Cu-II-azide polynuclear complexes of Cu-4 building clusters with Schiff-base co-ligands: synthesis, structures, magnetic behavior and DFT studies

Three new copper-azido complexes Cu-4(N-3)(8)(L-1)(2)](n) (1), Cu-4(N-3)(6)(L-2)(2)(H2O)(2)] (2), and Cu-4(N-3)(6)(L-3)(2)](n) (3) L-1 is the imine resulting from the condensation of pyridine-2-carboxaldehyde with N-methylethylenediamine, HL2 and HL3 are the condensation products of 2-hydroxy-3-methoxybenzaldehyde with N,N-diethylethylenediamine and N-ethylethylenediamine respectively] have been synthesized by using 0.5 molar equivalents of the Schiff base ligands with Cu(NO3)(2)center dot 3H(2)O and an excess of NaN3. Single crystal X-ray structures show that the basic unit of these complexes contains very similar Cu-4(II) building blocks. While 1 and 3 have overall 1D structures, 2 forms discrete tetranuclear clusters due to blocking of two coordination sites on the tetranuclear cluster by water molecules. Magnetic susceptibility measurements over a wide range of temperatures exhibit the presence of both antiferromagnetic and ferromagnetic exchanges within the tetranuclear unit structures. Density functional theory calculations (using B3LYP functional and two different basis sets) have been performed on the complexes 1-3 to provide a qualitative theoretical interpretation of their overall magnetic behavior.

Self-assembly of discrete metallamacrocycles employing half-sandwich octahedral diruthenium(II) building units and imidazole-based ligands

Equimolar combination of a series of binuclear half-sandwich p-cymene ruthenium(II) building units Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](OTf)(2) 1a](OTf)(2), Ru-2(mu-eta(4)-N,N'-diphenyloxamidato)( MeOH)(2)(eta(6)-p-cymene)(2)](OTf)(2) 1b](OTf)(2) and Ru-2(mu-eta(4)-C6H2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](OTf)(2) 1c](OTf)(2) separately with imidazole-based ditopic ligands (L-1-L-2) in methanol yielded a series of tetranuclear metallamacrocycles 2-7](OTf)(4), respectively L-1 = 1,4-bis(imidazole-1-yl)benzene; L-2 = 4,4'-bis(imidazole-1-yl)biphenyl; OTf- = O3SCF3-]. Similarly, the reaction of Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)2](OTf)(2) 1a](OTf)(2) with a triazine-based tritopic ligand 1,3,5-tris(imidazole-1-yl) triazine (L3) in 3: 2 M ratio afforded an unexpected tetranuclear macrocycle 8](OTf)(4) instead of an expected trigonal prismatic cage 8a](OTf)(6). All the self-assembled macrocycles 2-8](OTf)(4) were isolated in moderate to high yields and were fully characterized by multinuclear H-1, F-19] NMR, IR and electrospray ionization mass spectrometry (ESI-MS). In addition, X-ray diffraction study on the single crystals of 3](OTf)(4) and 8](OTf)(4) also indicated the formation 2 + 2] self-assembled macrocycles. Despite the possibility of formation of different conformational isomeric macrocycles (syn-and anti) and polymeric product due to free rotation of ligand sites of imidazole linkers, the selective formation of single conformational isomer (anti) as the only product is quite interesting. Furthermore, the photo-and electrochemical properties of these assemblies have been studied using UV/Vis absorption and cyclic voltammetry analysis. (c) 2013 Elsevier B.V. All rights reserved.

Building the perfect 3D hologram

A new liquid crystal device structure has been developed using a vertically grown Multi-Wall Carbon NanoTube (MWCNT) as a 3D electrode structure, which allows complicated phase only hologram to be displayed using conventional liquid crystal materials. The nanotubes act as an individual electrode sites that generate an electric field profile, dictating the refractive index profile with the liquid crystal cell. Changing the electric field applied makes it possible to tune the properties to modulate the light in an ideal kinoform. A perfect 3D image can be generated by a computer generated hologram by using the diffraction of the light from the hologram pixels to create an optical wave front that appears to come from 3D object. A multilevel phase modulating device based on nematic LC's is also under progress, which will be used with the LC/CNT devices on an LCOS backplane to project a full 3D image from the kinoform.

Ad valorem housing subsidies may reduce house building

In this paper it is shown that an ad valorem housing subsidy set by a central regulator (or a raise in the ad valorem housing subsidy rate) may reduce the number of houses built in the market and increase the price paid by the buyers of houses. The analysis considers a situation where there is imperfect competition in the housing market and a local regulator that decides on density, or on the number of sites for housing development, and that cares about a combination of the profits of housing developers and the surplus of buyers of houses.

Design de modelos colaborativos em sites de notícias

A colaboração de usuários em sites jornalísticos é um fenômeno crescente. Cada vez mais, a evolução tecnológica abre espaço para uma maior participação dos usuários no processo de construção da narrativa noticiosa. Nesse contexto, um olhar do design sobre os modelos colaborativos dos sites jornalísticos fornece subsídios para o entendimento deste fenômeno e para o aprofundamento em cada uma das etapas que compõe o processo colaborativo. Dessa forma, essa dissertação apresenta a análise teórica e prática dessas diferentes etapas, bem como das soluções de design aplicáveis aos modelos colaborativos, de maneira a estabelecer conceitos e diretrizes para a construção de modelos que otimizem o aproveitamento do conteúdo enviado por usuários e sua relação com o conteúdo editorial dos sites noticiosos.

Effect of urban climate on building integrated photovoltaics performance

It is generally recognized that BIPV (building integrated photovoltaics) has the potential to become a major source of renewable energy in the urban environment. The actual output of a PV module in the field is a function of orientation, total irradiance, spectral irradiance, wind speed, air temperature, soiling and various system-related losses. In urban areas, the attenuation of solar radiation due to air pollution is obvious, and the solar spectral content subsequently changes. The urban air temperature is higher than that in the surrounding countryside, and the wind speed in urban areas is usually less than that in rural areas. Three different models of PV power are used to investigate the effect of urban climate on PV performance. The results show that the dimming of solar radiation in the urban environment is the main reason for the decrease of PV module output using the climatic data of urban and rural sites in Mexico City for year 2003. The urban PV conversion efficiency is higher than that of the rural PV system because the PV module temperature in the urban areas is slightly lower than that in the rural areas in the case. The DC power output of PV seems to be underestimated if the spectral response of PV in the urban environment is not taken into account based on the urban hourly meteorological data of Sao Paulo for year 2004. © 2006 Elsevier Ltd. All rights reserved.

Social sensing in the field: Challenges in detecting social interactions in construction sites

Construction industry is a sector that is renowned for the slow uptake of new technologies. This is usually due to the conservative nature of this sector that relies heavily on tried and tested and successful old business practices. However, there is an eagerness in this industry to adopt Building Information Modelling (BIM) technologies to capture and record accurate information about a building project. But vast amounts of information and knowledge about the construction process is typically hidden within informal social interactions that take place in the work environment. In this paper we present a vision where smartphones and tablet devices carried by construction workers are used to capture the interaction and communication between workers in the field. Informal chats about decisions taken in the field, impromptu formation of teams, identification of key persons for certain tasks, and tracking the flow of information across the project community, are some pieces of information that could be captured by employing social sensing in the field. This information can not only be used during the construction to improve the site processes but it can also be exploited by the end user during maintenance of the building. We highlight the challenges that need to be overcome for this mobile and social sensing system to become a reality. © 2012 ACM.

Fluorene-Based Copolymers Containing Dinaphtho-s-indacene as New Building Blocks for High-Efficiency and Color-Stable Blue LEDs

By incorporating a new building block, 7,7,15,15-tetraoctyldinaphtho-s-indacene (NSI), into the backbone of poly(9,9-dioctylfluorene) (PFO), a novel series of blue light-emitting copolymers (PFO-NSI) have been developed. The insertion of the NSI unit into the PFO backbone leads to the increase of local effective conjugation length, to form low-energy fluorene-NSI-fluorene (FNF) segments that serve as exciton trapping sites, to which the energy transfers from the high-energy PFO segments. This causes these copolymers to show red-shifted emissions compared with PFO, with a high efficiency and good color stability and purity. The best device performance with a luminance efficiency of 3.43 cd . A(-1), a maximum brightness of 6 539 cd . m(-2) and CIE coordinates of (0.152, 0.164) was achieved.

Xanthoria parietina as a biomonitor of airborne heavy metal pollution in forest sites in the North East of Morocco

Xanthoria parietina, common foliose lichen, growing in its natural habitat, was analysed for the concentration of five heavy metals (Fe, Cr, Zn, Pb and Cu) from different forest sites of North East of Morocco (Kenitra, Sidi Boughaba, Mkhinza, Ceinture Verte near Temara city, Skhirate, Bouznika and Mohammedia). The quantification was carried out by inductively coupled plasma - atomic emission spectrometry (ICP-AES). Results were highly significant p<0,001. The concentration of metals is correlated with the vehicular activity and urbanization. The total metal concentration is highest at the Kenitra area, followed by Ceinture Verte site near Temara city, which experience heavy traffic throughout the year. Scanning electron microscopy (SEM) of particulate matter on lichen of Xanthoria parietina was assessed as a complementary technique to wet chemical analysis for source apportionment of airborne contaminant. Analysis revealed high level of Cu, Cr, Zn and Pb in samples near roads.  

Live Project love: building a framework for Live Projects

Live projects adopt a wide range of approaches: design/ build, community engagement, participation, protest, analysis, etc. They are driven by tutors with passion, expertise and the ability to manage risk, in ways that exhibit fluency and high levels of skill. They also offer sites of student-led and community co-learning, can support research, demonstrate ‘impact’ and satisfy universities’ policies on outreach. Whilst the breadth and reach of Live Projects is now demonstrably wide, we still fail to fully locate Live Projects within a pedagogical context, tending instead to limit our descriptions and hence analysis to the architectural process and outcome. This failure to locate Live Projects within a pedagogical framework means we still struggle to encapsulate, critique, progress, and indeed, elevate the work.

This chapter draws on some of the case studies presented in recent papers and international conferences in order to provide educators with signposts and important overviews around which and in respect to they can develop their own pedagogical frameworks.

Local materials for building houses: laterite valorization in Africa

This paper presents the preliminary results of geological and geomechanical studies on the laterite stone exploited at Dano quarry in Burkina Faso. The field work described the geological structure of quarry sites and their environment to determine the rocks alteration and the links between the bedrock and lateritic material. Physic-mechanical properties have been studied for assessing the potentiality of this material for lightweight housing, to be completed with thermal and environmental considerations. Some social and economic evaluations are in progress in order to foster its utilization under local conditions.

Local materials for building houses: Laterite valorization in Africa

This paper presents the preliminary results of geological and geomechanical studies on the laterite stone exploited at Dano quarry in Burkina Faso. The field work described the geological structure of quarry sites and their environment to determine the rocks alteration and the links between the bedrock and lateritic material. Physic-mechanical properties have been studied for assessing the potentiality of this material for lightweight housing, to be completed with thermal and environmental considerations. Some social and economic evaluations are in progress in order to foster its utilization under local conditions. © (2014) Trans Tech Publications, Switzerland.

The design, synthesis and characterization of new building blocks for the preparation of molecule-based magnetic materials /

Two new families of building blocks have been prepared and fully characterized and their coordination chemistry exploited for the preparation of molecule-based magnetic materials. The first class of compounds were prepared by exploiting the chemistry of 3,3'-diamino-2,2'-bipyridine together with 2-pyridine carbonyl chloride or 2-pyridine aldehyde. Two new ligands, 2,2'-bipyridine-3,3'-[2-pyridinecarboxamide] (Li, 2.3) and N'-6/s(2-pyridylmethyl) [2,2'bipyridine]-3,3'-diimine (L2, 2.7), were prepared and characterized. For ligand L4, two copper(II) coordination compounds were isolated with stoichiometrics [Cu2(Li)(hfac)2] (2.4) and [Cu(Li)Cl2] (2.5). The molecular structures of both complexes were determined by X-ray crystallography. In both complexes the ligand is in the dianionic form and coordinates the divalent Cu(II) ions via one amido and two pyridine nitrogen donor atoms. In (2.4), the coordination geometry around both Cu11 ions is best described as distorted trigonal bipyramidal where the remaining two coordination sites are satisfied by hfac counterions. In (2.5), both Cu(II) ions adopt a (4+1) distorted square pyramidal geometry. One copper forms a longer apical bond to an adjacent carbonyl oxygen atom, whereas the second copper is chelated to a neighboring Cu-Cl chloride ion to afford chloride bridged linear [Cu2(Li)Cl2]2 tetramers that run along the c-axis of the unit cell. The magnetic susceptibility data for (2.4) reveal the occurrence of weak antiferromagnetic interactions between the copper(II) ions. In contrast, variable temperature magnetic susceptibility measurements for (2.5) reveal more complex magnetic properties with the presence of ferromagnetic exchange between the central dimeric pair of copper atoms and weak antiferromagnetic exchange between the outer pairs of copper atoms. The Schiff-base bis-imine ligand (L2, 2.7) was found to be highly reactive; single crystals grown from dry methanol afforded compound (2.14) for which two methanol molecules had added across the imine double bond. The susceptibility of this ligand to nucleophilic attack at its imine functionality assisted via chelation to Lewis acidic metal ions adds an interesting dimension to its coordination chemistry. In this respect, a Co(II) quaterpyridine-type complex was prepared via a one-pot transformation of ligand L2 in the presence of a Lewis acidic metal salt. The rearranged complex was characterized by X-ray crystallography and a reaction mechanism for its formation has been proposed. Three additional rearranged complexes (2.13), (2.17) and (2.19) were also isolated when ligand (L2, 2.7) was reacted with transition metal ions. The molecular structures of all three complexes have been determined by X-ray crystallography. The second class of compounds that are reported in this thesis, are the two diacetyl pyridine derivatives, 4-pyridyl-2,6-diacetylpyridine (5.5) and 2,2'-6,6'-tetraacetyl-4,4'-bipyridine (5.15). Both of these compounds have been designed as intermediates for the metal templated assembly of a Schiff-base N3O2 macrocycle. From compound (5.15), a covalently tethered dimeric Mn(II) macrocyclic compound of general formula {[Mn^C^XJCl-FkO^Cl-lO.SFbO (5.16) was prepared and characterized. The X-ray analysis of (5.16) reveals that the two manganese ions assume a pentagonal-bipyramidal geometry with the macrocycle occupying the pentagonal plane and the axial positions being filled by a halide ion and a H2O molecule. Magnetic susceptibility data reveal the occurrence of antiferromagnetic interactions between covalently tethered Mn(II)-Mn(II) dimeric units. Following this methodology a Co(II) analogue (5.17) has also been prepared which is isostructural with (5.16).

A step-by-step guide for building localised versions of the MIC site. Version 1.1

This is a test version of the kit for localising the Moving Image Collections (MIC) site, designed in the context of a research project undertaken by the Audiovisual and Multimedia Section (AVMS) of IFLA.

Building a Canadian Virtual Health Library Database / Création de la Bibliothèque virtuelle canadienne de santé

Introduction: Avec l’abondance d’information gratuite disponible en ligne, la tâche de trouver, de trier et d’acheminer de l’information pertinente à l’auditoire approprié peut s’avérer laborieuse. En décembre 2010, la Bibliothèque virtuelle canadienne de santé / Canadian Virtual Health Library (BVCS) a formé un comité d’experts afin d’identifier, d’évaluer, de sélectionner et d’organiser des ressources d’intérêt pour les professionnels de la santé. Méthodes: Cette affiche identifiera les décisions techniques du comité d’experts, incluant le système de gestion de contenus retenu, l’utilisation des éléments Dublin Core et des descripteurs Medical Subject Headings pour la description des ressources, et le développement et l’adaptation de taxonomies à partir de la classification MeSH. La traduction française des descripteurs MeSH à l’aide du portail CISMeF sera également abordée. Résultats: Au mois de mai 2011, le comité a lancé la base de données BVCS de ressources en ligne gratuites sur la santé, regroupant plus de 1600 sites web et ressources. Une variété de types de contenus sont représentés, incluant des articles et rapports, des bases de données interactives et des outils de pratique clinique. Discussion: Les bénéfices et défis d’une collaboration pancanadienne virtuelle seront présentés, ainsi que l’inclusion cruciale d’un membre francophone pour composer avec la nature bilingue de la base de données. En lien avec cet aspect du projet, l’affiche sera présentée en français et en anglais. Introduction: With the abundance of freely available online information, the task of finding, filtering and fitting relevant information to the appropriate audience, is daunting. In December 2010 the Canadian Virtual Health Library / Bibliothèque virtuelle canadienne de santé (CVHL) formed an expert committee to identify, evaluate, select and organize resources relevant to health professionals. Methods: This poster will identify the key technical decisions of the expert committee including the content management system used to manage the data, the use of Dublin Core elements and Medical Subject Headings to describe the resources, and the development and adaptation of taxonomies from MeSH classification to catalog resources. The translation of MeSH terms to French using the CiSMeF portal will also be discussed. Results: In May 2010, the committee launched the CVHL database of free web-based health resources. Content ranged from online articles and reports to videos, interactive databases and clinical practice tools, and included more than 1,600 websites and resources. Discussion: The benefits and challenges of a virtual, pan-Canadian collaboration, and the critical inclusion of a Francophone member to address the bilingual nature of the database, will be presented. In keeping with the nature of the project, the poster will be presented in French and English.