The Chemical Percolation Devolatilization Model Applied to the Devolatilization of Coal in High Intensity Acoustic Fields

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Pressure Dependence of N-15 Chemical Shifts in Model Peptides Ac-Gly-Gly-X-Ala-NH2

High pressure NMR spectroscopy has developed into an important tool for studying conformational equilibria of proteins in solution. We have studied the amide proton and nitrogen chemical shifts of the 20 canonical amino acids X in the random-coil model peptide Ac-Gly-Gly-X-Ala-NH2, in a pressure range from 0.1 to 200 MPa, at a proton resonance frequency of 800 MHz. The obtained data allowed the determination of first and second order pressure coefficients with high accuracy at 283 K and pH 6.7. The mean first and second order pressure coefficients <B-1(15N)> and <B-2(15N)> for nitrogen are 2.91 ppm/GPa and -2.32 ppm/GPa(2), respectively. The corresponding values <B-1(1H)> and <B-2(1H)> for the amide protons are 0.52 ppm/GPa and -0.41 ppm/GPa(2). Residual dependent (1)J(1H15N)-coupling constants are shown.

Chemical Compatibility of Model Soil-Bentonite Backfill Containing Multiswellable Bentonite

The objective of this study was to evaluate the chemical compatibility of model soil-bentonite backfills containing multiswellable bentonite (MSB) relative to that of similar backfills containing untreated sodium (Na) bentonite or a commercially available, contaminant resistant bentonite (SW101). Flexible-wall tests were conducted on consolidated backfill specimens (effective stress =34.5 kPa) containing clean sand and 4.5–5.7% bentonite (by dry weight) using tap water and calcium chloride (CaCl2) solutions (10–1,000 mM) as the permeant liquids. Final values of hydraulic conductivity (k) and intrinsic permeability (K) to the CaCl2 solutions were determined after achieving both short-term termination criteria as defined by ASTM D5084 and long-term termination criteria for chemical equilibrium between the influent and effluent. Specimens containing MSB exhibited the smallest increases in k and K upon permeation with a given CaCl2 solution relative to specimens containing untreated Na bentonite or SW101. However, none of the specimens exhibited more than a five-fold increase in k or K, regardless of CaCl2 concentration or bentonite type. Final k values for specimens permeated with a given CaCl2 solution after permeation with tap water were similar to those for specimens of the same backfill permeated with only the CaCl2 solution, indicating that the order of permeation had no significant effect on k. Also, final k values for all specimens were within a factor of two of the k measured after achieving the ASTM D5084 termination criteria. Thus, use of only the ASTM D5084 criteria would have been sufficient to obtain reasonable estimates of long-term hydraulic conductivity for the specimens in this study.

A Model to Predict Percolation Threshold and Effective Conductivity of Infiltrated Electrodes for Solid Oxide Fuel Cells

We present a mechanistic modeling methodology to predict both the percolation threshold and effective conductivity of infiltrated Solid Oxide Fuel Cell (SOFC) electrodes. The model has been developed to mirror each step of the experimental fabrication process. The primary model output is the infiltrated electrode effective conductivity which provides results over a range of infiltrate loadings that are independent of the chosen electronically conducting material. The percolation threshold is utilized as a valuable output data point directly related to the effective conductivity to compare a wide range of input value choices. The predictive capability of the model is demonstrated by favorable comparison to two separate published experimental studies, one using strontium molybdate and one using La0.8Sr0.2FeO3-delta as infiltrate materials. Effective conductivities and percolation thresholds are shown for varied infiltrate particle size, pore size, and porosity with the infiltrate particle size having the largest impact on the results. (C) 2013 The Electrochemical Society. All rights reserved.

Mechanism and model of the oscillatory electro-oxidation of methanol

A mechanism for the kinetic instabilities observed in the galvanostatic electro-oxidation of methanol is suggested and a model developed. The model is investigated using stoichiometric network analysis as well as concepts from algebraic geometry (polynomial rings and ideal theory) revealing the occurrence of a Hopf and a saddle-node bifurcation. These analytical solutions are confirmed by numerical integration of the system of differential equations. (C) 2010 American Institute of Physics

Modeling ex vivo hematopoiesis using chemical engineering metaphors

Ex vivo hematopoiesis is increasingly used for clinical applications. Models of ex vivo hematopoiesis are required to better understand the complex dynamics and to optimize hematopoietic culture processes. A general mathematical modeling framework is developed which uses traditional chemical engineering metaphors to describe the complex hematopoietic dynamics. Tanks and tubular reactors are used to describe the (pseudo-) stochastic and deterministic elements of hematopoiesis, respectively. Cells at any point in the differentiation process can belong to either an immobilized, inert phase (quiescent cells) or a mobile, active phase (cycling cells). The model describes five processes: (1) flow (differentiation), (2) autocatalytic formation (growth),(3) degradation (death), (4) phase transition from immobilized to mobile phase (quiescent to cycling transition), and (5) phase transition from mobile to immobilized phase (cycling to quiescent transition). The modeling framework is illustrated with an example concerning the effect of TGF-beta 1 on erythropoiesis. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.

Evaluation of a computer model to simulate water table response to subirrigation

The objective of this work was to evaluate the water flow computer model, WATABLE, using experimental field observations on water table management plots from a site located near Hastings, FL, USA. The experimental field had scale drainage systems with provisions for subirrigation with buried microirrigation and conventional seepage irrigation systems. Potato (Solanum tuberosum L.) growing seasons from years 1996 and 1997 were used to simulate the hydrology of the area. Water table levels, precipitation, irrigation and runoff volumes were continuously monitored. The model simulated the water movement from a buried microirrigation line source and the response of the water table to irrigation, precipitation, evapotranspiration, and deep percolation. The model was calibrated and verified by comparing simulated results with experimental field observations. The model performed very well in simulating seasonal runoff, irrigation volumes, and water table levels during crop growth. The two-dimensional model can be used to investigate different irrigation strategies involving water table management control. Applications of the model include optimization of the water table depth for each growth stage, and duration, frequency, and rate of irrigation.

Distinção entre cachaças destiladas em alambiques e em colunas usando quimiometria

One hundred fifteen cachaça samples derived from distillation in copper stills (73) or in stainless steels (42) were analyzed for thirty five itens by chromatography and inductively coupled plasma optical emission spectrometry. The analytical data were treated through Factor Analysis (FA), Partial Least Square Discriminant Analysis (PLS-DA) and Quadratic Discriminant Analysis (QDA). The FA explained 66.0% of the database variance. PLS-DA showed that it is possible to distinguish between the two groups of cachaças with 52.8% of the database variance. QDA was used to build up a classification model using acetaldehyde, ethyl carbamate, isobutyl alcohol, benzaldehyde, acetic acid and formaldehyde as chemical descriptors. The model presented 91.7% of accuracy on predicting the apparatus in which unknown samples were distilled.

Free energy approximations in simple lattice proteins

This work addresses the question of whether it is possible to define simple pairwise interaction terms to approximate free energies of proteins or polymers. Rather than ask how reliable a potential of mean force is, one can ask how reliable it could possibly be. In a two-dimensional, infinite lattice model system one can calculate exact free energies by exhaustive enumeration. A series of approximations were fitted to exact results to assess the feasibility and utility of pairwise free energy terms. Approximating the true free energy with pairwise interactions gives a poor fit with little transferability between systems of different size. Adding extra artificial terms to the approximation yields better fits, but does not improve the ability to generalize from one system size to another. Furthermore, one cannot distinguish folding from nonfolding sequences via the approximated free energies. Most usefully, the methodology shows how one can assess the utility of various terms in lattice protein/polymer models. (C) 2001 American Institute of Physics.

Metastable chaos in the ammonia ring laser

We report experimental studies of metastable chaos in the far-infrared ammonia ring: laser. When the laser pump power is switched from above chaos threshold to slightly below, chaotic intensity pulsations continue for a varying time afterward before decaying to either periodic or cw emission. The behavior is in good qualitative agreement with that predicted by the Lorenz equations, previously used to describe this laser. The statistical distribution of the duration of the chaotic transient is measured and shown to be in excellent agreement with the Lorenz equations in showing a modified exponential distribution. We also give a brief numerical analysis and graphical visualization of the Lorenz equations in phase space illustrating the boundary between the metastable chaotic and the stable fixed point basins of attraction. This provides an intuitive understanding of the metastable dynamics of the Lorenz equations and the experimental system.

Review and future directions in the modelling and control of continuous drum granulation

Many granulation plants operate well below design capacity, suffering from high recycle rates and even periodic instabilities. This behaviour cannot be fully predicted using the present models. The main objective of the paper is to provide an overview of the current status of model development for granulation processes and suggest future directions for research and development. The end-use of the models is focused on the optimal design and control of granulation plants using the improved predictions of process dynamics. The development of novel models involving mechanistically based structural switching methods is proposed in the paper. A number of guidelines are proposed for the selection of control relevant model structures. (C) 2002 Published by Elsevier Science B.V.

Distinção entre cachaças destiladas em alambiques e em colunas usando quimiometria

One hundred fifteen cachaça samples derived from distillation in copper stills (73) or in stainless steels (42) were analyzed for thirty five itens by chromatography and inductively coupled plasma optical emission spectrometry. The analytical data were treated through Factor Analysis (FA), Partial Least Square Discriminant Analysis (PLS-DA) and Quadratic Discriminant Analysis (QDA). The FA explained 66.0% of the database variance. PLS-DA showed that it is possible to distinguish between the two groups of cachaças with 52.8% of the database variance. QDA was used to build up a classification model using acetaldehyde, ethyl carbamate, isobutyl alcohol, benzaldehyde, acetic acid and formaldehyde as chemical descriptors. The model presented 91.7% of accuracy on predicting the apparatus in which unknown samples were distilled.

RUMOR PROCESSES ON N

We study four discrete-time stochastic systems on N, modeling processes of rumor spreading. The involved individuals can either have an active or a passive role, speaking up or asking for the rumor. The appetite for spreading or hearing the rumor is represented by a set of random variables whose distributions may depend on the individuals. Our goal is to understand-based on the distribution of the random variables-whether the probability of having an infinite set of individuals knowing the rumor is positive or not.

The catalytic and other residues essential for the activity of the midgut trehalase from Spodoptera frugiperda

Trehalase (EC 3.2.1.28) hydrolyzes only alpha, alpha`- trehalose and is present in a variety of organisms, but is most important in insects and fungi. Crystallographic data showed that bacterial trehalase has 0312 and E496 as the catalytical residues and three Arg residues in the active site. Those residues have homologous in all family 37 trehalases including Spodoptera frugiperda trehalase (0322, E520, R169, R227, R287). To test the role of these residues, mutants of trehalase were produced. All mutants were at least four orders of magnitude less active than wild type trehalase and no structural difference between these mutants and wild type enzyme were discernible by circular dichroism. D322A and E520 pH-activity profile lacked the alkaline arm and the acid arm, respectively, suggesting that D322 is the acid and E520 the basic catalyst. Azide increases E520A activity three times, confirming its action as the basic catalyst. Taking into account the decrease in activity after substitution for alanine residue, the three arginine residues are as important as the catalytical ones to trehalase activity. This clarifies the previous misidentification of an Arg residue as the acid catalyst. As far as we know, this is the first report on the functional identification residues important for trehalase activity. (C) 2010 Elsevier Ltd. All rights reserved.