In situ SAXS investigation of dibromomethane adsorption in ordered mesoporous silica

A SAXS/WAXS apparatus with the aid of a specially designed sample cell capable for performing both SAXS and WAXS experiments was used for adsorption studies in nanoporous materials. The applicability of the instrument for structural investigations and its ability for adsorption experiments because of the advanced sample environment were demonstrated by carrying out in situ SAXS measurements during gas physisorption. SAXS profiles of ordered mesoporous silica were measured at selected equilibrium points alongside a dibromomethane (CH₂Br₂) adsorption isotherm at 293 K. SBA-15 was the adsorbent of choice because it consists of a regular 2D hexagonal array of cylindrical mesopores that gives rise to Bragg reflections in the small-angle regime. CH₂Br₂ was selected as a contrast-matching fluid because it has almost the same electron density as silica. We obtained high-quality data comparable to those resulting from experiments performed in synchrotron light sources which produce intense beams of x-rays and support advanced instrumentation for high-resolution diffraction and SAXS studies. The Bragg peaks of the pore lattice are clearly visible for the evacuated sample and at the early stages of the adsorption process. The intensity decrease and the elimination of the Bragg peaks for the saturated sample suggest that an almost perfect contrast matching was achieved. A model has been used for monitoring the fluid condensation and evaporation regime in SBA-15 by taking into account both the Bragg scattering and the diffuse scattering for spatially random pore filling. The results show the absence of spatial correlations between filled pores suggesting random pore filling.     

In situ small angle X-ray scattering and benzene adsorption on polymer-based carbon hollow fiber membranes

The structural changes and the mechanism of benzene adsorption on microporous carbon hollow fiber membranes with different surface and pore network properties have been investigated by in situ small-angle X-ray scattering (SAXS) and benzene adsorption. Benzene adsorption measurements have been carried out in situ with SAXS alongside an adsorption/desorption isotherm cycle at 293 K with the aid of a specially constructed adsorption sample cell. In addition low-pressure C₆H₆ and high-pressure CO₂, CH₄ and N₂ adsorption isotherms have been performed. Two carbon hollow fiber membranes, both prepared by controlled pyrolysis procedures of polyimide membrane precursor, were under study. During benzene adsorption the intensity of the SAXS curves changes in a way that depends on how the pores are filled and the contrast fluctuations occur. The SAXS data have been modeled by evaluating the form factor of lamellar micropores upon filling with C₆H₆. The existence of ultra micropores within the surrounding matrix was also taken into account. The results suggest that the arrangement of the ultra micropores on the non-activated membrane is in such a way that the access of benzene to the micropores is restricted, resulting in an incomplete filling. On the other hand, the activation process generates a more accessible pore network where the micropores are completely filled.     

Synthesis of Some [1,3]Benzodioxoles via the Reaction of o-Quinones with Phosphorus Ylides

3,5-Di(tert-butyl)benzo-1,2-quinone 1c, phenanthrene-9,10-quinone 11, and 1,2-naphthoquinone 18 react with 1-phenylethylidene(tri-phenyl)phosphorane 2j, cyclopentylidene(triphenyl)phosphorane 2k, cyclohexylidene(triphenyl)phosphorane 2l, and tetrahydro-2-furanyl-methylidene(triphenyl)phosphorane 8 to give the corresponding 2-substituted [1,3]benzodioxoles 5–7, 10, 12–14, 20–22 in low to high yields, instead of Wittig products, with exception of 11,12-dihydro-10H-cyclopenta[b]phenanthro[9,10-d]furan 17. A possible explanation for these reaction sequences is discussed.

     

Reactions Between 4-Hydroxycoumarins or 4-Hydroxy-1-Methylquinolinone and Dmad in the Presence of Phosphites. Synthesis of (Chromen-3-YL)- and (Quinolin-3-YL)-(Dialkoxyphosphoryl)Succinates

Abstract

Dimethyl (chromen-3-yl)-(dialkoxyphosphoryl)succinates are prepared from the reaction of 4-hydroxycoumarin with DMAD and P(OR)₃. 4-Hydroxy-1-methylquinolinone reacts with DMAD and P(OEt)₃ to give dimethyl (quinoline-3-yl)-(diethoxyphosphoryl)-succinate.

GRAPHICAL ABSTRACT      

Compatibility study between trandolapril and natural excipients used in solid dosage forms

Thermal analysis is an essential, analytic tool used in preliminary studies and preparation of new pharmaceutical formulations. This study was performed to investigate the possible interactions between trandolapril and three commonly used natural excipients, namely α-lactose monohydrate, microcrystalline cellulose, and pregelatinized starch. The compatibility studies were carried out using thermoanalytic along with other complementary techniques. Differential scanning calorimetry and thermogravimetric analysis have proved that trandolapril is fully compatible with all the studied excipients until 100 °C. The complementary techniques used in this study were X-ray powder diffraction, Fourier transform-infrared spectroscopy, and scanning electron microscopy which confirmed the findings of thermal analysis.     

A Novel One- and Zero-Dimensional Model for Turbulent Jet Ignition

Flow, Turbulence and Combustion - Turbulent jet ignition (TJI) is a promising combustion technology for burning highly diluted air-fuel mixtures. Computationally efficient models to assess the...     

Absolute metrology by phase and frequency modulation for multiwavelength interferometry

A fiber interferometer for absolute distance measurements is presented whereby wavelength variation is achieved via a sinusoidal strain modulation of a fiber Bragg grating to generate a series of beat wavelengths. The interferometer employs fiber laser sources where the design is based on the use of narrow-bandwidth fiber Bragg gratings. The accuracy of the beat wavelengths is improved compared to the use of multiple wavelengths measured with conventional optical spectrum analyzers or available wavemeters. Initial measurements are presented for beat wavelengths of 254.74 mm and 27.4 m over an optical path difference of 200 mm and 3.8 m, respectively. Combined with a two (or three) wavelength interferometer, this technique has the potential for ultrahigh dynamic range metrology ranging over several meters while preserving subfringe resolution and a low system complexity.     

Correlation between structure and thermal properties in 2-hydroxy-benzophenone Co(II) complexes

In this study, simultaneous TG/DTG–DTA technique was used for the simple cobalt(II) complex [Co(dpamH)₃]Br₂ (1) (dpamH = 2,2′-dipyridylamine) and the novel mixed-ligand complexes [Co(dpamH)₂(bpo)]Br (2) and [Co(dpamH)₂(opo)]Br (3), (bpo = the anion of 2-hydroxybenzophenone and opo = the anion of 2-hydroxy-4-methoxybenzophenone), in order to determine their thermal degradation in static air and dynamic nitrogen atmospheres. The cationic complexes were characterized by physicochemical methods, spectroscopy (FT-IR, UV–Vis), and single-crystal X-ray analysis, revealing octahedral coordination around cobalt(II) with chromophore CoN₄O₂, being chelated by one anionic 2-hydroxy-benzophenone ligand and two neutral dpamH molecules. The compounds crystallize as ethanol or ethanol/water solvates, with solvent molecules involved, to a different extent, in hydrogen bonding giving quite different packing modes and thus influencing their stability. The differences in crystal structures are reflected in thermal stabilities of the compounds. Thus, in the crystals of 3 ethanol is more weakly bound than in 2 and anticipate that the former one exhibit lower thermal stability, which is in agreement with the results found by TG–DTA. The thermal decomposition of the title complexes was found to be a multi-step decomposition related to the release of the solvent and ligand molecules, leading at 1,000 °C to pure metallic cobalt in nitrogen atmosphere, while in air atmosphere to the expected cobalt oxides.     

On categorical time series models with covariates

We study the problem of stationarity and ergodicity for autoregressive multinomial logistic time series models which possibly include a latent process and are defined by a GARCH-type recursive equation. We improve considerably upon the existing conditions about stationarity and ergodicity of those models. Proofs are based on theory developed for chains with complete connections. A useful coupling technique is employed for studying ergodicity of infinite order finite-state stochastic processes which generalize finite-state Markov chains. Furthermore, for the case of finite order Markov chains, we discuss ergodicity properties of a model which includes strongly exogenous but not necessarily bounded covariates.     

Spatial multicriteria decision support for robust land-use suitability: The case of landfill site selection in Northeastern Greece

Multicriteria spatial decision support systems (MC-SDSS) have emerged as an integration of geographical information systems (GIS) and multiple criteria decision aid (MCDA) methods for incorporating conflicting objectives and decision makers’ preferences into spatial decision models. In this paper, we present spatial UTASTAR (S-UTASTAR), a raster-based MC-SDSS for land-use suitability analysis. The multicriteria component of the system is based on the UTA-type disaggregation-aggregation approach. S-UTASTAR is applied in a raster-based case study concerning land-use suitability analysis to identify appropriate municipal solid waste landfill (MSW) sites in Northeast Greece. Moreover, robustness analysis tools are implemented to guarantee robust decision support results. More specifically, during the aggregation phase, the Stochastic Multiobjective Acceptability Analysis (SMAA) is used to indicate the frequency at which a site achieves the best ranking positions within a large set of alternative landfill sites.