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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 10

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.

Production of bioplastics from renewable biological resources is a prerequisite for the development of a circular and sustainable society. Current bioplastics are mostly heat‐sensitive aliphatic polymers, requiring thermoresistant aromatic bioplastics. Herein, 3‐amino‐4‐hydroxybenzoic acid (AHBA) and 4‐aminobenzoic acid (ABA) are produced from kraft pulp, an inedible cellulosic feedstock, using metabolically engineered bacteria. AHBA is chemically converted to 3,4‐diaminobenzoic acid (DABA); subsequently, poly(2,5‐benzimidazole) is obtained by the polycondensation of DABA and processed into an ultrahigh thermoresistant film. The copolymerization of DABA with a small amount of ABA dramatically increases the degradation temperatures of the resulting films (over 740 °C) to yield the most thermoresistant plastic on record. Density functional theory calculations indicate that the incorporation of ABA strengthens the interchain hydrogen bonds between aromatic imidazole rings. Thus, an alternative organic molecular design is proposed for thermoresistant plastics without using heavy inorganics, although continuous aromatic heterocycles are widely considered ideal for polymer thermoresistance. This innovative macromolecular design increases thermoresistance and can be widely applied to well‐processable plastics for the production of lightweight materials and is expected to contribute to the development of a more sustainable society.

Multi-walled carbon nanotubes (MWCNTs) were well dispersed in an aqueous solution of the cyanobacterial polysaccharide, sacran, with an ultra-high molecular weight >10 million g/mol. MWCNTs powder was put into aqueous solutions of various polysaccharides including sacran and was dispersed under sonication. As a result of the turbidity measurement of the supernatant, it was found that sacran showed the highest MWCNT-dispersion efficiency of all the polysaccharides used here. Cryogenic transmission electron microscopic (Cryo-TEM) studies directly demonstrated the existence of MWCNTs in the supernatant, and high-resolution TEM observation revealed that MWCNTs covered by sacran chains made their efficient dispersion in water. Raman spectroscopy demonstrated the existence of MWCNT in dried sample from supernatant and the interaction between MWCNT and sacran. The ζ-potential measurement of the dispersion indicated the negative surface charges of the sacran/MWCNT complexes. Then the MWCNT complexes were able to fabricate by ionic interaction; electrophoresis of the anionic complex formed the sacran/MWCNT gels on the anode while the droplet of sacran/MWCNT dispersion formed gel beads in the presence of the lanthanoid cations.

Cryogenic-transmission electron microscopy of metal complexes with cyanobacterial polysaccharides, sacran, extracted from Aphanothece sacrum biomaterials reveals that Nd3+ complexes form networks composed of thick strings with a thickness ranging 10–20 nm while Fe2+ ones make dense entanglement of very thin strings. When Fe2+ and Nd3+ double complexation occurs, dense nanonetworks composed of thick strings with a thickness around 10 nm are formed. Next we prepared heterogels by crosslinking poly(vinyl alcohol) chains in the presence of sacran and investigated the effects of double complexation on metal sorption. The amount of Nd3+ sorbed into the heterogels in the 1 : 1 miscible solution of Fe2+ and Nd3+ is higher than that in the solution containing only Nd3+, suggesting that Fe2+ assists the Nd3+ sorption. In addition, it is found that the amount of sorbed Nd3+ is much higher than that of sorbed Fe2+ even in the acidic condition of pH 2. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Acidolysis polymerization has been used to prepare phenol-derived polymers such as liquid crystalline (LC) polymers, and is catalyzed by mildly-alkaline salts. The catalytic effects of hydrotalcites (HTs), which are natural alkalescent minerals with controllable basicity, are investigated on the acidolysis copolymerization of coumarates such as p-coumaric acid and caffeic acid. As a result, the LC copolymer prepared in the presence of HT with a Mg/Al ratio of 3 shows higher molecular weight values than copolymers prepared in the presence of any other alkalescent salts. On the other hand, the copolymers prepared in the presence of HTs show a clear LC state where the polymer chains are oriented on the surface of the glass fibers. The resin, which is oriented by glass fiber fillers aligning along its longitudinal axis and is annealed at 300 °C for 20 min, shows a softening temperature of 305 °C while keeping a high mechanical strength of 85 MPa and a high mechanical modulus over 1 GPa.

We established a polymerization condition of 3-hydroxycinnamic acid, 3HCA, having photoreactive units over all the main chains. The polymers showed two types of photoreaction, that is, intramolecular E–Z isomerization and interchain [2 + 2] cycloaddition. Spectroscopic studies showed that the rate of the isomerization was higher than that of the cycloaddition. Although the original fiber was very brittle, the short-time UV-irradiation made the fiber softer and more elastic because the chain bending by the isomerization preferentially occurred. On the other hand, the long-time irradiation made the fiber harder because of the cross-linking by the cycloaddition, and simultaneously enhanced the elasticity. Besides we found that the cast film of P3HCA showed a photo-bending behavior with the convex surface facing the UV-lamp by the initial E–Z isomerization. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Highly flexible and transparent polylactic acids (PLAs) films were successfully prepared by manipulating their crystallization. The semicrystalline poly(L-lactic acid) (L) was blended with a noncrystalline poly(DL-lactic acid) (DL) together with diglycerol tetraacetate (DGTA). Optimal DGTA content to plasticize PLAs was about 17%. Addition of DL hindered the crystallization of the films. Tensile strengths of the films having DL content more than 5% were about 10 MPa while the elongations at break were boosted as DL content increased. Films having L/DL ratio of 50/50 showed elongations at break of 270%. Stretch ability and clarity of films containing 15-50% DL were fair although they were subjected to annealing at 60 °C for 1 h.

Liquid crystalline (LC) polymers of rigid monomers based on flora and fauna were prepared by in-bulk polymerization. Para-coumaric (p-coumaric) acid [4-hydroxycinnamic acid (4HCA)] and its derivatives were selected as phytomonomers and bile acids were selected as biomonomers. The 4HCA homopolymer showed a thermotropic LC phase only in a state of low molecular weight. The copolymers of 4HCA with bile acids such as lithocholic acid (LCA) and cholic acid (CA) showed excellent cell compatibilities but low molecular weights. However, P(4HCA-co-CA)s allowed LC spinning to create molecularly oriented biofibers, presumably due to the chain entanglement that occurs during in-bulk chain propagation into hyperbranching architecture. P[4HCA-co-3,4-dihydroxycinnamic acid (DHCA)]s showed high molecular weight, high mechanical strength, high Young's modulus, and high softening temperature, which may be achieved through the entanglement by in-bulk formation of hyperbranching, rigid structures. P(4HCA-co-DHCA)s showed a smooth hydrolysis, in-soil degradation, and photo-tunable hydrolysis. Thus, P(4HCA-co-DHCA)s might be applied as an environmentally degradable plastic with extremely high performance. © 2007 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 7: 210–219; 2007: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.20122

Porous poly(N-isopropylacrylarfide) (PNI-PAAm) hydrogels were successfully prepared in the presence of nanosized silica particles with network morphology and subsequent silica extraction by HF treatment. The nanosized pores induced very rapid deswelling of the hydrogels, accompanied by volume phase transitions from swelling to deswelling states at approximately 30 °C. Deswelling, which was analyzed by a quick change in temperature of the aqueous media from 20 to 40 °C, was facilitated by increased silica particle content. The deswelling rate constant of the hydrogel prepared using silica nanoparticles with a network morphology (NT gel) was about 1 900-fold greater than that of nonporous hydrogels and 13-fold larger than that of porous hydrogels perforated using spherical silica nanoparticles (SP gel). The releasing rate of the low-molecular weight chromophore from the NT gel was higher than that from the SP gel. In the chromophore-labeled macromolecules, the network morphology was effective for increasing the releasing rate based on the transfer inside the hydrogel, as well as for increasing the amount released based on the surface pore morphology.

The compound 4-hydroxycinnamic acid (4HCA), a naatural biomonomer, is polymerized by melt polycondensation to yield a liquid-crystalline biopolymer (P4HCA) with UV reactivity. L929 cells were successuflly incubated on P4HCA films at 37°C.

Thermosensitive biopolymers with an amphipathic structure were synthesized through the propyl esterification of the carboxyl groups of poly γ-glutamic acid) (γ-PGA). The clouding temperature on heating was controlled by the addition of different amounts of NaCl and by the degree of esterification. The clearing temperature on cooling was independent of the aqueous milieu, presumably because of the strong multiple hydrogen bonds between the polymer chains formed in the collapsed state. The hydrogel of γ-PGA propylate crosslinked by a chemical reaction with hexamethylene diisocyanate also showed pH-responsive and thermoresponsive shrinking, but the volume recovery was incomplete during the cooling process. A Fourier transform infrared/ attenuated total reflection study showed that the incomplete volume recovery might be associated with the amide hydrogen bonding being strengthened by the chemical crosslinkage. The addition of urea made the volume change complete.

The complexation of bile acids with various solvated polycations was studied. A one-to-one complex was precipitated when an aqueous solution of cholic acid sodium salt (CA) was mixed with aqueous solutions of 3,3-ionene and grew to form crystals with needle-like morphology, 3 millimeters in length. Hydrogen bonding of hydroxyls at the steroid face and the spacing between cationic sites of polycations were crucial for the formation of the giant needle.

Poly(aramid silicone) (PAS) multiblock copolymers were synthesized by the low-temperature solution polycondensation of isophthaloyl dichloride (IPC) and two diamines, diamino poly(dimethyl siloxane) (PDMS; number-average molecular weight = 1680) and 3,4'-diaminodiphenylether (3,4'-DAPE), in tetrahydrofuran/dimethylacetamide (2/1 v/v). Two synthetic methods for the control of the PAS sequence were used: a one-step synthesis that presumably gave PAS with a random sequence and the polymerization of 3,4'-DAPE with a presynthesized dimer, IPC-PDMS-IPC (two-step synthesis), that presumably gave PAS with an alternating sequence of 3,4'-DAPE and PDMS segments. In a 1 H NMR study of the amide protons of the 3,4'-DAPE component in PAS, the relative length of the 3,4'-DAPE segment of randomly sequenced PAS to that of ideally sequenced PAS could be estimated. The glass-transition temperatures of the 3,4'-DAPE and PDMS segments of random PAS were 152-234 and -104 to - 117 °C, respectively, whereas the alternating PAS sequences showed no glass transition for the 3,4'-DAPE segments. A tensile test indicated that randomly sequenced PAS behaved like a rubber-toughened material at lower PDMS contents and like a thermoplastic elastomer at higher PDMS contents, whereas the alternately sequenced PAS behaved like a very soft rubber, showing a high value of elongation at the breaking point.

Porous poly(N-isopropylacrylamide) hydrogels were prepared by the free-radical polymerization of its monomer and a suitable crosslinker in the presence of spherical silica particles of different sizes (74 and 1600 nm) and by the subsequent acid extraction of silica. The yields were 81–83%, and the yields were not affected by the silica content. Scanning electron microscopy observations revealed the porous structure of the hydrogels. Porous and nonporous hydrogels showed volume phase transitions from swelling states to deswelling states at approximately 30 °C, as analyzed by the ratio of the diameter of cylinder-shaped hydrogels to that of the glass tube used for the hydrogel preparation at the corresponding temperature. Deswelling, which was analyzed by rapid changes in the temperature of the aqueous media from 20 to 40 °C, was facilitated by decreased silica particle size and increased silica content. The deswelling rate constant of the hydrogel prepared with 74-nm silica at 10 v/v % (silica/solvent) was more than 1500 times greater than that of conventional hydrogels. Swelling was similarly analyzed through changes in the temperature from 40 to 20 °C and was independent of the pore structure. The deswelling–swelling cycle was repeatable with reasonable reproducibility. Moreover, the mechanical strength of the porous hydrogels was significantly maintained compared with that of conventional nonporous hydrogels. This method produced thermoresponsive hydrogels of suitable mechanical strength and remarkable deswelling properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4228–4235, 2002

Free radical polymerization of N-isopropylacrylamide (NIPAAm) and crosslinker solutions, which were fulfilled in silica particles with an interpenetrated and nanometer-sized porous structure (a diameter of 3 mm and mean pore sizes of 15, 30, and 50 nm), fabricated hybrids of organic hydrogels and inorganic silica. Differential scanning calorimetric analyses of the hybrids revealed that silica components affected the thermoresponsive properties of polyNIPAAm hydrogels. Porous polyNIPAAm hydrogels were prepared by the subsequent acid treatment of the hybrids to remove silica. Transmission Fourier transformed infrared spectra indicated the selective extraction of silica. Scanning electron microscopic observation of the hydrogels confirmed the porous structure. The deswelling rate of porous hydrogels was 7 times larger than that of conventional hydrogels and increased with increasing the pore size of silica used. However, the swelling was not affected by the pore formation. The thermoresponsiveness of porous polyNIPAAm hydrogels could be regulated by the pore size. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3542–3547, 2002

The water-soluble copolymers having pendant terthiophene, poly(AA3T-co-AA), were synthesized by radical copolymerization of [(2,2':5',2-terthiophen-5- yl)methyl acrylate] (AA3T) and acrylic acid (AA), and their molecular structures and thermal behaviors were studied. X-ray diffraction study showed that the copolymers containing a certain amount of AA3T can form the crystals with monolayer structure, while incorporation of too many AA units into the copolymers disrupted this structure. Possible mechanism of self-doping on heating was discussed in terms of interaction between AA3T unit with AA unit in the copolymers.

A 66-year-old woman underwent mitral valve replacement and surgical isolation of the posterior part of the left atrium for persistent AF. During sinus rhythm an isolated atrial rhythm was recorded from the isolated posterior left atrium using an esophageal electrode catheter. After the intravenous administration of adenosine triphosphate sinus rhythm was suppressed and 1:1 conduction from the posterior left atrium to the rest of the atrium was recorded. Unidirectional atrio-atrial conduction was revealed by a simple electrophysiological evaluation.(PACE 2004; 27[Pt. I]:812–814)

The inhibition of germination and development of zoospores originating from Laminaria angustata originated on various kinds of hydrogels is studied. The effects of the water content of the gel (the degree of swelling), the electrical nature (neutral, positive charge, negative charge), the charge density, the counterions of hydrogels on the inhibition of zoospore germination and development of gametophytes are phenomenologically investigated. Among the gels investigated, poly(acrylic acid) (PAA) gel showed a dramatic inhibition to germination, and might serve as a novel, environmentally safe inhibitor of zoospore adhesion.