Supported molybdena catalysts: Characterization of oxidized,reduced, and sulfided MoO3 prepared by an adsorption method

Highly dispersed molybdena-titania catalyst can be prepared by an equilibrium adsorption method. In this method, molybdate anions adsorb onto the positively charged titania surfaces via electrostatic attraction by controlling the pH of the impregnating solution and they increase as an inverse function of the pH. ⁹⁵Mo-NMR and UV spectroscopic studies of impregnating solution show that the polymeric species like Mo₇O₂₄ ⁶-ions are adsorbed on titania in the acidic impregnating solution. XRD, Raman, and XPS data of the calcined samples show that mono-layer coverage of molybdenum oxide over-layer possesses a highly distorted MoO₆ group with a molecular geometry resembling the distorted square pyramid. The catalytic oxidation of methanol over the surface molybdate species on titania possesses higher turnover numbers and higher selectivities of partial oxidation products than the catalysts supported on alumina, silica, zirconia, or magnesia. Changes of the surface properties either after reduction and sulfiding treatment over monolayer catalyst on titania have also been investigated. The NO chemisorption and XPS studies show that two types of active sites appeared after reduction treatment: one site is active for hydrogenation of 1,3-butadiene and the other site is active for metathesis of propene. A higher degree coordinative unsaturations of MO is required for hydrogenation than metathesis. After sulfiding treatments of the catalyst, hydrogenation of 1,3-butadiene also requires triply coordinative unsaturation, and hydrogenolysis of thiophene requires the ensemble of doubly or triply coordinative unsaturations.     

2,6-Diphenylbenzo[1,2-b:4,5-b']dichalcogenophenes: a new class of high-performance semiconductors for organic field-effect transistors

2,6-Diphenylbenzo[1,2-b:4,5-b']dichalcogenophenes including thiophene, selenophene, and tellurophene analogues as organic semiconductors for field-effect transistors were effectively synthesized in three steps from commercially available 1,4-dibromobenzene. All three benzodichalcogenophenes acted as good p-type semiconductors, and particularly the selenophene analogue, 2,6-diphenylbenzo[1,2-b:4,5-b']diselenophene, showed high FET mobility of 0.17 cm2 V-1 s-1.     

Genetic optical design for a compressive sensing task

We present a sophisticated optical design method for reducing the number of photodetectors for a specific sensing task. The chosen design parameter is the point spread function, and the selected task is object recognition. The point spread function is optimized iteratively with a genetic algorithm for object recognition based on a neural network. In the experimental demonstration, binary classification of face and non-face datasets was performed with a single measurement using two photodetectors. A spatial light modulator operating in the amplitude modulation mode was provided in the imaging optics and was used to modulate the point spread function. In each generation of the genetic algorithm, the classification accuracy with a pattern displayed on the spatial light modulator was fed-back to the next generation to find better patterns. The proposed method increased the accuracy by about 30 % compared with a conventional imaging system in which the point spread function was the delta function. This approach is practically useful for compressing the cost, size, and observation time of optical sensors in specific applications, and robust for imperfections in optical elements.     

Imprinting modulates processing of visual information in the visual wulst of chicks

Background

Results of the Women's Health Initiative Memory Study (WHIMS) raised concerns regarding the timing and formulation of hormone interventions. Conjugated equine estrogens (CEE), used as the estrogen therapy in the WHIMS trial, is a complex formulation containing multiple estrogens, including several not secreted by human ovaries, as well as other biologically active steroids. Although the full spectrum of estrogenic components present in CEE has not yet been resolved, 10 estrogens have been identified. In the present study, we sought to determine which estrogenic components, at concentrations commensurate with their plasma levels achieved following a single oral dose of 0.625 mg CEE (the dose used in the WHIMS trial) in women, are neuroprotective and whether combinations of those neuroprotective estrogens provide added benefit. Further, we sought, through computer-aided modeling analyses, to investigate the potential correlation of the molecular mechanisms that conferred estrogen neuroprotection with estrogen interactions with the estrogen receptor (ER).

Results

Cultured basal forebrain neurons were exposed to either β-amyloid_25–35 or excitotoxic glutamate with or without pretreatment with estrogens followed by neuroprotection analyses. Three indicators of neuroprotection that rely on different aspects of neuronal damage and viability, LDH release, intracellular ATP level and MTT formazan formation, were used to assess neuroprotective efficacy. Results of these analyses indicate that the estrogens, 17α-estradiol, 17β-estradiol, equilin, 17α-dihydroequilin, equilinen, 17α-dihydroequilenin, 17β-dihydroequilenin, and Δ^8,9-dehydroestrone were each significantly neuroprotective in reducing neuronal plasma membrane damage induced by glutamate excitotoxicity. Of these estrogens, 17β-estradiol and Δ^8,9-dehydroestrone were effective in protecting neurons against β-amyloid_25–35-induced intracellular ATP decline. Coadministration of two out of three neuroprotective estrogens, 17β-estradiol, equilin and Δ^8,9-dehydroestrone, exerted greater neuroprotective efficacy than individual estrogens. Computer-aided analyses to determine structure/function relationships between the estrogenic structures and their neuroprotective activity revealed that the predicted intermolecular interactions of estrogen analogues with ER correlate to their overall neuroprotective efficacy.

Conclusion

The present study provides the first documentation of the neuroprotective profile of individual estrogens contained within the complex formulation of CEE at concentrations commensurate with their plasma levels achieved after an oral administration of 0.625 mg CEE in women. Our analyses demonstrate that select estrogens within the complex formulation of CEE contribute to its neuroprotective efficacy. Moreover, our data predict that the magnitude of neuroprotection induced by individual estrogens at relatively low concentrations may be clinically undetectable and ineffective, whereas, a combination of select neuroprotective estrogens could provide an increased and clinically meaningful efficacy. More importantly, these data suggest a strategy for determining neurological efficacy and rational design and development of a composition of estrogen therapy to alleviate climacteric symptoms, promote neurological health, and prevent age-related neurodegeneration, such as AD, in postmenopausal women.     

Imprinting modulates processing of visual information in the visual wulst of chicks

Background  

Imprinting behavior is one form of learning and memory in precocial birds. With the aim of elucidating of the neural basis for visual imprinting, we focused on visual information processing.     

Isobutane alkylation over solid acid catalysts under supercritical conditions

Solid catalyzed isobutane alkylation has been investigated for decades, but it has not yet been applied in any commercial uses because of the rapid deactivation of the catalyst. Here, the alkylation reaction has been studied under supercritical conditions using metal-promoted and unpromoted sulfated zirconia as catalysts. The catalytic activity at the supercritical condition of 5.0 MPa, 423K was significantly higher than at lower reaction pressure conditions and the deactivation rate was clearly reduced, independent on the catalyst. Iron- and manganese-promoted sulfated zirconia (SFMZ) showed higher activities under all conditions than unpromoted sulfated zirconia (SZ).     

Facile synthesis, structure, and properties of benzo[1,2-b:4,5-b']dichalcogenophenes

[reaction, structures: see text] A general and convenient synthesis of benzo[1,2-b:4,5-b']dichalcogenophenes including the thiophene (BDT, 1), selenophene (BDS, 2), and tellurophene (BDTe, 3) homologues is developed. Thus synthesized heterocycles are structurally characterized by single-crystal X-ray analysis, and all three homologues are isostructural with one another. They all have completely planar molecular structures packed in a herringbone arrangement. Their physicochemical properties were also elucidated by means of cyclic voltammetry (CV) and UV-vis spectra.     

The Synthesis of Lead-Free Ferroelectric Bi<Subscript>1/2</Subscript>Na<Subscript>1/2</Subscript>TiO<Subscript>3</Subscript> Thin Film by Solution-Sol–Gel Method

Bi_1/2Na_1/2TiO₃ (described as BNT) is considered as a promising lead-free ferroelectric material. In this study, BNT sol was synthesized by mixing bismuth oxide and sodium carbonate dissolved in nitric acid and titanium tetraisopropoxide in ethylene glycol, which was called a solution-sol–gel method and very cost-effective synthesis method, while very high-cost metal alkoxides are used as precursors in conventional sol–gel method. FT-IR and Raman analyses indicated that the chemical modification of titanium tetraisopropoxide by glycolic acid or oxalic acid occurred and the synthesis of stable BNT sol was possible. In the results of high temperature X-ray analysis and DTA/TG analyses, the crystallization of BNT was thought to occur at between 500 and 700C following the evaporation of solvent and organics and poly-condensation processes. The main crystal phase of the film was identified as rhombohedral crystal phase of Bi_1/2Na_1/2TiO₃ by XRD and Raman spectroscopy analyses, although a small amount of Bi₄Ti₃O₁₂ existed as a second phase.