Understanding knowledge coordination dynamics in traditional and fast-response IT organizations

This research takes a dynamic view on the knowledge coordination process, aiming to explain how the process is affected by changes in the operating environment, from normal situations to emergencies in traditional and fast-response organizations, and why these changes occur. We first conceptualize the knowledge coordination process by distinguishing between four dimensions - what, when, how and who - that together capture the full scope of the knowledge coordination process. We use these dimensions to analyze knowledge coordination practices and the activities constituting these practices, in the IT functions of traditional and fast-response (military) organizations where we distinguish between "normal" and "emergency" operating conditions. Our findings indicate that (i) inter-relationships between knowledge coordination practices change under different operating conditions, and (ii) the patterns of change are different in traditional and fast-response organizations.

Study of the physical properties of metals and oxides at extreme pressure and temperature conditions

The high-pressure and temperature investigations on transition metals, metal doped-oxide system, nanocrystalline materials are presented in this dissertation. The metal-doped oxide systems are technologically important because of their applications, e.g. LSC, opto electronic applications, luminescence from lasers, etc., and from the earth sciences point of view, e.g. the study of trace elements in the MgO-SiO2 system, which accounts for 50% of the Earth's chondritic model. We have carried out thorough investigations on Cr2O3 and on chromium bearing oxides at high PT-conditions using in situ X-ray diffractometry and florescence spectroscopy techniques. Having obtained exciting results, an attempt to focus on the mechanism of the coordination of transition metals in oxides has been made. Additionally, the florescence from the metals in host oxides was found to be helpful to obtain information on structural variations like changes in the coordination of the doped element, formation of new phases, the diffusion processes. The possible reactions taking place at extreme conditions in the MgO-SiO2 system has been observed using florescence as markers. A new heating assemblage has been designed and fabricated for a precise determination of temperature at high pressures. An equation combining pressure shifts of ruby wavelength and temperature has been proposed. We observed that the compressibility of nanocrystalline material (MgO and Ni) is independent of crystallite size. A reduction in the transition pressure of nanocrystalline ceria at high-pressure has been observed as compare to the corresponding bulk material. ^

Echinometra sea urchins acclimatised to elevated pCO2 at volcanic vents outperform those under present-day pCO2 conditions

Rising atmospheric CO2 concentrations will significantly reduce ocean pH during the 21st century (ocean acidification, OA). This may hamper calcification in marine organisms such as corals and echinoderms, as shown in many laboratory-based experiments. Sea urchins are considered highly vulnerable to OA. We studied an Echinometra species on natural volcanic CO2 vents in Papua New Guinea, where they are CO2-acclimatized and also subjected to secondary ecological changes from elevated CO2. Near the vent site, the urchins experienced large daily variations in pH (> 1 unit) and pCO2 (> 2000 ppm) and average pH values (pHT 7.73) much below those expected under the most pessimistic future emission scenarios. Growth was measured over a 17-month period using tetracycline tagging of the calcareous feeding lanterns. Average-sized urchins grew more than twice as fast at the vent compared with those at an adjacent control site, and assumed larger sizes at the vent compared to the control site and two other sites at another reef near-by. A small reduction in gonad weight was detected at the vents, but no differences in mortality, respiration, or degree of test calcification were detected between urchins from vent and control populations. Thus, urchins did not only persist but actually 'thrived' under extreme CO2 conditions. We suggest an ecological basis for this response: increased algal productivity under increased pCO2 provided more food at the vent, resulting in higher growth rates. The wider implication of our observation is that laboratory studies on non-acclimatized specimens, which typically do not consider ecological changes, can lead to erroneous conclusions on responses to global change.

Direct linkage between dimethyl sulfide production and microzooplankton grazing, resulting from prey composition change under high partial pressure of carbon dioxide conditions

Oceanic dimethyl sulfide (DMS) is the enzymatic cleavage product of the algal metabolite dimethylsulfoniopropionate (DMSP) and is the most abundant form of sulfur released into the atmosphere. To investigate the effects of two emerging environmental threats (ocean acidification and warming) on marine DMS production, we performed a large-scale perturbation experiment in a coastal environment. At both ambient temperature and 2 °C warmer, an increase in partial pressure of carbon dioxide (pCO2) in seawater (160-830 ppmv pCO2) favored the growth of large diatoms, which outcompeted other phytoplankton species in a natural phytoplankton assemblage and reduced the growth rate of smaller, DMSP-rich phototrophic dinoflagellates. This decreased the grazing rate of heterotrophic dinoflagellates (ubiquitous micrograzers), resulting in reduced DMS production via grazing activity. Both the magnitude and sign of the effect of pCO2 on possible future oceanic DMS production were strongly linked to pCO2-induced alterations to the phytoplankton community and the cellular DMSP content of the dominant species and its association with micrograzers.

Ocean acidification slows nitrogen fixation and growth in the dominant diazotroph Trichodesmium under low-iron conditions

Dissolution of anthropogenic CO(2) increases the partial pressure of CO(2) (pCO(2)) and decreases the pH of seawater. The rate of Fe uptake by the dominant N(2)-fixing cyanobacterium Trichodesmium declines as pH decreases in metal-buffered medium. The slower Fe-uptake rate at low pH results from changes in Fe chemistry and not from a physiological response of the organism. Contrary to previous observations in nutrient-replete media, increasing pCO(2)/decreasing pH causes a decrease in the rates of N(2) fixation and growth in Trichodesmium under low-Fe conditions. This result was obtained even though the bioavailability of Fe was maintained at a constant level by increasing the total Fe concentration at low pH. Short-term experiments in which pCO(2) and pH were varied independently showed that the decrease in N(2) fixation is caused by decreasing pH rather than by increasing pCO(2) and corresponds to a lower efficiency of the nitrogenase enzyme. To compensate partially for the loss of N(2) fixation efficiency at low pH, Trichodesmium synthesizes additional nitrogenase. This increase comes partly at the cost of down-regulation of Fe-containing photosynthetic proteins. Our results show that although increasing pCO(2) often is beneficial to photosynthetic marine organisms, the concurrent decreasing pH can affect primary producers negatively. Such negative effects can occur both through chemical mechanisms, such as the bioavailability of key nutrients like Fe, and through biological mechanisms, as shown by the decrease in N(2) fixation in Fe-limited Trichodesmium.

Seawater carbonate chemistry and conditions of Mytilus edulis extracellular body fluids and shell composition in a pH-treatment experiment: Acid-base status, trace elements and delta11B, 2012

Mytilus edulis were cultured for 3 months under six different seawater pCO2 levels ranging from 380 to 4000 µatm. Specimen were taken from Kiel Fjord (Western Baltic Sea, Germany) which is a habitat with high and variable seawater pCO2 and related shifts in carbonate system speciation (e.g., low pH and low CaCO3 saturation state). Hemolymph (HL) and extrapallial fluid (EPF) samples were analyzed for pH and total dissolved inorganic carbon (CT) to calculate pCO2 and [HCO3]. A second experiment was conducted for 2 months with three different pCO2 levels (380, 1400 and 4000 µatm). Boron isotopes (delta11B) were investigated by LA-MC-ICP-MS (Laser Ablation-Multicollector-Inductively Coupled Plasma-Mass Spectrometry) in shell portions precipitated during experimental treatment time. Additionally, elemental ratios (B/Ca, Mg/Ca and Sr/Ca) in the EPF of specimen from the second experiment were measured via ICP-OES (Inductively Coupled Plasma-Optical Emission Spectrometry). Extracellular pH was not significantly different in HL and EPF but systematically lower than ambient water pH. This is due to high extracellular pCO2 values, a prerequisite for metabolic CO2 excretion. No accumulation of extracellular [HCO3] was measured. Elemental ratios (B/Ca, Mg/Ca and Sr/Ca) in the EPF increased slightly with pH which is in accordance with increasing growth and calcification rates at higher seawater pH values. Boron isotope ratios were highly variable between different individuals but also within single shells. This corresponds to a high individual variability in fluid B/Ca ratios and may be due to high boron concentrations in the organic parts of the shell. The mean delta11B value shows no trend with pH but appears to represent internal pH (EPF) rather than ambient water pH.

Coordination of phosphido-boratabenzene ligands to transition metals

Environ 90% des composés produits industriellement sont fabriqués à l’aide de catalyseurs. C’est pourquoi la conception de catalyseurs toujours plus performants pour améliorer les procédés industriels actuels est toujours d’intérêt. De la grande variété de complexes avec des métaux de transition rapportés jusqu’à présent, les complexes zwitterioniques attirent notre attention par leurs activités catalytiques souvent supérieures aux complexes cationiques normaux. Un complexe métallique zwitterionique est un fragment métal-ligand neutre où la charge positive est située sur le centre métallique et où la charge négative est délocalisée sur un des ligands liés au métal. Nous proposons la synthèse de ligands anioniques phosphine comportant des groupements borates et boratabenzènes. Cette dernière espèce est un cycle à 6 membres où l’un des atomes de carbone est remplacé par un atome de bore et qui est négativement chargé. La capacité de ces phosphines anioniques à se lier à un centre métallique à l’aide de la paire libre du phosphore est due à la nature du lien P-B qui défavorise l’interaction entre la paire libre du phosphore et l’orbitale p vide du bore. Les propriétés de di-tert-butylphosphido-boratabenzène (DTBB) comme ligand phosphine anionique hautement donneur et encombré ainsi que la découverte de ses modes de coordination inhabituels pour stabiliser les métaux de transition insaturés ont été étudiés au cours de ce travail. De nouvelles perspectives sur les modes de coordination de phosphido-boratabenzène et la force de l’interaction du lien P-B seront discutées ainsi que les applications catalytiques. Nous avons d’abord étudié la coordination η1 avec des complexes de fer, ce qui nous a fourni des données quantitatives précieuses sur la capacité du DTBB d’agir comme ligand très donneur par rapport aux autres ligands donneurs bien connus. La capacité du DTBB à changer de mode de coordination pour soutenir les besoins électroniques du métal a été démontrée par la découverte d’une nouvelle espèce ferrocenyl phosphido-boratabenzène et sa nucléophilie a été étudiée. Au meilleur de notre connaissance, aucun exemple d’un ligand boratabenzène coordonné aux métaux du groupe 11 n’existe dans la littérature. Voilà pourquoi nous avons décidé d’explorer les modes de coordination du ligand DTBB avec Cu(I), Ag(I) et Au(I). A notre grande surprise, le ligand DTBB est capable de stabiliser les métaux du groupe 11 aux états d’oxydation faibles par une liaison MP qui est une coordination du type η1, un mode de coordination guère observé pour les ligands boratabenzène. Pendant nos travaux, notre attention s’est tournée vers la synthèse d’un complexe de rhodium(I) afin de tester son utilité en catalyse. A notre grande satisfaction, le complexe Rh-DTBB agit comme un précatalyseur pour l’hydrogénation des alcènes et alcynes à la température ambiante et à pression atmosphérique et son activité est comparable à celle du catalyseur de Wilkinson. Dans un désir d’élargir les applications de notre recherche, notre attention se tourna vers l’utilisation des composés du bore autres que le boratabenzène. Nous avons décidé de synthétiser une nouvelle espèce phosphido-borate encombrée. Lorsqu’elle réagit avec des métaux, l’espèce phosphido-borate subit un clivage de la liaison P-B. Toutefois, cette observation met en évidence la singularité et les avantages de la stabilité de la liaison P-B lors de l’utilisation du fragment boratabenzène. Ces observations enrichissent notre compréhension des conditions dans lesquelles la liaison P-B du ligand DTBB peut être clivée. Ces travaux ont mené à la découverte d’un nouveau ligand ansa-boratabenzène avec une chimie de coordination prometteuse.

Production planning, pricing and market coordination for news vendor problem with price dependent demand

Thesis (Ph.D.)--University of Washington, 2016-08

Exploring coordination-driven self-assembly with autonomous chemical robots

The work presented herein focused on the automation of coordination-driven self assembly, exploring methods that allow syntheses to be followed more closely while forming new ligands, as part of the fundamental study of the digitization of chemical synthesis and discovery. Whilst the control and understanding of the principle of pre-organization and self-sorting under non-equilibrium conditions remains a key goal, a clear gap has been identified in the absence of approaches that can permit fast screening and real-time observation of the reaction process under different conditions. A firm emphasis was thus placed on the realization of an autonomous chemical robot, which can not only monitor and manipulate coordination chemistry in real-time, but can also allow the exploration of a large chemical parameter space defined by the ligand building blocks and the metal to coordinate. The self-assembly of imine ligands with copper and nickel cations has been studied in a multi-step approach using a self-built flow system capable of automatically controlling the liquid-handling and collecting data in real-time using a benchtop MS and NMR spectrometer. This study led to the identification of a transient Cu(I) species in situ which allows for the formation of dimeric and trimeric carbonato bridged Cu(II) assemblies. Furthermore, new Ni(II) complexes and more remarkably also a new binuclear Cu(I) complex, which usually requires long and laborious inert conditions, could be isolated. The study was then expanded to the autonomous optimization of the ligand synthesis by enabling feedback control on the chemical system via benchtop NMR. The synthesis of new polydentate ligands has emerged as a result of the study aiming to enhance the complexity of the chemical system to accelerate the discovery of new complexes. This type of ligand consists of 1-pyridinyl-4-imino-1,2,3-triazole units, which can coordinate with different metal salts. The studies to test for the CuAAC synthesis via microwave lead to the discovery of four new Cu complexes, one of them being a coordination polymer obtained from a solvent dependent crystallization technique. With the goal of easier integration into an automated system, copper tubing has been exploited as the chemical reactor for the synthesis of this ligand, as it efficiently enhances the rate of the triazole formation and consequently promotes the formation of the full ligand in high yields within two hours. Lastly, the digitization of coordination-driven self-assembly has been realized for the first time using an in-house autonomous chemical robot, herein named the ‘Finder’. The chemical parameter space to explore was defined by the selection of six variables, which consist of the ligand precursors necessary to form complex ligands (aldehydes, alkineamines and azides), of the metal salt solutions and of other reaction parameters – duration, temperature and reagent volumes. The platform was assembled using rounded bottom flasks, flow syringe pumps, copper tubing, as an active reactor, and in-line analytics – a pH meter probe, a UV-vis flow cell and a benchtop MS. The control over the system was then obtained with an algorithm capable of autonomously focusing the experiments on the most reactive region (by avoiding areas of low interest) of the chemical parameter space to explore. This study led to interesting observations, such as metal exchange phenomena, and also to the autonomous discovery of self assembled structures in solution and solid state – such as 1-pyridinyl-4-imino-1,2,3-triazole based Fe complexes and two helicates based on the same ligand coordination motif.

Distance and overcurrent relay coordination considering non standardized inverse time curves

Protective relaying comprehends several procedures and techniques focused on maintaining the power system working safely during and after undesired and abnormal network conditions, mostly caused by faulty events. Overcurrent relay is one of the oldest protective relays, its operation principle is straightforward: when the measured current is greater than a specified magnitude the protection trips; less variables are required from the system in comparison with other protections, causing the overcurrent relay to be the simplest and also the most difficult protection to coordinate; its simplicity is reflected in low implementation, operation, and maintenance cost. The counterpart consists in the increased tripping times offered by this kind of relays mostly before faults located far from their location; this problem can be particularly accentuated when standardized inverse-time curves are used or when only maximum faults are considered to carry out relay coordination. These limitations have caused overcurrent relay to be slowly relegated and replaced by more sophisticated protection principles, it is still widely applied in subtransmission, distribution, and industrial systems. In this work, the use of non standardized inverse-time curves, the model and implementation of optimization algorithms capable to carry out the coordination process, the use of different levels of short circuit currents, and the inclusion of distance relays to replace insensitive overcurrent ones are proposed methodologies focused on the overcurrent relay performance improvement. These techniques may transform the typical overcurrent relay into a more sophisticated one without changing its fundamental principles and advantages. Consequently a more secure and still economical alternative can be obtained, increasing its implementation area

Ammonia effects on proton conductivity properties of coordination polymers

Crystalline metal phosphonates are referred to as a type of structurally versatile coordination polymers [1]. Many of them contain guest molecules (H2O, heterocyclics, etc.), acidic sites and, furthermore, their structure can be also amenable for post‐synthesis modifications in order to enhance desired properties [2]. In the present work, we examine the relationships between crystal structure and proton conductivity for several metal phosphonates derive from multifunctional ligands, such as 5-(dihydroxyphosphoryl)isophthalic acid (PiPhtA) [3] and 2-hydroxyphosphonoacetic acid (H3HPAA). Crystalline divalent metal derivatives show a great structural diversity, from 1D to 3D open-frameworks, possessing hydrogen-bonded water molecules and acid groups. These solids present a proton conductivity range between 7.2·10-6 and 1.3·10−3 S·cm-1. Upon exposure to ammonia vapor, from an aqueous solution, solid state transformations are observed accompanied of enhance proton conductivities. The stability of these solids under different environment conditions (temperature and relative humidities) as well as the influence of the ammonia adsorption on the proton conduction properties of the resulting solids will be discussed.

Managing dynamic security networks: towards the strategic managing of cooperation, coordination and collaboration

Security networks are increasing in number and in importance across the security field as a means of providing inter-agency coordination. On the basis of a detailed qualitative study of networks in the field of national security in Australia, this article aims to advance our knowledge of the internal properties of security networks and conditions shaping their performance. It places ‘cooperation’, ‘coordination’ and ‘collaboration’ on a continuum, with cooperation at one end and collaboration at the other end, and aims to illustrate how each of these ‘Cs’ shape the performance of security networks. The central argument is that the performance of security networks increases as the network moves from cooperation to collaboration. Drawing on interviews with senior members of security, law enforcement and intelligence agencies, the article aims to highlight the lessons for how to strategically manage security networks in ways that promote collaboration.

Training a system-literate care coordination workforce.

People with chronic complex conditions continue to experience increasing health system fragmentation and poor coordination. To reverse these trends, one solution has been an investment in effective models of care coordination that use a care coordinator workforce. Care coordinators are not a homogenous workforce - but an applied professional role, providing direct and indirect care, and is often undertaken by nurses, allied health professionals, social workers or general practitioners. In Australia, there is no training curriculum nor courses, nor nationally recognised professional quality standards for the care coordinator workforce. With the growing complexity and fragmentation of the health care system, health system literacy - shared understanding of the roles and contributions of the different workforce professions, organisations and systems, among patients and indeed the health workforce is required. Efforts to improve health system literacy among the health workforce are increasing at a policy, practice and research level. However, insufficient evidence exists about what are the health system literacy needs of care coordinators, and what is required for them to be most effective. Key areas to build a health system literate care coordination workforce are presented. Care coordination is more than an optional extra, but one of the only ways we are going to be able to provide equitable health services for people with chronic complex conditions. People with low health literacy require more support with the coordination of their care, therefore we need to build a high performing care coordinator workforce that upholds professional quality standards, and is health literacy responsive.