Solvent- and Light-Sensitive AIEE-Active Azo Dye: From Spherical to 1D and 2D Assemblies

Fluorescent molecular assembly systems provide an exciting platform for creating stimuli-responsive nano- and microstructured materials with optical, electronic, and sensing functions. To understand the relationship between (i) the plausible molecular structures preferentially adopted depending on the solvent polarity (such as N,N-dimethylformamide [DMF], tetrahydrofuran [THF], and toluene), (ii) the resulting spectroscopic features, and (iii) self-assembled nano-, micro-, and macrostructures, we chose a sterically crowded triangular azo dye (3Bu) composed of a polar molecular core and three peripheral biphenyl wings. The chromophore changed the solution color from yellow to pink-red depending on the solvent polarity. In a yellow DMF solution, a considerable amount of the twisted azo form could be kept stable with the help of favorable intermolecular interactions with the solvent molecules. By varying the concentration of the DMF solution, the morphology of self-assembled structures was transformed from nanoparticles to micrometer-sized one-dimensional (1D) structures such as sticks and fibers. In a pink-red toluene solution, the periphery of the central ring became more planar. The resulting significant amount of the keto-hydrazone tautomer grew into micro- and millimeter-sized 1D structures. Interestingly, when THF-H₂O (1:1) mixtures were stored at a low temperature, elongated fibers were stacked sideways and eventually developed into anisotropic two-dimensional (2D) sheets. Notably, subsequent exposure of visible-light-irradiated sphere samples to solvent vapor resulted in reversible fluorescence off↔on switching accompanied by morphological restoration. These findings suggest that rational selection of organic dyes, solvents, and light is important for developing reusable fluorescent materials.     

Purification and characterisation of cathepsin L from the skeletal muscle of blue scad (Decapterus maruadsi) and comparison of its role with myofibril-bound serine proteinase in the degradation of myofibrillar proteins

The modori phenomenon during surimi production is caused by endogenous proteinases, especially cathepsin L and myofibril-bound serine proteinase (MBSP). Cathepsin L from the skeletal muscle of blue scad (Decapterus maruadsi) was purified to homogeneity by ammonium sulphate fractionation and a series of column chromatographies and revealed a single band with molecular mass of 30 kDa on SDS–PAGE. Peptide mass fingerprinting (PMF) obtained three fragments with 48 amino acid residues, which were highly identical to cathepsin L from other fish species. Its optimal pH and temperature were 5.5 and 55 °C, respectively. Meanwhile, MBSP was purified from the skeletal muscle of blue scad, and the roles of cathepsin L and MBSP in the degradation of myofibrillar proteins were compared. The results indicated that MBSP is more effective than cathepsin L in promoting the degradation of myofibrillar proteins, especially myosin heavy chain (MHC), suggesting that MBSP plays a more significant role.     

Effects of difructose anhydride III (DFA III) administration on rat intestinal microbiota

The effects of difructose anhydride III (di-D-fructofuranose-1,2':2,3'-dianhydride; DFA III) administration (3% DFA III for 4 weeks) on rat intestinal microbiota were examined using denaturing gradient gel electrophoresis (DGGE). According to DGGE profiles, the number of bacteria related to Bacteroides acidofaciens and uncultured bacteria within the Clostridium lituseburense group decreased, while that of bacteria related to Bacteroides vulgatus, Bacteroides uniformis and Ruminococcus productus increased in DFA III-fed rat cecum. In the cecal contents of DFA III-fed rats, a lowering of pH and an increase in short chain fatty acids (SCFAs), especially acetic acid, were observed. The DFA III-assimilating bacterium, Ruminococcus sp. M-1, was isolated from the cecal contents of DFA III-fed rats. The strain had 98% similarity with R. productus ATCC 27340T (L76595), and mainly produced acetic acid. These results confirmed that the bacteria harmful to host health were not increased by DFA III administration. Moreover, DFA III stimulated the growth of Ruminococcus sp. M-1 producing acetic acid, which may alter the intestinal microbiota towards a healthier composition. It is expected that DFA III would be a new candidate as a prebiotic.     

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.     

Unsteady behavior of leading-edge vortex and diffuser stall in a centrifugal compressor with vaned diffuser

The characteristics of a rotating stall of an impeller and diffuser and the evolution of a vortex generated at the diffuser leading-edge (i.e., the leading-edge vortex (LEV)) in a centrifugal compressor were investigated by experiments and numerical analysis. The results of the experiments revealed that both the impeller and diffuser rotating stalls occurred at 55 and 25 Hz during off-design flow operation. For both, stall cells existed only on the shroud side of the flow passages, which is very close to the source location of the LEV. According to the CFD results, the LEV is made up of multiple vortices. The LEV is a combination of a separated vortex near the leading- edge and a longitudinal vortex generated by the extended tip-leakage flow from the impeller. Therefore, the LEV is generated by the accumulation of vorticity caused by the velocity gradient of the impeller discharge flow. In partial-flow operation, the spanwise extent and the position of the LEV origin are temporarily transmuted. The LEV develops with a drop in the velocity in the diffuser passage and forms a significant blockage within the diffuser passage. Therefore, the LEV may be regarded as being one of the causes of a diffuser stall in a centrifugal compressor.     

Influence of electrolytes on the photovoltaic performance of organic dye-sensitized nanocrystalline TiO2 solar cells

We have studied the influence of electrolytes on the photovoltaic performance of mercurochrome-sensitized nanocrystalline TiO₂ solar cells using LiI, LiBr, and tetraalkylammonium iodides as the electrolyte. Short-circuit photocurrent density (J_sc) and open-circuit photovoltage (V_oc) depended strongly on the electrolyte. J_sc of 3.42 mA cm⁻² and V_oc of 0.52 V were obtained for the LiI electrolyte and J_sc of 2.10 mA cm⁻² and V_oc of 0.86 V were obtained for the Pr₄NI electrolyte. This difference in photovoltaic performance was due to the change in the conduction band level of the TiO₂ electrode. Large V_oc of 0.99 V was obtained for the LiBr electrolyte due to the large energy gap between the conduction band level of TiO₂ and the Br/Br₂ redox potential. Solar cell performance also depended strongly on organic solvent, suggesting that the physical properties of solvents such as Li ion conductivity and donor number affect photovoltaic performance.     

Poly(sulfonated phenylene)-block-poly(arylene ether sulfone) copolymer for polymer electrolyte fuel cell application

Novel poly(2-(3-sulfo)benzoyl-1,4-phenylene)-block-poly(arylene ether sulfone) copolymers (PSP-b-PAESs) were successfully synthesized by Ni(0)-catalyzed copolymerization of 2,5-dichloro-3′-sulfo-benzophenone (DCSB) and chlorobenzophenone-endcapped oligo(arylene ether sulfone). Their physical property, morphology and polymer electrolyte fuel cell (PEFC) performance were investigated compared to those of the DCSB-based random copolymers and Nafion112. PSP-b-PAES with a measured ion exchange capacity (IEC) of 1.82 meq g^?1, of which the hydrophilic/hydrophobic block lengths were evaluated as 17/8.4, showed the relatively small number of water molecules sorbed per sulfonic acid group (λ = 15) in water and the anisotropic membrane swelling with 2.4 times larger through-plane swelling than in-plane one, whereas it showed the almost isotropic proton conductivity. The PSP-b-PAES exhibited a microphase-separated structure composed of hydrophobic and hydrophilic domains, whereas the random copolymers exhibited a homogenous morphology. The PSP-b-PAES had the larger proton conductivity than the random copolymer with an IEC of 2.01 meq g^?1, especially under the low relative humidities. Even at a low humidification of 17% RH at 90 °C and 0.2 MPa, the PSP-b-PAES exhibited the high PEFC performance; namely, cell voltage of 0.69 V at load current density of 0.5 A cm^?2 and maximum output of 0.73 W cm^?2, which were much higher than those at 30% RH for the random copolymer (0.65 V and 0.51 W cm^?2) and Nafion112 (0.70 V and 0.61 W cm^?2). The PSP-b-PAES showed the fairly high durability of 750 h under PEFC operation at 90 °C in spite of the relatively low molecular weight. PSP-b-PAESs have the high potential as polymer electrolyte membrane for PEFC applications.     

Design of AVS/RS under group constraint

Distribution centers, which are essential to our society, are becoming increasingly important. Although the efficiency of an AVS/RS (Autonomous vehicle storage and retrieval system) makes it a promising system, there is still much to be studied regarding its effective use and design. This paper proposes a method of designing AVS/RSs through a quantitative consideration of group constraint by utilizing probability theory. The proposed algorithm also deals with the problem of designing the sizes of several buffers, and considers the effect of load fluctuations, which are important for real-world operation, by use of queuing network theory. Effectiveness of the proposed algorithm is shown with simulations of various number of groups, those of various safety factors for fluctuations, and those of various evasion rates for buffer overflow. The design results are shown to be much different from those which do not consider those factors. The results prove that the proposed method provides an accurate quantitative assessment of the AVS/RS’s constraints.     

Effects of ionic group incorporation into model polypeptide,poly(γ-benzyl-L-glutamate) (PBLG)

Effects of incorporation of ionic groups and ionic interactions to a model polypeptide, poly(γ-benzyl-L-glutamate) (PBLG), are studied. Partial conversion of γ-benzyl-L-glutamate residues to glutamic acid residues does not change molecular conformation (α-helix) and shows little change in properties. By contrast, partial conversion to sodium glutamates (ionic groups) leads to conversion from a rigid rod to a semi-flexible rod at low ion contents and causes significant changes in thermal stability and birefringence. In solution, lyotropic liquid crystalline behavior of PBLG is lost at ion content as low as 3.2 mol %. In solid, birefringence is still observed at this ion content, suggesting thermotropic liquid crystallinity of this ionic PBLG. Molecular composites made of ionic PBLG as a reinforcer and poly(4-vinylpyridine) (PVP) as a matrix polymer show significant enhancement in strength and toughness as a result of ion-dipole interactions between the component polymers.     

Bioconversion of 1-adamantanol to 1,3-adamantanediol using Streptomyces sp. SA8 oxidation system

To efficiently produce 1,3-adamantanediol (1,3-ad(OH)₂) from 1-adamantanol (1-adOH), our stocks of culture strains and soil microorganisms were surveyed for hydroxylation activity towards 1-adOH. Among them, the soil actinomycete SA8 showing the highest hydroxylation activity was identified as Streptomyces sp. based on 16S ribosomal DNA sequence analysis. The reaction products were purified by silica gel column chromatography, and from NMR and MS analyses, they were identified as 1,3-ad(OH)₂ and 1,4-ad(OH)₂. Streptomyces sp. SA8 produced 5.9 g l^? 1 1,3-ad(OH)₂from 6.2 g l^? 1 1-adOH in culture broth after 120 h at 25 °C. Using resting cells, 2.3 g l^? 1 1,3-ad(OH)₂ was produced after 96 h of incubation at a 69% conversion rate. In both cases, 1,4-ad(OH)₂ was formed as a byproduct at a rate of about 15%. Strain SA8 also hydroxylated 2-adamantanol and 2-methyl-2-adamantanol.