Synthesis, structure and magnetic properties of cobalt(II) and copper(II) coordination polymers assembled by phthalate and 4-methylimidazole

New coordination polymers [M(Pht)(4-MeIm)2(H2O)]n (M=Co (1), Cu (2); Pht2−=dianion of o-phthalic acid; 4-MeIm=4-methylimidazole) have been synthesized and characterized by IR spectroscopy, X-ray crystallography, thermogravimetric analysis and magnetic measurements. The crystal structures of 1 and 2 are isostructural and consist of [M(4-MeIm)2(H2O)] building units linked in infinite 1D helical chains by 1,6-bridging phthalate ions which also act as chelating ligands through two O atoms from one carboxylate group in the case of 1. In complex 1, each Co(II) atom adopts a distorted octahedral N2O4 geometry being coordinated by two N atoms from two 4-MeIm, three O atoms of two phthalate residues and one O atom of a water molecule, whereas the square-pyramidal N2O3 coordination of the Cu(II) atom in 2 includes two N atoms of N-containing ligands, two O atoms of two carboxylate groups from different Pht, and a water molecule. An additional strong O–H⋯O hydrogen bond between a carboxylate group of the phthalate ligand and a coordinated water molecule join the 1D helical chains to form a 2D network in both compounds. The thermal dependences of the magnetic susceptibilities of the polymeric helical Co(II) chain compound 1 were simulated within the temperature range 20–300 K as a single ion case, whereas for the Cu(II) compound 2, the simulations between 25 and 300 K, were made for a linear chain using the Bonner–Fisher approximation. Modelling the experimental data of compound 1 with MAGPACK resulted in: g=2.6, |D|=62 cm−1. Calculations using the Bonner–Fisher approximation gave the following result for compound 2: g=2.18, J=–0.4 cm−1.

Nickel(II)-, cobalt(II)-, copper(II)-, and zinc(II)-phthalate and 1-methylimidazole coordination compounds: synthesis, crystal structures and magnetic properties

Three new coordination polymers [M(Pht)(1-MeIm)2]n (where M=Cu (1), Zn (2), Co (3); Pht2−=dianion of o-phthalic acid; 1-MeIm=1-methylimidazole) and two compounds [M(1-MeIm)6](HPht)2 · 2H2O (M=Co (4), Ni (5)) have been synthesized and characterized by X-ray crystallography. The structures of 1–3 (2 is isostructural to 3) consist of [M(1-MeIm)2] building units connected by 1,6-bridging phthalate ions to form infinite chains. In complex 1, each copper(II) center adopts a square coordination mode of N2O2 type by two O atoms from different phthalate ions and two N atoms of 1-MeIm, whereas in 3 two independent metal atoms are tetrahedrally (N2O2) coordinated to a pair of Pht ligands and a pair of 1-MeIm molecules. There are only van der Waals interactions between the chains in 1, while the three-dimensional network in 3 is assembled by C–H⋯O contacts. In contrast to polymers 1–3 the structures of 4 and 5 (complexes are also isostructural) are made up of the [M(1-MeIm)6]2+ cation, two hydrogen phthalate anions (HPht−) and two H2O solvate molecules. The coordination around each metal(II) atom is octahedral with six nitrogen atoms of 1-MeIm. Extended hydrogen bonding networks embracing the solvate water molecules and a phthalate residue as well as the weak C–H⋯O interactions stabilize the three-dimensional structures. Magnetic studies clearly show that the magnetic ions do not interact with each other. Furthermore, in compound 4 we have another example of a highly anisotropic Co2+ ion with a rhombic g-tensor and large zero-field-splitting. The complexes were also characterized by IR and 1H NMR spectroscopy, thermogravimetric analysis, and all data are discussed in the terms of known structures.

Content-Aware Delivery of Scalable Video in Network Coding Enabled Named Data Networks

In this work, we propose a novel network coding enabled NDN architecture for the delivery of scalable video. Our scheme utilizes network coding in order to address the problem that arises in the original NDN protocol, where optimal use of the bandwidth and caching resources necessitates the coordination of the forwarding decisions. To optimize the performance of the proposed network coding based NDN protocol and render it appropriate for transmission of scalable video, we devise a novel rate allocation algorithm that decides on the optimal rates of Interest messages sent by clients and intermediate nodes. This algorithm guarantees that the achieved flow of Data objects will maximize the average quality of the video delivered to the client population. To support the handling of Interest messages and Data objects when intermediate nodes perform network coding, we modify the standard NDN protocol and introduce the use of Bloom filters, which store efficiently additional information about the Interest messages and Data objects. The proposed architecture is evaluated for transmission of scalable video over PlanetLab topologies. The evaluation shows that the proposed scheme performs very close to the optimal performance

NetCodCCN: a Network Coding approach for Content-Centric Networks

Content-Centric Networking (CCN) naturally supports multi-path communication, as it allows the simultaneous use of multiple interfaces (e.g. LTE and WiFi). When multiple sources and multiple clients are considered, the optimal set of distribution trees should be determined in order to optimally use all the available interfaces. This is not a trivial task, as it is a computationally intense procedure that should be done centrally. The need for central coordination can be removed by employing network coding, which also offers improved resiliency to errors and large throughput gains. In this paper, we propose NetCodCCN, a protocol for integrating network coding in CCN. In comparison to previous works proposing to enable network coding in CCN, NetCodCCN permit Interest aggregation and Interest pipelining, which reduce the data retrieval times. The experimental evaluation shows that the proposed protocol leads to significant improvements in terms of content retrieval delay compared to the original CCN. Our results demonstrate that the use of network coding adds robustness to losses and permits to exploit more efficiently the available network resources. The performance gains are verified for content retrieval in various network scenarios.

Contribution to integration and coordination mechanisms for mobile distributed services in publish/subscribe networks

Esta tesis doctoral está enmarcada en dos diferentes pero complementarias áreas de investigación: las redes de Publicación/Subscripción y los servicios móviles distribuidos. Con el paso de los años las redes de Publicación/Subscripción han ido ofreciendo el soporte de comunicaciones desacopladas y ligeras que a su vez, han mejorado la distribución de la información en muchos escenarios de aplicación como lo son la ejecución de servicios distribuidos en entornos fijos. Los servicios móviles distribuidos han de ser desplegados en ambientes inalámbricos en donde los dispositivos móviles deben confiar en las mismas características que las redes de Publicación/Subscripción han estado ofreciendo a sus contrapartes fijos. En este contexto, una de las líneas de investigación pendientes consiste en cómo tomar ventaja de estas características, y cómo avanzar hacia nuevas soluciones no existentes con el fin de mejorar la integración entre los dispositivos fijos y móviles, y la ejecución de los servicios móviles distribuidos. En esta tesis doctoral se pretende avanzar en los mecanismos de integración y coordinación de los servicios móviles distribuidos en el contexto de las redes de Publicación/Subscripción. Los objetivos específicos de esta disertación están enfocados en lograr la integración de los sistemas de Publicación/Suscripción fijos y móviles, y la pro-visión de una versión de red de Publicación/Subscripción específica y uniforme que cuente con mecanismos de coordinación que mejoren la ejecución de los servicios móviles distribuidos. Los resultados de esta tesis doctoral están enmarcados en una versión específica de una red de Publicación/Subscripción que integra brokers fijos y móviles, y permite una coordinación totalmente desacoplada y mejorada entre dispositivos móviles que ejecutan fragmentos de servicios. Las contribuciones específicas son las siguientes: una nueva arquitectura de broker móvil que he llamado Rendezvous Mobile broker, un modelo abstracto de servicios móviles distribuidos coordinados sobre una red de Publicación/Subscripción, mejoras en los mecanismos de enrutamiento epidémicos para diseminar eventos de control producidos por fragmentos de servicios, una solución para soportar servicios altamente fragmentados y geográficamente dispersos, y finalmente una solución de interconexión entre dos dominios de red basados en Publicación/Subscripción: una red basada en el protocolo PubSubHubbub y otro en una red basada en el Publish/Subscribe Internet Routing Paradigm (PSIRP). Los experimentos llevados a cabo confirman que la versión específica de red de Pu-blicación/Subscripción propuesta incrementa el rendimiento de la red en términos de tiempo de espera entre nodos finales, permite una coordinación de los servicios móviles distribuidos más resistente a interrupciones y un mejor uso de los recursos de red, y finalmente logra exitosamente, con variaciones mínimas en el rendimiento de las comunicaciones, la interconexión entre estos dominios de Publicación/Subscripción diferentes. ABSTRACT This dissertation is made up of two different but complementary research areas: Publish/Subscribe networks and mobile distributed services. Over the years, Publish/Subscribe networks have been offering the lightweight and decoupled communication characteristics to improve the information distribution in several application domains such as the execution of distributed services. Mobile distributed services are set to be deployed in wireless environments where mobile devices must rely on the same features Publish/Subscribe networks can offer; so one of the pending research directions consists of how to take advantage of these features and further advance to-wards new un-existing solutions that enhance the integration between mobile and fixed systems and the execution of mobile distributed services. This dissertation seeks to advance the integration and coordination mechanisms of mobile distributed services in the context of Publish/Subscribe networks. The specific objectives aim to enable the integration of mobile and fixed Publish/Subscribe systems and provide a uniform and specific version of a Publish/Subscribe network with new coordination mechanisms that improve the execution of mobile distributed services. The results of this dissertation are enclosed in one specific version of a Publish/Subscribe network that integrates mobile and fixed brokers and coordinates the execution of mobile distributed services. These specific contributions are: a new architecture of a mobile broker I called Rendezvous Mobile Broker, an abstract model for coordinating mobile distributed services executions using a Publish/Subscribe net-work, new gossip routing solutions to disseminate events of services, mechanisms to support highly partitioned and geographically dispersed services and finally, an inter-networking solution between two Publish/Subscribe domains: a PubSubHubbub-based network and the Publish/Subscribe Internet Routing Paradigm (PSIRP)-based network. The experimental efforts confirm that the specific version of the Publish/Subscribe proposed in this dissertation improves the performance of the overall network in terms of end-to-end delay, enables a more resilience execution of mobile distributed services, a better usage of the existing network resources, and finally successfully achieves, with minor variations in the network performance, the internetworking between two different Publish/Subscribe domains.

Evaluating alternative industrial network organizations and information systems

Purpose – The purpose of this paper is to present a simulation‐based evaluation method for the comparison of different organizational forms and software support levels in the field of supply chain management (SCM). Design/methodology/approach – Apart from widely known logistic performance indicators, the discrete event simulation model considers explicitly coordination cost as stemming from iterative administration procedures. Findings - The method is applied to an exemplary supply chain configuration considering various parameter settings. Curiously, additional coordination cost does not always result in improved logistic performance. Influence factor variations lead to different organizational recommendations. The results confirm the high importance of (up to now) disregarded dimensions when evaluating SCM concepts and IT tools. Research limitations/implications – The model is based on simplified product and network structures. Future research shall include more complex, real world configurations. Practical implications – The developed method is designed for the identification of improvement potential when SCM software is employed. Coordination schemes based only on ERP systems are valid alternatives in industrial practice because significant investment IT can be avoided. Therefore, the evaluation of these coordination procedures, in particular the cost due to iterations, is of high managerial interest and the method provides a comprehensive tool for strategic IT decision making. Originality/value – Reviewed literature is mostly focused on the benefits of SCM software implementations. However, ERP system based supply chain coordination is still widespread industrial practice but associated coordination cost has not been addressed by researchers.

Knowledge Modelling in Multiagent Systems: The Case of the Management of a National Network

This paper presents the knowledge model of a distributed decision support system, that has been designed for the management of a national network in Ukraine. It shows how advanced Artificial Intelligence techniques (multiagent systems and knowledge modelling) have been applied to solve this real-world decision support problem: on the one hand its distributed nature, implied by different loci of decision-making at the network nodes, suggested to apply a multiagent solution; on the other, due to the complexity of problem-solving for local network administration, it was useful to apply knowledge modelling techniques, in order to structure the different knowledge types and reasoning processes involved. The paper sets out from a description of our particular management problem. Subsequently, our agent model is described, pointing out the local problem-solving and coordination knowledge models. Finally, the dynamics of the approach is illustrated by an example.

Zinc- and iron-rubredoxins from Clostridium pasteurianum at atomic resolution: a high-precision model of a ZnS4 coordination unit in a protein.

The Zn(Scys)4 unit is present in numerous proteins, where it assumes structural, regulatory, or catalytic roles. The same coordination is found naturally around iron in rubredoxins, several structures of which have been refined at resolutions of, or near to, 1 A. The fold of the small protein rubredoxin around its metal ion is an excellent model for many zinc finger proteins. Zn-substituted rubredoxin and its Fe-containing counterpart were both obtained as the products of the expression in Escherichia coli of the rubredoxin-encoding gene from Clostridium pasteurianum. The structures of both proteins have been refined with an anisotropic model at atomic resolution (1.1 A, R = 8.3% for Fe-rubredoxin, and 1.2 A, R = 9.6% for Zn-rubredoxin) and are very similar. The most significant differences are increased lengths of the M-S bonds in Zn-rubredoxin (average length, 2.345 A) as compared with Fe-rubredoxin (average length, 2.262 A). An increase of the CA-CB-SG-M dihedral angles involving Cys-6 and Cys-39, the first cysteines of each of the Cys-Xaa-Xaa-Cys metal binding motifs, has been observed. Another consequence of the replacement of iron by zinc is that the region around residues 36-46 undergoes larger displacements than the remainder of the polypeptide chain. Despite these changes, the main features of the FeS4 site, namely a local 2-fold symmetry and the characteristic network of N-H...S hydrogen bonds, are conserved in the ZnS4 site. The Zn-substituted rubredoxin provides the first precise structure of a Zn(Scys)4 unit in a protein. The nearly identical fold of rubredoxin around iron or zinc suggests that at least in some of the sites where the metal has mainly a structural role-e.g., zinc fingers-the choice of the relevant metal may be directed by its cellular availability and mobilization processes rather than by its chemical nature.

Supramolecular coordination complexes as building blocks for porous and magnetic materials

In this work, new coordination polymers based on two different classes of synthons are presented. In addition, manganese-based metallacrowns of magnetic interest are studied, both in the solid state and in solution. Firstly, functionalized bispyrazolylmethane derivatives are employed as bridging ligands for the establishment of silver-based coordination polymers; the influence of the substituent groups and of the counterions on the supramolecular packing is also investigated. Secondly, the use of metallacrown (MC) complexes as building blocks for porous coordination polymers is discussed. The design of a new metallacrown species is presented, which shows the tendency of aggregating in the solid state to form coordination polymers. Two new coordination polymers are indeed reported, of which one is the first MC-based permanently porous coordination network ever presented. The solid resists solvent evacuation and exhibits gas uptake ability. Furthermore, the isolation and characterization of a new metallacryptate species based on manganese ions is described. The metal-rich structure comprises nine Mn(II)/Mn(III) ions and presents an inverse metallacrown core subunit that binds a μ3-O2- ion. The metallacryptate is isolated in high yields and stable in solution. Lastly, a family of 3d-4f heterometallic metallacrowns is characterized in solution by means of UV-Vis spectrophotometry and of paramagnetically shifted 1H-NMR. The lanthanide-induced shifts observed in the spectra are employed to describe the molecules behaviour in solution and are qualitatively related to the magnetic properties of the compounds.

Sol–Gel Coordination Chemistry: Building Catalysts from the Bottom-Up

The development of synthetic routes for the tailoring of efficient silica-based heterogeneous catalysts functionalized with coordination complexes or metallic nanoparticles has become a important goal in chemistry. Most of these techniques have been based on postsynthetic treatments of preformed silicas. Nevertheless, there is an emerging approach, so-called sol–gel coordination chemistry, based on co-condensation during the sol–gel preparation of the hybrid material of the corresponding complex or nanoparticle modified with terminal trialkoxysilane groups with a silica source (such as tetraethoxysilane) and in the presence of an adequate surfactant. This method leads to the production of new mesoporous metal complex-silica materials, with the metallic functionality incorporated homogeneously into the structure of the hybrid material, improving the stability of the coordination complex (which is protected by the silica network) and reducing the leaching of the active phase. This technique also offers the actual possibility of functionalizing silica or other metal oxides for a wider range of applications, such as photonics, sensing, and biochemical functions.

Essays on coordination problems in economics

No estudo da economia, há diversas situações em que a propensão de um indivíduo a tomar determinada ação é crescente na quantidade de outras pessoas que este indivíduo acredita que tomarão a mesma ação. Esse tipo de complementaridade estratégica geralmente leva à existência de múltiplos equilíbrios. Além disso, o resultado atingido pelas decisões decentralizadas dos agentes pode ser ineficiente, deixando espaço para intervenções de política econômica. Esta tese estuda diferentes ambientes em que a coordenação entre indivíduos é importante. O primeiro capítulo analisa como a manipulação de informação e a divulgação de informação afetam a coordenação entre investidores e o bem-estar em um modelo de corridas bancárias. No modelo, há uma autoridade reguladora que não pode se comprometer a revelar a verdadeira situação do setor bancário. O regulador observa informações idiossincráticas dos bancos (através de um stress test, por exemplo) e escolhe se revela essa informação para o público ou se divulga somente um relatório agregado sobre a saúde do sistema financeiro como um todo. O relatório agregado pode ser distorcido a um custo – um custo mais elevado significa maior credibilidade do regulador. Os investidores estão cientes dos incentivos do regulador a esconder más notícias do mercado, mas a manipulação de informação pode, ainda assim, ser efetiva. Se a credibilidade do regulador não for muito baixa, a política de divulgação de informação é estado-contingente, e existe sempre um conjunto de estados em que há manipulação de informação em equilíbrio. Se a credibilidade for suficientemente baixa, porém, o regulador opta por transparência total dos resultados banco-específicos, caso em que somente os bancos mais sólidos sobrevivem. Uma política de opacidade levaria a uma crise bancária sistêmica, independentemente do estado. O nível de credibilidade que maximiza o bem-estar agregado do ponto de vista ex ante é interior. O segundo e o terceiro capítulos estudam problemas de coordenação dinâmicos. O segundo capítulo analisa o bem-estar em um ambiente em que agentes recebem oportunidades aleatórias para migrar entre duas redes. Os resultados mostram que sempre que a rede de pior qualidade (intrínseca) prevalece, isto é eficiente. Na verdade, um planejador central estaria ainda mais inclinado a escolher a rede de pior qualidade. Em equilíbrio, pode haver mudanças ineficientes que ampliem a rede de qualidade superior. Quando indivíduos escolhem entre dois padrões ou redes com níveis de qualidade diferentes, se todos os indivíduos fizessem escolhas simultâneas, a solução eficiente seria que todos adotassem a rede de melhor qualidade. No entanto, quando há fricções e os agentes tomam decisões escalonadas, a solução eficiente difere ix do senso comum. O terceiro capítulo analisa um problema de coordenação dinâmico com decisões escalonadas em que os agentes são heterogêneos ex ante. No modelo, existe um único equilíbrio, caracterizado por thresholds que determinam as escolhas para cada tipo de agente. Apesar da heterogeneidade nos payoffs, há bastante conformidade nas ações individuais em equilíbrio. Os thresholds de diferentes tipos de agentes coincidem parcialmente contanto que exista um conjunto de crenças arbitrário que justifique esta conformidade. No entanto, as estratégias de equilíbrio de diferentes tipos nunca coincidem totalmente. Além disso, a conformidade não é ineficiente. A solução eficiente apresentaria estratégias ainda mais similares para tipos distintos em comparação com o equilíbrio decentralizado.

Network effects, network structure and consumer interaction in mobile telecommunications in Europe and Asia

This paper estimates the importance of (tariff-mediated) network effects and the impact of a consumer's social network on her choice of mobile phone provider. The study uses network data obtained from surveys of students in several European and Asian countries. We use the Quadratic Assignment Procedure, a non-parametric permutation test, to adjust for the particular error structure of network data. We find that respondents strongly coordinate their choice of mobile phone providers, but only if their provider induces network effects. This suggests that this coordination depends on network effects rather than on information contagion or pressure to conform to the social environment.

Hálózat – A globális gazdaság kvázi szervezete (The business network – the quasi organization of the global economy)

A tanulmány célja, hogy értelmezze a globális gazdaság alapvető fontosságú építőelemét, az üzleti hálózatot, majd megvizsgálja annak felépítését és működésének főbb vezérlőelveit. Először az alapfogalmak – üzleti hálózat, ellátási lánc és ellátási háló – meghatározására és azok felépítésének bemutatására kerül sor. Ezt követően a cikk röviden ismerteti, hogy melyek voltak azok a vállalati gazdálkodás környezetében végbement változások, melyek a gazdaság hálózatosodását elősegítették és ennek kapcsán elvezettek az üzleti hálózatok versenyképességben játszott szerepének erősödéséhez. A szerző ugyanakkor bemutatja a kialakuló új gazdasági modell, az ún. hálózati gazdaság működési modelljének lényeges új tulajdonságait. A tanulmány ezután ismerteti az üzleti hálózat – s ezen belül az ellátási lánc – működtetésében meghatározó koordinációs mechanizmusokban megfigyelhető markáns változásokat. Végül részletesen ismerteti az üzleti hálózat két fő építőelemét: a hálózatot alkotó üzleti egységeknek, illetve a közöttük kialakuló kapcsolatoknak az alapvető típusait. ________ The aim of the paper is to present and interpret the basic building element of global business: the business network, its structure and operation. First basic terms – network, supply chain, supply network – are defined and described, than those changes are introduced that played significant role in increasing their importance. Characteristics of the new network economy are presented; especially changes in the coordination mechanism between cooperating parties in the network are demonstrated. Finally the two building blocks of global business networks: (i) nodes (business units) and (ii) threads (partnerships) are described in details.

Optimizing Supply Chain Performance in China with Country-Specific Supply Chain Coordination

The implementation of country-specific supply chain coordination techniques ensures an optimal global supply chain performance. This paper looks at success factors going with a supply chain coordination strategy within the global supply chain of a successful, medium-sized, privately-owned company, one having locations in North America (USA), Europe (Hungary) and Asia (China). Through the shown GSL’s Chinese plant, we will endeavor to argue that increased collaboration in the supply network with appropriate supply chain coordination brings down not only the inventory level but can also improve conformance quality and reduce quoted lead times.

Modeling the Network of Dutch and Flemish Print Production, 1550-1750

The production of artistic prints in the sixteenth- and seventeenth-century Netherlands was an inherently social process. Turning out prints at any reasonable scale depended on the fluid coordination between designers, platecutters, and publishers; roles that, by the sixteenth century, were considered distinguished enough to merit distinct credits engraved on the plates themselves: invenit, fecit/sculpsit, and excudit. While any one designer, plate cutter, and publisher could potentially exercise a great deal of influence over the production of a single print, their individual decisions (Whom to select as an engraver? What subjects to create for a print design? What market to sell to?) would have been variously constrained or encouraged by their position in this larger network (Who do they already know? And who, in turn, do their contacts know?) This dissertation addresses the impact of these constraints and affordances through the novel application of computational social network analysis to major databases of surviving prints from this period. This approach is used to evaluate several questions about trends in early modern print production practices that have not been satisfactorily addressed by traditional literature based on case studies alone: Did the social capital demanded by print production result in centralized, or distributed production of prints? When, and to what extent, did printmakers and publishers in the Low countries favor international versus domestic collaborators? And were printmakers under the same pressure as painters to specialize in particular artistic genres? This dissertation ultimately suggests how simple professional incentives endemic to the practice of printmaking may, at large scales, have resulted in quite complex patterns of collaboration and production. The framework of network analysis surfaces the role of certain printmakers who tend to be neglected in aesthetically-focused histories of art. This approach also highlights important issues concerning art historians’ balancing of individual influence versus the impact of longue durée trends. Finally, this dissertation also raises questions about the current limitations and future possibilities of combining computational methods with cultural heritage datasets in the pursuit of historical research.