Affinity distribution functions in multicomponent heterogeneous adsorption. Analytical inversion of isotherms to obtain affinity spectra

An analytical approach for the interpretation of multicomponent heterogeneous adsorption or complexation isotherms in terms of multidimensional affinity spectra is presented. Fourier transform, applied to analyze the corresponding integral equation, leads to an inversion formula which allows the computation of the multicomponent affinity spectrum underlying a given competitive isotherm. Although a different mathematical methodology is used, this procedure can be seen as the extension to multicomponent systems of the classical Sips’s work devoted to monocomponent systems. Furthermore, a methodology which yields analytical expressions for the main statistical properties (mean free energies of binding and covariance matrix) of multidimensional affinity spectra is reported. Thus, the level of binding correlation between the different components can be quantified. It has to be highlighted that the reported methodology does not require the knowledge of the affinity spectrum to calculate the means, variances, and covariance of the binding energies of the different components. Nonideal competitive consistent adsorption isotherm, widely used in metal/proton competitive complexation to environmental macromolecules, and Frumkin competitive isotherms are selected to illustrate the application of the reported results. Explicit analytical expressions for the affinity spectrum as well as for the matrix correlation are obtained for the NICCA case. © 2004 American Institute of Physics.

Collective decision making in a heterogeneous environment: Lasius niger colonies preferentially forage at easy to learn locations

Many ants forage in complex environments and use a combination of trail pheromone information and route memory to navigate between food sources and the nest. Previous research has shown that foraging routes differ in how easily they are learned. In particular, it is easier to learn feeding locations that are reached by repeating (e.g. left-left or right-right) than alternating choices (left-right or right-left) along a route with two T-bifurcations. This raises the hypothesis that the learnability of the feeding sites may influence overall colony foraging patterns. We studied this in the mass-recruiting ant Lasius niger. We used mazes with two T-bifurcations, and allowed colonies to exploit two equidistant food sources that differed in how easily their locations were learned. In experiment 1, learnability was manipulated by using repeating versus alternating routes from nest to feeder. In experiment 2, we added visual landmarks along the route to one food source. Our results suggest that colonies preferentially exploited the feeding site that was easier to learn. This was the case even if the more difficult to learn feeding site was discovered first. Furthermore, we show that these preferences were at least partly caused by lower error rates (experiment 1) and greater foraging speeds (experiment 2) of foragers visiting the more easily learned feeder locations. Our results indicate that the learnability of feeding sites is an important factor influencing collective foraging patterns of ant colonies under more natural conditions, given that in natural environments foragers often face multiple bifurcations on their way to food sources.

Consumption, investment and life insurance strategies with heterogeneous discounting

[cat] En aquest treball s'analitza l'efecte que comporta l'introducció de preferències inconsistents temporalment sobre les decisions òptimes de consum, inversió i compra d'assegurança de vida. En concret, es pretén recollir la creixent importància que un individu dóna a la herència que deixa i a la riquesa disponible per a la seva jubilació al llarg de la seva vida laboral. Amb aquesta finalitat, es parteix d'un model estocàstic en temps continu amb temps final aleatori, i s'introdueix el descompte heterogeni, considerant un agent amb una distribució de vida residual coneguda. Per tal d'obtenir solucions consistents temporalment es resol una equació de programació dinàmica no estàndard. Per al cas de funcions d'utilitat del tipus CRRA i CARA es troben solucions explícites. Finalment, els resultats obtinguts s'il·lustren numèricament.

Consumption, investment and life insurance strategies with heterogeneous discounting

[cat] En aquest treball s'analitza l'efecte que comporta l'introducció de preferències inconsistents temporalment sobre les decisions òptimes de consum, inversió i compra d'assegurança de vida. En concret, es pretén recollir la creixent importància que un individu dóna a la herència que deixa i a la riquesa disponible per a la seva jubilació al llarg de la seva vida laboral. Amb aquesta finalitat, es parteix d'un model estocàstic en temps continu amb temps final aleatori, i s'introdueix el descompte heterogeni, considerant un agent amb una distribució de vida residual coneguda. Per tal d'obtenir solucions consistents temporalment es resol una equació de programació dinàmica no estàndard. Per al cas de funcions d'utilitat del tipus CRRA i CARA es troben solucions explícites. Finalment, els resultats obtinguts s'il·lustren numèricament.

Anti-MPER antibodies with heterogeneous neutralization capacity are detectable in most untreated HIV-1 infected individuals

Background The MPER region of the HIV-1 envelope glycoprotein gp41 is targeted by broadly neutralizing antibodies. However, the localization of this epitope in a hydrophobic environment seems to hamper the elicitation of these antibodies in HIV infected individuals. We have quantified and characterized anti-MPER antibodies by ELISA and by flow cytometry using a collection of mini gp41-derived proteins expressed on the surface of 293T cells. Longitudinal plasma samples from 35 HIV-1 infected individuals were assayed for MPER recognition and MPER-dependent neutralizing capacity using HIV-2 viruses engrafted with HIV-1 MPER sequences. Results Miniproteins devoid of the cysteine loop of gp41 exposed the MPER on 293T cell membrane. Anti-MPER antibodies were identified in most individuals and were stable when analyzed in longitudinal samples. The magnitude of the responses was strongly correlated with the global response to the HIV-1 envelope glycoprotein, suggesting no specific limitation for anti-MPER antibodies. Peptide mapping showed poor recognition of the C-terminal MPER moiety and a wide presence of antibodies against the 2F5 epitope. However, antibody titers failed to correlate with 2F5-blocking activity and, more importantly, with the specific neutralization of HIV-2 chimeric viruses bearing the HIV-1 MPER sequence; suggesting a strong functional heterogeneity in anti-MPER humoral responses. Conclusions Anti-MPER antibodies can be detected in the vast majority of HIV-1 infected individuals and are generated in the context of the global anti-Env response. However, the neutralizing capacity is heterogeneous suggesting that eliciting neutralizing anti-MPER antibodies by immunization might require refinement of immunogens to skip nonneutralizing responses.

Seismic characterization of heterogeneous sedimentary and fractured rocks based on Biot's theory of poroelasticity

Understanding and quantifying seismic energy dissipation, which manifests itself in terms of velocity dispersion and attenuation, in fluid-saturated porous rocks is of considerable interest, since it offers the perspective of extracting information with regard to the elastic and hydraulic rock properties. There is increasing evidence to suggest that wave-induced fluid flow, or simply WIFF, is the dominant underlying physical mechanism governing these phenomena throughout the seismic, sonic, and ultrasonic frequency ranges. This mechanism, which can prevail at the microscopic, mesoscopic, and macroscopic scale ranges, operates through viscous energy dissipation in response to fluid pressure gradients and inertial effects induced by the passing wavefield. In the first part of this thesis, we present an analysis of broad-band multi-frequency sonic log data from a borehole penetrating water-saturated unconsolidated glacio-fluvial sediments. An inherent complication arising in the interpretation of the observed P-wave attenuation and velocity dispersion is, however, that the relative importance of WIFF at the various scales is unknown and difficult to unravel. An important generic result of our work is that the levels of attenuation and velocity dispersion due to the presence of mesoscopic heterogeneities in water-saturated unconsolidated clastic sediments are expected to be largely negligible. Conversely, WIFF at the macroscopic scale allows for explaining most of the considered data while refinements provided by including WIFF at the microscopic scale in the analysis are locally meaningful. Using a Monte-Carlo-type inversion approach, we compare the capability of the different models describing WIFF at the macroscopic and microscopic scales with regard to their ability to constrain the dry frame elastic moduli and the permeability as well as their local probability distribution. In the second part of this thesis, we explore the issue of determining the size of a representative elementary volume (REV) arising in the numerical upscaling procedures of effective seismic velocity dispersion and attenuation of heterogeneous media. To this end, we focus on a set of idealized synthetic rock samples characterized by the presence of layers, fractures or patchy saturation in the mesocopic scale range. These scenarios are highly pertinent because they tend to be associated with very high levels of velocity dispersion and attenuation caused by WIFF in the mesoscopic scale range. The problem of determining the REV size for generic heterogeneous rocks is extremely complex and entirely unexplored in the given context. In this pilot study, we have therefore focused on periodic media, which assures the inherent self- similarity of the considered samples regardless of their size and thus simplifies the problem to a systematic analysis of the dependence of the REV size on the applied boundary conditions in the numerical simulations. Our results demonstrate that boundary condition effects are absent for layered media and negligible in the presence of patchy saturation, thus resulting in minimum REV sizes. Conversely, strong boundary condition effects arise in the presence of a periodic distribution of finite-length fractures, thus leading to large REV sizes. In the third part of the thesis, we propose a novel effective poroelastic model for periodic media characterized by mesoscopic layering, which accounts for WIFF at both the macroscopic and mesoscopic scales as well as for the anisotropy associated with the layering. Correspondingly, this model correctly predicts the existence of the fast and slow P-waves as well as quasi and pure S-waves for any direction of wave propagation as long as the corresponding wavelengths are much larger than the layer thicknesses. The primary motivation for this work is that, for formations of intermediate to high permeability, such as, for example, unconsolidated sediments, clean sandstones, or fractured rocks, these two WIFF mechanisms may prevail at similar frequencies. This scenario, which can be expected rather common, cannot be accounted for by existing models for layered porous media. Comparisons of analytical solutions of the P- and S-wave phase velocities and inverse quality factors for wave propagation perpendicular to the layering with those obtained from numerical simulations based on a ID finite-element solution of the poroelastic equations of motion show very good agreement as long as the assumption of long wavelengths remains valid. A limitation of the proposed model is its inability to account for inertial effects in mesoscopic WIFF when both WIFF mechanisms prevail at similar frequencies. Our results do, however, also indicate that the associated error is likely to be relatively small, as, even at frequencies at which both inertial and scattering effects are expected to be at play, the proposed model provides a solution that is remarkably close to its numerical benchmark. -- Comprendre et pouvoir quantifier la dissipation d'énergie sismique qui se traduit par la dispersion et l'atténuation des vitesses dans les roches poreuses et saturées en fluide est un intérêt primordial pour obtenir des informations à propos des propriétés élastique et hydraulique des roches en question. De plus en plus d'études montrent que le déplacement relatif du fluide par rapport au solide induit par le passage de l'onde (wave induced fluid flow en anglais, dont on gardera ici l'abréviation largement utilisée, WIFF), représente le principal mécanisme physique qui régit ces phénomènes, pour la gamme des fréquences sismiques, sonique et jusqu'à l'ultrasonique. Ce mécanisme, qui prédomine aux échelles microscopique, mésoscopique et macroscopique, est lié à la dissipation d'énergie visqueuse résultant des gradients de pression de fluide et des effets inertiels induits par le passage du champ d'onde. Dans la première partie de cette thèse, nous présentons une analyse de données de diagraphie acoustique à large bande et multifréquences, issues d'un forage réalisé dans des sédiments glaciaux-fluviaux, non-consolidés et saturés en eau. La difficulté inhérente à l'interprétation de l'atténuation et de la dispersion des vitesses des ondes P observées, est que l'importance des WIFF aux différentes échelles est inconnue et difficile à quantifier. Notre étude montre que l'on peut négliger le taux d'atténuation et de dispersion des vitesses dû à la présence d'hétérogénéités à l'échelle mésoscopique dans des sédiments clastiques, non- consolidés et saturés en eau. A l'inverse, les WIFF à l'échelle macroscopique expliquent la plupart des données, tandis que les précisions apportées par les WIFF à l'échelle microscopique sont localement significatives. En utilisant une méthode d'inversion du type Monte-Carlo, nous avons comparé, pour les deux modèles WIFF aux échelles macroscopique et microscopique, leur capacité à contraindre les modules élastiques de la matrice sèche et la perméabilité ainsi que leur distribution de probabilité locale. Dans une seconde partie de cette thèse, nous cherchons une solution pour déterminer la dimension d'un volume élémentaire représentatif (noté VER). Cette problématique se pose dans les procédures numériques de changement d'échelle pour déterminer l'atténuation effective et la dispersion effective de la vitesse sismique dans un milieu hétérogène. Pour ce faire, nous nous concentrons sur un ensemble d'échantillons de roches synthétiques idéalisés incluant des strates, des fissures, ou une saturation partielle à l'échelle mésoscopique. Ces scénarios sont hautement pertinents, car ils sont associés à un taux très élevé d'atténuation et de dispersion des vitesses causé par les WIFF à l'échelle mésoscopique. L'enjeu de déterminer la dimension d'un VER pour une roche hétérogène est très complexe et encore inexploré dans le contexte actuel. Dans cette étude-pilote, nous nous focalisons sur des milieux périodiques, qui assurent l'autosimilarité des échantillons considérés indépendamment de leur taille. Ainsi, nous simplifions le problème à une analyse systématique de la dépendance de la dimension des VER aux conditions aux limites appliquées. Nos résultats indiquent que les effets des conditions aux limites sont absents pour un milieu stratifié, et négligeables pour un milieu à saturation partielle : cela résultant à des dimensions petites des VER. Au contraire, de forts effets des conditions aux limites apparaissent dans les milieux présentant une distribution périodique de fissures de taille finie : cela conduisant à de grandes dimensions des VER. Dans la troisième partie de cette thèse, nous proposons un nouveau modèle poro- élastique effectif, pour les milieux périodiques caractérisés par une stratification mésoscopique, qui prendra en compte les WIFF à la fois aux échelles mésoscopique et macroscopique, ainsi que l'anisotropie associée à ces strates. Ce modèle prédit alors avec exactitude l'existence des ondes P rapides et lentes ainsi que les quasis et pures ondes S, pour toutes les directions de propagation de l'onde, tant que la longueur d'onde correspondante est bien plus grande que l'épaisseur de la strate. L'intérêt principal de ce travail est que, pour les formations à perméabilité moyenne à élevée, comme, par exemple, les sédiments non- consolidés, les grès ou encore les roches fissurées, ces deux mécanismes d'WIFF peuvent avoir lieu à des fréquences similaires. Or, ce scénario, qui est assez commun, n'est pas décrit par les modèles existants pour les milieux poreux stratifiés. Les comparaisons des solutions analytiques des vitesses des ondes P et S et de l'atténuation de la propagation des ondes perpendiculaires à la stratification, avec les solutions obtenues à partir de simulations numériques en éléments finis, fondées sur une solution obtenue en 1D des équations poro- élastiques, montrent un très bon accord, tant que l'hypothèse des grandes longueurs d'onde reste valable. Il y a cependant une limitation de ce modèle qui est liée à son incapacité à prendre en compte les effets inertiels dans les WIFF mésoscopiques quand les deux mécanismes d'WIFF prédominent à des fréquences similaires. Néanmoins, nos résultats montrent aussi que l'erreur associée est relativement faible, même à des fréquences à laquelle sont attendus les deux effets d'inertie et de diffusion, indiquant que le modèle proposé fournit une solution qui est remarquablement proche de sa référence numérique.

Detecting Heterogeneous Risk Attitudes with Mixed Gambles

We propose a task for eliciting attitudes toward risk that is close to real-world risky decisions which typically involve gains and losses. The task consists of accepting or rejecting gambles that provide a gain with probability p and a loss with probability 1−p . We employ finite mixture models to uncover heterogeneity in risk preferences and find that (i) behavior is heterogeneous, with one half of the subjects behaving as expected utility maximizers, (ii) for the others, reference-dependent models perform better than those where subjects derive utility from final outcomes, (iii) models with sign-dependent decision weights perform better than those without, and (iv) there is no evidence for loss aversion. The procedure is sufficiently simple so that it can be easily used in field or lab experiments where risk elicitation is not the main experiment.

Heterogeneous products and tests for an appropriate aggregation level considering different qualities: evidence from fresh hake at Barcelona’s wholesale market

[cat] Aquest estudi destaca la importància de considerar un nivell d’agregació adequat en els anàlisis de demanda, ja que treballar utilitzant un nivell d’agregació inadequat pot donar lloc a estimacions esbiaixades. Aquest fet es mostra a través de l’anàlisi de diferents productes de lluç fresc comercialitzats a Mercabarna, el mercat majorista de Barcelona. La literatura sobre la demanda de peix tracta al lluç com un únic producte i espècie. No obstant això, en el mercat espanyol, es comercialitzen molts peixos com a lluç, els quals mostren comportaments molt diferents (des de béns inferiors fins a béns de luxe). Els resultats obtinguts, en concordança amb les observacions empíriques, demostren que l’anàlisi s’ha de realitzar amb un major grau de detall que a nivell d’espècie. Això qüestiona els resultats d’anteriors estudis de demanda i la majoria de les bases de dades, on l’observació del nivell d’agregació adequat dels productes no es té en compte.

Heterogeneous products and tests for an appropriate aggregation level considering different qualities: evidence from fresh hake at Barcelona’s wholesale market

[cat] Aquest estudi destaca la importància de considerar un nivell d’agregació adequat en els anàlisis de demanda, ja que treballar utilitzant un nivell d’agregació inadequat pot donar lloc a estimacions esbiaixades. Aquest fet es mostra a través de l’anàlisi de diferents productes de lluç fresc comercialitzats a Mercabarna, el mercat majorista de Barcelona. La literatura sobre la demanda de peix tracta al lluç com un únic producte i espècie. No obstant això, en el mercat espanyol, es comercialitzen molts peixos com a lluç, els quals mostren comportaments molt diferents (des de béns inferiors fins a béns de luxe). Els resultats obtinguts, en concordança amb les observacions empíriques, demostren que l’anàlisi s’ha de realitzar amb un major grau de detall que a nivell d’espècie. Això qüestiona els resultats d’anteriors estudis de demanda i la majoria de les bases de dades, on l’observació del nivell d’agregació adequat dels productes no es té en compte.

Modificação de zeólitas para uso em catálise

The use of zeolites and other molecular sieves as catalysts is discussed at an introductory level. The text includes a brief historic background on the use of zeolites in catalysis, and a discussion of some chemical and physical properties of silicalite, aluminosilicate, and aluminophosphate molecular sieves. The strategies currently used to chemically modify zeolites and related materials to produce catalysts with increased activity and selectivity are discussed, including the use of redox molecular sieves for hydrocarbon oxidation and the leaching of the active metals from the support.

Produção de etilenoglicóis e derivados por reações catalíticas do óxido de eteno

Products resulting from the ethoxylation of hydroxylated compounds, especially water and ethanol, are of great commercial importance. This work presents several aspects concerning the catalytic reactions of ethylene oxide, a chemical substance used in the production of a wide variety of products. Mechanisms of ethoxylation, distribution of products, formation of undesired by-products and perspectives for new processes using heterogeneous catalysis are also reviewed and discussed.

Desafios da acidez na catálise em estado sólido

This study explores the similarities between solid and liquid acid catalysts highlighting the advantages and the main challenges of heterogeneous catalytic processes. We describe the main developments in technical procedures like selection of compounds and reaction models involved in: increasing acidity, characterization of solid acidity and in coke formation.

Low metal loading catalysts used for the selective hydrogenation of styrene

A series of Group VIII metal catalysts was obtained for the semi-hydrogenation of styrene. Catalysts were characterized by Hydrogen Chemisorption, TPR and XPS. Palladium, rhodium and platinum low metal loading prepared catalysts presented high activity and selectivity (ca. 98%) during the semi-hydrogenation of styrene, being palladium the most active catalyst. The ruthenium catalyst also presented high selectivity (ca. 98%), but the lowest activity. For the palladium catalyst, the influence of the precursor salt and of the reduction temperature on the activity and selectivity were studied. The following activity series was obtained: PdN-423 > PdCl-673 > PdCl-373> PtCl-673 > RhCl-673 >> RuCl-673. As determined by XPS, differences in activity could be attributed, at least in part, to electronic effects.

Preparation and characterization oF Ru-Sn/Al2O3 catalysts for the hydrogenation of fatty acid methyl esters

Ru-Sn/Al2O3 catalysts with different Sn loadings were prepared by the coimpregnation method. Several characterization techniques such as TPR, pyridine TPD and catalytic tests for dehydrogenation and hydrogenolysis were used to evaluate and compare such catalysts. TPR results indicate that Sn is deposited both onto the support and as species strongly interacting with Ru. Such non selective deposition modifies the acid and metallic functions of the catalysts. Both total acidity and acid strength distribution are affected: total acidity decreases and new sites of lower acid strength are created. Both dehydrogenating and hydrogenolytic activities are strongly diminished by the addition of Sn. Results of catalytic tests for methyl oleate hydrogenation indicate that methyl stearate is the main product, with only minute amounts of oleyl alcohol produced, and that the addition of Sn diminishes the hydrogenation activity.