Effect of grafted polymer species on particle monolayer structure at the air-water interface

We have studied poly(methyl methacrylate)-grafted(PMMA) particle monolayer systems at the air-water interface. In previous papers, we reported that PMMA chains grafted from particles (silica particle and polystyrene latex) were extended on water surfaces. Through observing deposited particle monolayers on substrates using SEM, we have confirmed that PMMA of large molecular weights were either dispersed or arrayed in structure with long inter-particle distances approximately 500 nm. In contrast, low molecular weight PMMA were observed to aggregate upon deposition. We speculated that the difference in morphology in deposited particle monolayers would be attributed to the affinity between the grafted polymer and the substrate. To examine the effect of this affinity three new polymer-grafted silica particles were synthesized with a fairly high graft density of about 0.14 approximately 0.43 nm(-2). As well as PMMA-grafted silica particles (SiO2-PMMA), poly(2-hydroxyethyl methacrylate) and poly(t-butyl methacrylate)--grafted silica particles (SiO2-PHEMA and SiO2-PtBuMA) were also prepared and subjected to pi-A isotherm measurements and SEM observations. These pi-A isotherms indicated that polymer-grafted silica formed monolayer at the air-water interface, and the onset area of increasing surface pressure suggests that the polymer chains are extended on a water surface. However, the morphology of the deposited monolayer is highly dependent on polymer species: SiO2-PHEMA showed that the dispersed particle monolayer structure was independent of grafted molecular weight while SiO2-tBuMA showed an aggregated structure that was also independent of grafted moleculer weight. SiO2-PMMA showed intermediate tendencies: dispersed structure was observed with high grafted molecular weight and aggregated structure was observed with low grafted molecule weight. The morphology on glass substrate would be explaiened by hydrophilic interaction between grafted polymer and hydrophilic glass substrate.     

Silica and titanium dioxide nanoparticles cause pregnancy complications in mice

The increasing use of nanomaterials has raised concerns about their potential risks to human health. Recent studies have shown that nanoparticles can cross the placenta barrier in pregnant mice and cause neurotoxicity in their offspring, but a more detailed understanding of the effects of nanoparticles on pregnant animals remains elusive. Here, we show that silica and titanium dioxide nanoparticles with diameters of 70 nm and 35 nm, respectively, can cause pregnancy complications when injected intravenously into pregnant mice. The silica and titanium dioxide nanoparticles were found in the placenta, fetal liver and fetal brain. Mice treated with these nanoparticles had smaller uteri and smaller fetuses than untreated controls. Fullerene molecules and larger (300 and 1,000 nm) silica particles did not induce these complications. These detrimental effects are linked to structural and functional abnormalities in the placenta on the maternal side, and are abolished when the surfaces of the silica nanoparticles are modified with carboxyl and amine groups.     

Electrochemical Na Insertion and Solid Electrolyte Interphase for Hard‐Carbon Electrodes and Application to Na‐Ion Batteries

Recently, lithium‐ion batteries have been attracting more interest for use in automotive applications. Lithium resources are confirmed to be unevenly distributed in South America, and the cost of the lithium raw materials has roughly doubled from the first practical application in 1991 to the present and is increasing due to global demand for lithium‐ion accumulators. Since the electrochemical equivalent and standard potential of sodium are the most advantageous after lithium, sodium based energy storage is of great interest to realize lithium‐free high energy and high voltage batteries. However, to the best of our knowledge, there have been no successful reports on electrochemical sodium insertion materials for battery applications; the major challenge is the negative electrode and its passivation. In this study, we achieve high capacity and excellent reversibility sodium‐insertion performance of hard‐carbon and layered NaNi_0.5Mn_0.5O₂ electrodes in propylene carbonate electrolyte solutions. The structural change and passivation for hard‐carbon are investigated to study the reversible sodium insertion. The 3‐volt secondary Na‐ion battery possessing environmental and cost friendliness, Na⁺‐shuttlecock hard‐carbon/NaNi_0.5Mn_0.5O₂ cell, demonstrates steady cycling performance as next generation secondary batteries and an alternative to Li‐ion batteries.     

Influence of humidity and of the electric and magnetic microwave radiation fields on the remediation of TCE-contaminated natural sandy soils

The influence of moisture content (15% w/w) on the remediation (vaporization) of trichloroethylene (TCE) present in natural sands, chosen as a TCE-polluted model system for soils, was investigated with regard to applied microwave power levels, the depth of the sand sample, and the dielectric factors. The heating process occurring in the sand samples arises through the microwave conduction loss heating and dielectric loss heating mechanisms. The characteristic relevance of the electric and magnetic microwave radiation fields to the heating mechanisms was also examined. Heating by the magnetic microwave radiation field was considerable when magnetite was added to the dry and wet sand samples as the microwave absorber. Optimal microwave conditions are reported for a single-mode microwave applicator. Near-quantitative elimination of the TCE contaminant was achieved for sandy soils within a very short time.     

Amorphous nanosilica induce endocytosis-dependent ROS generation and DNA damage in human keratinocytes

Background

The alveolar macrophage (AM) - first line of innate immune defence against pathogens and environmental irritants - constitutively expresses peroxisome-proliferator activated receptor γ (PPARγ). PPARγ ligand-induced activation keeps the AM quiescent, and thereby contributes to combat invaders and resolve inflammation by augmenting the phagocytosis of apoptotic neutrophils and inhibiting an excessive expression of inflammatory genes. Because of these presumed anti-inflammatory functions of PPARγ we tested the hypothesis, whether reduced functional receptor availability in mutant mice resulted in increased cellular and molecular inflammatory response during acute inflammation and/or in an impairment of its resolution.

Methods

To address this hypothesis we examined the effects of a carbon-nanoparticle (CNP) lung challenge, as surrogate for non-infectious environmental irritants, in a murine model carrying a dominant-negative point mutation in the ligand-binding domain of PPARγ (P465L/wt). Animals were instilled intratracheally with Printex 90 CNPs and bronchoalveolar lavage (BAL) was gained 24 h or 72 h after instillation to investigate its cellular and protein composition.

Results

Higher BAL cell numbers - due to higher macrophage counts - were found in mutants irrespective of treatment. Neutrophil numbers in contrast were slightly lower in mutants. Intratracheal CNP instillation resulted in a profound recruitment of inflammatory neutrophils into the alveolus, but genotype related differences at acute inflammation (24 h) and resolution (72 h) were not observed. There were no signs for increased alveolar-capillary membrane damage or necrotic cell death in mutants as determined by BAL protein and lactate-dehydrogenase content. Pro-inflammatory macrophage-derived cytokine osteopontin was higher, but galectin-3 lower in female mutants. CXCL5 and lipocalin-2 markers, attributed to epithelial cell stimulation did not differ.

Conclusions

Despite general genotype-related differences, we had to reject our hypothesis of an increased CNP induced lung inflammation and an impairment of its resolution in PPARγ defective mice. Although earlier studies showed ligand-induced activation of nuclear receptor PPARγ to promote resolution of lung inflammation, its reduced activity did not provide signs of resolution impairment in the settings investigated here.     

Drying process in a solvent-based paint analyzed by phase-shifting digital holography and an estimation of time for tack free

A technique to study the drying of paints, based on phase-shifting digital holography, is presented. The technique is applied to the drying process of solvent-based paint on a three-dimensional surface at different substrate temperatures. For processing the data, a cross-correlation function and phase change derived from reconstructed complex amplitudes are calculated to visualize and to evaluate the local variations in the dryness of paint. The relationship between the optical signal obtained by the holographic method and the actual microscopic variations occurring in the paint film is also investigated using the gravimetric technique and a microscope. It is shown that the holographic technique can determine the stationary state of a painted surface corresponding to the end of the falling rate period in the drying process. The holographic technique detects mainly the activity on the surface and is applicable to assessment of the early drying process of paint.     

Numerical simulation of MFM image of a magnetic nano-contact

A MFM image of a magnetic nano-contact is studied numerically. We show that the ring- or arc-shaped MFM images with diameter of the order of 100 nm appear while the size of a nano-contact is of the order of 1 nm. We also show that the origin of the ring or arc-shaped MFM image is the oscillation of the magnetization of a nano-contact induced by the interaction between the MFM-tip and the nano-contact.     

Effect of polymer chain scission on photodegradation behavior of polystyrene/multi‐wall carbon nanotube composite

To clarify an effect of polymer chain scission on a polystyrene (PS)/multi‐wall carbon nanotube (MWNT) composite photodegradation, a relationship between the change of molecular weight and photodegradation behavior was studied. The MWNT loading brought about severe PS chain scission and led to the increase of the low molecular weight (less than 10⁵) fraction. The increase of the fraction was not proportional to the loading amount and showed the minimum at the 2% loading. The strange behavior was due to a rheological effect bringing about a decrease of shear stress in the composite preparation. An unsaturated end group was produced by the chain scission and became the photodegradation initiator leading to auto‐oxidation and crosslink reactions. The MWNT scavenged radical species and worked as an antioxidant. The coexistence of the unsaturated end group and MWNT made the photodegradation behavior complicated. However, the MWNT radical scavenging ability was considerably poor, and the MWNT had little ability to inhibit the photodegradation initiation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40362.     

Electrical,mechanical, and crystallization properties of ethylene‐tetrafluoroethylene copolymer/multiwalled carbon nanotube composites

Multiwalled carbon nanotubes (MWCNTs) were melt‐mixed in a conical twin‐screw extruder with a random copolymer of ethylene and tetrafluoroethylene. Surprisingly, the electrical percolation threshold of the resultant composites was quite low; ～0.9 wt %. In fact, this value is as low or lower than the value for most MWCNT/semicrystalline polymer composites made with roughly equivalent aspect ratio tubes mixed in a similar manner, for example, melt mixing. This low percolation threshold, suggestive of good dispersion, occurred even though the polymer surface energy is quite low which should make tubes more difficult to disperse. Dynamic mechanical measurements confirmed the rather low percolation threshold. The effect of nanotubes on crystallization kinetics was quite small; suggesting perhaps that a lack of nucleation which in turn reduces/eliminates an insulating crystalline polymer layer around the nanotubes might explain the low percolation threshold. Finally, the modulus increased with the addition of nanotubes and the strain at break decreased. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41052.     

Cellulose–chitin hybrids: synthesis of branched amino polysaccharides by regioselective introduction of (N-acetyl-)d-glucosamine branches into cellulose

Cellulose–chitin hybrid-type branched polysaccharides, β-1,4-d-glucans having amino sugar branches at the C-6 position, have been synthesized through a series of site-specific modification reactions. Cellulose was first transformed to two kinds of acceptors having a reactive group only at C-6. Glycosylation reactions of these acceptors with an oxazoline donor derived from d-glucosamine resulted in the introduction of amino sugar branches into cellulose. An acceptor carrying the O-trimethylsilyl group at C-6 was particularly suitable for glycosylation in solution to form branched celluloses with various degrees of substitution up to about 0.5 per pyranose unit in a controlled manner. Deprotection of the product afforded the cellulose having N-acetyl-d-glucosamine or d-glucosamine branches depending on the reaction conditions. The deprotected nonnatural branched polysaccharides were readily soluble in neutral water as well as common organic solvents and would be promising as a new type of water-soluble amino polysaccharides.