The activation of furfuryl alcohol polymerization by oxygen and its enhanced mechanical properties

The effect of oxygen and additional oxygen providers on furfuryl alcohol polymerization was investigated through chemical analyses and mechanical evaluation. NMR, UV–vis, Fourier transform infrared, and gas chromatography–mass spectrometry (GC–MS) results suggested that atmospheric oxygen and the further addition of an oxygen source functioned as an activator for the entire network polymerization. Interestingly, the construction of a conjugated structure on the furan linear chain, which is key to three-dimensional cross-linking, also appears to be accelerated in the presence of oxygen. Furthermore, the introduction of oxygen providers into the curing system successfully enhanced the mechanical properties of the cured furan resin.     

Moment stability analysis of linear stochastic human controller model in visuomotor tracking task

We investigate the stability limits of linear stochastic human controller model. In our previous study, we had proposed a model by which the probability distributions of human visuomotor tracking data can be accurately reproduced. In this study, we conduct a stochastic analysis on our model by deriving a system of moment differential equations with respect to random state variables of this model. We evaluate the stability limits of our model by detecting zero-eigenvalue conditions of the Jacobian matrix of the moment differential equations. The resulting stability limits make it possible to characterize the human parameter values that were experimentally identified from the human participants in our previous study; this shows that during the visuomotor tracking experiments, the human participants generated huge fluctuations far from the stability limits while applying almost neutrally stable proportional gain.     

Smart polyion complex micelles for targeted intracellular delivery of PEGylated antisense oligonucleotides containing acid-labile linkages

A novel pH-sensitive and targetable antisense ODN delivery system based on multimolecular assembly into polyion complex (PIC) micelles of poly(L-lysine) (PLL) and a lactosylated poly(ethylene glycol)-antisense ODN conjugate (Lac-PEG-ODN) containing an acid-labile linkage (beta-propionate) between the PEG and ODN segments has been developed. The PIC micelles thus prepared had clustered lactose moieties on their peripheries and achieved a significant antisense effect against luciferase gene expression in HuH-7 cells (hepatoma cells), far more efficiently than that produced by the nonmicelle systems (ODN and Lac-PEG-ODN) alone, as well as by the lactose-free PIC micelle. In line with this pronounced antisense effect, the lactosylated PIC micelles showed better uptake than the lactose-free PIC micelles into HuH-7 cells; this suggested the involvement of an asialoglycoprotein (ASGP) receptor-mediated endocytosis process. Furthermore, a significant decrease in the antisense effect (27 % inhibition) was observed for a lactosylated PIC micelle without an acid-labile linkage (thiomaleimide linkage); this suggested the release of the active (free) antisense ODN molecules into the cellular interior in response to the pH decrease in the endosomal compartment is a key process in the antisense effect. Use of branched poly(ethylenimine) (B-PEI) instead of the PLL for PIC micellization led to a substantial decrease in the antisense effect, probably due to the buffer effect of the B-PEI in the endosome compartment, preventing the cleavage of the acid-labile linkage in the conjugate. The approach reported here is expected to be useful for the construction of smart intracellular delivery systems for antisense ODNs with therapeutic value.     

Limiting flux in microfiltration of colloidal suspensions by focusing on hydrodynamic forces in viscous sublayer

Cross‐flow microfiltration tests were performed on colloidal suspensions under turbulence conditions. By changing the particle diameter, flow rate, and channel height in the membrane housing to measure limiting fluxes, the influence of each parameter on the limiting flux was assessed from the viewpoint of hydrodynamic forces exerted on a particle in the viscous sublayer. In analyzing all the data taken, the particle Reynolds number calculated from the limiting flux is proportional to the 1.5 power of that calculated from the flow rate at the boundary between the viscous sublayer and the intermediate layer. This fact indicates that the limiting flux can be determined in situations where the drag force exerted by the flux is balanced by the lift force in the viscous sublayer. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1760–1765, 2018     

Contribution of known endocrine disrupting substances to the estrogenic activity in Tama River water samples from Japan using instrumental analysis and in vitro reporter gene assay

To quantitatively characterize the substances contributing to estrogenic activity in river water, in vitro bioassay using MVLN cells and instrumental analysis using liquid chromatograph–mass spectrometer (LC/MS) or liquid chromatograph–tandem mass spectrometer (LC/MS/MS) were applied to river water extracts taken from various locations in the Tama River, Japan. Tama River water samples were extracted using solid phase extraction and the crude extracts were fractionated by high-performance liquid chromatography (HPLC) into 10 fractions. The sixth fraction contained nonylphenol (NP) and octylphenol (OP) at concentrations in the range of 51.6–147 and 6.9–81.9 ng/L, respectively (concentrations corresponding to the original sample volumes). No estrogenic activity, expressed as 17β-estradiol equivalents (E2-EQ_B), however, was observed in this fraction (<0.6 ng-E2eq/L). Instrumentally determined estrogenic activity (E2-EQ_C), which is the concentrations of NP and OP multiplied by their corresponding relative potency, was below the detection limit of the MVLN cell bioassay. Estrogenic activities were detected only in HPLC fraction nos. 7, 8 and 9. Estrone (E1), estradiol (E2) and bisphenol A (BPA) were detected in these fractions. Estriol (E3) and ethynylestradiol (EE2) were not detected (<0.2 ng/L) in these fractions. The calculated E2-EQ_C for BPA was below the detection limit of bioassay. The E2-EQ_C for E1 and E2 were on the same order as the estrogenic activity determined by the bioassay (E2-EQ_B). The ratios of E2-EQ_C and E2-EQ_B for E1 and E2 in the three factions collectively (nos. 7–9) were 0.49–0.97 and 0.29–1.12, respectively. Above results indicated that the major causal substances to the estrogenic activity in the Tama River were E1 and E2.     

Effect of molding pressure on fabrication of low-crystalline calcite block

We have reported that low-crystalline porous calcite block, which is useful as a bone substitute or a source material to prepare apatite-type bone fillers could be fabricated by exposing calcium hydroxide compact to carbon dioxide gas saturated with water vapor. In the present study, we investigated the effect of molding pressure on the transformation of calcium hydroxide into calcite and the mechanical strength of the carbonated compact. Transformation into calcite was almost completed within 72 h, however, a small amount of Ca(OH)₂ still remained unreacted at higher molding pressure because of incomplete penetration of CO₂ gas into the interparticle space due to dense packing of Ca(OH)₂ particles. On the other hand, high molding pressure resulted in an increase in diametral tensile strength (DTS) of the calcite compact formed. Critical porosity of the calcite block was calculated as approximately 68%.     

Controlled nanoporous structures of a marine diatom

We demonstrated chemical etching of a marine diatom shell with 1 N NaOH for controlling the pore size of nanoporous structures of the shell under various conditions. Scanning electron microscopy (SEM) images clearly revealed that the pore size of the diatom shells was regulated in the case of etching at 25 degrees C. In contrast, fluctuations in the etched structures was relatively high even during short periods degradation at 40, 60, and 90 degrees C; therefore, controlled nanoporous structures could not be fabricated. This is the first example of artificial modification of natural diatom shells at the nanoscale although diatom shells have been widely used in industry. In addition, a backbone-like structure was observed during the etching process. The structure was similar to the intermediate structure observed during the primitive stage of the diatom cell growth. Probably, this information is valuable for studying the mechanism of nanoporous structures of diatoms.     

Solubility of propylene in semicrystalline polypropylene

Gas solubilities and polymer swelling in propylene and semicrystalline polypropylene system at temperatures of 323.2 and 348.2 K and pressures up to propylene's vapor pressure were measured. Pressure, specific volume, and temperature (PVT) measurements of polypropylene were carried out at temperatures from 313 to 573 K and pressures up 200 MPa. Two kinds of polypropylenes, which had different stereoregularities, were used for both solubility and PVT measurements. The solubilities were correlated with the Sanchez–Lacombe equation of state (EOS) with temperature‐dependent binary interaction parameters to within 5% average relative percentage deviation. Swelling ratios estimated with Sanchez–Lacombe EOS coupled with optimized interaction parameters were 20% lower than the experimental values. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1134–1143, 2001     

Gelation of poly(vinyl alcohol)/water/dimethylformamide solutions and properties of dried films

The properties of solutions for syndiotacticity-rich poly(vinyl alcohol) (s-PVA)/dimethylformamide (DMF)/water systems, the gelation of the s-PVA solutions, and the properties of the dried s-PVA gel films were examined. From the results of the dissolution temperature of the polymer, the gelation temperature of the solutions, the melting temperature of the gels, and the compressive modulus of the gels, the solubility of the polymer was the highest at DMF contents of 10–20 vol %. The maximum dynamic tensile modulus of the drawn (×18) films obtained from the dried gel films with a DMF content of 10 vol % was 54.9 GPa at 20°C. The orientation of the polymer chains in the amorphous regions was higher than that in the crystalline regions. The orientation of the polymer chains in the amorphous regions for the drawn films with a DMF content of 10 vol % was higher than that for the drawn films with a DMF content of 60 vol %. The orientation of the polymer chains in the amorphous regions was considered to play an important role in the properties of high strength and high modulus. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1661–1667, 1998     

Linked‐BINOL: An Approach towards Practical Asymmetric Multifunctional Catalysis

The development and application of a novel linked‐1,1′‐binaphthol (linked‐BINOL) as an approach towards practical asymmetric multifunctional catalysis is described. Linked‐BINOL was first designed to increase the stability of a Ga‐Li‐BINOL complex against ligand exchange with 4‐methoxyphenol. An oxygen‐containing linked‐BINOL, which is a semi crown ether, was effective in both promoting the formation of a monomer complex and increasing the stability of the Ga‐Li complex. A Ga‐Li‐linked‐BINOL complex promoted the epoxide opening reaction in up to 96% enantiomeric excess (ee). Second, based on the X‐ray structural information of the Ga‐Li‐linked‐BINOL complex, we designed a more stable lanthanide linked‐BINOL complex. An air‐stable, storable, and reusable La‐linked‐BINOL complex promoted the Michael reaction in up to >99% ee. The catalyst activity remained unchanged after storage under air for 4 weeks. Calculations suggested that the linked‐BINOL would function as a pentadentate ligand in a lanthanum complex, thus efficiently improving the stability of the complex. Finally, the linked‐BINOL was applied to a new homobimetallic multifunctional catalysis. A dinuclear Zn‐Zn‐linked‐BINOL complex promoted the enantio‐ and diastereoselective direct aldol reaction in up to 99% ee, where one Zn cation might function as a Lewis acid and the other Zn‐phenoxide as a Brønsted base.