Matrix-isolation and electronic structure of vinyl-substituted silylenes and their complexes with bases [1]

Vinyl-substituted silylenes, 2,5-bis(methylene)-1-silacyclopentane-1,1-diyl ( 1 ) and 2-methylene-1-silacyclopentane-1,1-diyl ( 2 ), generated photochemically from the corresponding trisilanes in 3-methylpentane (3-MP) at 77 K, showed broad bands at 505 and 475 nm, respectively, which were assigned to the n(Si)-3p(Si) transition. The origin of the red shift in the n(Si)-3p(Si) transition is ascribed to the significant lowering of the 3p(Si) orbital level caused by the vinyl substitution on the silylene; the relatively high-lying 3p(Si) orbital can interact more effectively with the antibonding π* orbital than with the bonding π orbital of the vinyl group. The absorption spectra for 1 and 2 in the presence of several bases in 3-MP glass matrix shifted significantly to blue due to the formation of the corresponding base complexes. Analysis of the spectral change of the silylenes upon complexation with bases was very constructive for the understanding of the structural characteristics of substituted silylenes.     

Effects of Roxadustat on Erythropoietin Production in the Rat Body

Anemia is a major complication of chronic renal failure. To treat this anemia, prolylhydroxylase domain enzyme (PHD) inhibitors as well as erythropoiesis-stimulating agents (ESAs) have been used. Although PHD inhibitors rapidly stimulate erythropoietin (Epo) production, the precise sites of Epo production following the administration of these drugs have not been identified. We developed a novel method for the detection of the Epo protein that employs deglycosylation-coupled Western blotting. With protein deglycosylation, tissue Epo contents can be quantified over an extremely wide range. Using this method, we examined the effects of the PHD inhibitor, Roxadustat (ROX), and severe hypoxia on Epo production in various tissues in rats. We observed that ROX increased Epo mRNA expression in both the kidneys and liver. However, Epo protein was detected in the kidneys but not in the liver. Epo protein was also detected in the salivary glands, spleen, epididymis and ovaries. However, both PHD inhibitors (ROX) and severe hypoxia increased the Epo protein abundance only in the kidneys. These data show that, while Epo is produced in many tissues, PHD inhibitors as well as severe hypoxia regulate Epo production only in the kidneys.     

Electron beam treatment of lignite-burning flue gas with high concentrations of sulfur dioxide and water

Experiments were carried out to investigate the removals of SO₂ and NO_x from simulated lignite-burning flue gas containing SO₂ (4800 ppm), NO (320 ppm) and H₂O (22%) by electron beam irradiation. Removal efficiencies of SO₂ and NO_x were achieved to reach 97 and 88% at 70°C, and 74 and 85% at 80°C, respectively, with the dose of 10.3 kGy without NH₃ leakage. The higher removal efficiencies of SO₂ and NO_x were observed in simulated lignite-burning flue gas than in coal-fired flue gas containing 800 ppm of SO₂, 225 ppm of NO and 7.5% H₂O at the same treatment condition. The higher removal efficiencies were attributed to the higher concentrations of SO₂, H₂O, and added NH₃. Simulation calculations indicated that the higher concentrations of these components enhance the effective radical reactions to oxidize NO to form NO₂ with HO₂ radical, and to oxidize SO₂ to form SO₃ with OH radical and O₂. The reactions of NO_x with N and NH₂ radicals to produce N₂ and N₂O also promote the NO_x removal. By-product was determined to be the mixture of (NH₄)₂SO₄ and NH₄NO₃ containing a small amount of H₂SO₄.     

Analysis of Individual High-Frequency Traders’ Buy–Sell Order Strategy Based on Multivariate Hawkes Process

Traders who instantly react to changes in the financial market and place orders in milliseconds are called high-frequency traders (HFTs). HFTs have recently become more prevalent and attracting attention in the study of market microstructures. In this study, we used data to track the order history of individual HFTs in the USD/JPY forex market to reveal how individual HFTs interact with the order book and what strategies they use to place their limit orders. Specifically, we introduced an 8-dimensional multivariate Hawkes process that included the excitations due to the occurrence of limit orders, cancel orders, and executions in the order book change, and performed maximum likelihood estimations of the limit order processes for 134 HFTs. As a result, we found that the limit order generation processes of 104 of the 134 HFTs were modeled by a multivariate Hawkes process. In this analysis of the EBS market, the HFTs whose strategies were modeled by the Hawkes process were categorized into three groups according to their excitation mechanisms: (1) those excited by executions; (2) those that were excited by the occurrences or cancellations of limit orders; and (3) those that were excited by their own orders.     

Widely tunable terahertz-wave generation using an N-benzyl-2-methyl-4-nitroaniline crystal

Widely tunable terahertz (THz)-wave generation using difference frequency generation (DFG) in an organic N-benzyl-2-methyl-4-nitroaniline (BNA) crystal was demonstrated. To our knowledge, this is the first report of THz-wave generation by BNA DFG. Large, high-quality single crystals of BNA (phi 8 mm x 30 mm) were grown using the vertical Bridgman method. The nonlinear optical (NLO) coefficient d(33) of the BNA crystal is approximately 234 pm/V, which is the largest value reported for any yellow NLO material. The collinear phase-matching condition of the type-0 configuration is satisfied using a 0.7-1 microm band pump wavelength. We generated THz waves using an organic BNA crystal; the generation range is 0.1-15 THz.     

High-energy quasi-phase-matched optical parametric oscillation in a 3-mm-thick periodically poled MgO:LiNbO3 device

We have demonstrated high-energy quasi-phase-matched optical parametric oscillation in a 3-mm-thick periodically poled 5-mol. % MgO-doped LiNbO3 device with a 32.1-microm grating period and a 30-mm length. With a large-spot-size pump laser of 2.2-mm diameter, we obtained a total output pulse energy of 22 mJ for both the signal (wavelength 1.82 microm) and the idler (2.56 microm) waves at an input pump energy of 46 mJ.     

Scaling reduction of the contrast of fractal speckles detected with a finite aperture

It is known that speckle patterns with fractal properties, called fractal speckles, are produced by illuminating a diffuser with the coherent light having the intensity distribution obeying a negative power law. One of key properties of fractal speckles is the spatial correlation function obeying a negative power law, which implies that such speckles have scaling properties. In detecting fractal speckles, the effect of the spatial integration is inevitable in most cases since they have speckle grains of various scales including very fine ones. To evaluate this effect, in this paper, the contrast of spatially integrated intensity distributions is investigated theoretically and experimentally for fractal speckles. The results show that the contrast reduction with the size of the detector aperture obeys a negative power function related with the exponent of the intensity correlation coefficient of fractal speckles.     

Water vapor adsorption onto activated carbons prepared from cattle manure compost (CMC)

Activated carbons were prepared from cattle manure compost (CMC) using zinc chloride activation. The structural and surface chemical characteristics of CMC-based activated carbons were determined by N₂ adsorption-desorption and Boehm titration, respectively. The water vapor adsorption properties of the prepared activated carbons with various pore structure and surface nature were examined, and the mechanism of water adsorbed onto activated carbon was also discussed. The results show that the adsorption of water vapor on carbons begins at specific active sites at low relative humidity (RH), followed by micropore filling at medium RH through the formation of pentamer cluster of water molecules in the narrow micropores. The water vapor adsorption capacity of activated carbon is predominantly dependent on its pore volume and surface area. Although capillary condensation is not the mechanism for water adsorption onto activated carbon, water can adsorb on narrow mesopore to some extent.     

Pulsed EPR Dipolar Spectroscopy under the Breakdown of the High-Field Approximation: The High-Spin Iron(III) Case

Pulsed EPR dipolar spectroscopy (PDS) offers several methods for measuring dipolar coupling and thus the distance between electron-spin centers. To date, PDS measurements to metal centers were limited to ions that adhere to the high-field approximation. Here, the PDS methodology is extended to cases where the high-field approximation breaks down on the example of the high-spin Fe³⁺/nitroxide spin-pair. First, the theory developed by Maryasov et al. (Appl. Magn. Reson. 2006 , 30, 683–702) was adapted to derive equations for the dipolar coupling constant, which revealed that the dipolar spectrum does not only depend on the length and orientation of the interspin distance vector with respect to the applied magnetic field but also on its orientation to the effective g-tensor of the Fe³⁺ ion. Then, it is shown on a model system and a heme protein that a PDS method called relaxation-induced dipolar modulation enhancement (RIDME) is well-suited to measuring such spectra and that the experimentally obtained dipolar spectra are in full agreement with the derived equations. Finally, a RIDME data analysis procedure was developed, which facilitates the determination of distance and angular distributions from the RIDME data. Thus, this study enables the application of PDS to for example, the highly relevant class of high-spin Fe³⁺ heme proteins.     

Injectable Polypeptide Hydrogel Depot System for Assessment of the Immune Response–Inducing Efficacy of Sustained Antigen Release Alone

Vaccines typically contain an antigen, delivery system (vehicle), and adjuvant, all of which contribute to inducing a potent immune response. Consequently, design of new vaccines is difficult, because the contributions and interactions of these components are difficult to distinguish. Here, it is aimed to develop an easy‐to‐use, non‐immunogenic, injectable depot system for sustained antigen release that will be suitable for assessing the efficacy of prolonged antigen exposure per se for inducing an immune response. This should mimic real‐life infections. Recombinant elastin‐like polypeptides with periodic cysteine residues (cELPs) are selected, which reportedly show little or no immunogenicity, as carriers and tetanus toxoid (Ttd) as an antigen. After subcutaneous injection of the mixture, cELP rapidly forms a disulfide cross‐linked hydrogel in situ, within which Ttd is physically incorporated, affording a biodegradable antigen depot. A series of Ttd‐containing hydrogels is examined. A single injection induces high levels of tetanus antibody with high avidity for at least 20 weeks in mice. The chain length of cELP proves critical, whereas differences in hydrophobicity has little effect, although hydrophilic cELPs are more rapidly biodegraded. This system's ability to distinguish the contribution of sustained antigen release to antibody induction should be helpful for rational design of next‐generation vaccines.