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).

Application of a building cost estimation model to the appraisal of the churches damaged by earthquakes in Lorca (Spain)

The objective of this paper is the development of a building cost estimation model whose purpose is to quickly and precisely evaluate rebuilding costs for historic heritage buildings affected by catastrophic events. Specifically, this study will be applied to the monumental buildings owned by the Catholic Church that were affected by two earthquakes on May 11, 2011 in the town of Lorca. To estimate the initial total replacement cost new, calculation model will be applied which, on the one hand, will use two-dimensional metric exterior parameters and, on the other, three-dimensional interior cubic parameters. Based on the total of the analyzed buildings, and considering damage caused by the seismic event, the final reconstruction cost for the building units ruined by the earthquakes can be estimated. The proposed calculation model can also be applied to other emergency scenarios and situations for the quick estimation of construction costs necessary for rebuilding historic heritage buildings which have been affected by catastrophic events that deteriorate or ruin their structural or constructive configuration.

Plasma Nanoscience : from nature's mastery to deterministic plasma-aided nanofabrication

This paper introduces the plasma-nanoscience research area and shows the way from Nature's mastery in assembling nanosized dust grains in the Universe to deterministic plasma-aided nanofabrication. The concept of deterministic nanoassembly is explained, and the multidisciplinary approach to bridge the spatial gap of nine orders of magnitude between the sizes of plasma reactors and atomic building units is discussed. Ongoing numerical simulation and experimental efforts on highly controlled synthesis of carbon nanotip and semiconducting quantum-dot structures show potential benefits of using ionized-gas environments in nanofabrication. © 2007 IEEE.

Surface science of plasma exposed surfaces : a challenge for applied plasma science

This article introduces a deterministic approach to using low-temperature, thermally non-equilibrium plasmas to synthesize delicate low-dimensional nanostructures of a small number of atoms on plasma exposed surfaces. This approach is based on a set of plasma-related strategies to control elementary surface processes, an area traditionally covered by surface science. Major issues related to balanced delivery and consumption of building units, appropriate choice of process conditions, and account of plasma-related electric fields, electric charges and polarization effects are identified and discussed in the quantum dot nanoarray context. Examples of a suitable plasma-aided nanofabrication facility and specific effects of a plasma-based environment on self-organized growth of size- and position-uniform nanodot arrays are shown. These results suggest a very positive outlook for using low-temperature plasma-based nanotools in high-precision nanofabrication of self-assembled nanostructures and elements of nanodevices, one of the areas of continuously rising demand from academia and industry.

Nanostructures of various dimensionalities from plasma and neutral fluxes

A complex multi-scale model and numerical simulations are used to demonstrate, by simulating the development of patterns of nanotips, nanowalls, nanoislands and nanovoids of a characteristic size of 5-100 nm, a greater degree of determinism in the formation of various nanostructures by using the low-density, low-temperature plasma-based processes. It is shown that in the plasma, in contrast to the neutral gas-based processes, one can synthesize nanostructures of various dimensionalities and shapes with a larger surface density, desired geometrical parameters and narrower size distribution functions. This effect is mainly attributed to strong ion focusing by irregular electric fields in the nanopatterns, which effectively redistributes the influxes of plasma-generated building units and thus provides a selective control of their delivery to the growing nanostructures.

Computational plasma nanoscience : where plasma physics meets surface science

Multiscale hybrid simulations that bridge the nine-order-of-magnitude spatial gap between the macroscopic plasma nanotools and microscopic surface processes on nanostructured solids are described. Two specific examples of carbon nanotip-like and semiconductor quantum dot nanopatterns are considered. These simulations are instrumental in developing physical principles of nanoscale assembly processes on solid surfaces exposed to low-temperature plasmas.

New laws for off the plan contracts in Queensland

The Land Sales Act 1984 regulates “off the plan” sales in Queensland in conjunction with several provisions in the Body Corporate and Community Management Act 1997. Together the Acts regulate sales in both unit developments and housing estates. From 2010 to 2013 the Queensland Government undertook a comprehensive review of the Land Sales Act 1984 to identify opportunities to modernise and improve the legislation. Significant changes were recommended by the Review to align the Land Sales Act 1984 (LSA) with current surveying and conveyancing practice and to overcome a number of practical issues faced by developers under the current legislation. A significant outcome of the review is the removal of provisions related to off the plan community title sales from the LSA to the Body Corporate and Community Management Act 1997 (BCCMA) and the Building Units and Group Titles Act 1980 (BUGTA). This article examines the Land Sales and Other Legislation Amendment Act 2014 due to commence in November 2014.

Sustainable life cycles of natural-precursor-derived nanocarbons

Sustainable societal and economic development relies on novel nanotechnologies that offer maximum efficiency at minimal environmental cost. Yet, it is very challenging to apply green chemistry approaches across the entire life cycle of nanotech products, from design and nanomaterial synthesis to utilization and disposal. Recently, novel, efficient methods based on nonequilibrium reactive plasma chemistries that minimize the process steps and dramatically reduce the use of expensive and hazardous reagents have been applied to low-cost natural and waste sources to produce value-added nanomaterials with a wide range of applications. This review discusses the distinctive effects of nonequilibrium reactive chemistries and how these effects can aid and advance the integration of sustainable chemistry into each stage of nanotech product life. Examples of the use of enabling plasma-based technologies in sustainable production and degradation of nanotech products are discussed—from selection of precursors derived from natural resources and their conversion into functional building units, to methods for green synthesis of useful naturally degradable carbon-based nanomaterials, to device operation and eventual disintegration into naturally degradable yet potentially reusable byproducts.

Interaction Energy Based Protein Structure Networks

The three dimensional structure of a protein is formed and maintained by the noncovalent interactions among the amino acid residues of the polypeptide chain These interactions can be represented collectively in the form of a network So far such networks have been investigated by considering the connections based on distances between the amino acid residues Here we present a method of constructing the structure network based on interaction energies among the amino acid residues in the protein We have investigated the properties of such protein energy based networks (PENs) and have shown correlations to protein structural features such as the clusters of residues involved in stability formation of secondary and super secondary structural units Further we demonstrate that the analysis of PENs in terms of parameters such as hubs and shortest paths can provide a variety of biologically important information such as the residues crucial for stabilizing the folded units and the paths of communication between distal residues in the protein Finally the energy regimes for different levels of stabilization in the protein structure have clearly emerged from the PEN analysis

Hydrothermal synthesis and structure of organically templated one-dimensional and three-dimensional iron fluorophosphate

Two new open-framework iron fluorophosphates, [C(4)N(2)H(12)](0.5) [FeF(HPO(4))(H(2)PO(4))] (I) and [C(4)N(2)H(12)][Fe(4)F(2)(H(2)O)(4)(PO(4))(4)]. 0.5H(2)O (II), were synthesized hydrothermally using piperazine as a templating agent. The structures were determined by single-crystal X-ray diffraction. Compound I crystallizes in the orthorhombic space group Pbca, a = 7.2126(2) Angstrom, b = 14.2071(4) Angstrom, c = 17.1338(2) Angstrom, Z = 8. The structure is composed of infinite anionic chains of [FeF(HPO(4))(H(2)PO(4))](n)(-) built by trans-fluorine sharing FeF(2)O(4) octahedra. These chains are similar to those found in tancoite-type minerals. Compound II crystallizes in the monoclinic space group P2(1)/n, a = 9.9045(3) Angstrom, b = 12.3011(3) Angstrom, c = 17.3220(4) Angstrom, beta = 103.7010(10)degrees, Z = 4. The structure of compound II has a three-dimensional (3D) architecture with an eight-membered channel along the b axis, in which protonoted piperazine molecules reside. The complex framework is built from two types of secondary building unit (SBU): one hexamer [Fe(3)F(2)(H(2)O)(2)(PO(4))(3)] (SBU6), and one dimer [FeO(4)(H(2)O)(2)PO(4)] (SBU2). The vertex sharing between these SBUs create the 3D structure.

Triarylborane-Appended New Triad and Tetrad: Chromogenic and Fluorogenic Anion Recognition

Facile synthesis of triad 3 and tetrad 4 incorporating -B(Mes)(2) (Mes = mesityl (2,4,6-trimethylphenyl)), boron dipyrromethene (BODIPY), and triphenylamine is reported. Introduction of two dissimilar acceptors (triarylborane and BODIPY) on a single donor resulted in two distinct intramolecular charge transfer processes (amine-to-borane and amine-to-BODIPY). The absorption and emission properties of the new triad and tetrad are highly dependent on individual building units. The nature of electronic communication among the individual fluorophore units has been comprehensively investigated and compared with building units. Compounds 3 and 4 showed chromogenic and fluorogenic responses for small anions such as fluoride and cyanide.

Structural Diversity in Multinuclear PdII Assemblies that Show Low- Humidity Proton Conduction

Systematic investigation on synergetic effects of geometry, length, denticity, and asymmetry of donors was performed through the formation of a series of uncommon Pd-II aggregates by employing the donor in a multicomponent self-assembly of a cis-blocked 90 degrees Pd-II acceptor and a tetratopic donor. Some of these assemblies represent the first examples of these types of structures, and their formation is not anticipated by only taking the geometry of the donor and the acceptor building units into account. Analysis of the crystal packing of the X-ray structure revealed several H bonds between the counteranions (NO3-) and water molecules (OHON). Moreover, H-bonded 3D-networks of water are present in the molecular pockets, which show water-adsorption properties with some variation in water affinity. Interestingly, these complexes exhibit proton conductivity (1.87x10(-5)-6.52x10(-4)Scm(-1)) at 296K and low relative humidity (ca. 46%) with activation energies of 0.29-0.46eV. Moreover, the conductivities further increase with the enhancement of humidity. The ability of these assemblies to exhibit proton-conducting properties under low-humidity conditions makes these materials highly appealing as electrolytes in batteries and in fuel-cell applications.

Ionic Bonding between Artificial Atoms

Conventional solids are prepared from building blocks that are conceptually no larger than a hundred atoms. While van der Waals and dipole-dipole interactions also influence the formation of these materials, stronger interactions, referred to as chemical bonds, play a more decisive role in determining the structures of most solids. Chemical bonds that hold such materials together are said to be ionic, covalent, metallic, dative, or otherwise a combination of these. Solids that utilize semiconductor nanocrystal quantum dots as building units have been demonstrated to exist; however, the interparticle forces in such materials are decidedly not chemical. Here we demonstrate the formation of charge transfer states in a binary quantum dot mixture. Charge is observed to reside in quantum confined states of one of the participating quantum dots. These interactions lead to materials that may be regarded as the nanoscale analog of an ionic solid. The process by which these materials form has interesting parallels to chemical reactions in conventional chemistry.

Redox-Active Metal-Organic Frameworks: Highly Stable Charge-Separated States through Strut/Guest-to-Strut Electron Transfer

Molecular organization of donor and acceptor chromophores in self-assembled materials is of paramount interest in the field of photovoltaics or mimicry of natural light-harvesting systems. With this in mind, a redox-active porous interpenetrated metal-organic framework (MOF), {Cd(bpdc)(bpNDI)]4.5H(2)ODMF}(n) (1) has been constructed from a mixed chromophoric system. The -oxo-bridged secondary building unit, {Cd-2(-OCO)(2)}, guides the parallel alignment of bpNDI (N,N-di(4-pyridyl)-1,4,5,8-naphthalenediimide) acceptor linkers, which are tethered with bpdc (bpdcH(2)=4,4-biphenyldicarboxylic acid) linkers of another entangled net in the framework, resulting in photochromic behaviour through inter-net electron transfer. Encapsulation of electron-donating aromatic molecules in the electron-deficient channels of 1 leads to a perfect donor-acceptor co-facial organization, resulting in long-lived charge-separated states of bpNDI. Furthermore, 1 and guest encapsulated species are characterised through electrochemical studies for understanding of their redox properties.

A vida após a alta

Esta tese discute a vida após a alta hospitalar através de uma etnografia da experiência de um grupo de famílias, ao cuidarem de um membro dependente de cuidados de saúde. Foi realizada entre agosto de 2001 e julho de 2005 em Juiz de Fora-MG. O foco da investigação foi a convivência cotidiana da família com um membro requerendo cuidados de saúde especializados após ter recebido assistência de alta complexidade. O objetivo foi compreender a questão: como a família cuida, em casa, de um familiar que necessita de cuidados de saúde após a alta hospitalar? Adotamos a etnografia orientada por Geertz (1989), que nos permitiu, através da análise interpretativa das teias de significados apreendidas pela observaçãoconvivência com os sujeitos, uma compreensão de como o fenômeno (cuidado) se evidencia e se transforma em experiência nas relações que se estabelecem dentro e fora da família. A identificação das famílias-sujeito iniciou com a observação das internações na Unidade de Terapia Intensiva (UTI) do Hospital Universitário da Universidade Federal de Juiz de Fora, no segundo semestre de 2003, seguida da observação nas enfermarias e, posteriormente, nos seus domicílios. De 137 pacientes internados nesta UTI naquele semestre, 59 foram a óbito, 12 foram transferidos para outro hospital da cidade, por demandarem tecnologias não oferecidas pela instituição e 66 tiveram alta hospitalar na condição de melhorado. Destes, observamos 12 casos, residentes na cidade de Juiz de Fora, que compartilham de uma mesma cultura assistencial e que foram submetidas a um mesmo padrão de organização e de fluxo de atendimento no sistema de saúde local. Destas, uma família se destacou como principal sujeito, pela repetição de eventos significativos à questão principal da pesquisa e utilizamos dados de outras cinco dentre as observadas. Os dados foram arquivados em um banco de dados qualitativos LOGOS. A prioridade nos cuidados com o corpo; a dependência dos serviços de saúde especializados do SUS e as alterações na organização e no funcionamento da família, com redefinições de papéis, para se adaptar à realidade de convivência com um membro doente, estão dentre os achados. Dois fenômenos que se relacionam com o desenvolvimento da experiência de cuidar pelas famílias se destacaram: a individualização na família, que parece influenciar a forma de abordagem clínica (individualizada) pelos profissionais de saúde, e uma concepção de família como sujeito coletivo Bourdieu (1998) como possibilidade para o planejamento de ações coletivas. O sofrimento, observado pela contínua convivência dos sujeitos com sentimentos de angústia nas trajetórias de busca de cuidados no Sistema, nas instituições de saúde, evidenciou a desassistência a que esse grupo de cidadãos está exposto no modelo assistencial vigente. A lida das famílias com uma diversidade de cuidados, incluindo a prática de cuidados técnicos desencadeou uma rede extrafamiliar de aproximações, para o enfrentamento das necessidades. Apesar da dependência de tecnologias, de saberes técnicos e das restrições no acesso a esses, evidenciou-se um tipo de autonomia pelos sujeitos na prática de cuidados no espaço intrafamiliar e no entorno micro-sociológico de convivência. No Sistema de Saúde a preferência primeira das famílias para busca de ajuda é o hospital, depois, as unidades de referência secundária e, por último, as Equipes de Saúde da Família (ESF). A procura pelas ESF é por que estas representam parte obrigatória no fluxo inicial dos usuários do SUS local, garantem a aquisição de medicamentos, oferecem serviços de natureza cartorial, como atestados e pareceres para juiz e, ainda, encaminhamentos e solicitação de exames.