Topology-Dependent Interaction of Cyclic Poly(ethylene glycol) Complexed with Gold Nanoparticles against Bovine Serum Albumin for a Colorimetric Change.

Unique physical and chemical properties arising from a polymer topology recently draw significant attention. In this study, cyclic poly(ethylene glycol) (c-PEG) was found to significantly interact with bovine serum albumin (BSA), suggested by nuclear magnetic resonance, dynamic light scattering, and fluorescence spectroscopy. On the other hand, linear HO-PEG-OH and MeO-PEG-OMe showed no affinity. Furthermore, a complex of gold nanoparticles and c-PEG (AuNPs/c-PEG) attracted BSA to form aggregates, and the red color of the AuNPs dispersion evidently disappeared, whereas ones with linear PEG or without PEG did not demonstrate such a phenomenon. The interactions among BSA, AuNPs, and PEG were investigated by changing the incubation time and concentration of the components by using UV-Vis and fluorescence spectroscopy.

Detailed Structural Analyses of Nanofibrillated Bacterial Cellulose and Its Application as Binder Material for a Display Device.

Nanofibrillated bacterial cellulose (NFBC) is produced by culturing a cellulose-producing bacterium under agitated aerobic conditions in a carboxymethylcellulose (CMC)-supplemented medium. Detailed structural analyses revealed that NFBC fiber widths varied with the degree of substitution of the CMC used, and zeta potential values decreased with the increment of CMC concentration in the medium. Transmission electron microscopy observation after immunostaining demonstrated that CMC molecules were present on the NFBC microfibril surfaces. We tested NFBC for utility as a binder for a display device that uses electrochromic (EC) material. Introduction of a quaternary ammonium group into the EC molecules enhanced their interactions with the negatively charged NFBC microfibrils. A casting process homogeneously adsorbed the EC molecules onto the surface of a transparent electrode with NFBC. A homogeneous color change was successfully observed upon applying an electric field, suggesting that NFBC could be used as a binder material for uniform surface adsorption.

Organic-Inorganic Nanocomposite Film for High-Performance Stretchable Resistive Memory Device.

A compatible organic/inorganic nanocomposite film for a stretchable resistive memory device with high performance is demonstrated using poly(4-vinylpyridine)-block-poly(propyl methacrylate) (P4VP-b-PPMA) with zinc oxide (ZnO) nanoparticle. The PPMA soft segment is designed for reducing the rigidity of the active layer, while the P4VP block serves as a charge-trapping component to induce conductive filament and also a compatible moiety for inorganic nanoparticles through hydrogen bonding. The experimental results show that the P4VP-b-PPMA-based electrical memory device exhibits write-once-read-many-times memory behavior and an excellent ON/OFF current ratio of over 105 with a stable turn-on voltage (Vset ) around -2.0 V and stable memory behavior upon stretching up to 60% strain. On the other hand, P4VP-b-PPMA/ZnO nanocomposite film switches the memory characteristic to the dynamic random access memory behavior. The stretchable memory device prepared from the nanocomposite film can have a stretching durability over 40% strain and up to 1000 times cycling stretch-relaxation test. This work demonstrates a new strategy using nanocomposite films with tunable electrical characteristics and enhanced mechanical properties for stretchable electrical devices.

Phase Transition Behaviors and Nanoscale Film Morphologies of Poly(δ-valerolactone) Axles Bearing Movable and Fixed Rotaxane Wheels.

In this study, poly(δ-valerolactone) (PVL) axles bearing movable and fixed dibenzo-24-crown-8-ether wheels (rot-M and rot-F) are investigated for the first time in the terms of phase transition and nanoscale film morphology: PVL-rot-M and PVL-rot-F. Interestingly, the PVL axles reveal a strong tendency to form a horizontal lamellar structure with three different rotational crystal lattice domains in nanoscale films. The morphological structural parameters are discernibly varied by the movable and fixed rotaxane wheels. In particular, the rot-M wheel tends to be populated in both the interfacial and amorphous layers. The rot-M wheel is found to significantly influence the phase transition characteristics of the PVL axle because of its movability along the polymer backbone chain. In contrast, the rot-F wheel tends to be more localized in the interfacial layer rather than in the amorphous layer because of its immovability constrained at the polymer chain end. The rot-F wheel causes severe thermal instability in the PVL axle, which can be attributed mainly to the presence of its counter anion (PF6 - ).

One-Step Production of Amphiphilic Nanofibrillated Cellulose Using a Cellulose-Producing Bacterium.

Nanofibrillated bacterial cellulose (NFBC) is produced by culturing a cellulose-producing bacterium (Gluconacetobacter intermedius NEDO-01) with rotation or agitation in medium supplemented with carboxymethylcellulose (CMC). Despite a high yield and dispersibility in water, the product immediately aggregates in organic solvents. To broaden its applicability, we prepared amphiphilic NFBC by culturing strain NEDO-01 in medium supplemented with hydroxyethylcellulose or hydroxypropylcellulose instead of CMC. Transmission electron microscopy analysis revealed that the resultant materials (HE-NFBC and HP-NFBC, respectively) comprised relatively uniform fibers with diameters of 33 ± 7 and 42 ± 8 nm, respectively. HP-NFBC was dispersible in polar organic solvents such as methanol, acetone, isopropyl alcohol, acetonitrile, tetrahydrofuran (THF), and dimethylformamide, and was also dispersible in poly(methyl methacrylate) (PMMA) by solvent mixing using THF. HP-NFBC/PMMA composite films were highly transparent and had a higher tensile strength than neat PMMA film. Thus, HP-NFBC has a broad range of applications, including as a filler material.

Advanced functionalization of polyhydroxyalkanoate via the UV-initiated thiol-ene click reaction.

Polyhydroxyalkanoates (PHAs) incorporating vinyl-bearing 3-hydroxyalkanoates were prepared in 8.5-12.9 g L(-1) yield. The molar ratios (0-16 mol%) of the vinyl-bearing 3-hydroxyalkanoate derivatives were controlled by the continuous feeding of undecylenate at various concentrations. Subsequently, the PHAs were functionalized by UV-initiated thiol-ene click reaction and chemical modification. (1)H NMR spectra suggested that 3-mercaptopropionic acid and 2-aminoethanethiol were successfully introduced into the vinyl-bearing PHA. Subsequently, chemical modification using fluorescein or a fibronectin active fragment (GRGDS) was attempted. The former yielded a PHA derivative capable of emitting fluorescence under UV irradiation, which was useful for determining the miscibility of PHA in a composite film comprising poly-ʟ-lactic acid (PLLA) and PHA. In the latter case, PHA bearing GRGDS peptides exhibited cell adhesiveness, suggesting that its biocompatibility was improved upon peptide introduction. Taken together, the UV-initiated thiol-ene click reaction was demonstrated to be useful in PHA modification.

Effect of degree of substitution on the microphase separation and mechanical properties of cellooligosaccharide acetate-based elastomers.

Thermoplastic elastomers (TPEs) have long been used in a wide range of industries. However, most existing TPEs are petroleum-derived polymers. To realize environmentally benign alternatives to conventional TPEs, cellulose acetate is a promising TPE hard segment because of its sufficient mechanical properties, availability from renewable sources, and biodegradability in natural environments. Because the degree of substitution (DS) of cellulose acetate governs a range of physical properties, it is a useful parameter for designing novel cellulose acetate-based TPEs. In this study, we synthesized cellulose acetate-based ABA-type triblock copolymers (AcCelx-b-PDL-b-AcCelx) containing a celloologosaccharide acetate hard A segment (AcCelx, where x is the DS; x = 3.0, 2.6, and 2.3) and a poly(δ-decanolactone) (PDL) soft B segment. Small-angle X-ray scattering showed that decreasing the DS of AcCelx-b-PDL-b-AcCelx resulted in the formation of a more ordered microphase-separated structure. Owing to the microphase separation of the hard cellulosic and soft PDL segments, all the AcCelx-b-PDL-b-AcCelx samples exhibited elastomer-like properties. Moreover, the decrease in DS improved toughness and suppressed stress relaxation. Furthermore, preliminary biodegradation tests in an aqueous environment revealed that the decrease in DS endowed AcCelx-b-PDL-b-AcCelx with greater biodegradability potential. This work demonstrates the usefulness of cellulose acetate-based TPEs as next-generation sustainable materials.

Enhanced dispersion stability of gold nanoparticles by the physisorption of cyclic poly(ethylene glycol).

Nano-sized metal particles are attracting much interest in industrial and biomedical applications due to the recent progress and development of nanotechnology, and the surface-modifications by appropriate polymers are key techniques to stably express their characteristics. Herein, we applied cyclic poly(ethylene glycol) (c-PEG), having no chemical inhomogeneity, to provide a polymer topology-dependent stabilization for the surface-modification of gold nanoparticles (AuNPs) through physisorption. By simply mixing c-PEG, but not linear counterparts, enables AuNPs to maintain dispersibility through freezing, lyophilization, or heating. Surprisingly, c-PEG endowed AuNPs with even better dispersion stability than thiolated PEG (HS-PEG-OMe). The stronger affinity of c-PEG was confirmed by DLS, ζ-potential, and FT-IR. Furthermore, the c-PEG system exhibited prolonged blood circulation and enhanced tumor accumulation in mice. Our data suggests that c-PEG induces physisorption on AuNPs, supplying sufficient stability toward bio-medical applications, and would be an alternative approach to the gold-sulfur chemisorption.

Synthesis of hyperbranched carbohydrate polymers by ring-opening multibranching polymerization of anhydro sugar.

The synthesis of novel hyperbranched carbohydrate polymers, prepared by the ring-opening multibranching polymerizations of anhydro and dianhydro sugars, is described. The hyperbranched carbohydrate polymers were formed by the cationic polymerization of 1,6-anhydro-beta-D-hexopyranose, 1,4-anhydrotetritol, 2,3-anhydrotetritol, and 1,2:5,6-dianhydro-D-mannitol. These polymerizations proceeded without gelation to produce water-soluble hyperbranched carbohydrate polymers with controlled molecular weights and narrow polydispersities. The values for the degree of branching of the polymers were in the range of 0.28-0.50. The polymerization method, which proceeds through a ring-opening reaction by a proton-transfer reaction mechanism, is a facile method leading to a spherical carbohydrate polymer with a high degree of branching.

Synthesis and characterization of Eu(III) complexes of modified d-glucosamine and poly(N-isopropylacrylamide).

A series of chain-end functional polymers composed of poly(N-isopropylacrylamide) (PNIPAM) and 2-amino-2-deoxy-d-glucopyranose(d-glucosamine, GA) was synthesized via atom transfer radical polymerization (ATRP). Novel fluorescent complexes of glucosamine-PNI- PAM/Eu(III) were then formed by chelation of the polymers and europium(III) ions. The aqueous solutions of the polymers and its Eu(III) complexes exhibited a lower critical solution temperatures (LCSTs), and which were approximately equal to body temperature. Cell viability assays suggested that these thermosensitive polymers and Eu(III) complexes showed excellent biocompatibility in vitro.

In vitro synthesis of polyhydroxyalkanoates using thermostable acetyl-CoA synthetase, CoA transferase, and PHA synthase from thermotorelant bacteria.

Thermostable enzymes are required for the rapid and sustainable production of polyhydroxyalkanoate (PHA) in vitro. The in vitro synthesis of PHA using the engineered thermostable synthase PhaC1SG(STQK) has been reported; however, the non-thermostable enzymes acetyl-CoA synthetase (ACS) and CoA transferase (CT) from mesophilic strains were used as monomer-supplying enzymes in this system. In the present study, acs and ct were cloned from the thermophilic bacteria Pelotomaculum thermopropionicum JCM10971 and Thermus thermophilus JCM10941 to construct an in vitro PHA synthesis system using only thermostable enzymes. ACS from P. thermopropionicum (ACSPt) and CT from T. thermophilus (CTTt) were confirmed to have high thermostability, and their optimal temperatures were around 60°C and 75°C, respectively. The in vitro PHA synthesis was successfully performed by ACSPt, CTTt, PhaC1SG(STQK), and poly(3-hydroxybutyrate) [P(3HB)] was synthesized at 45°C. Furthermore, the yields of P(3HB) and P(lactate-co-3HB) at 37°C were 1.4-fold higher than those of the in vitro synthesis system with non-thermostable ACS and CT from mesophilic strains. Overall, the thermostable ACS and CT were demonstrated to be useful for the efficient in vitro PHA synthesis at relatively high temperatures.

Synthesis and characterization of aminoporphyrin-end-functionalized poly(N-isopropylacrylamide) with photodynamic and thermoresponsive effects.

The novel aminoporphyrin-end-functionalized poly(N-isopropylacrylamide) (PNIPAM) polymer H2N-TPP-PNIPAM (TPP = 5,10,15,20-tetraphenyl-21H,23H-porphyrin) behaves as a multifunctional platform that displays a photodynamic effect, thermosensitivity, and fluorescence properties. The polymer was designed by using an asymmetrical aminoporphyrin (i.e., H2N-TPP-Cl) as the initiator for the atom-transfer radical polymerization of N-isopropylacrylamide (NIPAM). The polydispersity index (PDI) obtained by gel-permeation chromatography indicated that the molecular-weight distribution was narrow (1.09

Synthesis and characterization of Eu(III) complexes of modified cellulose and poly(N-isopropylacrylamide).

A series of thermo-responsive copolymers of poly(N-isopropylacrylamide) (PNIPAM) and cellulose were synthesized via atom transfer radical polymerization (ATRP) using N-isopropylacrylamide as the monomer, cellulose acetate as the initiator, and CuCl/tris(2-dimethylaminoethyl)amine (Me6TREN) as a catalytic system. The resulting polymers had a narrow range of polydispersity indexes 1.27-1.37, and molecular weights of 8600-17,300 g mol(-1). Novel functional complexes of cellulose-g-PNIPAM/Eu(III) with excellent thermosensitive and fluorescent properties were then formed by the chelation of copolymers and europium(III) ions. The maximum emission intensity of the complexes at 613 nm was enhanced by a factor of approximately 10 relative to that of the corresponding Eu(III) complexes. Additionally, the lower critical solution temperatures (LCSTs) of cellulose-g-PNIPAM/Eu(III) were slightly greater than those of the copolymers.

Polystyrene microgel amphiphiles with maltohexaose. Synthesis, characterization, and potential applications.

4-Vinylbenzyl maltohexaoside peracetate (1) was copolymerized with divinylbenzene (DVB) using 1-phenyl-1-(2',2',6',6'-tetramethyl-1'-piperidinyloxy)ethane (2) in m-xylene. The copolymerizations were performed at 138 degrees C for 20 h using the mole fraction of 1 in the total feed of 1 and DVB (F1: [1]/[1]+[DVB]) varying from 0.11 to 0.38, affording polymeric products in yields ranging from 32 to 40%. The characterizations by linear PS-calibrated size exclusion chromatography (SEC), dynamic laser light scattering (DLS) measurements, and 1H NMR spectroscopy indicated that the product was assignable to the cross-linked poly(4-vinylbenzyl maltohexaoside peracetate) particle which is able to produce stable solutions, i.e., the PSt microgel with acetyl maltohexaose, 3. The specific rotations ([alpha]D23, c = 1.0 CHCl3) of 3 ranged from +43.3 degrees to +85.6 degrees. The average molar masses determined by the static laser light scattering (SLS) measurement of 3, M(w,SLS)'s, were from 64,700 to 118,000, which were calculated using the respective refractive index increments, dn/dc's, ranging from 0.03387 to 0.08340. The apparent numbers of the 1, 2, and DVB units in 3, N1, N2, and N(DVB), which were estimated from the respective [alpha]D23 values, M(w,SLS)'s, and real yields, ranged from 22 to 35, from 7 to 26, and from 146 to 506, respectively. The deacetylation of 3 was achieved by treatment with sodium methoxide in dry 1,4-dioxane to produce the PSt microgel with maltohexaose as the hydrophilic segment, 4, as a white solid. The solubility of 4 in various solvents was examined, indicating that a hydrophilic property was effectively introduced. Notably, 4 gave clear solutions in the mixed solvent of 1,4-dioxane and H2O. The ability to solubilize fullerite (mixture of fullerenes, C60/C70 = ca. 9/1) in aqueous solutions was examined according to the literature method. Approximately, 100 mg of 4 (1.7 micromol) solubilizes 1.3 mg of fullerite (1.7 micromol).