Radiative transfer of acoustic waves in continuous complex media: Beyond the Helmholtz equation

Heterogeneity can be accounted for by a random potential in the wave equation. For acoustic waves in a fluid with fluctuations of both density and compressibility (as well as for electromagnetic waves in a medium with fluctuation of both permittivity and permeability) the random potential entails a scalar and an operator contribution. For simplicity, the latter is usually overlooked in multiple scattering theory: whatever the type of waves, this simplification amounts to considering the Helmholtz equation with a sound speed $c$ depending on position $\mathbf{r}$. In this work, a radiative transfer equation is derived from the wave equation, in order to study energy transport through a multiple scattering medium. In particular, the influence of the operator term on various transport parameters is studied, based on the diagrammatic approach of multiple scattering. Analytical results are obtained for fundamental quantities of transport theory such as the transport mean-free path $\ell^*$, scattering phase function $f$ and anisotropy factor $g$. Discarding the operator term in the wave equation is shown to have a significant impact on $f$ and $g$, yet limited to the low-frequency regime i.e., when the correlation length of the disorder $\ell_c$ is smaller than or comparable to the wavelength $\lambda$. More surprisingly, discarding the operator part has a significant impact on the transport mean-free path $\ell^*$ whatever the frequency regime. When the scalar and operator terms have identical amplitudes, the discrepancy on the transport mean-free path is around $300\,\%$ in the low-frequency regime, and still above $30\,\%$ for $\ell_c/\lambda=10^3$ no matter how weak fluctuations of the disorder are. Analytical results are supported by numerical simulations of the wave equation and Monte Carlo simulations

Water Splitting Using Cobalt-Based Amidopyridine Complexes

As part of the ongoing search for clean energy sources, splitting water into oxygen and hydrogen has emerged as a promising source of alternative energy. We are interested in developing electrocatalysts capable of performing water reduction and water oxidation. In this dissertation, a variety of catalytic platforms based on an amidopyridine framework are studied. A novel monomeric cobalt complex in an amidopyridine ligand environment, ([CoIII(L1)(pyrr)2]PF6), was investigated for electrocatalytic water reduction and found to have an onset overpotential of 0.54 V and an observed TOF of 23 min-1. The catalytic decomposition pathway was explored with the aim of designing more stable catalysts. Following the initial design, we prepared a modified catalyst in which the amidopyridine framework is extended over a phenylene tetraamine bridge to yield [(CoIII)2L2(pyrr)4](PF6)2. The bimetallic cobalt complex showed significant improvement in catalytic activity: onset overpotential decreased to 0.45 V and the TOF was found to be 60 min-1 per cobalt center under identical catalytic conditions. To the best of our knowledge this is one of the first examples where a dimeric catalyst is more active than its monomeric counterpart. Moreover, we showed that the dimer operates using a voltage-dependent mechanism, in which side reactions associated with deactivation are avoided at low applied potentials. Finally, we demonstrate that we can drive water oxidation by modification of conductive carbon black-based supports with the hydrophobic octadecyloxy substituted catalyst in an N2N2’ environment, [CoIII(LOC18H37)(pyrr)2]ClO4. The prepared assemblies can catalyze water oxidation at an onset overpotential of 0.32 V, and reach a current density of 10 mA/cm2 at an overpotential of 0.37 V. The molecular nature of the catalyst was ascertained using XPS analysis. A DFT-supported mechanism suggests the ligand is heavily involved in catalysis as an electron reservoir. The work presented in this dissertation emphasizes the importance of taking into account ligand involvement while designing novel catalysts. In the case of water reduction, we showed that ligand involvement had deleterious effects on catalysis, however for water oxidation we showed that ligand involvement can lower the activation barrier needed for catalysis. Future work will focus on using these lessons to design more active catalysts

Learning probabilistic interaction models

We live in a multi-modal world; therefore it comes as no surprise that the human brain is tailored for the integration of multi-sensory input. Inspired by the human brain, the multi-sensory data is used in Artificial Intelligence (AI) for teaching different concepts to computers. Autonomous Agents (AAs) are AI systems that sense and act autonomously in complex dynamic environments. Such agents can build up Self-Awareness (SA) by describing their experiences through multi-sensorial information with appropriate models and correlating them incrementally with the currently perceived situation to continuously expand their knowledge. This thesis proposes methods to learn such awareness models for AAs. These models include SA and situational awareness models in order to perceive and understand itself (self variables) and its surrounding environment (external variables) at the same time. An agent is considered self-aware when it can dynamically observe and understand itself and its surrounding through different proprioceptive and exteroceptive sensors which facilitate learning and maintaining a contextual representation by processing the observed multi-sensorial data. We proposed a probabilistic framework for generative and descriptive dynamic models that can lead to a computationally efficient SA system. In general, generative models facilitate the prediction of future states while descriptive models enable to select the representation that best fits the current observation. The proposed framework employs a Probabilistic Graphical Models (PGMs) such as Dynamic Bayesian Networks (DBNs) that represent a set of variables and their conditional dependencies. Once we obtain this probabilistic representation, the latter allows the agent to model interactions between itself, as observed through proprioceptive sensors, and the environment, as observed through exteroceptive sensors. In order to develop an awareness system, not only an agent needs to recognize the normal states and perform predictions accordingly, but also it is necessary to detect the abnormal states with respect to its previously learned knowledge. Therefore, there is a need to measure anomalies or irregularities in an observed situation. In this case, the agent should be aware that an abnormality (i.e., a non-stationary condition) never experienced before, is currently present. Due to our specific way of representation, which makes it possible to model multi-sensorial data into a uniform interaction model, the proposed work not only improves predictions of future events but also can be potentially used to effectuate a transfer learning process where information related to the learned model can be moved and interpreted by another body

Cannabinoid signalling in TNF-alpha induced IL-8 release

Original article can be found at: http://www.sciencedirect.com/science/journal/00142999 Copyright Elsevier B.V. DOI : 10.1016/j.ejphar.2006.04.015Peer reviewe

An experimental investigation of adhesive wear extension in fretting interface: application of the contact oxygenation concept

This paper investigates the transition from abrasive to adhesive wear in gross-slip fretting assuming contact oxygenation concept which suggests that adhesion appears in the inner part of the interface if the di-oxygen partial pressure is below a threshold value. In the lateral sides, where di-oxygen molecules are sufficient, oxidation and abrasion prevail. To assess this phenomenon, 34NiCrMo16 flat-on-flat contacts are tested. Contact oxygenation is quantified using the ''oxygen-distance, '' parameter defined as the averaged width of the external abrasion corona. Confirming this concept, decreases with contact pressure and frequency but remains constant versus sliding amplitude, fretting cycles and contact area. evolution is formalized using a power law formulation which allowed predicting wear transitions for plain and macro-textured surfaces

Ultrasound Guided Placement of Single-Lumen Peripheral Intravenous Catheters in the Internal Jugular Vein

Introduction: The peripheral internal jugular (IJ), also called the “easy IJ,” is an alternative to peripheral venous access reserved for patients with difficult intravenous (IV) access. The procedure involves placing a single-lumen catheter in the IJ vein under ultrasound (US) guidance. As this technique is relatively new, the details regarding the ease of the procedure, how exactly it should be performed, and the safety of the procedure are uncertain. Our primary objective was to determine the success rate for peripheral IJ placement. Secondarily, we evaluated the time needed to complete the procedure and assessed for complications. Methods: This was a prospective, single-center study of US-guided peripheral IJ placement using a 2.5-inch, 18-gauge catheter on a convenience sample of patients with at least two unsuccessful attempts at peripheral IV placement by nursing staff. Peripheral IJ lines were placed by emergency medicine (EM) attending physicians and EM residents who had completed at least five IJ central lines. All physicians who placed lines for the study watched a 15-minute lecture about peripheral IJ technique. A research assistant monitored each line to assess for complications until the patient was discharged. Results: We successfully placed a peripheral IJ in 34 of 35 enrolled patients (97.1%). The median number of attempts required for successful cannulation was one (interquartile range (IQR): 1 to 2). The median time to successful line placement was 3 minutes and 6 seconds (IQR: 59 seconds to 4 minutes and 14 seconds). Two lines failed after placement, and one of the 34 successfully placed peripheral IJ lines (2.9%) had a complication – a local hematoma. There were, however, no arterial punctures or pneumothoraces. Although only eight of 34 lines were placed using sterile attire, there were no line infections. Conclusion: Our research adds to the growing body of evidence supporting US-guided peripheral internal jugular access as a safe and convenient procedure alternative for patients who have difficult IV access