Design for Survival: Sustainability for Planet and Structure

Buildings in Port Aransas encounter drastic environmental challenges: the potential catastrophic storm surge and high winds from a hurricane, and daily conditions hostile to buildings, vehicles, and even most vegetation. Its location a few hundred feet from the Gulf of Mexico and near-tropical latitude expose buildings to continuous high humidity, winds laden with scouring sand and corrosive salt, and extremes of temperature and ultraviolet light. Building construction methods are able to address each of these, but doing so in a sustainable way creates significant challenges. The new research building at the Marine Science Institute has been designed and is being constructed to meet the demand for both survivability and sustainability. It is tracking towards formal certification as a LEED Gold structure while being robust and resistant to the harsh coastal environment. The effects of a hurricane are mitigated by elevating buildings and providing a windproof envelope. Ground-level enclosures are designed to be sacrificial and non-structural so they can wash or blow away without imposing damage on the upper portions of the building, and only non-critical functions and equipment will be supported within them. Design features that integrate survivability with sustainability include: orientation of building axis; integral shading from direct summer sunlight; light wells; photovoltaic arrays; collection of rainwater and air conditioning condensate for use in landscape irrigation; reduced impervious cover; xeriscaping and indigenous plants; recycling of waste heat from air conditioning systems; roofing system that reflects light and heat; long life, low maintenance stainless steel, high-tensile vinyl, hard-anodized aluminum and hot-dipped galvanized mountings throughout; chloride-resistant concrete; reduced visual impact; recycling of construction materials.

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.

Design, Synthesis, and Study of Novel Platforms for Iron-N2 Chemistry and Photoinduced, Copper-mediated C-N Bond Formation

Several new ligand platforms designed to support iron dinitrogen chemistry have been developed. First, we report Fe complexes of a tris(phosphino)alkyl (CP^iPr₃) ligand featuring an axial carbon donor intended to conceptually model the interstitial carbide atom of the nitrogenase iron-molybdenum cofactor (FeMoco). It is established that in this scaffold, the iron center binds dinitrogen trans to the C_alkyl anchor in three structurally characterized oxidation states. Fe-C_alkyl lengthening is observed upon reduction, reflective of significant ionic character in the Fe-C_alkyl interaction. The anionic (CP^iPr₃)FeN₂^- species can be functionalized by a silyl electrophile to generate (CP^iPr₃)Fe-N₂SiR₃. This species also functions as a modest catalyst for the reduction of N₂ to NH₃. Next, we introduce a new binucleating ligand scaffold that supports an Fe(μ-SAr)Fe diiron subunit that coordinates dinitrogen (N₂-Fe(μ-SAr)Fe-N₂) across at least three oxidation states (Fe^IIFe^II, Fe^IIFe^I, and Fe^IFe^I). Despite the sulfur-rich coordination environment of iron in FeMoco, synthetic examples of transition metal model complexes that bind N₂ and also feature sulfur donor ligands remain scarce; these complexes thus represent an unusual series of low-valent diiron complexes featuring thiolate and dinitrogen ligands. The (N₂-Fe(μ-SAr)Fe-N₂) system undergoes reduction of the bound N₂ to produce NH₃ (~50% yield) and can efficiently catalyze the disproportionation of N₂H₄ to NH₃ and N₂. The present scaffold also supports dinitrogen binding concomitant with hydride as a co-ligand. Next, inspired by the importance of secondary-sphere interactions in many metalloenzymes, we present complexes of iron in two new ligand scaffolds ([SiP^NMe₃] and [SiP^iPr₂P^NMe]) that incorporate hydrogen-bond acceptors (tertiary amines) which engage in interactions with nitrogenous substrates bound to the iron center (NH₃ and N₂H₄). Cation binding is also facilitated in anionic Fe(0)-N₂ complexes. While Fe-N₂ complexes of a related ligand ([SiP^iPr₃]) lacking hydrogen-bond acceptors produce a substantial amount of ammonia when treated with acid and reductant, the presence of the pendant amines instead facilitates the formation of metal hydride species.

Additionally, we present the development and mechanistic study of copper-mediated and copper-catalyzed photoinduced C-N bond forming reactions. Irradiation of a copper-amido complex, ((m-tol)₃P)₂Cu(carbazolide), in the presence of aryl halides furnishes N-phenylcarbazole under mild conditions. The mechanism likely proceeds via single-electron transfer from an excited state of the copper complex to the aryl halide, generating an aryl radical. An array of experimental data are consistent with a radical intermediate, including a cyclization/stereochemical investigation and a reactivity study, providing the first substantial experimental support for the viability of a radical pathway for Ullmann C-N bond formation. The copper complex can also be used as a precatalyst for Ullmann C-N couplings. We also disclose further study of catalytic C_alkyl-N couplings using a CuI precatalyst, and discuss the likely role of [Cu(carbazolide)₂]^- and [Cu(carbazolide)₃]^- species as intermediates in these reactions.

Finally, we report a series of four-coordinate, pseudotetrahedral P₃Fe^II-X complexes supported by tris(phosphine)borate ([PhBP₃Fe^R]^-) and phosphiniminato X-type ligands (-N=PR'₃) that in combination tune the spin-crossover behavior of the system. Low-coordinate transition metal complexes such as these that undergo reversible spin-crossover remain rare, and the spin equilibria of these systems have been studied in detail by a suite of spectroscopic techniques.

Distributed Optimal Control of Cyber-Physical Systems: Controller Synthesis, Architecture Design and System Identification

The centralized paradigm of a single controller and a single plant upon which modern control theory is built is no longer applicable to modern cyber-physical systems of interest, such as the power-grid, software defined networks or automated highways systems, as these are all large-scale and spatially distributed. Both the scale and the distributed nature of these systems has motivated the decentralization of control schemes into local sub-controllers that measure, exchange and act on locally available subsets of the globally available system information. This decentralization of control logic leads to different decision makers acting on asymmetric information sets, introduces the need for coordination between them, and perhaps not surprisingly makes the resulting optimal control problem much harder to solve. In fact, shortly after such questions were posed, it was realized that seemingly simple decentralized optimal control problems are computationally intractable to solve, with the Wistenhausen counterexample being a famous instance of this phenomenon. Spurred on by this perhaps discouraging result, a concerted 40 year effort to identify tractable classes of distributed optimal control problems culminated in the notion of quadratic invariance, which loosely states that if sub-controllers can exchange information with each other at least as quickly as the effect of their control actions propagates through the plant, then the resulting distributed optimal control problem admits a convex formulation.

The identification of quadratic invariance as an appropriate means of "convexifying" distributed optimal control problems led to a renewed enthusiasm in the controller synthesis community, resulting in a rich set of results over the past decade. The contributions of this thesis can be seen as being a part of this broader family of results, with a particular focus on closing the gap between theory and practice by relaxing or removing assumptions made in the traditional distributed optimal control framework. Our contributions are to the foundational theory of distributed optimal control, and fall under three broad categories, namely controller synthesis, architecture design and system identification.

We begin by providing two novel controller synthesis algorithms. The first is a solution to the distributed H-infinity optimal control problem subject to delay constraints, and provides the only known exact characterization of delay-constrained distributed controllers satisfying an H-infinity norm bound. The second is an explicit dynamic programming solution to a two player LQR state-feedback problem with varying delays. Accommodating varying delays represents an important first step in combining distributed optimal control theory with the area of Networked Control Systems that considers lossy channels in the feedback loop. Our next set of results are concerned with controller architecture design. When designing controllers for large-scale systems, the architectural aspects of the controller such as the placement of actuators, sensors, and the communication links between them can no longer be taken as given -- indeed the task of designing this architecture is now as important as the design of the control laws themselves. To address this task, we formulate the Regularization for Design (RFD) framework, which is a unifying computationally tractable approach, based on the model matching framework and atomic norm regularization, for the simultaneous co-design of a structured optimal controller and the architecture needed to implement it. Our final result is a contribution to distributed system identification. Traditional system identification techniques such as subspace identification are not computationally scalable, and destroy rather than leverage any a priori information about the system's interconnection structure. We argue that in the context of system identification, an essential building block of any scalable algorithm is the ability to estimate local dynamics within a large interconnected system. To that end we propose a promising heuristic for identifying the dynamics of a subsystem that is still connected to a large system. We exploit the fact that the transfer function of the local dynamics is low-order, but full-rank, while the transfer function of the global dynamics is high-order, but low-rank, to formulate this separation task as a nuclear norm minimization problem. Finally, we conclude with a brief discussion of future research directions, with a particular emphasis on how to incorporate the results of this thesis, and those of optimal control theory in general, into a broader theory of dynamics, control and optimization in layered architectures.

Workshop on turtle bycatch mitigation for longline fisheries: experimental design and data analysis, 7-8 November 2007, San Ramón de Alajuela, Costa Rica

Large numbers of fishing vessels operating from ports in Latin America participate in surface longline fisheries in the eastern Pacific Ocean (EPO), and several species of sea turtles inhabit the grounds where these fleets operate. The endangered status of several sea turtle species, and the success of circle hooks (‘treatment’ hooks) in reducing turtle hookings in other ocean areas, as compared to J-hooks and Japanese-style tuna hooks (‘control’ hooks), prompted the initiation of a hook exchange program on the west coast of Latin America, the Eastern Pacific Regional Sea Turtle Program (EPRSTP)1. One of the goals of the EPRSTP is to determine if circle hooks would be effective at reducing turtle bycatch in artisanal fisheries of the EPO without significantly reducing the catch of marketable fish species. Participating fishers were provided with circle hooks at no cost and asked to replace the J/Japanese-style tuna hooks on their longlines with circle hooks in an alternating manner. Data collected by the EPRSTP show differences in longline gear and operational characteristics within and among countries. These aspects of the data, in addition to difficulties encountered with implementation of the alternating-hook design, pose challenges for analysis of these data.

Design and implementation of fishery modules in integrated household surveys in developing countries

Fish and other aquatic animals contribute to the food security of citizens of developing countries, both as a source of income and as a component of healthy diets, yet fishing is not currently captured in most integrated household surveys. This sourcebook provides essential technical guidance on the design of statistical modules and questionnaires aimed at collecting fishery data at the household level. Background on the main policies important to the fishery sector, information on the data needed to analyze issues of policy relevance, and methodology on the construction of survey questions to collect necessary data are also provided. The document is organized to provide essential technical guidance on how to design statistical modules and questionnaires aimed at collecting fishery data at the household level. It includes an overview of the main technical and statistical challenges related to sampling fishery-dependent households. The document starts with an introductory section identifying the potential reasons why fisheries and in particular small-scale fisheries have not been adequately included in national statistical systems in a large number of countries. The report then proposes a succinct review of what is known (and what remains unknown) about small-scale fisheries and their contribution to the livelihoods of households in sub-Saharan Africa. It also provides readers with background on the main policies that are important to the fishery sector, information on the data needed to analyze issues of policy relevance, and methodology on the construction of survey questions to collect necessary data.

Zooplankton population periodicity in a tropical pond

Results of a study on periodicity of zooplankton in small tropical pond are presented. This study was conducted in order to facilitate the design of a pond-based zooplankton production system.

Can the age of the tropical species be determined by otolith measurement?: a study using Pristipomoides filamentosus (Pisces: Lutjanidae) from the Mahe Plateau, Seychelles

The sagittal otoliths of bluespot jobfish (Pristipomoides flamentosus) from the Mahe Plateau, Seychelles, were examined for growth rings using light microscopy. Banding with putative annual and monthly frequency were observed. Consistent age estimates were derived from each of the two patterns. The resulting length-at-age data were use t estimate the parameters K and t sub(0), viz: K=0.33, t sub(0) = 0.16 for males and K = 0.36, t sub(0) = 0.06 for females (using von Bertalanffy plots). Possible causes of the banding are discussed.

Temporal Changes in a Tropical Nekton Assemblage and Performance of a Prawn Selective Gear

The temporal variation of components of a moderately diverse (H=1.46) tropical estuarine fish assemblage (long. 146°30'E, lat. 8°45'S) was directed by salinities that had been determined by local oceanographic and probably topographic conditions. For this assemblage, two types of intrayear component profiles are predicted. Pooled data (1988-91) reveal a large component of regular/resident species (43%) in an assemblage which has been under a narrow temperature regime «5T). These results facilitate a discussion on the relevance and usefulness of three hypotheses often cited in studies concerning species diversity and component characteristics of the subtropical/tropical coastal nonreef fish assemblages. Manifestations of the assemblage are reflected in catch composition and weights of 39 trials conducted for a selective prawning gear whose performance in bycatch reduction, mainly for finfishes, is judged by an index, E, we have previously proposed. This gear is capable of harvesting the prawn while conserving the demersal fish. Behavioral responses to netting of the prawns and the finfishes, especially the nearshore surface schoolers such as leiognathids, are discussed from several points of view. An adaptation in terms of group selection for leiognathids of their locking mechanism of median fin spines has been interpreted. For the purpose of bycatch reduction or E enhancement, suggestions for improvements in net design and trawl configuration by considering the behavioral features of fish are made. Our original formula of E is modified for general use. Bycatch problems in the regional prawn fisheries and their possible impacts on fishery planning and development in Papua New Guinea as a developing country are discussed. The gear tested may offer enormous ecological and economic benefits. The gear is multipurpose, extremely simple, and can also be used as a biological sampler.

Environmental inventory and the distribution of inorganic nutrients in a tropical estuary of the south-west coast of India

Dissolved nutrients (PO sub(4)-P, NO sub(3)-N, NO sub(2)-N and SiO sub(4)-Si) estimated in the surface and bottom waters of five selected stations of the Paravur Lake, Kerala, India, during February 1987 to January 1988 revealed distinct seasonal variations. Rainfall and land drainage play significant roles in the nutrient economy, particularly NO sub(3)-N and SiO sub(4)-Si, of this water body. Abnormally high values of PO sub(4)-P indicated extremely polluted condition at the wetting zone of the lake during the premonsoon season. SiO sub(4)-Si showed significant negative relationship with salinity.

Mercury toxicity in two intertidal tropical marine molluscs

Lethal and sub-lethal effects of mercury have been studied in Perna viridis and Modiolus carvalhoi. For P. viridis LC30 is 1.0 p.p.m. at 48 h and 0.23 p.p.m. at 96 h. Recorded LC50 values for M. carvalhoi are 0.5 p.p.m. and 0.19 p.p.m. at 48 h and 96 h respectively. The results document that these two species, although inhabiting the same area in the tidal belt, exhibit clear differences in mercury resistance. It is further shown that the duration of exposure affects mortality rates. In sub-lethal concentration, between 0.01 and 0.10 p.p.m. decrease in pedal-gland activity is conspicuous in P. viridis. At concentrations much below LC50 values (at 96 h), although some animals are alive, pedal-gland activity is totally suspended, supporting the assumption that shell closure ability plays a minor role in byssus thread production. In M. carvalhoi total cessation of pedal gland activity occurred at 0.09 p.p.m. of mercury.

Theoretical study of line narrowing in a sub-terahertz monolithic dual laser source with an integrated reflector

A monolithic design is proposed for low-noise sub-THz signal generation by integrating a reflector onto a dual laser source. The reflectivity and the position of such a reflector can be adjusted to obtain constructive feedback from the reflector to both lasers, thus causing a Vernier feedback effect. As a result, 10-fold line narrowing, the narrowing being limited by the resolution of the simulation, is predicted using a transmission line model. Finally, a simple control scheme using an electrical feedback loop to adjust laser biases is proposed to maintain the line narrowing performance. This line narrowing technique, comprising a passive integrated reflector, could allow the development of a low-cost, compact and energy-efficient solution for high-purity sub-THz signal generation. © The Institution of Engineering and Technology 2014.

Design, simulation and testing of large area silicon drift detectors and detector array for X-ray spectroscopy

Large area (25 mm(2)) silicon drift detectors and detector arrays (5x5) have been designed, simulated, and fabricated for X-ray spectroscopy. On the anode side, the hexagonal drift detector was designed with self-biasing spiral cathode rings (p(+)) of fixed resistance between rings and with a grounded guard anode to separate surface current from the anode current. Two designs have been used for the P-side: symmetric self-biasing spiral cathode rings (p(+)) and a uniform backside p(+) implant. Only 3 to 5 electrodes are needed to bias the detector plus an anode for signal collection. With graded electrical potential, a sub-nanoamper anode current, and a very small anode capacitance, an initial FWHM of 1.3 keV, without optimization of all parameters, has been obtained for 5.9 keV Fe-55 X-ray at RT using a uniform backside detector.

Design considerations for a silicon-based p-i-n phase modulator in a double ridge waveguide with side isolating grooves

We present detail design considerations and simulation results of a forward biased carrier injection p-i-n modulator integrated on SOI rib waveguides. To minimize the free carrier absorption loss while keeping the comparatively small lateral dimensions of the modulator as required for high speed operation, we proposed two structural improvements, namely the double ridge (terrace ridge) structure and the isolating grooves at both sides of the double ridge. With improved carrier injection and optical confinement structure, the simulated modulator response time is in sub-ns range and absorption loss is minimized.