Production of hyaluronic‐acid‐based cell‐enclosing microparticles and microcapsules via enzymatic reaction using a microfluidic system

This article describes the preparation of cell‐enclosing hyaluronic acid (HA) microparticles with solid core and microcapsules with liquid core through cell‐friendly horseradish peroxidase (HRP)‐catalyzed hydrogelation. The spherical vehicles were made from HA derivative possessing phenolic hydroxyl moieties (HA‐Ph) cross‐linkable through the enzymatic reaction by extruding cell‐suspending HA‐Ph aqueous solution containing HRP from a needle of 180 μm in inner diameter into the ambient coaxial flow of liquid paraffin containing H₂O₂ in a microtubule of 600 μm in diameter. By altering the flow rate of liquid paraffin, the diameters of gelatin and HA‐Ph microparticles were varied in the range of 120–220 μm and 100–300 μm, respectively. The viability of the enclosed human hepatoma HepG2 cells in the HA‐Ph microparticles of 180 μm in diameter was 94.2 ± 2.3%. The growth of the enclosed HepG2 cells was enhanced by decreasing the HRP concentration. The microcapsules of 200 μm in diameter were obtained by extruding HA‐Ph aqueous solution containing thermally liquefiable cell‐enclosing gelatin microparticles of 150 μm in diameter using the same microfluidic system. The enclosed cells grew and filled the cavity within 10 days. Spherical tissues covered with a heterogeneous cell layer were obtained by degrading the microcapsule membrane using hyaluronidase after covering the surface with a heterogeneous cell layer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43107.     

Visible Light Irradiation of [60]Fullerene Causes Killing and Initiation of Transformation in Balb/3T3 Cells

Abstract

Cell transformation in vitro is a model of carcinogenesis in vivo. Two-stage transformation assay increases the sensitivity of cells to chemicals and permits detection of carcinogens acting as initiating agents. [60]Fullerene (C₆₀) was cytotoxic in BALB/3T3 cells when it was irradiated by visible light, but not without light irradiation. Under conditions when C₆₀ was cytotoxic, it acted as an initiating agent for cell transformation, but it did not act as a complete transforming agent. the initiating activity of visible-light-irradiated C₆₀ was statistically significant in a modified two-stage transformation assay including a procedure for replating cells treated by C₆₀ and light, but it was equivocal in the standard two-stage transformation assay.     

Total reflection X-ray spectroscopy as a rapid analytical method for uranium determination in drainage water

Uranium concentrations in drainage water are typically determined by α-spectrometry. However, due to the low specific radioactivity of uranium, the evaporation of large volumes of drainage water, followed by several hours of measurements, is required. Thus, the development of a rapid and simple detection method for uranium in drainage water would enhance the operation efficiency of radiation control workers. We herein propose a novel methodology based on total reflection X-ray fluorescence (TXRF) for the measurement of uranium in contaminated water. TXRF is a particularly desirable method for the rapid and simple evaluation of uranium in contaminated water, as chemical pretreatment of the sample solution is not necessary, measurement times are typically several seconds, and the required sample volume is low. We herein employed sample solutions containing several different concentrations of uranyl acetate with yttrium as an internal standard. The solutions were placed onto sample holders, and were dried prior to TXRF measurements. The relative intensity, otherwise defined as the net intensity ratio of the Lα peak of uranium to the Kα peak of yttrium, was directly proportional to the uranium concentration. Using this method, a TXRF detection limit for uranium in contaminated water of 0.30 µg/g was achieved.     

Preparation and mesostructure control of highly ordered zirconia particles having crystalline walls

Mesostructured zirconia particles having monoclinic-type crystalline walls were prepared using a low-temperature crystallization technique. Crystalline zirconia particles with highly-ordered mesostructures were obtained through the sol–gel process of zirconium sulfate tetrahydrate at 333 K in the presence of molecular self-assemblies of cetyltrimethylammonium bromide (CTAB) or mixtures of CTAB and anionic molecules such as sodium dodecyl sulfate and sodium p-toluenesulfonate. Variations in the molar ratios of CTAB and the chemical species of anionic molecules led to the variations in the periods of highly-ordered zirconia having crystalline walls. Calcination of the mesostructured zirconia particles prepared using templates consisting solely of CTAB yielded crystalline mesoporous zirconia particles.     

Improved electrochemical activity of LiMnPO4 by high-energy ball-milling

Olivine lithium manganese phosphate (LiMnPO₄) becomes research focus because of its high energy density and improved thermal stability. However, its application in lithium ion batteries suffers severely from poor electrochemical activity due to low conductivity and structural instability upon the charge and discharge process. By applying a high-energy ball-milling method we succeed in improving the capacity delivery and rate capability. LiMnPO₄ materials ball-milled without or with acetylene black are able to deliver a high capacity of 135 and 127 mAh g⁻¹, respectively, more than 50% greater than the pristine one. Particularly, the latter also shows an improved discharge plateau and stable cyclability. High-energy synchrotron radiation X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, laser particle analysis, and galvanostatic charge and discharge are employed to understand the effect of ball-milling on the LiMnPO₄ material.     

Strong Surface‐Termination Effect on Electroresistance in Ferroelectric Tunnel Junctions

Tunnel electroresistance in ferroelectric tunnel junctions (FTJs) has attracted considerable interest, because of a promising application to nonvolatile memories. Development of ferroelectric thin‐film devices requires atomic‐scale band‐structure engineering based on depolarization‐field effects at interfaces. By using FTJs consisting of ultrathin layers of the prototypical ferroelectric BaTiO₃, it is demonstrated that the surface termination of the ferroelectric in contact with a simple‐metal electrode critically affects properties of electroresistance. BaTiO₃ barrier‐layers with TiO₂ or BaO terminations show opposing relationships between the polarization direction and the resistance state. The resistance‐switching ratio in the junctions can be remarkably enhanced up to 10⁵% at room temperature, by artificially controlling the fraction of BaO termination. These results are explained in terms of the termination dependence of the depolarization field that is generated by a dead layer and imperfect charge screening. The findings on the mechanism of tunnel electroresistance should lead to performance improvements in the devices based on nanoscale ferroelectrics.     

Phenolic resin‐crosslinked natural rubber/clay nanocomposites: Influence of clay loading and interfacial adhesion on strain‐induced crystallization behavior

Nanocomposites of natural rubber (NR) and pristine clay (clay) were prepared by latex mixing, then crosslinked with phenolic resin (PhOH). For comparative study, the PhOH‐crosslinked neat NR was also prepared. Influence of clay loading (i.e., 1, 3, 5, and 10 phr) on mechanical properties and structural change of PhOH‐crosslinked NR/clay nanocomposites was studied through X‐ray diffraction (XRD), transmission electron microscopic (TEM), wide‐angle X‐ray diffraction (WAXD), tensile property measurement, and Fourier transform infrared spectroscopy (FTIR). XRD and TEM showed that the clay was partly intercalated and aggregated, and that the dispersion state of clay was non‐uniform at higher clay loading (>5 phr). From tensile test measurement, it was found that the pronounced upturn of tensile stress was observed when the clay loading was increased and a maximum tensile strength of the PhOH‐crosslinked NR/clay nanocomposites was obtained at 5 phr clay. WAXD observations showed that an increased addition of clay induced more orientation and alignment of NR chains, thereby lowering onset strain of strain‐induced crystallization and promoting crystallinity of the NR matrix during tensile deformation. FTIR investigation indicated a strong interfacial adhesion between NR matrix and clay filler through a phenolic resin bridge. This suggested that the PhOH did not only act as curative agent for crosslinking of NR, but it also worked as coupling agent for promoting interfacial reaction between NR and clay. The presence of strong interfacial adhesion was found to play an important role in the crystallization process, leading to promotion of mechanical properties of the PhOH‐crosslinked NR/clay nanocomposites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43214.     

Photoreduction of Shewanella oneidensis Extracellular Cytochromes by Organic Chromophores and Dye‐Sensitized TiO2

The transfer of photoenergized electrons from extracellular photosensitizers across a bacterial cell envelope to drive intracellular chemical transformations represents an attractive way to harness nature's catalytic machinery for solar‐assisted chemical synthesis. In Shewanella oneidensis MR‐1 (MR‐1), trans‐outer‐membrane electron transfer is performed by the extracellular cytochromes MtrC and OmcA acting together with the outer‐membrane‐spanning porin ? cytochrome complex (MtrAB). Here we demonstrate photoreduction of solutions of MtrC, OmcA, and the MtrCAB complex by soluble photosensitizers: namely, eosin Y, fluorescein, proflavine, flavin, and adenine dinucleotide, as well as by riboflavin and flavin mononucleotide, two compounds secreted by MR‐1. We show photoreduction of MtrC and OmcA adsorbed on Ru^II‐dye‐sensitized TiO₂ nanoparticles and that these protein‐coated particles perform photocatalytic reduction of solutions of MtrC, OmcA, and MtrCAB. These findings provide a framework for informed development of strategies for using the outer‐membrane‐associated cytochromes of MR‐1 for solar‐driven microbial synthesis in natural and engineered bacteria.     

离子筛MnO_2·0.4H_2O的固相法制备及特性研究

以单水氢氧化锂和四氧化三锰为原料,用固相法制备出锂离子筛锰酸锂,改变n(锂)/n(锰)之后,用同样的方法制备出另一物质Li1.33Mn1.67O4,经硝酸洗涤脱锂后制备了锂离子筛MnO2·0.4H2O。测定了酸洗时前驱体的锂洗脱率、锰溶损率,研究了锂离子筛MnO2·0.4H2O的饱和吸附量、稳定性、pH滴定曲线。结果表明,前驱体Li1.33Mn1.67O4经硝酸二次酸洗后,锂洗脱率和锰溶损率分别为62.7%和6.0%。在含0.1 mol/L氢氧化钠和10 mmol/L氯化锂的溶液中,经固相法制备的锂离子筛MnO2·0.4H2O对锂离子的饱和吸附量达到24.6 mg/g,并且具有较好的稳定性,pH滴定曲线表明锂离子筛对锂离子具有很好的选择性。