Advancements in jet turbulence and noise modeling: accurate one-way solutions and empirical evaluation of the nonlinear forcing of wavepackets

Jet noise reduction is an important goal within both commercial and military aviation. Although large-scale numerical simulations are now able to simultaneously compute turbulent jets and their radiated sound, lost-cost, physically-motivated models are needed to guide noise-reduction efforts. A particularly promising modeling approach centers around certain large-scale coherent structures, called wavepackets, that are observed in jets and their radiated sound. The typical approach to modeling wavepackets is to approximate them as linear modal solutions of the Euler or Navier-Stokes equations linearized about the long-time mean of the turbulent flow field. The near-field wavepackets obtained from these models show compelling agreement with those educed from experimental and simulation data for both subsonic and supersonic jets, but the acoustic radiation is severely under-predicted in the subsonic case. This thesis contributes to two aspects of these models. First, two new solution methods are developed that can be used to efficiently compute wavepackets and their acoustic radiation, reducing the computational cost of the model by more than an order of magnitude. The new techniques are spatial integration methods and constitute a well-posed, convergent alternative to the frequently used parabolized stability equations. Using concepts related to well-posed boundary conditions, the methods are formulated for general hyperbolic equations and thus have potential applications in many fields of physics and engineering. Second, the nonlinear and stochastic forcing of wavepackets is investigated with the goal of identifying and characterizing the missing dynamics responsible for the under-prediction of acoustic radiation by linear wavepacket models for subsonic jets. Specifically, we use ensembles of large-eddy-simulation flow and force data along with two data decomposition techniques to educe the actual nonlinear forcing experienced by wavepackets in a Mach 0.9 turbulent jet. Modes with high energy are extracted using proper orthogonal decomposition, while high gain modes are identified using a novel technique called empirical resolvent-mode decomposition. In contrast to the flow and acoustic fields, the forcing field is characterized by a lack of energetic coherent structures. Furthermore, the structures that do exist are largely uncorrelated with the acoustic field. Instead, the forces that most efficiently excite an acoustic response appear to take the form of random turbulent fluctuations, implying that direct feedback from nonlinear interactions amongst wavepackets is not an essential noise source mechanism. This suggests that the essential ingredients of sound generation in high Reynolds number jets are contained within the linearized Navier-Stokes operator rather than in the nonlinear forcing terms, a conclusion that has important implications for jet noise modeling.

The Design and Synthesis of Transition Metal Complexes Supported by Non-innocent Ligand Scaffolds for Small Molecule Activation

This dissertation focuses on the incorporation of non-innocent or multifunctional moieties into different ligand scaffolds to support one or multiple metal centers in close proximity. Chapter 2 focuses on the initial efforts to synthesize hetero- or homometallic tri- or dinuclear metal carbonyl complexes supported by para-terphenyl diphosphine ligands. A series of [M₂M’(CO)₄]-type clusters (M = Ni, Pd; M’ = Fe, Co) could be accessed and used to relate the metal composition to the properties of the complexes. During these studies it was also found that non-innocent behavior was observed in dinuclear Fe complexes that result from changes in oxidation state of the cluster. These studies led to efforts to rationally incorporate central arene moieties capable managing both protons and electrons during small molecule activation.

Chapter 3 discusses the synthesis of metal complexes supported by a novel para-terphenyl diphosphine ligand containing a non-innocent 1,4-hydroquinone moiety as the central arene. A Pd⁰-hydroquinone complex was found to mediate the activation of a variety of small molecules to form the corresponding Pd⁰-quinone complexes in a formal two proton ⁄ two electron transformation. Mechanistic investigations of dioxygen activation revealed a metal-first activation process followed by subsequent proton and electron transfer from the ligand. These studies revealed the capacity of the central arene substituent to serve as a reservoir for a formal equivalent of dihydrogen, although the stability of the M-quinone compounds prevented access to the PdII-quinone oxidation state, thus hindering of small molecule transformations requiring more than two electrons per equivalent of metal complex.

Chapter 4 discusses the synthesis of metal complexes supported by a ligand containing a 3,5-substituted pyridine moiety as the linker separating the phenylene phosphine donors. Nickel and palladium complexes supported by this ligand were found to tolerate a wide variety of pyridine nitrogen-coordinated electrophiles which were found to alter central pyridine electronics, and therefore metal-pyridine π-system interactions, substantially. Furthermore, nickel complexes supported by this ligand were found to activate H-B and H-Si bonds and formally hydroborate and hydrosilylate the central pyridine ring. These systems highlight the potential use of pyridine π-system-coordinated metal complexes to reversibly store reducing equivalents within the ligand framework in a manner akin to the previously discussed 1,4-hydroquinone diphosphine ligand scaffold.

Chapter 5 departs from the phosphine-based chemistry and instead focuses on the incorporation of hydrogen bonding networks into the secondary coordination sphere of [Fe₄(μ₄-O)]-type clusters supported by various pyrazolate ligands. The aim of this project is to stabilize reactive oxygenic species, such as oxos, to study their spectroscopy and reactivity in the context of complicated multimetallic clusters. Herein is reported this synthesis and electrochemical and Mössbauer characterization of a series of chloride clusters have been synthesized using parent pyrazolate and a 3-aminophenyl substituted pyrazolate ligand. Efforts to rationally access hydroxo and oxo clusters from these chloride precursors represents ongoing work that will continue in the group.

Appendix A discusses attempts to access [Fe₃Ni]-type clusters as models of the enzymatic active site of [NiFe] carbon monoxide dehydrogenase. Efforts to construct tetranuclear clusters with an interstitial sulfide proved unsuccessful, although a (μ₃-S) ligand could be installed through non-oxidative routes into triiron clusters. While [Fe₃Ni(μ₄-O)]-type clusters could be assembled, accessing an open heterobimetallic edge site proved challenging, thus prohibiting efforts to study chemical transformations, such as hydroxide attack onto carbon monoxide or carbon dioxide coordination, relevant to the native enzyme. Appendix B discusses the attempts to synthesize models of the full H-cluster of [FeFe]-hydrogenase using a bioinorganic approach. A synthetic peptide containing three cysteine donors was successfully synthesized and found to chelate a preformed synthetic [Fe₄S₄] cluster. However, efforts to incorporate the diiron subsite model complex proved challenging as the planned thioester exchange reaction was found to non-selectively acetylate the peptide backbone, thus preventing the construction of the full six-iron cluster.

Estimation of catalyst activity profiles and deactivation parameters from reactor operating data with applications to naphtha reforming

Techniques are developed for estimating activity profiles in fixed bed reactors and catalyst deactivation parameters from operating reactor data. These techniques are applicable, in general, to most industrial catalytic processes. The catalytic reforming of naphthas is taken as a broad example to illustrate the estimation schemes and to signify the physical meaning of the kinetic parameters of the estimation equations. The work is described in two parts. Part I deals with the modeling of kinetic rate expressions and the derivation of the working equations for estimation. Part II concentrates on developing various estimation techniques.

Part I: The reactions used to describe naphtha reforming are dehydrogenation and dehydroisomerization of cycloparaffins; isomerization, dehydrocyclization and hydrocracking of paraffins; and the catalyst deactivation reactions, namely coking on alumina sites and sintering of platinum crystallites. The rate expressions for the above reactions are formulated, and the effects of transport limitations on the overall reaction rates are discussed in the appendices. Moreover, various types of interaction between the metallic and acidic active centers of reforming catalysts are discussed as characterizing the different types of reforming reactions.

Part II: In catalytic reactor operation, the activity distribution along the reactor determines the kinetics of the main reaction and is needed for predicting the effect of changes in the feed state and the operating conditions on the reactor output. In the case of a monofunctional catalyst and of bifunctional catalysts in limiting conditions, the cumulative activity is sufficient for predicting steady reactor output. The estimation of this cumulative activity can be carried out easily from measurements at the reactor exit. For a general bifunctional catalytic system, the detailed activity distribution is needed for describing the reactor operation, and some approximation must be made to obtain practicable estimation schemes. This is accomplished by parametrization techniques using measurements at a few points along the reactor. Such parametrization techniques are illustrated numerically with a simplified model of naphtha reforming.

To determine long term catalyst utilization and regeneration policies, it is necessary to estimate catalyst deactivation parameters from the the current operating data. For a first order deactivation model with a monofunctional catalyst or with a bifunctional catalyst in special limiting circumstances, analytical techniques are presented to transform the partial differential equations to ordinary differential equations which admit more feasible estimation schemes. Numerical examples include the catalytic oxidation of butene to butadiene and a simplified model of naphtha reforming. For a general bifunctional system or in the case of a monofunctional catalyst subject to general power law deactivation, the estimation can only be accomplished approximately. The basic feature of an appropriate estimation scheme involves approximating the activity profile by certain polynomials and then estimating the deactivation parameters from the integrated form of the deactivation equation by regression techniques. Different bifunctional systems must be treated by different estimation algorithms, which are illustrated by several cases of naphtha reforming with different feed or catalyst composition.

Gerenciamento de resíduos químicos em ambientes hospitalares: necessidades e dificuldades - estudo de caso: Hospital Universitário Federal localizado no Estado do Rio de Janeiro.

O tema do presente estudo é o gerenciamento de resíduos químicos em ambientes hospitalares. Os resíduos químicos são gerados nas atividades auxiliares dos estabelecimentos prestadores de serviços de saúde, tais como hospitais, laboratórios, serviços de diagnóstico e tratamento, centros de saúde, clínicas, institutos de medicina legal e outros. Dentre todos, os hospitais, por suas características de atendimento, são, sem dúvida, os maiores geradores deste tipo de resíduo. Controlar e diminuir os riscos inerentes a este tipo de resíduos, além de ser uma exigência legal, passa a ser uma necessidade ambiental e um desafio a ser enfrentado pelos administradores de estabelecimentos assistenciais à saúde. O objetivo geral desta pesquisa passa então por avaliar o gerenciamento dos resíduos químicos gerados nos hospitais públicos da região metropolitana do Estado do Rio de Janeiro, abordando às necessidades e dificuldades enfrentadas por estes geradores que incluí aspectos políticos, administrativos, econômicos e em alguns casos físico-estruturais. Para atingir tal objetivo o método empregado foi dividido em duas etapas: I) Pesquisa Aplicada, onde foram visitados alguns hospitais públicos do Estado e utilizou-se um questionário para avaliar as questões relacionadas com o gerenciamento de resíduos químicos e II) Estudo de Caso, onde se considerou, através de observações e entrevistas, o gerenciamento de resíduos químicos de um hospital universitário de grande porte de maneira efetiva. Foram utilizadas como fontes secundárias informações obtidas em seminários relacionados ao tema, reportagens de jornais e entrevistas publicadas em fontes especializadas. Os resultados obtidos mostram que as dificuldades enfrentadas no gerenciamento de RSS, inclusos neste grupo os resíduos químicos, é uma realidade para a maioria dos hospitais da rede pública. Conclusão: o maior problema a ser enfrentado por estas instituições está diretamente ligado à conscientização, ou melhor, a falta de conscientização, de funcionários, médicos e gerência dos hospitais, quanto à importância da correta segregação, armazenagem e manuseio destes resíduos. Além disso, a falta de recursos financeiros e, em alguns casos, até de espaço físico também dificulta o efetivo gerenciamento deste tipo de resíduos. Problemas secundários relacionam-se com a falta de fiscalização dos órgãos sanitário-ambientais competentes e o descaso da própria população que não atenta para os problemas ambientais e de saúde e segurança, decorrentes de um incorreto gerenciamento não só dos resíduos químicos, mas de todos os resíduos de serviço de saúde. Como recomendação, pode-se dizer que se faz necessária uma maior mobilização por parte dos estabelecimentos hospitalares para a discussão e atendimento das legislações aplicáveis e também, o desenvolvimento de uma estrutura gerencial com responsabilidades definidas e ações planejadas, compatíveis com a realidade do serviço público, e que possam levar a alcançar os objetivos e metas de um gerenciamento dos resíduos de serviço de saúde.

Biomolecule storage on non-modified thermoplastic microfluidic chip by ink-jet printing of ionogels

[EN] This paper reports an innovative technique for reagents storage in microfluidic devices by means of a one-step UV-photoprintable ionogel-based microarray on non-modified polymeric substrates. Although the ionogel and the ink-jet printing technology are well published, this is the first study where both are used for long-term reagent storage in lab-on-a-chip devices. This technology for reagent storage is perfectly compatible with mass production fabrication processes since pre-treatment of the device substrate is not necessary and inkjet printing allows for an efficient reagent deposition process. The functionality of this microarray is demonstrated by testing the release of biotin-647 after being stored for 1 month at room temperature. Analysis of the fluorescence of the ionogel-based microarray that contains biotin-647 demonstrated that 90% of the biotin-647 present was released from the ionogel-based microarray after pumping PBS 0.1% Tween at 37 °C. Moreover, the activity of biotin-647 after being released from the ionogel-based microarray was investigated trough the binding capability of this biotin to a microcontact printed chip surface with avidin. These findings pave the way for a novel, one-step, cheap and mass production on-chip reagents storage method applicable to other reagents such as antibodies and proteins and enzymes.

Uptake and intracytoplasmic storage of pigmented particles by human CD34+stromal cells/telocytes: endocytic property of telocytes

We studied the phagocytic-like capacity of human CD34+ stromal cells/telocytes (TCs). For this, we examined segments of the colon after injection of India ink to help surgeons localize lesions identified at endoscopy. Our results demonstrate that CD34+ TCs have endocytic properties (phagocytic-like TCs: phTCs), with the capacity to uptake and store India ink particles. phTCs conserve the characteristics of TCs (long, thin, bipolar or multipolar, moniliform cytoplasmic processes/telopodes, with linear distribution of the pigment) and maintain their typical distribution. Likewise, they are easily distinguished from pigment-loaded macrophages (CD68+ macrophages, with oval morphology and coarse granules of pigment clustered in their cytoplasm). A few c-kit/CD117+ interstitial cells of Cajal also incorporate pigment and may conserve the phagocytic-like property of their probable TC precursors. CD34+ stromal cells in other locations (skin and periodontal tissues) also have the phagocytic-like capacity to uptake and store pigments (hemosiderin, some components of dental amalgam and melanin). This suggests a function of TCs in general, which may be related to the transfer of macromolecules in these cells. Our ultrastructural observation of melanin-storing stromal cells with characteristics of TCs (telopodes with dichotomous branching pattern) favours this possibility. In conclusion, intestinal TCs have a phagocytic-like property, a function that may be generalized to TCs in other locations. This function (the ability to internalize small particles), together with the capacity of these cells to release extracellular vesicles with macromolecules, could close the cellular bidirectional cooperative circle of informative exchange and intercellular interactions.

The E2F2 Transcription Factor Sustains Hepatic Glycerophospholipid Homeostasis in Mice

Increasing evidence links metabolic signals to cell proliferation, but the molecular wiring that connects the two core machineries remains largely unknown. E2Fs are master regulators of cellular proliferation. We have recently shown that E2F2 activity facilitates the completion of liver regeneration after partial hepatectomy (PH) by regulating the expression of genes required for S-phase entry. Our study also revealed that E2F2 determines the duration of hepatectomy-induced hepatic steatosis. A transcriptomic analysis of normal adult liver identified "lipid metabolism regulation" as a major E2F2 functional target, suggesting that E2F2 has a role in lipid homeostasis. Here we use wild-type (E2F2(+/+)) and E2F2 deficient (E2F2(-/-)) mice to investigate the in vivo role of E2F2 in the composition of liver lipids and fatty acids in two metabolically different contexts: quiescence and 48-h post-PH, when cellular proliferation and anabolic demands are maximal. We show that liver regeneration is accompanied by large triglyceride and protein increases without changes in total phospholipids both in E2F2(+/+) and E2F2(-/-) mice. Remarkably, we found that the phenotype of quiescent liver tissue from E2F2(-/-) mice resembles the phenotype of proliferating E2F2(+/+) liver tissue, characterized by a decreased phosphatidylcholine to phosphatidylethanolamine ratio and a reprogramming of genes involved in generation of choline and ethanolamine derivatives. The diversity of fatty acids in total lipid, triglycerides and phospholipids was essentially preserved on E2F2 loss both in proliferating and non-proliferating liver tissue, although notable exceptions in inflammation-related fatty acids of defined phospholipid classes were detected. Overall, our results indicate that E2F2 activity sustains the hepatic homeostasis of major membrane glycerolipid components while it is dispensable for storage glycerolipid balance.

Dynamic storage performance of two cyanine dye films and optimization design for a recordable compact disk

The optical constants of two cyanine dye films that we prepared were measured with a RAP-1-type (RAP is rotating analyzer and polarizer) spectroscopic ellipsometer. Toward making a simplified model for the wafers of a recordable compact disk (CD-R), we give their optimization designs developed with the cyanine dye films. in addition, the dynamic storage performances of two sample disks were tested by our dynamic storage testing system. Measurement results of the sample disks were obtained to test and verify our film designs. (C) 2000 Optical Society of America. OCIS codes: 160.4890, 160.4760, 210.4810.

Optical setup and analysis of disk-type photopolymer high-density holographic storage

A relatively simple scheme for disk-type photopolymer high-density holographic storage based on angular and spatial multiplexing is described. The effects of the optical setup on the recording capacity and density are studied. Calculations and analysis show that this scheme is more effective than a scheme based on the spatioangular multiplexing for disk-type photopolymer high-density holographic storage, which has a limited medium thickness. Also an optimal beam recording angle exists to achieve maximum recording capacity and density. (C) 2002 Society of Photo-Optical Instrumentation Engineers.

New approach for improving transverse superresolution in optical data storage

We have proposed a new confocal readout system which is based on the combination of two N-zone circular phase-only transverse superresolving pupils to improve transverse superresolution. The procedure for designing such an improved system is presented. Results of comparisons between the performance of the proposed system and the transverse superresolving pupils indicate that with the same Strehl ratio the former has much higher transverse superresolution capacity and significantly lower sidelobe intensity. (c) 2005 Society of Photo-Optical Instrumentation Engineers.

Simulation of an apodizer's effect for high-density optical storage

The effect of an apodizer with two parallel taper refractive surfaces is theoretically investigated for high-density optical storage. The apodizer may modulate an incident Gaussian beam into an annular beam. Simulation shows that with the increasing inner radius of the modulated beam, the focal spot shrinks obviously. The depolarization effect gets strong simultaneously, which induces the circular symmetry loss of the focal spot. In this process, pattern density of the orthogonal and longitudinal diffractive fields increases remarkably.

New approach for improving transverse superresolution in optical data storage

We have proposed a new confocal readout system which is based on the combination of two N-zone circular phase-only transverse superresolving pupils to improve transverse superresolution. The procedure for designing such an improved system is presented. Results of comparisons between the performance of the proposed system and the transverse superresolving pupils indicate that with the same Strehl ratio the former has much higher transverse superresolution capacity and significantly lower sidelobe intensity. (c) 2005 Society of Photo-Optical Instrumentation Engineers.

Design and construction of a static tester for blue ray optical storage

Blue ray optical storage is one of the important trends in the area of information storage, and attracts a number of researchers. Static tester for blue ray optical storage plays an important role in storage media research. We designed and constructed a static tester, in which modularization makes it very convenient to expand function. Employment of modulation/demodulation technique weakens test error so as to increase test precision. Focus move mode and the nano-positioners facilitate the relocation of recording marks. Only one laser with wavelength 406.7 nm is used. In this paper, system design and characteristics are represented in detail, and some experimental results are also given to show that the static tester can perform successfully, acting as research platform for blue ray optical storage. (c) 2005 Elsevier GmbH. All rights reserved.

Riboflavin sensitized photopolymer materials for holographic storage

Riboflavin is employed as the photosensitizer of a novel photopolyrner material for holographic recording, This material has a broad absorption spectrum range (More than 200nm) due to the addition of this dye. The experimental results show that our material has high diffraction efficiency and large refractive index modulation. The maximum diffraction efficiency of the photopolymer is about 56%. The digital data pages are stored in this medium and the reconstructed data page has a good fidelity, with the bit-error-ratio of about 1.8 X 10(-4). it is found that the photopolymer material is suitable for high-density volume holographic digital storage.

Design of super-resolution filters with a Gaussian beam in optical data storage systems

Super-resolution filters based on a Gaussian beam are proposed to reduce the focusing spot in optical data storage systems. Both of amplitude filters and pure-phase filters are designed respectively to gain the desired intensity distributions. Their performances are analysed and compared with those based on plane wave in detail. The energy utilizations are presented. The simulation results show that our designed super-resolution filters are favourable for use in optical data storage systems in terms of performance and energy utilization.