Original Article in 2014

Orientation dynamics of small additive molecules in polymeric films during hot-stretching was investigated by using birefringence analysis and polarized Fourier-transfer infrared (FT-IR) spectroscopy. Birefringence data indicated parallel orientation of the small molecules to main chain of the matrix polymer. Furthermore, polarized FT-IR spectra demonstrated that the ratio of orientation functions of rigid and flexible portions in hexa-methylene naphthalate oligomer showed temperature dependence. The result suggests that the small molecules exhibit two-step orientation in the matrix polymer during stretching.

Applications of l-Glu molecularly imprinted cellulose membranes to chiral separation were studied. LiCl, which was adopted to dissolve cellulose into solvent, N,N-dimethylactamide (DMAc), worked well as a print molecule to construct recognition sites toward Li⁺ (or LiCl). The chiral separation ability was greatly dependent on LiCl. The permselectivity was increased with the LiCl concentration and asymptotically reached the maximum value at higher LiCl concentration region. The affinity constants between LiCl and LiCl recognition sites in both control and l-Glu molecularly imprinted membranes were determined to be 65 mol⁻¹ dm³.

Protein nanogels were prepared by using the vitamin B₆ (pyridoxal)-bearing pullulan (PLPP) as a bio-crosslinker. The binding of the PLPP to the serum albumin via the formation of Schiff bases was significantly enhanced in the presence of zinc ions because of the coordination of the Schiff base to metal ions. Dynamic light scattering measurements, high-performance liquid chromatography, and transmission electron microscopy confirmed that the zinc ions enhanced the ability of PLPP to form nanogels by crosslinking with the anionic BSA despite the strong electrostatic repulsion between the two molecules.

Novel organic–inorganic hybrid nanoparticles with a bisphenol A (BPA)-responsive hydrogel layer on the surface of SiO₂ nanoparticles were prepared via surface-initiated atom transfer radical polymerization of acrylamide (AAm), acryloyl-modified β-cyclodextrin (CD) and N, N′-methylenebisacrylamide. The resulting CD-PAAm/SiO₂ nanoparticles shrank in response to BPA because of an increase in the crosslinking density of the CD-PAAm hydrogel layer, which resulted from the formation of sandwich-like CD-BPA-CD complexes acting as dynamic crosslinks.

A ‘box-shaped’ three-dimensional (3D) DNA origami of ~40-nm dimensions was selectively formed by closing a symmetric open motif with three orthogonal faces. This 3D DNA origami was used as an intelligent nano-container to encapsulate exactly one 10-nm gold nanoparticle (AuNP). AuNPs were functionalized with thiol-modified DNA strands and attached to one of the faces of the open motif, which was designed to be an interior surface of the box and decorated with three complementary strands. The open motif was then closed into the box shape as triggered by the addition of DNA strands joining the remaining edges. An examination of the suitable folding path of an M13 scaffold using fluorescently labeled staple strands revealed that the flexibility at the hinge was essential for the efficient closing of the DNA origami container. Atomic force microscope and transmission electron microscope imaging of agarose-gel-purified complexes clearly showed the successful encapsulation of one AuNP inside the shell.

Poly(l-lactic acid-co-glycolic acid)/hydroxyapatite composites were prepared by in situ polymerization of l-lactide and glycolide in porous HAp pellets for their application to the artificial bone materials. Effect of l-lactic acid/glycolic acid ratio on the mechanical properties and biocompatibility were investigated.

Thin-film inorganic/organic hybrids of CaCO₃ and poly(cyclodextrin) were prepared. The cavities of CDs inside the hybrids facilitated functionalization of these fusion materials by dye molecules.

The effect of the content of carboxy groups in oxidized cellulose nanofiber (CeNF) on hydroxyapatite (HAp) formation capability in biomimetic processing using a solution mimicking human body fluid (simulated body fluid; SBF) was systematically investigated. Oxidized CeNF with different carboxy group contents (0–27% per glucose units of cellulose) were soaked in 1.5SBF, in which concentration was 1.5 times higher than that of SBF. It was found that there was optimum amount of carboxy groups for the effective induction of HAp nucleation on CeNF.

Electropolymerization of pendant groups in a copolymer of TEMPO- and aniline-substituted norbornene gave a layer of TEMPO-populated polynorbornene in which polyaniline chains were incorporated. The polyaniline chain served as a conducting path to reduce charge-transfer resistance for redox mediation, which gave rise to an excellent rate performance for charging/discharging process.

A polysilsesquioxane-based organic-inorganic hybrid membrane was prepared and applied as a proton-conducting membrane for fuel cells. A membrane of a random copolymer of ethyl 4-(2-methyl-3-triethoxysilylpropoxy)benzenesulfonate and triethoxy(methyl)silane showed proton conductivity of 2.0 × 10⁻⁵ to 1.1 × 10⁻³ S cm⁻¹ at room temperature. A membrane of a block copolymer of poly(3-(4-ethoxysulfonylphenoxy)-2-methylpropyl)silsesquioxane (SPES) and polymethylsilsesquioxane showed proton conductivity of 2.5 × 10⁻³ S cm⁻¹. The mixture of SPES and poly(vinyl alcohol), poly(ethylene oxide), or polyoctahedralpolysilsesquioxane showed proton conductivity of 2.7 × 10⁻³, 1.5x10⁻³ or 2.5 × 10⁻³ S cm⁻¹, respectively. The open-circuit voltage of the SPES membrane was 0.92 V.

HEC (or HMHEC) gel swells due to increasing SDS concentration, while the cooperative diffusion becomes faster. This indicates that the HEC (or HMHEC) gel can swell until the osmotic pressure equals the modulus when the charge effect dominates over the effect of configurational entropy for uncharged gels interacting with charged surfactants.

Dendritic morphologies of a metal oxide, metal and conductive polymer were obtained by using the dendrites of a transition metal salt as a template. Dendrites of the transition metal salt, copper acetate monohydrate (Cu(CH₃COO)₂·H₂O), were prepared under diffusion-controlled conditions in a polymer matrix, such as poly(vinyl alcohol). The resultant dendritic morphologies of Cu(CH₃COO)₂·H₂O were replicated to copper oxide (CuO), metallic copper (Cu) and polypyrrole without morphological changes. These methods can be applied to other metal oxides, metals and polymers.

Amphiphilic block copolymers poly[(2-ethoxyethyl vinyl ether)-block-(2-methoxyethyl vinyl ether)] (EOVE-b-MOVE) induce the ring assembly of silica nanospheres (SNSs, ca. 15 nm) in the liquid phase. Nanorings form with appropriate polymer concentration, pH and temperature. EOVE-b-MOVEs with varying block lengths successfully induce the ring assembly of SNSs, whereas a random copolymer fails, indicating that polymer’s molecular structure critically affects the assembly mode of SNSs. Interestingly, SNSs of a larger size (ca. 30 nm) one-dimensionally assemble into nanochains with these block copolymers under otherwise identical conditions.

Second- and third-generation hydroxy-terminated polyhedral oligomeric silsesquioxane (POSS)-core dendrons (that is, G2POSS-OH and G3POSS-OH, respectively) and third-generation carboxylic acid-terminated POSS-core dendron (G3POSS-COOH) were prepared. Casting of a methanol solution of G3POSS-OH provided optically transparent films. Methanol solution of G2POSS-OH generated opaque whitish films. Casting of a 2.6 m formic acid solution of G3POSS-COOH resulted in a highly transparent free-standing film. The peripheral functional groups may have been exposed on the surface of the cast films, which enabled control of the wettability of the films via the polarity of the COOH groups.

An initiating system composed of GaCl₃ and an alkylbenzene was demonstrated to be highly effective for the controlled cationic polymerization of a plant-derived monomer, β-pinene. When two equivalents of hexamethylbenzene were added to GaCl₃ in conjunction with 2-chloro-2,4,4-trimethylpentane as an initiator, cationic polymerization of β-pinene successfully proceeded in a living manner at –78 °C. Successful control over the reaction was attributed to the formation of a complex between GaCl₃ and the alkylbenzene, as confirmed by UV–vis and ⁷¹Ga NMR analyses.

The distribution of polarization during the polarization reversal in a VDF/TrFE copolymer was studied by the piezoresponse force microscopy, PFM. After an application of a positive voltage pulse to a negatively polarized sample, PFM image was obtained. The regions of blue color corresponding to positively polarized domains were shown to nucleate and grow in negatively polarized regions (red color) as the duration of pulse increased. The change of each domain with the pulse duration was analyzed quantitatively and the nucleation rate and the growth speed of domains were obtained separately.

Relationships between the interfacial area between PS and PMMA in a PS/PMMA (1/1, w/w) composite particles including various amounts (white circles 0; filled circles 0.05; white triangles 0.11; filled triangles 0.18 (wt % relative to the total amount of PS and PMMA)) of PS-b-PMMA (B11:Mn 10.6 × 10⁴–b-9.9 × 10⁴) and the required time to cleave into two parts (cleavage time, T_c) by addition of the acetone/water (9:1, v/v) solution to the dried particles

Nanogel particles (NP) that bind with the Fc fragment of immunoglobulin G (IgG) were immobilized on the pore surface of macroporous hard gel beads (GB) containing quaternary ammonium cations on the surface via multipoint electrostatic interactions. The model target protein (IgG) was reversibly captured by the NP-immobilized GBs through NP–IgG interactions. NP-immobilized GBs have potential applications as a novel affinity purification medium for proteins, combining an inexpensive and stable ligand with a high-performance support.

Anti-reflective coating films were fabricated via the layer-by-layer assembly of mesoporous silica nanoparticles and cationic polyelectrolytes. The thickness and packing density of coating films can be controlled by layer number and concentration of mesoporous silica nanoparticle dispersion to obtain excellent anti-reflective performance.

Three-dimensional structural analyses of huge spherulites of poly(oxyethylene) (PEG) using X-ray computerized tomography (CT) in blends of PEG and amorphous poly(d,l-lactic acid) are reported for the first time. Slit-shaped cracks that were straight or curved were clearly observed using X-ray CT. Furthermore, they appeared to form a set of spokes, presenting a signature of a huge spherulite. Several aspects that are representative of an axialite structure are presented, and they are in good agreement with the intuitively proposed structural model for axialite long ago, although the size scale is much larger in our study.