Tungsten(VI) oxide supported rhodium nanoparticles: Highly active catalysts in hydrogen generation from ammonia borane

Herein, we report the use of tungsten(VI) oxide (WO₃) as support for Rh⁰ nanoparticles. The resulting Rh⁰/WO₃ nanoparticles are highly active and stable catalysts in H₂ generation from the hydrolysis of ammonia borane (AB). We present the results of our investigation on the particle size distribution, catalytic activity and stability of Rh⁰/WO₃ catalysts with 0.5%, 1.0%, 2.0% wt. Rh loadings in the hydrolysis reaction. The results reveal that Rh⁰/WO₃ (0.5% wt. Rh) is very promising catalyst providing a turnover frequency of 749 min^?1 in releasing 3.0 equivalent H₂ per mole of AB from the hydrolysis at 25.0 °C. The high catalytic activity of Rh⁰/WO₃ catalyst is attributed to the reducible nature of support. The report covers the results of kinetics study as well as comparative investigation of activity, recyclability, and reusability of colloidal(0) nanoparticles and Rh⁰/WO₃ (0.5 % wt. Rh) catalyst in the hydrolysis reaction.     

Real-time organic aerosol chemical speciation in the indoor environment using extractive electrospray ionization mass spectrometry

Understanding the sources and composition of organic aerosol (OA) in indoor environments requires rapid measurements, since many emissions and processes have short timescales. However, real-time molecular-level OA measurements have not been reported indoors. Here, we present quantitative measurements, at a time resolution of five seconds, of molecular ions corresponding to diverse aerosol-phase species, by applying extractive electrospray ionization mass spectrometry (EESI-MS) to indoor air analysis for the first time, as part of the highly instrumented HOMEChem field study. We demonstrate how the complex spectra of EESI-MS are screened in order to extract chemical information and investigate the possibility of interference from gas-phase semivolatile species. During experiments that simulated the Thanksgiving US holiday meal preparation, EESI-MS quantified multiple species, including fatty acids, carbohydrates, siloxanes, and phthalates. Intercomparisons with Aerosol Mass Spectrometer (AMS) and Scanning Mobility Particle Sizer suggest that EESI-MS quantified a large fraction of OA. Comparisons with FIGAERO-CIMS shows similar signal levels and good correlation, with a range of 100 for the relative sensitivities. Comparisons with SV-TAG for phthalates and with SV-TAG and AMS for total siloxanes also show strong correlation. EESI-MS observations can be used with gas-phase measurements to identify co-emitted gas- and aerosol-phase species, and this is demonstrated using complementary gas-phase PTR-MS observations.     

Enzyme activity and partial characterization of proteases obtained from Bromelia karatas fruit and compared with Bromelia pinguin proteases

Food Science and Biotechnology - The enzymatic activity and partial characterization of proteases from Bromelia karatas fruits were evaluated and compared with Bromelia pinguin proteases. The...     

Control of reactive distillation production of high-purity isopropanol

The process characteristics and control strategy of a high-purity IPA reactive distillation column were investigated. A robust nominal operation was found by maintaining an excess of propylene feed to the column and recycling the unreacted propylene to the feed instead of the top stage. Stage temperature and propylene composition with one-to-one relationship with reboiler duty and propylene feed are selected as controlled variables for maintaining bottom purity and feed ratio in the presence of possible measurement bias respectively. High nonlinearity between selected input–output pair was reduced by using variable transformation. Dynamic simulations demonstrated that such a control scheme with nonlinear transformed variable was capable of providing much superior control performance than the one using natural variable.     

Dissociating uncertainty responses and reinforcement signals in the comparative study of uncertainty monitoring.

Although researchers are exploring animals' capacity for monitoring their states of uncertainty, the use of some paradigms allows the criticism that animals map avoidance responses to error-causing stimuli not because of uncertainty monitored but because of feedback signals and stimulus aversion. The authors addressed this criticism with an uncertainty-monitoring task in which participants completed blocks of trials with feedback deferred so that they could not associate reinforcement signals to particular stimuli or stimulus-response pairs. Humans and 1 of 2 monkeys were able to make cognitive, decisional uncertainty responses that were independent of feedback or reinforcement history within a task. This finding unifies the comparative literature on uncertainty monitoring. The dissociation of performance from reinforcement has theoretical implications, and the deferred-feedback technique has many applications. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

The day of the week when you were born in 700 ms: Calendar computation in an autistic savant.

Some individuals are able to determine the weekday of a given date in a few seconds (finding for instance that June 12, 1900, was a Tuesday). This ability has fascinated scientists for many years because it is predominantly observed in people with limited intelligence and may appear very early in life. Exceptional visual memory, exceptional concentration abilities, or privileged access to lower levels of information not normally available through introspection have been advanced to explain such phenomena. In the present article, the authors show that a simple cognitive model can explain all aspects of the performance of Donny, a young autistic savant who is possibly the fastest and most accurate calendar prodigy ever described. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Co-digestion of ruminal content and blood from slaughterhouse industries: influence of solid concentration and ammonium generation.

At the present time, organic solid wastes from industries and agricultural activities are considered to be promising substrates for biogas production via anaerobic digestion. Moreover solids stabilisation is required before reutilization or disposal. Slaughterhouses are among the most important industries in Uruguay and produce 150,000 tons of ruminal content (RC) and 30,000 tons of blood per year. In order to determine the influence of the solids and blood contents, the ammonia inhibition and the inoculum adaptation co-digestion batch tests were performed. A set of experiences with TS concentration of 2.5%, 5% and 7.5% and different ratios of RC/blood were carried out using an inoculum from an UASB reactor. In all experiences fast blood hydrolisation was observed. A higher methane production was detected in the experiences with higher TS content. However, the fraction of solids degradation was lower in these experiences. A plateau in the biogas production was found. The free ammonia level, which was above the reported inhibitory levels, could explain this behaviour. After the inhibition period the biogas production restarted probably due to the biomass acclimatisation to the ammonia. In order to determine the inoculum adaptation a new experiment was performed. The inoculum used was the sludge coming from the first set of experiences. Based upon batch tests a 3.5 m3 pilot reactor was designed and started up. Ammonia inhibition was avoided by the start-up strategy and in two weeks the biogas production was 3.5 m3/d. The VS stabilisation with a solid retention time of 20 days was of 43%. The pilot reactor working at steady state had a TS concentration of 3-4% with a ratio of RC/blood of 10:1 at the entrance.     

Robust nonlinear feedback–feedforward control of a coupled kinetic Monte Carlo–finite difference simulation

Robust nonlinear feedforward–feedback controllers are designed for a multiscale system that dynamically couples kinetic Monte Carlo (KMC) and finite difference (FD) simulation codes. The coupled codes simulate the copper electrodeposition process for manufacturing on-chip copper interconnects in electronic devices. The control objective is to regulate the current density subject to the condition that the steady-state fluctuation of the overpotential remains bounded within ±0.01 V. The controller designs incorporate a low-order stochastic model that captures the input–output behavior of the coupled KMC–FD code. The controllers achieve the objectives and the closed-loop responses implemented on the low-order model and the coupled KMC–FD code match well within stochastic variations. The nonlinear feedforward control reduces the rise time of the controller response while the feedback control ensures robustness in the presence of model uncertainty.     

On the linear correlation between microhardness and mechanical properties in polar polymers and blends

The tensile elastic modulus (E), yield stress (σ_Y) and microhardness (MH) of neat and binary and ternary blends of glassy semicrystalline ethylene–vinyl alcohol copolymer (EVOH), a glassy amorphous polyamide and a semicrystalline nylon‐containing ionomer covering a broad range of properties were examined. The tests were carried out on dry and water‐equilibrated samples to produce stiffer and softer materials, respectively. From the results, more accurate linear correlations were found to describe adequately the microhardness, modulus and yield stress of these strongly self‐associated polymers through hydrogen bonding. Copyright © 2003 Society of Chemical Industry