Mechanistic aspects of the water–gas shift reaction on alumina-supported noble metal catalysts: In situ DRIFTS and SSITKA-mass spectrometry studies

Steady-state isotopic transient kinetic analysis (SSITKA) experiments coupled with mass spectrometry were performed for the first time to study essential mechanistic aspects of the water–gas shift (WGS) reaction over alumina-supported Pt, Pd, and Rh catalysts. In particular, the concentrations (μmol g⁻¹) of active intermediate species found in the carbon-path from CO to the CO₂ product gas (use of ¹³CO), and in the hydrogen-path from H₂O to the H₂ product gas (use of D₂O) of the reaction mechanism were determined. It was found that by increasing the reaction temperature from 350 to 500 °C the concentration of active species in both the carbon-path and hydrogen-path increased significantly. Based on the large concentration of active species present in the hydrogen-path (OH/H located on the alumina support), the latter being larger than six equivalent monolayers based on the exposed noble metal surface area (θ > 6.0), the small concentration of OH groups along the periphery of metal-support interface, and the significantly smaller concentration (μmol g⁻¹) of active species present in the carbon-path (adsorbed CO on the noble metal and COOH species on the alumina support and/or the metal-support interface), it might be suggested that diffusion of OH/H species on the alumina support towards catalytic sites present in the hydrogen-path of reaction mechanism might be considered as a slow reaction step. The formation of labile OH/H species is the result of dissociative chemisorption of water on the alumina support, where the role of noble metal is to activate the CO chemisorption and likely to promote formate decomposition into CO₂ and H₂ products. It was found that there is a good correlation between the surface concentration and binding energy of CO on the noble metal (Pt, Pd or Rh) with the activity of alumina-supported noble metal towards the WGS reaction.     

Towards social behavior in virtual-agent navigation

We present Social Groups and Navigation (SGN), a method to simulate the walking behavior of small pedestrian groups in virtual environments. SGN is the first method to simulate group behavior on both global and local levels of an underlying planning hierarchy. We define quantitative metrics to measure the coherence and the sociality of a group based on existing empirical data of real crowds. SGN does not explicitly model coherent and social formations, but it lets such formations emerge from simple geometric rules. In addition to a previous version, SGN also handles group-splitting to smaller groups throughout navigation as well as social sub-group behavior whenever a group has to temporarily split up to re-establish its coherence. For groups of four, SGN generates between 13% and 53% more socially-friendly behavior than previous methods, measured over the lifetime of a group in the simulation. For groups of three, the gain is between 15% and 31%, and for groups of two, the gain is between 1% and 4%. SGN is designed in a flexible way, and it can be integrated into any crowd-simulation framework that handles global path planning and any path following as separate steps. Experiments show that SGN enables the simulation of thousands of agents in real time.     

Elastic block ciphers: method, security and instantiations

We introduce the concept of an elastic block cipher which refers to stretching the supported block size of a block cipher to any length up to twice the original block size while incurring a computational workload that is proportional to the block size. Our method uses the round function of an existing block cipher as a black box and inserts it into a substitution- permutation network. Our method is designed to enable us to form a reduction between the elastic and the original versions of the cipher. Using this reduction, we prove that the elastic version of a cipher is secure against key-recovery attacks if the original cipher is secure against such attacks. We note that while reduction-based proofs of security are a cornerstone of cryptographic analysis, they are typical when complete components are used as sub-components in a larger design. We are not aware of the use of such techniques in the case of concrete block cipher designs. We demonstrate the general applicability of the elastic block cipher method by constructing examples from existing block ciphers: AES, Camellia, MISTY1, and RC6. We compare the performance of the elastic versions to that of the original versions and evaluate the elastic versions using statistical tests measuring the randomness of the ciphertext. We also use our examples to demonstrate the concept of a generic key schedule for block ciphers.

Catadioptric Projective Geometry

Catadioptric sensors are devices which utilize mirrors and lenses to form a projection onto the image plane of a camera. Central catadioptric sensors are the class of these devices having a single effective viewpoint. In this paper, we propose a unifying model for the projective geometry induced by these devices and we study its properties as well as its practical implications. We show that a central catadioptric projection is equivalent to a two-step mapping via the sphere. The second step is equivalent to a stereographic projection in the case of parabolic mirrors. Conventional lens-based perspective cameras are also central catadioptric devices with a virtual planar mirror and are, thus, covered by the unifying model. We prove that for each catadioptric projection there exists a dual catadioptric projection based on the duality between points and line images (conics). It turns out that planar and parabolic mirrors build a dual catadioptric projection pair. As a practical example we describe a procedure to estimate focal length and image center from a single view of lines in arbitrary position for a parabolic catadioptric system.     

Rotation recovery from spherical images without correspondences

This paper addresses the problem of rotation estimation directly from images defined on the sphere and without correspondence. The method is particularly useful for the alignment of large rotations and has potential impact on 3D shape alignment. The foundation of the method lies in the fact that the spherical harmonic coefficients undergo a unitary mapping when the original image is rotated. The correlation between two images is a function of rotations and we show that it has an SO(3)-Fourier transform equal to the pointwise product of spherical harmonic coefficients of the original images. The resolution of the rotation space depends on the bandwidth we choose for the harmonic expansion and the rotation estimate is found through a direct search in this 3D discretized space. A refinement of the rotation estimate can be obtained from the conservation of harmonic coefficients in the rotational shift theorem. A novel decoupling of the shift theorem with respect to the Euler angles is presented and exploited in an iterative scheme to refine the initial rotation estimates. Experiments show the suitability of the method for large rotations and the dependence of the method on bandwidth and the choice of the spherical harmonic coefficients.     

Linear pose estimation from points or lines

Estimation of camera pose from an image of n points or lines with known correspondence is a thoroughly studied problem in computer vision. Most solutions are iterative and depend on nonlinear optimization of some geometric constraint, either on the world coordinates or on the projections to the image plane. For real-time applications, we are interested in linear or closed-form solutions free of initialization. We present a general framework which allows for a novel set of linear solutions to the pose estimation problem for both n points and n lines. We then analyze the sensitivity of our solutions to image noise and show that the sensitivity analysis can be used as a conservative predictor of error for our algorithms. We present a number of simulations which compare our results to two other recent linear algorithms, as well as to iterative approaches. We conclude with tests on real imagery in an augmented reality setup.     

Molecular Advances in Preeclampsia and HELLP Syndrome

Preeclampsia (PE) constitutes one of the principal reasons for maternal and perinatal morbidity and mortality worldwide. The circumstance typically implicates formerly healthful normotensive women, after 20 weeks of gestation, typically withinside the third trimester, without regarded threat elements or past deliveries. PE can be further complicated with hemolysis and thrombocytopenia, leading to the emergence of HELLP syndrome (Hemolysis, Elevated Liver enzymes, Low platelets). Both conditions are classified as hypertensive diseases of pregnancy (HDP), and their pathogenesis has been linked to an excessive maternal inflammatory response, accompanied by enhanced endothelial activation. Several studies have found that in pregnancies affected by PE/HELLP, von Willebrand factor (vWF) antigen levels (vWF:Ag) are significantly elevated, while its cleaving protease (ADAMTS-13, A Disintegrin-like and Metalloprotease with Thrombospondin type 1 motif, member 13) activity is normal to decreased. Furthermore, the higher urine excretion of the terminal complement complex C5b-9, as well as its greater deposition in the placental surface in preeclamptic women, imply that the utero-placental unit’s distinctive deficits are intimately tied to disproportionate complement activation. The goal of this updated evaluation is to provide the most up-to-date molecular advances in the pathophysiology of PE/HELLP syndromes. Recent medical data on vWF:Ag levels in patients with PE, ADAMTS-13, and dysregulation of the complement system, are highlighted and evaluated. Furthermore, we discuss the relationship between those entities and the progression of the disease, as well as their significance in the diagnostic process. Finally, considering the difficulties in analyzing and controlling those symptoms in pregnant women, we can provide a current diagnostic and therapeutic algorithm.     

Low-temperature H2-SCR of NO on a novel Pt/MgO-CeO2 catalyst

The selective catalytic reduction of NO by H₂ under strongly oxidizing conditions (H₂-SCR) in the low-temperature range of 100–200 °C has been studied over Pt supported on a series of metal oxides (e.g., La₂O₃, MgO, Y₂O₃, CaO, CeO₂, TiO₂, SiO₂ and MgO-CeO₂). The Pt/MgO and Pt/CeO₂ solids showed the best catalytic behavior with respect to N₂ yield and the widest temperature window of operation compared with the other single metal oxide-supported Pt solids. An optimum 50 wt% MgO-50wt% CeO₂ support composition and 0.3 wt% Pt loading (in the 0.1–2.0 wt% range) were found in terms of specific reaction rate of N₂ production (mols N₂/g_cat s). High NO conversions (70–95%) and N₂ selectivities (80–85%) were also obtained in the 100–200 °C range at a GHSV of 80,000 h⁻¹ with the lowest 0.1 wt% Pt loading and using a feed stream of 0.25 vol% NO, 1 vol% H₂, 5 vol% O₂ and He as balance gas. Addition of 5 vol% H₂O in the latter feed stream had a positive influence on the catalytic performance and practically no effect on the stability of the 0.1 wt% Pt/MgO-CeO₂ during 24 h on reaction stream. Moreover, the latter catalytic system exhibited a high stability in the presence of 25–40 ppm SO₂ in the feed stream following a given support pretreatment. N₂ selectivity values in the 80–85% range were obtained over the 0.1 wt% Pt/MgO-CeO₂ catalyst in the 100–200 °C range in the presence of water and SO₂ in the feed stream. The above-mentioned results led to the obtainment of patents for the commercial exploitation of Pt/MgO-CeO₂ catalyst towards a new NO_x control technology in the low-temperature range of 100–200 °C using H₂ as reducing agent. Temperature-programmed desorption (TPD) of NO, and transient titration of the adsorbed surface intermediate NO_x species with H₂ experiments, following reaction, have revealed important information towards the understanding of basic mechanistic issues of the present catalytic system (e.g., surface coverage, number and location of active NO_x intermediate species, NO_x spillover).