Primitive chain network simulations for asymmetric star polymers

For branched polymers, the curvilinear motion of the branch point along the backbone is a significant relaxation source but details of this motion have not been well understood. This study conducts multi-chain sliplink simulations to examine effects of the spatial fluctuation and curvilinear hopping of the branch point on the viscoelastic relaxation. The simulation is based on the primitive chain network model that allows the spatial fluctuations of sliplink and branch point and the chain sliding along the backbone according to the subchain tension, chemical potential gradients, drag force against medium, and random force. The sliplinks are created and∕or disrupted through the motion of chain ends. The curvilinear hopping of the branch point along the backbone is allowed to occur when all sliplinks on a branched arm are lost. The simulations considering the fluctuation and the hopping of the branch point described well the viscoelastic data for symmetric and asymmetric star polymers with a parameter set common to the linear polymer. On the other hand, the simulations without the branch point motion predicted unreasonably slow relaxation for asymmetric star polymers. For asymmetric star polymers, further tests with and without the branch point hopping revealed that the hopping is much less important compared to the branch point fluctuation when the lengths of the short and long backbone arms are not very different and the waiting time for the branch point hopping (time for removal of all sliplinks on the short arm) is larger than the backbone relaxation time. Although this waiting time changes with the hopping condition, the above results suggest a significance of the branch point fluctuation in the actual relaxation of branch polymers.     

Preparations of anthraquinone and naphthoquinone derivatives and their cytotoxic effects

Chrysophanol and 1,8-di-O-hexylchrysophanol derivatives having nucleic acid bases at position 5 were synthesized. Furthermore, derivatives of menadione substituted at position 11 (type A naphthoquinone derivatives) or methylmenadione substituted at position 7 (type B naphthoquinone derivatives) modified with nucleic acid bases, amines and thiocyano, selenocyano or thioacetyl groups were synthesized. The cytotoxic effects of these derivatives on HCT 116 cells, which poorly express P-glycoprotein (P-gp), and Hep G2 cells, which stably express P-gp, were evaluated by performing 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. Results were compared with those obtained using 5-fluorouracil (5-FU), which has been used clinically. Several of these derivatives exhibited markedly higher potent cytotoxic effects not only on HCT cancer cells but also Hep G2 cancer cells as compared with 5-FU.     

Crystal structure and superconductive characteristics of Nb0.89Al0.11 oxynitrides

The crystal structure and superconductive characteristics of the niobium-aluminum oxynitrides were investigated. Single-phase products were successfully obtained starting from a cation ratio of Nb_0.89Al_0.11. The as-nitrided product crystallized in a cation-deficient rock-salt type structure with a chemical formula of (Nb_0.60Al_0.08□_0.32)(O_0.21N_0.79), while annealing at 1773 K under a nitrogen pressure of 0.5 MPa led to a highly crystallized product with a simple rock-salt type structure represented as (Nb_0.89Al_0.11)(O_0.17N_0.85). Upon post-annealing, both the critical temperature (T_c) and the superconductive volume fraction (V_SC) of the oxynitride were significantly enhanced from T_c≈7 K and V_SC=23% for the as-nitrided product to T_c=17.3 K and V_SC=91% for the post-annealed product.     

Detailed balance condition and effective free energy in the primitive chain network model

We consider statistical mechanical properties of the primitive chain network (PCN) model for entangled polymers from its dynamic equations. We show that the dynamic equation for the segment number of the PCN model does not reduce to the standard Langevin equation which satisfies the detailed balance condition. We propose heuristic modifications for the PCN dynamic equation for the segment number, to make it reduce to the standard Langevin equation. We analyse some equilibrium statistical properties of the modified PCN model, by using the effective free energy obtained from the modified PCN dynamic equations. The PCN effective free energy can be interpreted as the sum of the ideal Gaussian chain free energy and the repulsive interaction energy between slip-links. By using the single chain approximation, we calculate several distribution functions of the PCN model. The obtained distribution functions are qualitatively different from ones for the simple slip-link model without any direct interactions between slip-links.     

Nitrogen‐Rich Manganese Oxynitrides with Enhanced Catalytic Activity in the Oxygen Reduction Reaction

The catalytic activity of manganese oxynitrides in the oxygen reduction reaction (ORR) was investigated in alkaline solutions to clarify the effect of the incorporated nitrogen atoms on the ORR activity. These oxynitrides, with rock‐salt‐like structures with different nitrogen contents, were synthesized by reacting MnO, Mn₂O₃, or MnO₂ with molten NaNH₂ at 240–280 °C. The anion contents and the Mn valence states were determined by combustion analysis, powder X‐ray diffraction, and X‐ray absorption near‐edge structure analysis. An increase in the nitrogen content of rock‐salt‐based manganese oxynitrides increases the valence of the manganese ions and reinforces the catalytic activity for the ORR in 1 m KOH solution. Nearly single‐electron occupancy of the antibonding e_g states and highly covalent Mn?N bonding thus enhance the ORR activity of nitrogen‐rich manganese oxynitrides.