Structural Analyses of Polysaccharides Extracted from Cyanobacterial Extracellular Gels and Oriented Liquid Crystalline Microfiber Processing by Poly(vinyl alcohol)-Assisted Electrospinning.

Sacran is a supergiant cyanobacterial polysaccharide that forms mesogenic supercoil rods that exhibit liquid crystalline (LC) gels at deficient concentrations of around 0.5 wt%, and has several bioactive stimuli-responsive functions. Here, we attempted to form oriented microfibers of sacran by electrospinning, following structural analyses of the sacran rods. A heterogeneous acid-hydrolysis method using a protonated cation-exchange resin was adopted to examine the short-time exposition of concentrated acid to sacran rods. From the supernatant, the oligomeric fraction that was soluble in water and methanol was isolated. The oligomeric fraction had a main sugar ratio of α-Glc:ß-Glc:α-Xyl:ß-Xyl:α-Rha of 2:5:1.5:1.5:4 (Glc:Xyl:Rha = 7 (=4 + 3):3:4), and it was speculated that the sacran structure includes rhamnoglucan and xyloglucan (4:3), which are generally rigid enough to exhibit LC. To make oriented microfibers of LC sacran, solubility testing was performed on sacran to find good new solvents of polyhydroxy alcohols such as ethylene glycol, 1,2-propanediol, and glycerol. The oriented film was prepared from a sacran aqueous solution where calcium compound particles deposited on the film are different from polyhydroxy alcohol solutions. Although sacran could not form microfibers by itself, polymer composite microfibers of sacran with poly(vinyl alcohol) were prepared by electrospinning. Cross-polarizing microscopy revealed the molecular orientation of the microfibers.

Metal-Assisted Injection Spinning of Ultra Strong Fibers from Megamolecular LC Polysaccharides.

The molecular orientation of liquid crystalline (LC) hydrogels has the potential to induce a range of functionalities that can deliver great mechanical strength. Sacran is a supergiant LC polysaccharide isolated from the cyanobacterium Aphanothece sacrum with a high amount of anionic functional groups such as sulfates and carboxylates. In this article, ultra-strong sacran hydrogels and their dried fibers were produced by cross-linking under injection flow with trivalent metal ions such as Al3+, Cr3+, Fe3+, In3+, and rare-earth metal ions such Er3+ and Sr3+. Crossed-polarizing microscopy and X-ray diffraction imaging revealed a uniaxial molecular orientation in the LC gel fiber, resulting in outstanding mechanical characteristics.

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.

Effect of Water Absorption on Electric Properties of Temperature-Resistant Polymers.

The effects of water absorption on the electric resistivity and dielectric constant of polyimide (PI) and poly(ethylene terephthalate) (PET) were investigated, and the mechanism of deterioration in electrical insulation properties was discussed. The polyimides are poly(oxydianiline pyromellitimide) (PMDA-ODA) and poly(para-phenylene diamine biphenyltetracarboxydiimide) (BPDA-PDA). These polymer films were immersed in pure water for various immersion times at room temperature, and the water absorption ratio was evaluated. The electric resistance for these films was measured at room temperature using a high-resistance meter, and the dielectric constant at room temperature was measured using an LCR meter in a frequency range of 200 kHz to 2 MHz. The absorption ratios at equilibrium absorption for PMDA-ODA, BPDA-PDA, and PET were 2.7, 2.5, and 0.5%, respectively. The critical volume fraction of the percolation threshold of electric conductivity due to water absorption was 0.034 for both PMDA-ODA and BPDA-PDA. On the other hand, PET did not show a significant decrease in the resistivity. For both PIs and PET, the dielectric constant observed could be explained by a series model of the respective capacitances of pure water and polymer. Actually, the resistivity of samples cut from the edges of the film after water absorption was almost the same value as that in the dry state. These results suggest that the absorbed water molecules are not uniformly dispersed in the film but are localized at the edges of the film even after the absorption equilibrium has been reached.

High transparency, water vapor barrier and antibacterial properties of chitosan/carboxymethyl glucan/poly(vinyl alcohol)/nanoparticles encapsulating citral composite film for fruit packaging.

Utilizing antibacterial packaging material is an effective approach to delay fruit rotting and spoilage thereby minimizing financial losses and reducing health harm. However, the barrier and mechanical properties of biodegradable antibacterial packaging materials are barely compatible with transparency. Herein, antimicrobial nanoparticles encapsulating citral (ANPs) were first prepared by emulsification under the stabilization of oxidized dextran (ODE) and ethylene diamine. Then, composite films with high transparency, good water vapor barrier, and mechanical and antibacterial properties for fruits packaging were prepared from chitosan (CS), carboxymethyl-glucan (CMG), poly(vinyl alcohol) (PVA), and ANPs by solvent casting strategy. The synergistic effects of electrostatic interaction and hydrogen bonding could regulate crystalline architecture, generating high transparency of the composite films (90 %). The mechanical properties of the composite film are improved with elongation at break up to 167 % and stress up to 32 MPa. The water vapor barrier property of the film is appropriate to the packed fruit for less weight loss and firmness remaining. Simultaneously, the addition of ANPs endowed the film with excellent antimicrobial and UV-barrier capabilities to reduce fruit mildew, thereby extending the shelf life of fruits. More importantly, the composite polymer solution could be sprayed or dipped directly on fruits as a coating for food storage to improve food shelf life, substantially expanding its ease of use and scope of use.

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.

Skin-Inspired Patterned Hydrogel with Strain-Stiffening Capability for Strain Sensors.

Flexible materials with ionic conductivity and stretchability are indispensable in emerging fields of flexible electronic devices as sensing and protecting layers. However, designing robust sensing materials with skin-like compliance remains challenging because of the contradiction between softness and strength. Herein, inspired by the modulus-contrast hierarchical structure of biological skin, we fabricated a biomimetic hydrogel with strain-stiffening capability by embedding the stiff array of poly(acrylic acid) (PAAc) in the soft polyacrylamide (PAAm) hydrogel. The stress distribution in both stiff and soft domains can be regulated by changing the arrangement of patterns, thus improving the mechanical properties of the patterned hydrogel. As expected, the resulting patterned hydrogel showed its nonlinear mechanical properties, which afforded a high strength of 1.20 MPa while maintaining a low initial Young's modulus of 31.0 kPa. Moreover, the array of PAAc enables the patterned hydrogel to possess protonic conductivity in the absence of additional ionic salts, thus endowing the patterned hydrogel with the ability to serve as a strain sensor for monitoring human motion.

Ultra-tough artificial woods of polyphenol-derived biodegradable Co-polymer with Poly(butylene succinate).

Large productions of plastics worldwide are greater concern to the environment because of their non degradability and thus, damaging the ecosystem. Recent advancements in biobased plastics are growing exponentially because of their promise of a sustainable environment. Biobased polycoumarates plastics have a wood-like appearance with liquid crystalline grains, light brown color, and cinnamon-like aroma, but have very low toughness. The polycoumarates were hybridized via main-chain transesterification with poly (butylene succinate) (PBS). PBS itself being a biobased material has added more value to the final product due to biodegradability. The mechanical flexibility and toughness of the bio-based copolymers were controlled by varying the PBS content. As a result, well-processable and in-soil degradable artificial woods with a high strain energy density of approximately 76 MJ/m3 were developed while maintaining the wood-like appearance.

Dataset of Sac/CNF-Ag nanocomposites for antibacterial properties.

The data in this article includes a variety of analysis, including swelling, viscosity and FT-IR to better understand the thermal-mechanical, viscoelastic and swelling properties of sacran, CNF, and Ag nanoparticles individually and collectively. The fabrication method of Sacran, CNF, and Sac/CNF-Ag composite films is also demonstrated in this data item and are related to the research article "Facile design of antibacterial sheets of sacran and nanocellulose". This data article summarizes all the information so that it is evident how silver nanoparticle-polysaccharide hydrogels might be employed as an on-demand dressings due to their proven ability to reduce bacterial viability.

High-Strength, Degradable and Recyclable Epoxy Resin Based on Imine Bonds for Its Carbon-Fiber-Reinforced Composites.

Carbon fiber (CF) is widely used in the preparation of carbon-fiber-reinforced polymer composites (CFRP) in which it is combined with epoxy resin due to its good mechanical properties. Thermosetting bisphenol A epoxy resin, as one of the most common polymer materials, is a non-renewable resource, leading to a heavy environmental burden and resource waste. To solve the above problems and achieve high mechanical and thermal properties comparable to those of bisphenol A, herein, a high-performance, degradable and recyclable bio-based epoxy resin was developed by reacting the lignin derivative vanillin with 4-amino cyclohexanol via Schiff base. This bio-based epoxy resin showed a Young's modulus of 2.68 GPa and tensile strength of 44 MPa, 36.8% and 15.8% higher than those of bisphenol A epoxy, respectively. Based on the reversible exchange reaction of the imine bond, the resin exhibited good degradation in an acidic environment and was recoverable by heat treatment. Moreover, the prepared epoxy resin could be used to prepare carbon fiber (CF)-reinforced composites. By washing off the epoxy resin, the carbon fiber could be completely recycled. The recovered carbon fiber was well preserved and could be used again for the preparation of composite materials to realize the complete recovery and utilization of carbon fiber. This study opens a way for the preparation of high-performance epoxy resin and the effective recycling of carbon fiber.

Self- and Cross-Fusing of Furan-Based Polyurea Gels Dynamically Cross-Linked with Maleimides.

Bio-based polyureas (PUs) with main-chain furan rings were synthesized by the polyaddition of 2,5-bis(aminomethyl)furan with various diisocyanates, such as methylene diphenyl diisocyanate. Several PU's were soluble in polar organic solvents, and were cast to form thermomechanically stable films with softening temperatures of over 100 °C. The furan rings of the PU main chains underwent a dynamic Diels-Alder (DA) reaction with bismaleimide (BMI) cross-linkers. While the mixed solution of PU and BMI did not show any apparent signs of reaction at room temperature, the DA reaction proceeded to form gels upon heating to 60 °C, which became a solution again by further heating to 80 °C (retro-DA reaction). The solution phase was maintained by rapid quenching from 80 °C to room temperature, while the gel was reformed upon slow cooling. The recovered gels exhibited self-healing properties. A scratch made by a hot knife at temperatures above 80 °C disappeared spontaneously. When two different gels were cut using a knife at room temperature, placed in contact with each other, and heated to 60 °C, they fused. The ability to control the DA/retro-DA reaction allowed gels of varying composition to heal.

Mechanical Properties and Reinforcement of Paper Sheets Composited with Carboxymethyl Cellulose.

The mechanical properties for paper sheets composited with glucose (Glc), methyl cellulose (MC), and carboxymethyl cellulose (CMC) were investigated. The paper composites were prepared by immersing paper sheets in aqueous solutions of these materials and drying at 100 °C for 30 min. The stress-strain curves for these paper composites were measured by a uniaxial tensile apparatus with a stretching speed of 2 mm/min. The breaking stress and strain for untreated paper were 24 MPa and 0.016, respectively. The paper composites demonstrated stress-strain curves similar to the untreated paper; however, the breaking point largely differed for these composites. The breaking strain and breaking stress for the Glc composite slightly decreased and those for the MC composite gradually increased with the concentration of materials composited. Significant increases in the mechanical properties were observed for the CMC composite. The breaking stress, breaking strain, and breaking energy for the 3 wt.% CMC composite were 2.0-, 3.9-, and 8.0-fold higher than those for untreated paper, respectively. SEM photographs indicated that the CMC penetrated into the inner part of the paper. These results strongly suggest that the mechanical improvement for CMC composites can be understood as an enhancement of the bond strength between the paper fibrils by CMC, which acts as a bonding agent. It was also revealed that the breaking strain, breaking stress, and breaking energy for the CMC composites were at maximum at the first cycle and decreased gradually as the immersion cycles increased.

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.

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.

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.

Stepwise copolymerization of polybenzimidazole for a low dielectric constant and ultrahigh heat resistance.

Bio-based polymer materials having great potential due to the depletion of fossil-fuel resources have been applied as single-use and medicinal materials but their low thermomechanical resistance have limited wider applications. Here, ultrahigh thermoresistant bio-based terpolymers with a low dielectric constant, comprising polybenzimidazole and poly(benzoxazole-random-aramid), were prepared by a method involving stepwise polycondensation of three monomers, 3,4-diaminobenzoic acid for benzimidazoles, 3-amino-4-hydroxylbenzoic acid for benzoxazoles, and 4-aminobenzoic acid for aramids. For optimized monomer compositions, the obtained terpolymers exhibited dielectric constants lower than 3, and a 10% mass loss at approximately 760 °C which is a temperature higher than that for any other polymer material reported so far. The high thermal degradation temperatures of the prepared terpolymers were a result of the high interaction enthalpies of hydrogen bonding between imidazole rings in the polymer chains, which were obtained from density functional theory calculations using trimer models. Furthermore, the applicability of the prepared terpolymers as a wire-coating material for a simple motor insulation was demonstrated, indicating that it has significant potential to be used as a thermostable material with a low dielectric constant (k).

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.

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.

Recent advances in lignocellulosic biomass white biotechnology for bioplastics.

Lignocellulosic biomass has great potential as an inedible feedstock for bioplastic synthesis, although its use is still limited compared to current edible feedstocks of glucose and starch. This review focuses on recent advances in the production of biopolymers and biomonomers from lignocellulosic feedstocks with downstream processing and chemical polymer syntheses. In microbial production, four routes composed of existing poly (lactic acid) and polyhydroxyalkanoates (PHAs) and the emerging biomonomers of itaconic acid and aromatic compounds were presented to review present challenges and future perspectives, focusing on the use of lignocellulosic feedstocks. Recently, advances in purification technologies decreased the number of processes and their environmental burden. Additionally, the unique structures and high-performance of emerging lignocellulose-based bioplastics have expanded the possibilities for the use of bioplastics. The sequence of processes provides insight into the emerging technologies that are needed for the practical use of bioplastics made from lignocellulosic biomass.