Effect of W incorporation on the product distribution in steam reforming of bio-oil derived acetic acid over Ni based Zr-SBA-15 catalyst

Zirconia incorporated SBA-15 type mesoporous material was synthesized following a one-pot hydrothermal route, characterized and used as the catalyst support in the synthesis of Ni and bi-metallic Ni–W based catalysts. Performances of these catalysts were tested in steam reforming of AcOH. Catalytic activity tests proved that the performances of SBA-15 and Zr-SBA-15 supported Ni based catalysts were highly stable and they also showed very high activity in steam reforming of acetic acid, giving complete conversion at temperatures over 700 °C. Product distributions were shown to be strongly influenced by the composition of the catalyst. In the case of 5Ni@Zr-SBA-15, syngas produced at 750 °C contained about 54% H₂, 22% CO, 20% CO₂ and 4% CH₄. These results indicated that decarboxylation reaction of AcOH to CH₄ and CO₂ was minimized over this catalyst. Results were considered to be highly promising for the production of hydrogen rich syngas. It was most interesting to observe that modification of this catalyst by the addition of tungsten caused significant changes in the product distribution. For instance, syngas produced over 5Ni-50W@Zr-SBA-15 at the same reaction conditions, contained equimolar quantities of H₂ and CO (about 47.5% each) with very small amounts of CO₂ and CH₄ (about 3% and 2%, respectively). Production of a syngas with such a composition was considered to be highly attractive from the point of view of a resource gas for dimethyl ether and Fischer-Tropsch synthesis.     

A genetic algorithm approach to determine stratum boundaries and sample sizes of each stratum in stratified sampling

Stratified sampling is a methodology in which a heterogeneous population is partitioned into homogeneous subgroups called strata. The focus is on solving the combined problem of sample allocation and stratum boundary determination with the genetic algorithm (GA). Assuming that the number of strata and the total sample size are arbitrarily predetermined, stratum boundaries are determined using an objective function of minimum variance of the estimator; with sample size allocated through equal, proportional, Neyman, and GA allocation methods. Some numerical examples are given and the performance of GA is compared with the geometric and the cumulative root frequency methods.     

Computed tomography with linear shift-invariant optical systems

Optical systems capable of three-dimensional transmission imaging are considered; these systems employ a conventional tomographic setup with an added linear shift-invariant optical system between the sample and the detector. A theoretical analysis is presented of image formation and sample reconstruction in such systems, examples of which include diffraction tomography and phase-contrast tomography with the use of analyzer crystals. An example is introduced in which the image is obtained by scanning the beam along the line orthogonal to the optic axis and to the axis of rotation with a one-dimensional slit or grating parallel to the rotation axis. We show that under certain conditions the proposed system may allow quantitative local (region-of-interest) tomography.     

Synthesis of comb-type amphiphilic graft copolymers derived from chlorinated poly(ɛ-caprolactone) via click reaction

This work refers to the synthesis of a series of novel chlorinated poly(?-caprolactone) (PCL) for further functionalization of PCL. For this aim, chlorine gas was passed through into the chloroform solution to obtain chlorinated polycaprolactone. The chlorine contents in chlorinated PCL were between 0.9 and 1.6 mol%. The molecular weights of the polymers (M _n) changed from 4853 to 9497 g/mol. As the amount of passing chlorine gas increases, the molecular weight of the chlorinated PCL was found to decrease. Pendant chloride groups of PCL were reacted with sodium azide to prepare PCL with pendant azide groups (PCL-N₃). Poly-(ethylene glycol) methyl ether (mPEG) was reacted with propargyl chloride to achieve alkynyl mPEG (mPEG-alkyn). Click reaction was then carried out by the reaction between PCL-N₃ and mPEG-alkyn to obtain PCL-g-PEG comb-type amphiphilic graft copolymer. Interestingly, SEM images of the PCL-g-PEG comb-type amphiphilic graft copolymers showed the highly microporous structure. The resulting products were characterized by ¹H NMR, FT-IR, gel-permeation chromatography, SEM, surface tension, contact angle and water uptake measurements, differential scanning calorimeter and thermogravimetric analyses techniques.     

Drop‐and‐catch (DnC) calorimetry using aerodynamic levitation and laser heating

Design, calibration, and operation of a system for drop‐and‐catch (DnC) calorimetry on oxides from temperature above 1500°C are described. This system allows the measurement of heat contents and heats of fusion by drop calorimetry of small (100 mg or less) samples held by containerless levitation at high temperature and dropped in a calorimeter at room temperature. The spheroids, 2‐3 mm in diameter, prepared by laser melting of powders, are aerodynamically levitated in a splittable nozzle levitator and laser heated to the desired temperature monitored by radiation thermometry. The sample is dropped by splitting the nozzle and caught by splittable water‐cooled calorimetric plates at 25°C, which provide complete enclosure of the sample to avoid heat loss by radiation. The drop time is ~0.1 seconds, calorimeter equilibration time after the drop is ~15 minute. DnC experiments are automated with software‐controlled laser power and programmable delay between splitting the nozzle and catching the sample. The fusion enthalpy of Al₂O₃ measured by DnC calorimeter, 120 ± 10 kJ/mol, agrees well with previously reported values. The system can be used for measurements of fusion enthalpies of refractory oxides amenable to laser heating as well as for splat quenching of oxide melts.     

A cultural task analysis of implicit independence: Comparing North America, Western Europe, and East Asia.

Informed by a new theoretical framework that assigns a key role to cultural tasks (culturally prescribed means to achieve cultural mandates such as independence and interdependence) in mediating the mutual influences between culture and psychological processes, the authors predicted and found that North Americans are more likely than Western Europeans (British and Germans) to (a) exhibit focused (vs. holistic) attention, (b) experience emotions associated with independence (vs. interdependence), (c) associate happiness with personal achievement (vs. communal harmony), and (d) show an inflated symbolic self. In no cases were the 2 Western European groups significantly different from one another. All Western groups showed (e) an equally strong dispositional bias in attribution. Across all of the implicit indicators of independence, Japanese were substantially less independent (or more interdependent) than the three Western groups. An explicit self-belief measure of independence and interdependence showed an anomalous pattern. These data were interpreted to suggest that the contemporary American ethos has a significant root in both Western cultural heritage and a history of voluntary settlement. Further analysis offered unique support for the cultural task analysis. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

DFT Quantum-Chemical Calculation of Thermodynamic Parameters and DSC Measurement of Thermostability of Novel Benzofuroxan Derivatives Containing Triazidoisobutyl Fragments

New derivatives of benzofuroxan containing triazidoisobutyl fragments, opening the way for the creation of highly effective compositions with an increased value of energy characteristics, were synthesized for the first time. Such compounds are also an excellent platform for further modification and for the preparation of new biologically-active compounds containing tetrazole and triazole fragments. Calculations of heats of formation performed with the DFT (density functional theory) method showed that the studied compounds are high-energetic density ones, the enthalpies of formation of which are comparable to the enthalpies of formation of similar benzofuroxan derivatives and exceeds experimental enthalpy of formation of CL-14 (5,7-diamino-4,6-dinitrobenzofuroxan). The analysis of DSC indicates a sufficiently high thermal stability of the synthesized azidobenzofuroxans, which are acceptable for their use as components in the creation of highly efficient compositions with an increased value of energy characteristics.     

Refolding of Lysozyme in Glycerol as Studied by Fast Scanning Calorimetry

The folding of lysozyme in glycerol was monitored by the fast scanning calorimetry technique. Application of a temperature–time profile with an isothermal segment for refolding allowed assessment of the state of the non-equilibrium protein ensemble and gave information on the kinetics of folding. We found that the non-equilibrium protein ensemble mainly contains a mixture of unfolded and folded protein forms and partially folded intermediates, and enthalpic barriers control the kinetics of the process. Lysozyme folding in glycerol follows the same or similar triangular mechanism described in the literature for folding in water. The unfolding enthalpy of the intermediate must be no lower than 70% of the folded form, while the activation barrier for the unfolding of the intermediate (ca. 140 kJ/mol) is about 100 kJ/mol lower than that of the folded form (ca. 240–260 kJ/mol).