Kinetics and dissolution of intratracheally administered nickel oxide nanomaterials in rats

Background

The toxicokinetics of nanomaterials are an important factor in toxicity, which may be affected by slow clearance and/or distribution in the body.

Methods

Four types of nickel oxide (NiO) nanoparticles were single-administered intratracheally to male F344 rats at three doses of 0.67–6.0 mg/kg body weight. The rats were sacrificed under anesthesia and the lung, thoracic lymph nodes, bronchoalveolar lavage fluid, liver, and other organs were sampled for Ni burden measurement 3, 28, and 91 days post-administration; Ni excretion was measured 6 and 24 h after administration. Solubility of NiO nanoparticles was determined using artificial lysosomal fluid, artificial interstitial fluid, hydrogen peroxide solution, pure water, and saline. In addition, macrophage migration to trachea and phagosome-lysosome-fusion rate constants were estimated using pulmonary clearance and dissolution rate constants.

Results

The wire-like NiO nanoparticles were 100% dissolved by 24 h when mixed with artificial lysosomal fluid (dissolution rate coefficient: 0.18/h); spherical NiO nanoparticles were 12% and 35% dissolved after 216 h when mixed with artificial lysosomal fluid (1.4?×?10^?3 and 4.9?×?10^?3/h). The largest irregular-shaped NiO nanoparticles hardly dissolved in any solution, including artificial lysosomal fluid (7.8?×?10^?5/h). Pulmonary clearance rate constants, estimated using a one-compartment model, were much higher for the NiO nanoparticles with a wire-shape (0.069–0.078/day) than for the spherical and irregular-shaped NiO nanoparticles (0–0.012/day). Pulmonary clearance rate constants of the largest irregular-shaped NiO nanoparticles showed an inverse correlation with dose. Translocation of NiO from the lungs to the thoracic lymph nodes increased in a time- and dose-dependent manner for three spherical and irregular-shaped NiO nanoparticles, but not for the wire-like NiO nanoparticles. Thirty-five percent of the wire-like NiO nanoparticles were excreted in the first 24 h after administration; excretion was 0.33–3.6% in that time frame for the spherical and irregular-shaped NiO nanoparticles.

Conclusion

These findings suggest that nanomaterial solubility differences can result in variations in their pulmonary clearance. Nanoparticles with moderate lysosomal solubility may induce persistent pulmonary inflammation.

     

Unsteady stirring method staged used in suspension polymerization of styrene

The results of an unsteady stirring method staged, used in the suspension polymerization of styrene in a lab‐scale batch reactor, are presented. Variation of droplet size during the whole polymerization process under the unsteady stirring condition, compared with that under a steady stirring condition, was found to be small. According to the variable droplet size character, two methods were used to divide the polymerization process into four stages and the unsteady stirring method was used in only one stage of each experimental run. By these operations, the optimum operation of obtaining large particle product with uniform particle size distribution was achieved. The results suggest that controlling the droplet coalescence process is more important than controlling the initial droplet size distribution to obtain uniform final particle products. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1873–1881, 2001     

Polymerization of vinyl chloride with butyllithiums and metallocene catalysts

Polymerizations of vinyl chloride (VC) with butyllithium (BuLi) and metallocene catalysts were investigated. In the polymerization of VC with BuLi, the activity for polymerization decreased in the following order; t‐BuLi > n‐BuLi > s‐BuLi. A polymer controlled structurally in the main chain was found to be synthesized from the polymerization of VC with BuLi. The molecular weights of polymers obtained in bulk polymerization were higher than those of polymers obtained in solution. A linear relationship of the M_n of the polymer and the polymer yields was observed. The M_w/M_n of the polymer did not change significantly during polymerization, although the M_w/M_n was around 2. Thermal stability of the polymer obtained with BuLi was higher than that of polymer obtained with radical initiators, as determined by TGA measurements. In the polymerization of VC with Cp*TiX₃/MAO (X: Cl and OCH₃) catalysts, polymers were obtained with both catalysts, although the rate of polymerization was slow. The Cp*Ti(OCH₃)₃//MAO catalyst in CH₂Cl₂ gave higher‐molecular‐weight polymers in a better yield than in toluene. From elemental analysis and the NMR spectra of the polymers, the Cp*Ti(OCH₃)₃/MAO catalyst gave polymers consisting of repeating regular head‐to‐tail units, in contrast to the Cp*TiCl₃/MAO catalyst, which gave polymers having anomalous units.     

Quantitative evaluation of rate‐determining steps in polymer complexation

A quantitative method to find the rate determining steps in the ion‐adsorption kinetics of polymer complexation agents is theoretically formulated and experimentally established. The degree of film‐diffusion control and particle‐diffusion control is simultaneously evaluated based on the law of addition of kinetic resistances combined with Einstein's viscosity expression. The change in the initial rate with respect to the resin concentration was scrutinized by plotting the effective rate constant versus the initial rate, and the film mass transfer coefficient was calculated. This is a concise and practical procedure to analyze the rate determining steps of polymer complexation kinetics. The validity of the method was confirmed by studying the adsorption of Cu(II) ion on crosslinked chitosans. In these materials, the importance of film diffusion was found both in adsorption and desorption processes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44738.     

Effects of La addition to Ni/Al2O3 catalysts on rates and carbon deposition during steam reforming of n-dodecane

Steam reforming of n-dodecane on La-Ni/γ-Al₂O₃ catalysts was investigated at a relatively low temperature (773 K) to elucidate the catalytic behavior at the inlet of a practical reformer. The addition of lanthanum to the Ni/γ-Al₂O₃ formulation completely suppressed carbon deposition, which otherwise occurs to a significant extent on unmodified Ni/γ-Al₂O₃. Modification with La also enhanced the initial turnover rates of hydrogen formation. The La-Ni/γ-Al₂O₃ catalysts, however, deactivated with increased time-on-stream at a high steam-to-carbon ratio of 3.5, because of oxidation of the active Ni metal. Reduction at 873 K almost fully regenerated the catalytic activity, indicating that the deactivation was not primarily a result of sintering or carbon deposition, but was due to the oxidation of active Ni metal.     

Two_stage procedures for estimating a linear function of multinormal mean vectors

We consider the problenl of const,ructing a fixed-size confidence region for a linear functioll of mean vectors of k multinormal populations. The covariance matrices are assunlcd to be known except for the unknown scalar multipliers. A two-stage procedure is proposed to derive such a confidence region. We also discuss the asylnptotic efficiency of the procedure.     

Thermodynamic and Spectroscopic Studies on Am(III) and Eu(III) in the Extraction System of N,N,N',N'-Tetraoctyl-3-Oxapentane-1,5-Diamide in n-Dodecane/Nitric Acid

Abstract

Thermodynamic parameters (ΔG, ΔH, and ΔS) for the extraction of trivalent f-elements, M(III) (M = Am, Eu), with N,N,N',N'-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) were determined in nitric acid/n-dodecane extraction system. The extraction of M(III) with TODGA was more exothermic than those with octyl(phenyl)-N,N-diisobutylcarbamoylmethyl phosphine oxide (CMPO) and dihexyl-N,N-diethylcarbamoylmethyl phosphonate (DHDECMP). The difference in ΔH between the extractants was attributed to the difference in the binding mode between them, i.e. tridentate (TODGA) and bidentate (CMPO and DHDECMP). In addition, from the results of luminescence lifetime measurement, it was found that the inner-sphere of extracted Eu(III) was dehydrated completely, and occupied by TODGA and/or NO₃ ^?.     

Generation of high photocurrent in three-dimensional silicon quantum dot superlattice fabricated by combining bio-template and neutral beam etching for quantum dot solar cells

We fabricated a three-dimensional (3D) stacked Si nanodisk (Si-ND) array with a high aspect ratio and uniform size by using our advanced top-down technology consisting of bio-template and neutral beam etching processes. We found from conductive atomic microscope measurements that conductivity became higher as the arrangement was changed from a single Si-ND to two-dimensional (2D) and 3D arrays with the same matrix of SiC, i.e., the coupling of wave functions was changed. Moreover, our theoretical calculations suggested that the formation of minibands enhanced tunneling current, which well supported our experimental results. Further analysis indicated that four or more Si-NDs basically maximized the advantage of minibands in our structure. However, it appeared that differences in miniband widths between 2D and 3D Si-ND arrays did not affect the enhancement of the optical absorption coefficient. Hence, high photocurrent could be observed in our Si-ND array with high photoabsorption and carrier conductivity due to the formation of 3D minibands.     

Temperature–field phase diagrams in Pb(Zn1/3Nb2/3)O3–4.5%PbTiO3 II

Temperature and field dependences of the dielectric constants under the DC biasing fields along the [011]- and [111]-directions in the cubic coordinate in Pb(Zn_1/3Nb_2/3)O₃–4.5%PbTiO₃ were investigated. The temperature–field phase diagrams were constructed in the field range below 10 kV/cm. It was confirmed that in Pb(Zn_1/3Nb_2/3)O₃–4.5%PbTiO₃ the intermediate tetragonal phase as a ground state of the system exists even without the DC field, and the tetragonal phase disappears in the external field above 4 and 3 kV/cm along the [011]- and [111]-directions, respectively. The field-induced orthorhombic-phase in the field along the [011]-direction was also found.     

Synthesis and properties of multiferroic 0.7BiFeO3−0.3BaTiO3 thin films by Mn doping

Multiferroic BiFeO₃?BaTiO₃ thin films that simultaneously exhibit ferroelectricity and ferromagnetism at room temperature were prepared by chemical solution deposition. Perovskite single-phase 0.7BiFeO₃?0.3BaTiO₃ thin films were successfully fabricated in the temperature range 600–700 °C on Pt/TiO_x/SiO₂/Si substrates. As the crystallization temperature was increased, grain growth proceeded, resulting in higher crystallinity at 700 °C. Although the 0.7BiFeO₃?0.3BaTiO₃ thin films exhibited poor polarization (P)?electric field (E) hysteresis loops owing to their low insulating resistance. The leakage current at high applied fields was effectively reduced by Mn doping at the Fe site of the 0.7BiFeO₃?0.3BaTiO₃ thin films, leading to improved ferroelectric properties. The 5 mol% Mn-doped 0.7BiFeO₃?0.3BaTiO₃ thin films simultaneously exhibited ferroelectric polarization and ferromagnetic magnetization hysteresis loops at room temperature.