miniaturized devices. In this study, self-standing nanomembranes were developed by spin-casting supertough polyamides over dimethylformamide solution. The polyamides were synthesized by the polycondensation of two derivatives of 4,4'-diamino-α-truxillic acid (4ATA) with slightly bent diphenylcyclobutane in the core. Mechanical evaluation of the 4ATA polyamides having an appropriate composition of aliphatic diacids revealed a high strain-energy density of 231 MJ m-3 at its maximum, which is significantly tougher than spider silk. The nanocoats with a thickness of several hundred nanometers showing interference fringes were able to be peeled off the glass substrate without breaking, owing to its ultrahigh toughness. The self-standing nanomembrane would be applied to flexible devices in the future.

Voids induce wide-range modulation of elasticity for magnetic elastomers.

The relationship between the magnetorheological effect and the void ratio for a polyurethane magnetic elastomer with voids was investigated using a dynamic viscoelastic measurement under a magnetic field of 500 mT. The magnetic elastomer contains iron particles with a diameter of 235 µm at a concentration of 85 wt% (volume fraction: 0.43). The void ratio defined using the volume of vacancies in the non-filled volume of magnetic particles was increased by reducing the amount of polyurethane up to a maximum void ratio of 0.56. The storage modulus of the magnetic elastomer without voids was 1.5 × 105 Pa at 0 mT and 3.1 × 105 Pa at 500 mT, respectively; that is, no significant change in the modulus was observed. The storage modulus at 0 mT for the magnetic elastomer was independent of the void ratio, while the storage modulus at 500 mT increased in proportion to the void ratio. At a void ratio of 0.56, the storage modulus for the magnetic elastomer was 5.6 × 105 Pa at 0 mT and 6.1 × 106 Pa at 500 mT, respectively; that is, the magnetic elastomer demonstrated a significant change in the storage modulus on the order of MPa. This strongly indicates that production of voids enables movement of magnetic particles in the elastomer. Under both strains of 10-4 and 1, a significant and reversible response of storage modulus was observed after the first application of magnetic field even though the magnetic field was applied for 20 cycles, meaning that the change in the modulus is perfectly reversible although the elastomer contains many voids. SEM/EDX observations revealed that the area composed of carbon decreased with the increasing void ratio while the area composed of iron remained unchanged.

Super-Moisturizing Materials from Morphological Deformation of Suprapolysaccharides.

The evaporative interface on polysaccharides has evolved to form hierarchical structures with moisture sensitivity to enable organisms to live in drying environments. Here, the discovery of the morphological instability of polysaccharides, especially the reversible self-assembly/disassembly between micron-fibers and microparticles in response to changes in aquatic environments, is reported. This is similar but different to the dynamic instability observed in cytoskeletal proteins, in terms of an accompanying the polymeric deformation. The formation of the polymeric fibers containing crystalline structures can be flexibly controlled by controlling the polymer concentration and salt concentration in aqueous mixtures. Moreover, the microparticles having crosslinking points in the interior acquire the ability to retain a larger number of water molecules in drying environments and behave as super-moisturizing materials.

Fermentative production of 2-(4-aminophenyl)ethylamine to synthesize a novel heat-resistant biopolyurea.

The aromatic diamine 2-(4-aminophenyl)ethylamine (4APEA) is a potential monomer for polymers and advanced materials. Here, 4APEA was produced by fermentation using genetically engineered Escherichia coli (Masuo et al.2016). Optimizing fed-batch cultures of this strain produced the highest reported yield to date of 4APEA (7.2%; 3.5 g/L versus glucose) within 72 h. Appropriate aeration was important to maximize production and avoid unfavorable 4APEA degradation. Fermented 4APEA was purified from culture medium and polymerized with methylene diphenyldiisocyanate and hexamethylene diisocyanate to produce polyureas PU-1 and PU-2, respectively. The decomposition temperatures for 10% weight loss (Td10) of PU-1 and PU-2 were 276 °C and 302 °C, respectively, and were comparable with that of other thermostable aromatic polyureas. This study is the first to synthesize polyureas from the microbial aromatic diamine. Their excellent thermostability will be useful for the industrial production of heat-resistant polymer materials.

A Concise Review on the Physicochemical Properties of Biopolymer Blends Prepared in Ionic Liquids.

An enhancement of environmental concern lately has improved the awareness of researchers in employing eco-friendly solvents for processing biopolymers. Recently, ionic liquids have been utilized to prepare biopolymer blends as they are non-volatile and recyclable. Biopolymers such as cellulose, chitin, chitosan, keratin, lignin, silk, starch, and zein are widely used for the preparation of biopolymer blends via dissolution in ionic liquids, followed by coagulation procedure. In this concise review, three types of ionic liquids based on imidazolium cations combined with different counter anions that are frequently utilized to prepare biopolymer blends are described. Moreover, three types of biopolymer blends that are prepared in ionic liquids were classified, specifically polysaccharide/polysaccharide blends, polysaccharide/polypeptide blends, and polysaccharide/bioplastic blends. The physicochemical properties of biopolymer blends prepared in different imidazolium-based ionic liquids are also concisely reviewed. This paper may assist the researchers in the polymer blend area and generate fresh ideas for future research.

Vapor-Sensitive Materials from Polysaccharide Fibers with Self-Assembling Twisted Microstructures.

Polysaccharides play a variety of roles in nature, including molecular recognition and water retention. The microscale structures of polysaccharides are seldom utilized in vitro because of the difficulties in regulating self-assembled structures. Herein, it is demonstrated that a cyanobacterial polysaccharide, sacran, can hierarchically self-assemble as twisted fibers from nanoscale to microscale with diameters of ≈1 µm and lengths >800 µm that are remarkably larger than polysaccharides previously reported. Unlike other rigid fibrillar polysaccharides, the sacran fiber is capable of flexibly transforming into two-dimensional (2D) snaking and three-dimensional (3D) twisted structures at an evaporative air-water interface. Furthermore, a vapor-sensitive film with a millisecond-scale response time is developed from the crosslinked polymer due to the spring-like behavior of twisted structures. This study increases understanding of the functions of fibers in nature and establishes a novel approach to the design of environmentally adaptive materials for soft sensors and actuators.

Cationic Polymer Brush/Giant Polysaccharide Sacran Assembly: Structure and Lubricity.

A highly effective aqueous lubrication strategy employing electrostatic assembly of a negatively charged ultrahigh molecular weight natural polysaccharide named "sacran" and a positively charged poly[2-(methacryloyloxy)ethyltrimethylammonium chloride] (PMTAC) brush was investigated. The PMTAC brush was compressed through the adsorption of sacran to produce the layered structure of a PMTAC brush/sacran hybrid bottom layer and a poorly hydrated sacran top layer. The dynamic friction coefficients of the PMTAC brush were drastically reduced in salt-free sacran aqueous solutions, and the lubrication mode transition from the brush-lubrication regime to hydrodynamic lubrication was promoted. The electrostatic assembly was inhibited by the addition of NaCl into the lubricant solutions, leading to the loss of the lubrication effect. The hydrodynamic lubrication would be encouraged by the local viscosity enhancement at the friction boundary due to the poorly hydrated and highly viscous PMTAC brush/sacran hybrid film produced by the spontaneous electrostatic assembly.

Structure and Properties of Hybrid Film Fabricated by Spin-Assisted Layer-by-Layer Assembly of Sacran and Imogolite Nanotubes.

A free-standing (biomacomolecule/synthetic inorganic nanotubes) hybrid film was fabricated through an alternative layer-by-layer (LBL) assembly of sacran and imogolite nanotubes. Sacran is a natural polysaccharide extracted from the cyanobacterium Aphanothece sacrum, while imogolite is a natural tubular aluminosilicate clay found in volcano ash. The hybrid film thickness increased linearly with the number of the bilayers, because of the interaction between the negatively charged surface of sacran and the positively charged surface of imogolite. UV-vis spectroscopy indicated that the LBL film exhibited good transparency. The surface morphology of the LBL film was smooth in the micrometer scale; many imogolite nanotubes were adsorbed onto the sacran layer, while no imogolite clusters were observed. Furthermore, the structure, stability, gas permeability, and mechanical properties of the LBL films were investigated.

Injectable and Near-Infrared-Responsive Hydrogels Encapsulating Dopamine-Stabilized Gold Nanorods with Long Photothermal Activity Controlled for Tumor Therapy.

Gold nanorods (AuNRs) are confirmed to have excellent and repeated photothermal properties under near-infrared (NIR)-light irradiation above 780 nm. However, AuNRs easily leaked out from local pathological tissues and circulated in the body, reducing photothermal therapy (PTT) efficacy. By complexing AuNRs with a scaffold via interactions, AuNRs might be dispersed in the scaffold and fixed in the tumor site. Thus, based on the mussel-mimetic adhesion concept, AuNRs were designed to be coated with polydopamine (PDA), and then the prepared polydopamine-coated AuNRs (AuNR-PDA) were incorporated into a thermosensitive injectable hydrogel composed of ß-glycerophosphate-bound chitosan (CGP) and dopamine-modified alginate (Alg-DA) efficiently. Due to the strong interactions between PDA and polymers, AuNR-PDA could be immobilized stably and evenly into the obtained CGP/Alg-DA/AuNR composite hydrogel, which can avoid overheating locally or leaking out. The sol-gel transition temperature of the composite hydrogel was adjusted to the body temperature at around 37 °C to be conveniently injectable in vivo. With NIR irradiation at 808 nm of wavelength, the composite hydrogel was locally heated quickly to over 50 °C depending on controlling the irradiation powers and times. Moreover, the in vitro cytotoxicity test of the composite hydrogel showed good biocompatibility to normal cells but obvious suppression to tumor cells' growth under multiple times of photothermal therapy. Furthermore, the in vivo antitumor test demonstrated the obvious suppression to tumor growth of the CGP/Alg-DA/AuNR composite hydrogel under multiple PTTs. Therefore, the injectable CGP/Alg-DA/AuNR hydrogel could be a promising candidate for the long-term repeated photothermal treatment of tumors.

Sacran Hydrogel Film Containing Keratinocyte Growth Factor Accelerates Wound Healing by Stimulating Fibroblast Migration and Re-epithelization.

Regenerative therapy with keratinocyte growth factor (KGF) is a novel therapeutic approach for treatment of chronic wounds. However, KGF cannot be used directly to the wound site due to its physicochemical instability. In previous study, sacran, a natural megamolecular polysaccharide, showed potential properties as a biomaterial for hydrogel film in wound healing. In this study, we fabricated sacran hydrogel film containing KGF (Sac/KGF-HF) and evaluated the effects of Sac/KGF-HF on fibroblasts migration and re-epithelialization process. We successfully prepared a homogenous and -amorphous Sac/KGF-HF by a casting method. In addition, Sac/KGF-HF had a high swelling ratio and flexibility. Sac/KGF-HF promoted a migration process of NIH3T3 cells and improved wound healing ability in mice with a percentage of wound closure reaching 90.4% at 9 d. Interestingly, the addition of KGF in Sac-HF considerably increased the number of epithelial cells compared to control, which is important in the re-epithelialization process. It could be concluded that KGF in Sac-HF has the potential for promoting Sac-HF abilities in wound healing process.

Micelle-Mediated Self-Assembly of Microfibers Bridging Millimeter-Scale Gap To Form Three-Dimensional-Ordered Polysaccharide Membranes.

Micelle-mediated three-dimensional-ordered polysaccharide membranes are constructed by introducing cationic/anionic surfactant into a liquid crystalline polysaccharide solution. Upon drying mixtures of the polysaccharide solution with the surfactant such as cetyltrimethylammonium bromide or sodium dodecyl sulfate (SDS), the polymeric microfibers deposit as a nucleus to form a membrane, bridging millimeter-scale gap with high probability. In particular, in a solution with SDS micellar structures, the microscale fibers with diameter ∼1 µm disassemble into nanoscale fibers with diameter ∼50 nm. This transformation allows the polymeric network to become finer in nanoscale, and the vertical membrane is formed much more easily than that from a pure polysaccharide solution. Furthermore, it is clarified that the vertical membrane has been successfully formed with three-dimensionally ordered microstructures with a linearly oriented and layered structure. This method will shed light on the preparation of hybrid materials with biocompatibility and responsivity to stimuli such as magnetics, electrics, and optics via hybridization with nanomaterials dispersed by surfactants.

Development of Functional Bionanocomposites Using Cyanobacterial Polysaccharides.

Cyanobacteria are regarded as very eco-friendly microreactors for the production of various biomolecules such as polysaccharides by fixing not only carbon but also nitrogen in water. Cyanobacterial polysaccharides having various functional groups such as hydroxyls, carboxyls, sulfates, etc. have the ability to interact with metals or inorganics, to create bionanocomposites. Sacran, a supergiant cyanobacterial anionic polysaccharide extracted from the extracellular matrix of Aphanothece sacrum which is mass-cultivated in freshwater, is mainly used to create functional bionanocomposites. Gel-type bionanocomposites of sacran with various metal cations are formed and showed photoresponsive functions. Metal recovery is performed from the sacran bionanocomposite gels. Sacran chains are complexed with multi-wall carbon nanotubes (MWCNT) to give viscose dispersion from which MWCNT bionanocomposites can be collected by electrophoresis. The MWCNT/sacran dispersion retains the capability of adsorbing various metal ions to form hardened hydrogel beads. Finally, natural inorganic sepiolite can be used for sacran bionanocomposites which show an efficient neodymium ion adsorption ability. Thus, cyanobacterial polysaccharides are useful for preparing eco-friendly and functional bionanocomposites with various hard materials.

Novel polycondensed biopolyamide generated from biomass-derived 4-aminohydrocinnamic acid.

Biomass plastics are expected to contribute to the establishment of a carbon-neutral society by replacing conventional plastics derived from petroleum. The biomass-derived aromatic amine 4-aminocinnamic acid (4ACA) produced by recombinant bacteria is applied to the synthesis of high-performance biopolymers such as polyamides and polyimides. Here, we developed a microbial catalyst that hydrogenates the α,ß-unsaturated carboxylic acid of 4ACA to generate 4-aminohydrocinnamic acid (4AHCA). The ability of 10 microbial genes for enoate and xenobiotic reductases expressed in Escherichia coli to convert 4ACA to 4AHCA was assessed. A strain producing 2-enoate reductase from Clostridium acetobutylicum (ca2ENR) reduced 4ACA to 4AHCA with a yield of > 95% mol mol-1 and reaction rates of 3.4 ± 0.4 and 4.4 ± 0.6 mM h-1 OD600-1 at the optimum pH of 7.0 under aerobic and anaerobic conditions, respectively. This recombinant strain reduced caffeic, cinnamic, coumaric, and 4-nitrocinnamic acids to their corresponding propanoic acid derivatives. We polycondensed 4AHCA generated from biomass-derived 4ACA by dehydration under a catalyst to form high-molecular-weight poly(4AHCA) with a molecular weight of M n = 1.94 MDa. This polyamide had high thermal properties as indicated by a 10% reduction in weight at a temperature of T d10 = 394 °C and a glass transition temperature of T g = 240 °C. Poly(4AHCA) derived from biomass is stable at high temperatures and could be applicable to the production of high-performance engineering plastics.

Drying-Induced Self-Similar Assembly of Megamolecular Polysaccharides through Nano and Submicron Layering.

We propose a self-similar assembly to generate planar orientation of megamolecular polysaccharides on the nanometer scale and submicron scale. Evaporating the aqueous liquid crystalline (LC) solution on a planar air-LC interface induces polymer layering by self-assembly and rational action of macroscopic capillary forces between the layers. To clarify the mechanisms of nanometer- and submicron-scale layering, the polymer films are investigated by electron microscopy.

Comparison of the Long-Term Outcomes of Mechanical and Bioprosthetic Aortic Valves　- A Propensity Score Analysis.

BACKGROUND: The aim of this study was to assess the long-term outcomes of aortic valve replacement (AVR) with either mechanical or bioprosthetic valves according to age at operation.Methods and Results:A total of 1,002 patients (527 mechanical valves and 475 bioprosthetic valves) undergoing first-time AVR were categorized according to age at operation: group Y, age <60 years; group M, age 60-69 years; and group O, age ≥70 years). Outcomes were compared on propensity score analysis (adjusted for 28 variables). Hazard ratio (HR) was calculated using the Cox regression model with adjustment for propensity score with bioprosthetic valve as a reference (HR=1). There were no significant differences in overall mortality between mechanical and bioprosthetic valves for all age groups. Valve-related mortality was significantly higher for mechanical valves in group O (HR, 2.53; P=0.02). Reoperation rate was significantly lower for mechanical valves in group Y (HR, 0.16; P<0.01) and group M (no events for mechanical valves). Although the rate of thromboembolic events was higher in mechanical valves in group Y (no events for tissue valves) and group M (HR, 9.05; P=0.03), there were no significant differences in bleeding events between all age groups. CONCLUSIONS: The type of prosthetic valve used in AVR does not significantly influence overall mortality.

Optical second-harmonic images of sacran megamolecule aggregates.

We have detected a second-order nonlinear optical response from aggregates of the ampholytic megamolecular polysaccharide sacran extracted from cyanobacterial biomaterials by using optical second-harmonic-generation (SHG) microscopy. The SHG images of sacran cotton-like lump, fibers, and cast films showed SHG intensity microspots of several tens of micrometers in size. The dependence of the SHG spot intensity on an excitation light polarization angle was observed to illustrate sacran molecular orientation in these microdomains. We also observed SHG signals around a special region of the cast film edges of sacran. These results show that sacran megamolecules aggregate in several different ways.