Development of Metal–Organic Frameworks for Catalysis : Designing Functional and Porous Crystals

Metal–organic frameworks, or MOFs, have emerged as a new class of porous materials made by linking metal and organic units. The easy preparation, structural and functional tunability, ultrahigh porosity, and enormous surface areas of MOFs have led to them becoming one of the fastest growing fields in chemistry. MOFs have potential applications in numerous areas such as clean energy, adsorption and separation processes, biomedicine, and sensing. One of the most promising areas of research with MOFs is heterogeneous catalysis. This thesis describes the design and synthesis of new, carboxylate-based MOFs for use as catalysts. These materials have been characterized using diffraction, spectroscopy, adsorption, and imaging techniques. The thesis has focused on preparing highly-stable MOFs for catalysis, using post-synthetic methods to modify the properties of these crystals, and applying a combination of characterization techniques to probe these complex materials. In the first part of this thesis, several new vanadium MOFs have been presented. The synthesis of MIL-88B(V), MIL-101(V), and MIL-47 were studied using ex situ techniques to gain insight into the synthesis–structure relationships. The properties of these materials have also been studied. In the second part, the use of MOFs as supports for metallic nanoparticles has been investigated. These materials, Pd@MIL-101–NH2(Cr) and Pd@MIL-88B–NH2(Cr), were used as catalysts for Suzuki–Miyaura and oxidation reactions, respectively. The effect of the base on the catalytic activity, crystallinity, porosity, and palladium distribution of Pd@MIL-101–NH2(Cr) was studied. In the final part, the introduction of transition-metal complexes into MOFs through different synthesis routes has been described. A ruthenium complex was grafted onto an aluminium MOF, MOF-253, and an iridium metallolinker was introduced into a zirconium MOF, UiO-68–2CH3. These materials were used as catalysts for alcohol oxidation and allylic alcohol isomerization, respectively.

Designing for User-facing Uncertainty in Everyday Sensing and Prediction

Thesis (Ph.D.)--University of Washington, 2016-07

Efficient Security and Privacy Enhancing Solutions in Untrusted Environments

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

Learning to Interpret and Generate Instructional Recipes

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

Extending the capabilities of smartphone sensors for applications in interaction and health

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

The Role of Art in Computer Game Design

Computer games are significant since they embody our youngsters’ engagement with contemporary culture, including both play and education. These games rely heavily on visuals, systems of sign and expression based on concepts and principles of Art and Architecture. We are researching a new genre of computer games, ‘Educational Immersive Environments’ (EIEs) to provide educational materials suitable for the school classroom. Close collaboration with subject teachers is necessary, but we feel a specific need to engage with the practicing artist, the art theoretician and historian. Our EIEs are loaded with multimedia (but especially visual) signs which act to direct the learner and provide the ‘game-play’ experience forming semiotic systems. We suggest the hypothesis that computer games are a space of deconstruction and reconstruction (DeRe): When players enter the game their physical world and their culture is torn apart; they move in a semiotic system which serves to reconstruct an alternate reality where disbelief is suspended. The semiotic system draws heavily on visuals which direct the players’ interactions and produce motivating gameplay. These can establish a reconstructed culture and emerging game narrative. We have recently tested our hypothesis and have used this in developing design principles for computer game designers. Yet there are outstanding issues concerning the nature of the visuals used in computer games, and so questions for contemporary artists. Currently, the computer game industry employs artists in a ‘classical’ role in production of concept sketches, storyboards and 3D content. But this is based on a specification from the client which restricts the artist in intellectual freedom. Our DeRe hypothesis places the artist at the generative centre, to inform the game designer how art may inform our DeRe semiotic spaces. This must of course begin with the artists’ understanding of DeRe in this time when our ‘identities are becoming increasingly fractured, networked, virtualized and distributed’ We hope to persuade artists to engage with the medium of computer game technology to explore these issues. In particular, we pose several questions to the artist: (i) How can particular ‘periods’ in art history be used to inform the design of computer games? (ii) How can specific artistic elements or devices be used to design ‘signs’ to guide the player through the game? (iii) How can visual material be integrated with other semiotic strata such as text and audio?

Unreal PowerPoint™: Immersing PowerPoint Presentations in a Virtual Computer Game Engine World

At a recent conference on games in education, we made a radical decision to transform our standard presentation of PowerPoint slides and computer game demonstrations into a unified whole, inserting the PowerPoint presentation to the computer game. This opened up various questions relating to learning and teaching theories, which were debated by the conference delegates. In this paper, we reflect on these discussions, we present our initial experiment, and relate this to various theories of learning and teaching. In particular, we consider the applicability of “concept maps” to inform the construction of educational materials, especially their topological, geometrical and pedagogical significance. We supplement this “spatial” dimension with a theory of the dynamic, temporal dimension, grounded in a context of learning processes, such as Kolb’s learning cycle. Finally, we address the multi-player aspects of computer games, and relate this to the theories of social and collaborative learning. This paper attempts to explore various theoretical bases, and so support the development of a new learning and teaching virtual reality approach.

Security through Obscurity: Layout Obfuscation of Digital Integrated Circuits using Don't Care Conditions

Contemporary integrated circuits are designed and manufactured in a globalized environment leading to concerns of piracy, overproduction and counterfeiting. One class of techniques to combat these threats is circuit obfuscation which seeks to modify the gate-level (or structural) description of a circuit without affecting its functionality in order to increase the complexity and cost of reverse engineering. Most of the existing circuit obfuscation methods are based on the insertion of additional logic (called “key gates”) or camouflaging existing gates in order to make it difficult for a malicious user to get the complete layout information without extensive computations to determine key-gate values. However, when the netlist or the circuit layout, although camouflaged, is available to the attacker, he/she can use advanced logic analysis and circuit simulation tools and Boolean SAT solvers to reveal the unknown gate-level information without exhaustively trying all the input vectors, thus bringing down the complexity of reverse engineering. To counter this problem, some ‘provably secure’ logic encryption algorithms that emphasize methodical selection of camouflaged gates have been proposed previously in literature [1,2,3]. The contribution of this paper is the creation and simulation of a new layout obfuscation method that uses don't care conditions. We also present proof-of-concept of a new functional or logic obfuscation technique that not only conceals, but modifies the circuit functionality in addition to the gate-level description, and can be implemented automatically during the design process. Our layout obfuscation technique utilizes don’t care conditions (namely, Observability and Satisfiability Don’t Cares) inherent in the circuit to camouflage selected gates and modify sub-circuit functionality while meeting the overall circuit specification. Here, camouflaging or obfuscating a gate means replacing the candidate gate by a 4X1 Multiplexer which can be configured to perform all possible 2-input/ 1-output functions as proposed by Bao et al. [4]. It is important to emphasize that our approach not only obfuscates but alters sub-circuit level functionality in an attempt to make IP piracy difficult. The choice of gates to obfuscate determines the effort required to reverse engineer or brute force the design. As such, we propose a method of camouflaged gate selection based on the intersection of output logic cones. By choosing these candidate gates methodically, the complexity of reverse engineering can be made exponential, thus making it computationally very expensive to determine the true circuit functionality. We propose several heuristic algorithms to maximize the RE complexity based on don’t care based obfuscation and methodical gate selection. Thus, the goal of protecting the design IP from malicious end-users is achieved. It also makes it significantly harder for rogue elements in the supply chain to use, copy or replicate the same design with a different logic. We analyze the reverse engineering complexity by applying our obfuscation algorithm on ISCAS-85 benchmarks. Our experimental results indicate that significant reverse engineering complexity can be achieved at minimal design overhead (average area overhead for the proposed layout obfuscation methods is 5.51% and average delay overhead is about 7.732%). We discuss the strengths and limitations of our approach and suggest directions that may lead to improved logic encryption algorithms in the future. References: [1] R. Chakraborty and S. Bhunia, “HARPOON: An Obfuscation-Based SoC Design Methodology for Hardware Protection,” IEEE Transactions on Computer-Aided Design of Integrated Circuits and Systems, vol. 28, no. 10, pp. 1493–1502, 2009. [2] J. A. Roy, F. Koushanfar, and I. L. Markov, “EPIC: Ending Piracy of Integrated Circuits,” in 2008 Design, Automation and Test in Europe, 2008, pp. 1069–1074. [3] J. Rajendran, M. Sam, O. Sinanoglu, and R. Karri, “Security Analysis of Integrated Circuit Camouflaging,” ACM Conference on Computer Communications and Security, 2013. [4] Bao Liu, Wang, B., "Embedded reconfigurable logic for ASIC design obfuscation against supply chain attacks,"Design, Automation and Test in Europe Conference and Exhibition (DATE), 2014 , vol., no., pp.1,6, 24-28 March 2014.

An SVM-Fuzzy system design for diabetes risk classification

Electronic Publishing -- a Journal and its Production

The use of the term "Electronic Publishing" transcends any notions of the paperless office and of a purely electronic transfer and dissemination of information over networks. It now encompasses all computer-assisted methods for the production of documents and includes the imaging of a document on paper as one of the options to be provided by an integrated processing scheme. Electronic publishing draws heavily on techniques from computer science and information technology but technical, legal, financial and organisational problems have to be overcome before it can replace traditional publication mechanisms. These problems are illustrated with reference to the publication arrangements for the journal `Electronic Publishing Origination, Dissemination and Design'. The authors of this paper are the co-editors of this journal, which appears in traditional form and relies on a wide variety of support from electronic technologies in the pre-publication phase.

An Adaptive and Hybrid Approach to Revisiting the Visibility Pipeline

We revisit the visibility problem, which is traditionally known in Computer Graphics and Vision fields as the process of computing a (potentially) visible set of primitives in the computational model of a scene. We propose a hybrid solution that uses a dry structure (in the sense of data reduction), a triangulation of the type , to accelerate the task of searching for visible primitives. We came up with a solution that is useful for real-time, on-line, interactive applications as 3D visualization. In such applications the main goal is to load the minimum amount of primitives from the scene during the rendering stage, as possible. For this purpose, our algorithm executes the culling by using a hybrid paradigm based on viewing-frustum, back-face culling and occlusion models. Results have shown substantial improvement over these traditional approaches if applied separately. This novel approach can be used in devices with no dedicated processors or with low processing power, as cell phones or embedded displays, or to visualize data through the Internet, as in virtual museums applications.

Dynamically balanced and plausible trajectory planning for human-like characters

International audience

Effects of Information and Time of Use Pricing on Irish Electricity Demand and Supply

In this dissertation I quantify residential behavior response to interventions designed to reduce electricity demand at different periods of the day. In the first chapter, I examine the effect of information provision coupled with bimonthly billing, monthly billing, and in-home displays, as well as a time-of-use (TOU) pricing scheme to measure consumption over each month of the Irish Consumer Behavior Trial. I find that time-of-use pricing with real time usage information reduces electricity usage up to 8.7 percent during peak times at the start of the trial but the effect decays over the first three months and after three months the in-home display group is indistinguishable from the monthly treatment group. Monthly and bi-monthly billing treatments are not found to be statistically different from another. These findings suggest that increasing billing reports to the monthly level may be more cost effective for electricity generators who wish to decrease expenses and consumption, rather than providing in-home displays. In the following chapter, I examine the response of residential households after exposure to time of use tariffs at different hours of the day. I find that these treatments reduce electricity consumption during peak hours by almost four percent, significantly lowering demand. Within the model, I find evidence of overall conservation in electricity used. In addition, weekday peak reductions appear to carry over to the weekend when peak pricing is not present, suggesting changes in consumer habit. The final chapter of my dissertation imposes a system wide time of use plan to analyze the potential reduction in carbon emissions from load shifting based on the Ireland and Northern Single Electricity Market. I find that CO2 emissions savings are highest during the winter months when load demand is highest and dirtier power plants are scheduled to meet peak demand. TOU pricing allows for shifting in usage from peak usage to off peak usage and this shift in load can be met with cleaner and cheaper generated electricity from imports, high efficiency gas units, and hydro units.

CAREGIVING FOR A FAMILY MEMBER WITH HEAD AND NECK CANCER

Objective: To know the perception of informal caregivers regarding the care for a family member with head and neck cancer. Methods: Qualitative study conducted between March and May 2014 in the radiotherapy outpatient center of the Centro de Alta Complexidade em Oncologia – CACON (Oncology High Complexity Center) of the Hospital Universitário de Brasília – HUB (University Hospital of Brasília) using semi-structured interviews with nine caregivers about the experience of caring for family members. Data underwent Content Analysis and four units of meaning were identified: “Representation of cancer in the Family”, “The care as debt, individual reward or reconstruction of family ties”, “Repercussions of cancer on the caregiver’s personal life” and “Social support and network used by caregivers”. Results: Feelings of sadness and surprise at the moment of diagnosis were attributed to cancer, as well as the idea of punishment. The care was seen as personal satisfaction, accomplishment and opportunity for family rapprochement. Work overload and change in routine were altered functions. Religiosity, exchange of experience in the waiting room and institutional support appeared as coping strategies. Conclusion: The experience of caring for family members with head and neck cancer directly interferes in the lives of caregivers. Pointing out the institutional embracement as a strategy within the social network reinforces the importance of integrating the caregivers as a significant part of the health care plan developed by the health team.

Fundamental Rights and Reverse Discrimination

Reverse discrimination – whereby member states may treat their own nationals worse than nationals of other member states by invoking a “purely internal situation” in which European law does not apply – has long been a problem within the European Economic Community turned European Union. Using as a touchstone the Zambrano case, to be decided shortly, this paper argues that introducing citizenship alters the status of individuals vis-à-vis their governments, implies equality of treatment among citizens, and should eliminate reverse discrimination. Raising examples from the United States and Canada, I show how the introduction of federal rights empowered individuals and redrew the relationship between the governments of the center and the units. Citizenship limits the power of member states to treat their own nationals worse than nationals of other member states. This does not eliminate the tension between center and unit (or federal and regional; EU and member state) law but should give extra weight to former over the latter. Jurisdictional issues remain, but the rise of Union citizenship means that EU law should grow to encompass any right protected or promoted by shared citizenship.