Molecular Dynamics Study of Atomic Structure and Diffusion Behavior in Amorphous Silicon Nitride Containing Boron

We have performed molecular dynamics simulations of amorphous Si₃N₄ containing boron (Si-B-N). We have examined short-range atomic arrangements and self-diffusion constants of amorphous Si-B-N systems with various boron contents. Our simulations show that boron atoms are threefold coordinated by nitrogen atoms and that nitrogen atoms are bonded to both silicon and boron atoms in the amorphous network of Si-B-N. Also, the self-diffusion constant of nitrogen in Si-B-N is much decreased compared with that in amorphous Si₃N₄. This suggests that boron is important in decreasing the mobility of atoms in amorphous Si-B-N, which may explain the improved thermal stability of amorphous Si-B-N relative to amorphous Si₃N₄ observed experimentally.     

Size-dependent separation of graphene oxide by deformation of packed-gel in a chromatographic column

ABSTRACT

A deformable gel-packed chromatographic column was used to separate as-synthesized graphite oxide with different sizes. The synthesized gel (56 µm) was deformed by pressure of the fluid flow and the gaps in the gels showed a range of sizes. A suspension of graphene oxide (0.1 g/L, 10 mL) was injected, and graphene oxide in the elution had a size at 0.56 μm and 0.14 μm, whereas in half upper and bottom domain of the gel layer graphene oxide had a size at 33 µm and 2.9 µm, respectively, demonstrating that graphene oxide suspension was separated by size through gel layer.     

Hydrostatic Pressure Influences HIF-2 Alpha Expression in Chondrocytes

Hypoxia-inducible factor (HIF)-2α is considered to play a major role in the progression of osteoarthritis. Recently, it was reported that pressure amplitude influences HIF-2α expression in murine endothelial cells. We examined whether hydrostatic pressure is involved in expression of HIF-2α in articular chondrocytes. Chondrocytes were cultured and stimulated by inflammation or hydrostatic pressure of 0, 5, 10, or 50 MPa. After stimulation, heat shock protein (HSP) 70, HIF-2α, nuclear factor kappa B (NF-κB), matrix metalloproteinase (MMP)-13, MMP-3, and vascular endothelial growth factor (VEGF) gene expression were evaluated. The levels of all gene expression were increased by inflammatory stress. When chondrocytes were exposed to a hydrostatic pressure of 5 MPa, HIF-2α, MMP-13, and MMP-3 gene expression increased significantly although those of HSP70 and NF-κB were not significantly different from the control group. In contrast, HIF-2α gene expression did not increase under a hydrostatic pressure of 50 MPa although HSP70 and NF-κB expression increased significantly compared to control. We considered that hydrostatic pressure of 5 MPa could regulate HIF-2α independent of NF-κB, because the level of HIF-2α gene expression increased significantly without upregulation of NF-κB expression at 5 MPa. Hydrostatic pressure may influence cartilage degeneration, inducing MMP-13 and MMP-3 expression through HIF-2α.     

Development of Novel Inhibitors for Histone Methyltransferase SET7/9 based on Cyproheptadine

The histone methyltransferase SET7/9 methylates not only histone but also non‐histone proteins as substrates, and therefore, SET7/9 inhibitors are considered candidates for the treatment of diseases. Previously, our group identified cyproheptadine, used clinically as a serotonin receptor antagonist and histamine receptor (H1) antagonist, as a novel scaffold of the SET7/9 inhibitor. In this work, we focused on dibenzosuberene as a substructure of cyproheptadine and synthesized derivatives with various functional groups. Among them, the compound bearing a 2‐hydroxy group showed the most potent activity. On the other hand, a 3‐hydroxy group or another hydrophilic functional group such as acetamide decreased the activity. Structural analysis clarified a rationale for the improved potency only by tightly restricted location and type of the hydrophilic group. In addition, a SET7/9 loop, which was only partially visible in the complex with cyproheptadine, became more clearly visible in the complex with 2‐hydroxycyproheptadine. These results are expected to be helpful for further structure‐based development of SET7/9 inhibitors.     

Enhanced amination and adsorption performance of functional copolymer synthesized <Emphasis Type="Italic">via</Emphasis> RAFT-mediated radiation grafting in emulsion

Grafted polymer substrates bearing diglycol amic acid (DA) ligands for Eu and Sm adsorption were prepared using a two-step post-grafting modification of polyethylene/polypropylene-g-poly(glycidyl methacrylate) (PE/PP-g-PGMA) that was synthesized through reversible addition-fragmentation chain transfer (RAFT)-mediated γ-radiation induced graft polymerization in emulsion phase. The PE/PP-g-PGMA prepared with RAFT mediation exhibited better reactivity towards amination reaction at 40 °C than the graft copolymers prepared without RAFT mediation, with the epoxide to amino group conversion of the former exceeding the latter by as much as 20%. The DA ligands were incorporated to the aminated graft copolymer by subsequent reaction with diglycolic anhydride to yield the DA-modified PE/PP-g-PGMA adsorbent. The effects of pH and competing ions on the uptake of Eu and Sm have been investigated. The DA-modified PE/PP-g-PGMA prepared with RAFT mediation showed higher Eu and Sm adsorption percentage than the DA adsorbent that was synthesized without RAFT mediation. The DA-modified PE/PP-g-PGMA exhibited higher affinity for Eu over Cu and Fe in acidic solutions.     

Critical temperature for production of MAG by esterification of different FA with glycerol using <Emphasis Type="Italic">Penicillium camembertii</Emphasis> lipase

Production of MAG by a lipase-catalyzed reaction is known to be effective at low temperature. This phenomenon can be explained by assuming that synthesized MAG are excluded from the reaction system because MAG, which have low m.p., are solidified at low temperatures. Consequently, MAG are efficiently accumulated and do not serve as the precursor of DAG. If this hypothesis is correct, the critical temperature for MAG production, defined as the highest temperature at which DAG synthesis is repressed, should depend on the m.p. of the MAG. Esterification of FFA with glycerol using Candida rugosa, Rhizopus oryzae, and Penicillium camembertii lipases produced MAG efficiently at low temperatures. However, Candida lipase showed very low esterification activity at high temperatures (>20°C), and Rhizopus lipase produced not only MAG but also DAG even at low temperatures. Meanwhile, P. camembertii lipase catalyzed synthesis of MAG only from FFA and glycerol at low temperatures, although the enzyme catalyzed synthesis of DAG from MAG in addition to synthesis of MAG at high temperatures. We thus studied the effect of temperature on esterification of C₁₀−C₁₈ FFA with glycerol using Penicillium lipase as a catalyst and determined the critical temperatures for production of MAG. The critical temperature for production of each MAG showed a linear correlation with m.p. of the MAG, which supported the hypothesis. In addition, because the m.p. of MAG are estimated from that of the constituent FA, the optimal temperature for production of MAG can be predicted from the m.p. of the FFA used as a substrate.     

利用普通小球藻Chlorella vulgaris C9-JN2010处理氨基酸工业废水的研究

用普通小球藻Chlorella vulgaris C9-JN2010处理氨基酸工业废水,实现废水无害化利用。在微型鼓泡式光反应器中,(25±1)℃,pH(6.5±0.5),0.1 vvm空气流速,4 000 lux,16 h:8 h光暗比条件下,分别考察小球藻在体积分数为20%、40%、60%、80%及100%的氨基酸废水中培养生物量变化及TN、TP、COD的去除率。结果表明,体积分数40%氨基酸废水处理效果最好,停留时间3～4 d,藻细胞干重、比生长速率和最大生产强度分别为0.731 g/L、0.565 d-1、0.243 g/(L.d);废水中TN、TP及COD的去除率分别为92.0%、98.0%及80.0%,对应去除强度分别为30.7、3.28、133.3mg/(L.d)。利用小球藻可以较彻底的去除氨基酸废水中氮、磷及COD等营养,达到污水处理效果。     

Thermodynamic Properties of Ionic Semiclathrate Hydrate Formed with Tetrabutylammonium Propionate

The phase equilibrium temperature and dissociation heat of tetrabutylammonium propionate (TBAPr) hydrate are reported. TBAPr hydrate is a type of ionic semiclathrate hydrates and also could potentially be used as thermal energy storage material. The temperature‐composition phase diagram of the TBAPr hydrate was determined in a defined range of mass fractions. Considering the dissociation heat of differential scanning calorimetry (DSC) measurements, multiple peaks of heat flow were observed in the TBAPr‐water system at the TBAPr mass fraction lower than 0.35, and there was a single peak at the mass fraction higher than 0.37.     

Stereo-Preference in the degradation of the erythro and threo isomers of β-O-4-type lignin model compounds in oxidation processes. part 2: In the reaction with hydroxyl and oxyl anion radicals under hydrogen peroxide bleaching conditions

We examined which isomer, the erythro or threo, of non-phenolic β-O-4-type lignin model compounds is stereo-preferentially attacked by hydroxyl radical and its conjugate base, oxyl anion radical, generated by the decomposition of hydrogen peroxide in the presence of ferric ion and its precipitates under hydrogen peroxide bleaching conditions. The intrinsic stereo-preference of oxyl anion radical was slightly toward the erythro isomer, while hydroxyl radical had a further smaller stereo-preference. These stereo-preferences can be explained by our prior knowledge that oxyl anion radical preferentially attacks the side-chain of the lignin model compounds rather than the aromatic nucleus. The amount of the degraded lignin model compounds became less great with decreasing pH, but reversely and intensively greater in the pH range below 10. This phenomenon can be attributed to the change in the decomposition mechanism of hydrogen peroxide accompanying the pH variation.     

RAFT‐mediated graft polymerization of glycidyl methacrylate in emulsion from polyethylene/polypropylene initiated with γ‐radiation

The successful reversible addition‐fragmentation (RAFT)‐mediated graft polymerization of glycidyl methacrylate (GMA) in emulsion phase from polyethylene/polypropylene nonwoven fabric using 4‐cyano‐4‐[(phenylcarbonothioyl)thio]pentanoic acid under γ‐irradiation at ambient condition is reported. While conventional graft polymerization in emulsion phase yielded grafted materials with low of grafting (Dg) values [<7.5% at 10% (wt/wt) GMA], addition of RAFT agent to the graft polymerization system allowed the synthesis of polyethylene/polypropylene‐g‐poly(GMA) with more tunable Dg (8% ≤ Dg ≤ 94%) by controlling the grafting parameters. Relatively good control (PDI ～1.2 for selected grafting conditions) during polymerization was attained at 100:1 monomer‐to‐RAFT agent molar ratio. The number average molecular weight of free poly(glycidyl methacrylate) (PGMA) increased as a function of monomer conversion. NMR analyses of the free PGMA homopolymers indicate the presence of dithiobenzoate group from 4‐cyano‐4‐((phenylcarbonothioyl)thio) pentanoic acid on the polymer chain. The reactive pendant oxirane group of the grafted GMA can be modified for various environmental and industrial applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45270.