Synthesis, structure, and stability of metal-organic frameworks

Metal-organic frameworks (MOFs) obtained much attention because of their unusual structures and properties as well as their potential applications. This dissertation research was focused on (1) the effects of synthesis conditions on the structures of MOFs, (2) the thermal stability of MOFs, (3) pressure-induced amorphization, and (4) the effect of high-valent ions on the structure of a MOF. This research demonstrated that the crystal structure of MOF-5 could be controlled by drying solvents. If the vacuum solvent is dimethylformamide (DMF), the crystal structure of MOF-5 is tetragonal. In contrast, if the DMF is displaced by CH2Cl2 before the vacuum, the obtained MOF-5 occupies a cubic structure. Furthermore, it was found that the tetragonal MOF-5 exhibited a mediate surface area (300-1000 m2/g). The surface area of tetragonal MOF-5 is also dependent on Zn(NO3)2/H2BDC (H2BDC: terephthalic acid) molar ratios used for its synthesis. The optimum ratio is 1.38, at which synthesized tetragonal MOF-5 exhibits the highest crystallinity and surface area (1297 m2/g). The thermal stability and decomposition of MOF-5 were systematically investigated. The thermal decomposition of cubic and tetragonal MOF-5s resulted in the same products: CO2, benzene, amorphous carbon, and crystal ZnO. The thermal decomposition is due to breaking carboxylic bridges between benzene rings and Zn4O clusters. Identifying structural relationships between crystalline and noncrystalline states is of fundamental interest in materials research. Currently, amorphization of solid materials at ambient temperature requires an ultra-high pressure (several GPa). However, this research demonstrated that MOF-5 and IRMOF-8 can be irreversibly amorphized at ambient temperature by employing a low compressing pressure of 3.5 MPa, which is 100 times lower than that required for amorphization of other solids. Furthermore, the pressure-induced amorphization (PIA) of MOFs is strongly dependent on the changeability of bond angles. If the geometric structure of a MOF can allow bond angles to be changed without breaking bonds, it can easily be amorphized by compression. This can explain why MOF-5 and IRMOF-8 can easily be amorphized via compression than Cu-BTC. It is generally recognized that zeolitic imidazolate frameworks (ZIFs) occupy much higher stability than other types of MOFs. The representative of ZIFs is Zn(2-methylimidazole)2 (ZIF-8) exhibiting high-decomposition temperature and high chemical resistance to various solvents. However, so far, it is still unknown whether the high stability of ZIF-8 can be challenged by ions, which is important for its modification by doping ions. In this research, we performed aqueous salt solution treatment on ZIF-8, and the results showed that anions (Cl¯ and NO3¯) in a solution exhibited no effect on the crystal structure of ZIF-8. However, the effect of cations (in a solution) on structure of ZIF-8 strongly depends on the cation valences. The univalent metal cations showed no effect on the structure of ZIF-8, whereas the bivalent or higher-valent metal cations caused the collapse of ZIF-8 crystal structure. Therefore, structure stability of ZIF-8 is considered when it is subjected to the application, in which high-valent metal cations are involved.

EXAMINING POLICY CAPACITY INITIATIVES WITHIN CLIMATE CHANGE FRAMEWORKS IN THREE US AND CANADIAN SECTORS USING NVIVO CONTENT ANALYSIS

The climate change narrative has changed from one of mitigation to one of adaptation. Governments around the world have created climate change frameworks which address how the country can better cope with the expected and unexpected changes due to global climate change. In an effort to do so, federal governments of Canada and the United States, as well as some provinces and states within these countries, have created detailed documents which outline what steps must be taken to adapt to these changes. However, not much is mentioned about how these steps will be translated in to policy, and how that policy will eventually be implemented. To examine the ability of governments to acknowledge and incorporate the plethora of scientific information to policy, consideration must be made for policy capacity. This report focuses on three sectors: water supply and demand; drought and flood planning; and forest and grassland ecosystems, and the word ‘capacity’ as related to nine different forms of policy capacity acknowledged in these frameworks. Qualitative content analysis using NVivo was carried out on fifty four frameworks and the results obtained show that there is a greater consideration for managerial capacity compared to analytical or political capacity. The data also indicated that although there were more Canadian frameworks which referred to policy capacity, the frameworks from the United States actually considered policy capacity to a greater degree.

Functionalized Adamantane Tectons Used in the Design of Mixed-Ligand Copper(II) 1,2,4-Triazolyl/Carboxylate Metal–Organic Frameworks

Bistriazoles, 1,3-bis(1,2,4-triazol-4-yl)propane (tr2pr) and 1,3-bis(1,2,4-triazol-4-yl)adamantane (tr2ad), were examined in combination with the rigid tetratopic 1,3,5,7-adamantanetetracarboxylic acid (H4-adtc) platform for the construction of neutral heteroleptic copper(II) metal−organic frameworks. Two coordination polymers, [{Cu4(OH)2(H2O)2}{Cu4(OH)2}(tr2pr)2(H-adtc)4]·2H2O (1) and [Cu4(OH)2(tr2ad)2(H-adtc)2(H2O)2]·3H2O (2), were synthesized and structurally characterized. In complexes 1 and 2, the N1,N2-1,2,4-triazolyl (tr) and μ3-OH− groups serve as complementary bridges between adjacent metal centers supporting the tetranuclear dihydroxo clusters. The structure of 1 represents a unique association of two different kinds of centrosymmetrical {Cu4(OH)2} units in a tight 3D framework, while in compound 2, another configuration type of acentric tetranuclear metal clusters is organized in a layered 3,6-hexagonal motif. In both cases, the {Cu4(OH)2} secondary building block and trideprotonated carboxylate H-adtc3− can be viewed as covalently bound six- and three-connected nodes that define the net topology. The tr ligands, showing μ3- or μ4-binding patterns, introduce additional integrating links between the neighboring {Cu4(OH)2} fragments. A variable-temperature magnetic susceptibility study of 2 demonstrates strong antiferromagnetic intracluster coupling (J1 = −109 cm−1 and J2 = −21 cm−1), which combines for the bulk phase with a weak antiferromagnetic intercluster interaction (zj = −2.5 cm−1).

Electron density building block approach for metal organic frameworks

A general introduction to the state of the art in modeling metal organic materials using transferable atomic multipoles is provided. The method is based on the building block partitioning of the electron density, which is illustrated with some examples of potential applications and with detailed discussions of the advantages and pitfalls. The interactions taking place between building blocks are summarized and are used to discuss the properties that can be calculated.

Cooperative Effects of Electron Donors and Acceptors for the Stabilization of Elusive Metal Cluster Frameworks: Synthesis and Solid-State Structures of Pt-19(CO)(24)(mu(4)-AuPPh3)(3)](-) and Pt-19(CO)(24){mu(4)-Au-2(PPh3)(2)}(2)]

The anionic cluster Pt-19(CO)(22)](4-) (1), of pentagonal symmetry, reacts with CO and AuPPh3+ fragments. Upon increasing the Au:Pt-19, molar ratio, different species are sequentially formed, but only the last two members of the series could be characterized by X-ray diffraction, namely, Pt-19(CO)(24)(mu(4)-AuPPh3)(3)](-) (2) and Pt-19(CO)(24){mu(4)-Au-2(PPh3)(2)}(2)] (3).The metallic framework of the starting cluster is completely modified after the addition of CO and AuL+, and both products display the same platinum core of trigonal symmetry, with closely packed metal atoms. The three AuL+ units cap three different square faces in 2, whereas four AuL+ fragments are grouped in two independent bimetallic units in the neutral cluster 3. Electrochemical and spectroelectrochemical studies on 2 showed that its redox ability is comparable with that of the homometallic 1.

Combining analytical frameworks to assess livelihood vulnerability to climate change and analyse adaptation options

Experts working on behalf of international development organisations need better tools to assist land managers in developing countriesmaintain their livelihoods, as climate change puts pressure on the ecosystemservices that they depend upon. However, current understanding of livelihood vulnerability to climate change is based on a fractured and disparate set of theories andmethods. This reviewtherefore combines theoretical insights from sustainable livelihoods analysis with other analytical frameworks (including the ecosystem services framework, diffusion theory, social learning, adaptive management and transitions management) to assess the vulnerability of rural livelihoods to climate change. This integrated analytical framework helps diagnose vulnerability to climate change,whilst identifying and comparing adaptation options that could reduce vulnerability, following four broad steps: i) determine likely level of exposure to climate change, and how climate change might interact with existing stresses and other future drivers of change; ii) determine the sensitivity of stocks of capital assets and flows of ecosystem services to climate change; iii) identify factors influencing decisions to develop and/or adopt different adaptation strategies, based on innovation or the use/substitution of existing assets; and iv) identify and evaluate potential trade-offs between adaptation options. The paper concludes by identifying interdisciplinary research needs for assessing the vulnerability of livelihoods to climate change.

New magnetic frameworks of [(CuF 2 (H 2 O) 2 ) x (pyz)]

Pressure-driven orbital reordering in the quantum magnet [CuF2(H2O)2- (pyz)], (pyz = pyrazine), dramatically affects its magnetic exchange interactions. The crystal chemistry of this system is enriched with a new phase above 3 GPa, surprisingly concomitant with other polymorphs. Moreover, we discovered an unprecedented compound with a different stoichiometry, [(CuF2(H2O)2)2(pyz)], featuring magnetic bi-layers.

Precision of fit of implant-supported screw-retained 10-unit computer-aided-designed and computer-aided-manufactured frameworks made from zirconium dioxide and titanium: an in vitro study

OBJECTIVE To analyze the precision of fit of implant-supported screw-retained computer-aided-designed and computer-aided-manufactured (CAD/CAM) zirconium dioxide (ZrO) frameworks. MATERIALS AND METHODS Computer-aided-designed and computer-aided-manufactured ZrO frameworks (NobelProcera) for a screw-retained 10-unit implant-supported reconstruction on six implants (FDI positions 15, 13, 11, 21, 23, 25) were fabricated using a laser (ZrO-L, N = 6) and a mechanical scanner (ZrO-M, N = 5) for digitizing the implant platform and the cuspid-supporting framework resin pattern. Laser-scanned CAD/CAM titanium (TIT-L, N = 6) and cast CoCrW-alloy frameworks (Cast, N = 5) fabricated on the same model and designed similar to the ZrO frameworks were the control. The one-screw test (implant 25 screw-retained) was applied to assess the vertical microgap between implant and framework platform with a scanning electron microscope. The mean microgap was calculated from approximal and buccal values. Statistical comparison was performed with non-parametric tests. RESULTS No statistically significant pairwise difference was observed between the relative effects of vertical microgap between ZrO-L (median 14 μm; 95% CI 10-26 μm), ZrO-M (18 μm; 12-27 μm) and TIT-L (15 μm; 6-18 μm), whereas the values of Cast (236 μm; 181-301 μm) were significantly higher (P < 0.001) than the three CAD/CAM groups. A monotonous trend of increasing values from implant 23 to 15 was observed in all groups (ZrO-L, ZrO-M and Cast P < 0.001, TIT-L P = 0.044). CONCLUSIONS Optical and tactile scanners with CAD/CAM technology allow for the fabrication of highly accurate long-span screw-retained ZrO implant-reconstructions. Titanium frameworks showed the most consistent precision. Fit of the cast alloy frameworks was clinically inacceptable.

International Frameworks for Disaster Risk Reduction: Useful Guidance for Sustainable Mountain Development?

In recent decades, a number of global frameworks have been developed for disaster risk reduction (DRR). The Hyogo Framework for Action 2005–2015 and its successor document, the Sendai Framework for Disaster Risk Reduction, adopted in Japan in March 2015, provide general guidance for reducing risks from natural hazards. This is particularly important for mountainous areas, but DRR for mountain areas and sustainable mountain development received little attention in the recent policy debate. The question remains whether the Hyogo and Sendai frameworks can provide guidance for sustainable mountain development. This article evaluates the 2 frameworks in light of the special challenges of DRR in mountain areas and argues that, while the frameworks offer valuable guidance, they need to be further adapted for local contexts—particularly for mountain areas, which require special attention because of changing risk patterns like the effects of climate change and high land-use pressure.

Evaluation and implementation of a hybrid cross-platform application combining mobile web-technologies and native device functions

Este Proyecto de Fin de Carrera presenta un prototipo de aplicación móvil híbrida multi-plataforma para Android y iOS. Las aplicaciones móviles híbridas son una combinación de aplicaciones web móviles y aplicaciones móviles nativas. Se desarrollan parcialmente con tecnologías web y pueden acceder a la capa nativa y sensores del teléfono. Para el usuario se presentan como aplicaciones nativas, ya que se pueden descargar de las tiendas de aplicaciones y son instaladas en el dispositivo. El prototipo consiste en la migración del módulo de noticias financieras de las aplicaciones actuales para móviles de una compañía bancaria reimplementándolo como aplicación híbrida utilizando uno de los entornos de desarrollo disponibles en el mercado para este propósito. El desarrollo de aplicaciones híbridas puede ahorrar tiempo y dinero cuando se pretende alcanzar más de una plataforma móvil. El objetivo es la evaluación de las ventajas e inconvenientes que ofrece el desarrollo de aplicaciones híbridas en términos de reducción de costes, tiempo de desarrollo y resultado final de la aplicación. El proyecto consta de varias fases. Durante la primera fase se realiza un estudio sobre las aplicaciones híbridas que podemos encontrar hoy en día en el mercado utilizando los ejemplos de linkedIn, Facebook y Financial times. Se hace hincapié en las tecnologías utilizadas, uso de la red móvil y problemas encontrados. Posteriormente se realiza una comparación de distintos entornos de desarrollo multi-plataforma para aplicaciones híbridas en términos de la estrategia utilizada, plataformas soportadas, lenguajes de programación, acceso a capacidades nativas de los dispositivos y licencias de uso. Esta primera fase da como resultado la elección del entorno de desarrollo más adecuado a las exigencias del proyecto, que es PhoneGap, y continua con un análisis más detallado de dicho entorno en cuanto a su arquitectura, características y componentes. La siguiente fase comienza con un estudio de las aplicaciones actuales de la compañía para extraer el código fuente necesario y adaptarlo a la arquitectura que tendrá la aplicación. Para la realización del prototipo se hace uso de la característica que ofrece PhoneGap para acceder a la capa nativa del dispositivo, esto es, el uso de plugins. Se diseña y desarrolla un plugin que permite acceder a la capa nativa para cada plataforma. Una vez desarrollado el prototipo para la plataforma Android, se migra y adapta para la plataforma iOS. Por último se hace una evaluación de los prototipos en cuanto a su facilidad y tiempo de desarrollo, rendimiento, funcionalidad y apariencia de la interfaz de usuario. ABSTRACT. This bachelor's thesis presents a prototype of a hybrid cross-platform mobile application for Android and iOS. Hybrid mobile applications are a combination of mobile web and mobile native applications. They are built partially with web technologies and they can also access native features and sensors of the device. For a user, they look like native applications as they are downloaded from the application stores and installed on the device. This prototype consists of the migration of the financial news module of current mobile applications from a financial bank reimplementing them as a hybrid application using one of the frameworks available in the market for that purpose. Development of applications on a hybrid way can help reducing costs and effort when targeting more than one platform. The target of the project is the evaluation of the advantages and disadvantages that hybrid development can offer in terms of reducing costs and efforts and the final result of the application. The project starts with an analysis of successfully released hybrid applications using the examples of linkedIn, Facebook and Financial Times, emphasizing the different used technologies, the transmitted network data and the encountered problems during the development. This analysis is followed by a comparison of most popular hybrid crossplatform development frameworks in terms of the different approaches, supported platforms, programming languages, access to native features and license. This first stage has the outcome of finding the development framework that best fits to the requirements of the project, that is PhoneGap, and continues with a deeper analysis of its architecture, features and components. Next stage analyzes current company's applications to extract the needed source code and adapt it to the architecture of the prototype. For the realization of the application, the feature that PhoneGap offers to access the native layer of the device is used. This feature is called plugin. A custom plugin is designed and developed to access the native layer of each targeted platform. Once the prototype is finished for Android, it is migrated and adapted to the iOS platform. As a final conclusion the prototypes are evaluated in terms of ease and time of development, performance, functionality and look and feel.

Spanish Nuclear Safety Research under International Frameworks

The Nuclear Safety research requires a wide international collaboration of several involved groups. In this sense this paper pretends to show several examples of the Nuclear Safety research under international frameworks that is being performed in different Universities and Research Institutions like CIEMAT, Universitat Politècnica de Catalunya (UPC), Universidad Politécnica de Madrid (UPM) and Universitat Politècnica de València (UPV).

Embedding logical frameworks in scala

El Framework Lógico de Edimburgo ha demostrado ser una poderosa herramienta en el estudio formal de sistemas deductivos, como por ejemplo lenguajes de programación. Sin embargo su principal implementación, el sistema Twelf, carece de expresividad, obligando al programador a escribir código repetitivo. Este proyecto presenta una manera alternativa de utilizar Twelf: a través de un EDSL (Lenguaje Embebido de Dominio Específico) en Scala que permite representar firmas del Framework Lógico, y apoyándonos en Twelf como backend para la verificación, abrimos la puerta a diversas posibilidades en términos de metaprogramación. El código fuente, así como instrucciones para instalar y configurar, está accesible en https://github.com/akathorn/elfcala. ---ABSTRACT---The Edinburgh Logical Framework has proven to be to be a powerful tool in the formal study of deductive systems, such as programming languages. However, its main implementation, the Twelf system, lacks expressiveness, requiring the programmer to write repetitive code. This project presents an alternative way of using Twelf: by providing a Scala EDSL (Embedded Domain Specific Language) that can encode Logical Framework signatures and relying on Twelf as a backend for the verification, we open the door to different possibilities in terms of metaprogramming. The source code, along with instructions to install and configure, is accessible at https://github.com/akathorn/elfcala