Original Article in 2018

Liquid-crystalline Au complexes with siloxane groups at the termini of flexible chains were synthesized. The effects of the molecular and molecular aggregate structures on the luminescence behavior of the complexes were investigated. In condensed phases, different luminescence colors were observed depending on the aggregate structure due to the effect of intermolecular interactions; thus, the luminescence color of the Au complexes can be controlled by the intermolecular interactions based on the structure of the molecular aggregates.

The alignment of azobenzene molecule was induced by a new-alignment-patterning technique based on a scanning wave photopolymerization (SWaP) concept with unpolarized light. This finding indicates that SWaP could be employed as a novel and simple fabrication process for preparing a wide variety of highly functional optical devices requiring alignment control.

A series of amphiphilic block oligomers were designed and synthesized using ruthenium-catalyzed living radical polymerization with poly(ethylene glycol) and butyl methacrylates (BMA). These PEGylated oligomers showed high binding efficiencies for liposomal preparations as model cell membranes, and also had low cytotoxicity. BMA contents and monomer sequences in the copolymers strongly affected their binding efficiencies. Current method enabled precise control of the primary structures of amphiphilic oligomers, allowing tuning of their binding efficiencies. These amphiphilic block oligomers have promise as novel membrane anchors for many biomedical applications.

Multi-walled carbon nanotube (MWCNT)/dendrimer sheet scaffolds, i.e., dendrimers attached to the surface of MWCNT buckypaper, were fabricated, and a hydroxyapatite (HAp) coating prepared on dendrimer-modified buckypaper using an alternate soaking process (ASP) is described. The amount of the HAp that is retained on the surface of the MWCNT/dendrimer sheet scaffolds depends on the dendrimer contents. Moreover, biomimetic crystallization of calcium phosphate on buckypaper in simulated body fluid (SBF) was carried out. TEM analysis of the resulting MWCNT/dendrimer sheet scaffolds revealed that the MWCNT backbone was covered with scaly crystals.

To a thermocell consisting of the redox pair of ferrocenecarboxylate/ferroceniumcarboxylate was added β-cyclodextrin as host matrix. The Seebeck coefficient increases to −1.20 mV/K by the host–guest interaction between ferrocenecarboxylate and β-CD.

A perfluorinated oligo (ethylene oxide) monoalkyl ether containing a terminal methyl carbonate has been developed for potential application as quasi-solid-state electrolytes for Li-ion batteries. The fluorinated block-structured molecule self-assembles to form nanosegregated bilayer structures, which can be used for anisotropic Li ion transport when complexed with a Li salt. The complex shows ionic conductivities on the order of 10⁻⁶ S cm⁻¹ in the ordered smectic phase formed at ambient temperature.

We prepared a series of ionic complexes, [CnMim][CHP] (n = 6–18), by neutralizing cholesterol hydrogen phthalate (CHP) with 1-alkyl (Cn)-3-methylimidazolium hydroxide ([CnMim][OH]) derived from [CnMim][Br]. The complexes of n ≥ 10 formed a thermotropic mesophase in each individual temperature range and solidified into a mesomorphic glass upon cooling, although two samples of n = 6 and 8 showed no ordered structure. Enthalpy relaxation behavior of the mesomorphic glasses (n = 10, 18) was also examined as a function of the aging temperature and time

A novel concept for cellular scaffolds with 2D-patterned mechanical properties was proposed. Thin films of glassy polystyrene (PS) with thicknesses ranging from 100 nm to 1 μm were prepared on epoxy resin-based line and space (L&S) patterned substrates. Although the outermost surface of PS was sufficiently flat regardless of the L&S patterned substrates, the mechanical responses differed depending on the presence of the underlying resin foundation. The initial cell adhesion and spreading and the proliferation on the scaffolds were affected by the 2D-patterned mechanical properties.

Poly(N-isopropylacrylamide) nanogels having catechol substituents were prepared. It was found that the aqueous dispersion of the nanogel showed thermal aggregation responding to body temperature only in the case that Fe³⁺ was mixed and then pH increased. It can be said that this thermal aggregation system of the nanogel is one kind of AND-type logic gate aggregation system. We also showed the possibility that this AND-type nanogel aggregation can be used as a smart valve system regulating water flow.

Noticeable molecular weight and temperature dependency for physisorption behavior of semiflexible, non-charged poly(9,9-n-dioctylfluorene) (PF8) onto cuboidal γ-alumina in toluene were found. MM/MD simulations (CVFF) and quantum mechanical (MP2/6-31G(d,p)) calculations suggested that PF8 swaps interacting toluene for (110) surface of γ-alumina by changing the interaction from CH/π interactions to C-H/O interactions of γ-alumina in toluene. The competition between multiple intermolecular CH/π and C-H/O interactions was crucial whether the spontaneous physisorption of PF8 occurs in place of solvent quantity of toluene. The solution-phase physisorption systems should be the consequence of several weak attractive intermolecular interactions coexisting between polymers, surface, and solvents

Amyloid ß-protein (Aß) is converted to toxic forms through interactions with the ganglioside in neuronal membranes. The highly ganglioside-enriched microdomain (ganglioside cluster) in neuronal membranes plays a key role in Aß assembly. In the present study, lipid components of synaptosome extracted from mouse aged brain was determined by LC-MS spectroscopy. We demonstrated that ganglioside ratio (GM3 to GM1) and cholesterol content are an important factor for inducing Aß assembly. These results provides important insight into the mechanism of polypeptide assembly on the neuronal membrane in Alzheimer’s disease patients.

Glycosylated double-hydrophilic block copolymers composed of polyacrylamide bearing maltose moieties and poly(N-isopropylacrylamide) were synthesized by a RAFT polymerization technique. The resulting glycosylated block copolymer aggregated, interacted strongly with the lectin Con A, and formed a precipitate in aqueous media above the LCST. The precipitate dissociated into the aqueous medium below the LCST. This behavior of the block copolymer in aqueous media is reversible in response to changes in temperature.

We report a facile method for synthesizing Au NPs based on alkali/urea regenerated cellulose hydrogels. By controlling the precursor concentration and the reaction temperature, the size of the Au NPs can be adjusted. The Au NP/cellulose hydrogels can be used as efficient heterogeneous catalysts in the reduction of 4-nitrophenol.

A versatile and simple strategy for building self-healing hydrogels with tunable mechanical properties and shape memory behavior has been developed using diethylenetriamine to crosslink polyacrylic acid chains. Hydrophobic domains form in the network in addition to ionic bonds between the amino and carboxylic acid groups. The combination of ionic bonds and hydrophobic interactions not only provides self-healing ability but also drastically improves the strength.

6 groups of blend membranes based on carboxymethyl chitosan (CMCTS) or carboxymethyl chitin (CMCT) were prepared. CMCTS-Gel (1#) and CMCT-Gel (4#) blend membranes with high transmittance and surface properties were more suitable for cell growth. Although primary corneal epithelial cells (CECs) on the two blend membranes could keep marker proteins and prevent cell fibrosis, CECs on membrane 4# could maintain the original epithelial morphology and improve the K12 protein level seriously. The potential mechanism of anti-fibrosis effect was proved that both of the membranes could block phosphorylation levels of Smad2 and Smad3, and membrane 4# could also depress the total native Smad2 and Smad3 expressions.

Photoinduced molecular switches were achieved by atropisomeric polymers containing conjugated structures of azo and binaphthyl units. trans-cis Photoisomerization of the azo unit led to molecular twisting motion of the binaphthyl unit, yielding chiroptical switching in a neat film. The atropisomeric polymers also displayed photoswitchable fluorescence by repeated irradiation of UV and visible light. Irradiation of the neat film with linearly polarized light caused selective excitation of the atropisomeric polymer, leading to anisotropic molecular orientation.

We synthesized side-chain crystalline block copolymer that exhibit an adsorptive interaction with polyethylene (PE) using a monomer with a long alkane side chain and a hydrophilic monomer. By coating PE with a dilute solution of these block copolymers, the PE surface can easily be endowed with hydrophilicity in a uniform manner. This method does not require a special experimental apparatus or reagents and is more viable than conventional methods in terms of energy efficiency and cost, which means it has a lower environmental impact. Based on the measured contact angle on the modified PE surface, we also evaluated the effects of copolymer concentration in the coating solution and the degree of polymerization in the functional region of the copolymer. The results suggest that the hydrophilicity of the PE surface can be controlled by adjusting these parameters.

The introduction of structural defects into ordered mesoporous carbons is demonstrated based on block copolymer-templating and high-temperature carbonization of N-containing polymers. N-atom removal during high-temperature heat treatment induces structural defect formation, and the use of soft-templating yields dense mesostructures tough enough to maintain ordering upon defect introduction.Please change the graphical abstract to the revised one sent by email separately.

This study demonstrated convenient preparation methods for the introduction of cationic and cross-linkable moieties into 2-branched and 4-branched PCL and their corresponding stable materials. The cationic content and the ratio of 2-branched and 4-branched monomers could be simultaneously controlled by incorporating non-cationic macromonomers. Zeta potential measurements proved that the cationic charge could be controlled by changing the temperatures. Human MSC adhesion was observed on the PCL materials with different cationic contents and lower contents of cationic contents seem to be preferable. Consequently, such materials are promising for biomaterials research.

The influence of poly(butylene succinate) (PBS) crystals on the crystallinity of poly(ethylene oxide) (PEO) in PBS/PEO blends, which exhibit interpenetrating spherulites, was examined. The degree of crystallinity, ϕ, of each component was obtained by pulsed nuclear magnetic resonance (NMR). The dilution effect, order of crystallization, and change in the glass transition temperature upon blending were discussed as factors contributing to the ϕ. PEO exhibited an apparent secondary crystallization, where ϕ gradually increased and the mobility of the chain segments was suppressed. The secondary process of PBS was nearly negligible.