First stereocontrolled acetylation of a hydroxypropargylpiperidone by lipase CALB

Hydroxypropargylpiperidones rac-1-3 were efficiently obtained by a one-pot three-component coupling reaction; enantioenriched propargylpiperidones were then obtained by a kinetic resolution process using the lipase from Candida antarctica. Lipase CALB has been shown to efficiently catalyse the stereocontrolled acetylation of hydroxypropargylpiperidones rac-3 by promoting stereodiscrimination at the carbinolic centre. The enzymatic catalytic processes allow the separation of the (S,R)- and (S,S)-3 diastereoisomers into the corresponding acetates produced as a (R,S)- and (R,R)-6 diastereoisomeric pair. The CALB was able to discriminate the stereogenic centre of the secondary (R)-enantiomer of rac-3 according to the Kaslauzkas rule. The remote stereogenic centre was not discriminated by the lipase. The functionalised enantioenriched diastereoisomers obtained are important building blocks in organic synthesis. (C) 2010 Elsevier Ltd. All rights reserved.

A large-scale synthesis of enantiomerically pure gamma-hydroxy-organochalcogenides

Enantiomerically pure (R)- and (S)-gamma-hydroxy-organochalcogenides are prepared using poly-[R]-3-hydroxybutanoate (PHB) as the starting material. (C) 2009 Elsevier Ltd. All rights reserved.

Isosorbide Polyesters from Enzymatic Catalysis

The synthesis of isosorbide aliphatic polyesters is demonstrated by the use of Novozym 435, a catalyst consisting of Candida antarctica lipase B immobilized on a macroporous support Several experimental procedures were tested and azeotropic distillation was most effective in removing low mass byproduct Furthermore, the use of diethyl ester derivatives of diacid comonomers gave isosorbide copolyesters with highest Isolated yield and molecular weights The length of the diacid aliphatic chain was less restrictive, but with a clear preference for longer aliphatic chains The molecular mass values of the obtained products were equivalent or higher than those obtained by nonenzymatic polymerizations, a clear illustration of the potential of enzymatic over conventional catalysis The ability of Novozym 435 to catalyze the synthesis of isosorbide polyester with weight-average molecular weights in excess of 40000 Da was unexpected given that isosorbide has two chemically distinct secondary hydroxyl groups This is the first example in which isosorbide polyesters were synthesized by enzyme catalysis, opening a large array of possibilities for this important class of biomass-derived building blocks Because these polymers are potential biomaterials the total absence of conventional Lewis acid catalyst residues represents a major Improvement in the toxicity of the material

Synthesis, Structural Characterization, and Biological Evaluation of Oxorhenium(V) Complexes with a Novel Type of Thiosemicarbazones Derived from N-[N `,N `-Dialkylamino(thiocarbonyl)]benzimidoyl Chlorides

Reactions of N-[N`,N`-diethylamino(thiocarbonyl)]benzimidoyl chloride with 4,4-dialkylthiosemicarbazides give a novel class of thiosemicarbazides/thiosemicarbazones, H(2)L, which causes a remarkable reduction of cell growth in in vitro experiments. These strong antiproliferative effects are also observed for oxorhenium(V) complexes of the general composition [ReOCl(L)], which are formed by reactions of the potentially tridentate ligands with (NBu(4))[ReOCl(4)]. A systematic substitution of the alkyl groups in the thiosemicarbazone building blocks of the ligands do not significantly influence the biological activity of the metal complexes, while the replacement of the chloro ligand by a PPh(3) ligand (by the replacement of the oxo unit by a nitrido ligand) completely terminated the cytotoxicity of the metal complexes.

Synthesis and characterization of mono and polymeric cyclopalladated compounds: Crystal and molecular structure of [{Pd(dmba)(ONO(2))}(2)(mu-pz)] center dot H(2)O (pz = pyrazine)

In the treatment of cyclometallated dimer [Pd(dmba)(mu-Cl)](2) (dmba = N,N-dimethylbenzylamine) with AgNO(3) and acetonitrile the result was the monomeric cationic precursor [Pd(dmba)(NCMe)(2)](NO(3)) (NCMe=acetonitrile) (1). Compound 1 reacted with m-nitroaniline (m-NAN) and pirazine (pz), originating [Pd(dmba)(ONO(2))(m-NAN)] (2) and [{Pd(dmba)(ONO(2))}(2)(mu-pz)] center dot H(2)O (3), respectively. These compounds were characterized by elemental analysis, IR and NMR spectroscopy. The IR spectra of (2-3) display typical bands of monodentade O-bonded nitrate groups, whereas the NMR data of 3 are consistent with the presence of bridging pyrazine ligands. The structure of compound 3 was determined by Xray diffraction analysis. This packing consists of a supramolecular chain formed by hydrogen bonding between the water molecule and nitrato ligands of two consecutive [Pd(2)(dmba)(2)(ONO(2))2(mu-pz)] units. (c) 2008 Elsevier Ltd. All rights reserved.

Fyra röster om människan vid dopet : Fyra representanter från Svenska kyrkan och Pingstkyrkan om människosynen i doptraditionen

The purpose of this study was to investigate what view of humans that emerges when priests/reverends talk about man in relation to baptism. The study consists of qualitative interviews with four priests/reverends. There were two representatives from the church of Sweden, and two from the Pentecostal church. The aim and questions in the study focus on what view of humans that emerges. Will there be similarities and differences in the view of humans, and is it possible to refer the result to the respective church. The theory that is being used focusses on so called components of how humans are viewed and these components can be seen as building blocks in how a view of humans is formed. The background comes from the varying view of the baptism tradition that exists in Christianity. The church of Sweden mainly baptizes children, whereas the Pentecostal church practices believer´s baptism. The result demonstrates that the reflected view of humans in different ways can prove what each church of the interviewee represents.

Styrning och ideologiska dilemman i Skolverkets skolutveckling : exemplet ANDT-undervisning

Governing and ideological dilemmas in drug education Drug education (ANT) in Swedish schools has a history over decades. Here, the pedagogical approaches fluctuated between transfer of solid knowledge from the teacher to the pupil, and working with values and have a more pupil-driven teaching – a classic dichotomy. Rhetoric about the school’s way of teaching has thus always been ambivalent and subject to reexamination. The study analyses various textual material on ANT education. As a methodological tool Billigs concept Ideological dilemmas is used, which is a fruitful way to identify the rhetorical building blocks of (school) politics, but also to analyse political talk in more detail. The article analyses the ideological dilemmas under three dichotomies: Knowledge vs. values, teacher control vs. learner control, and prevention vs. promotion. Throughout we can see this question of how teaching could be successful, given the tension between authority and democracy. The article concludes by relating this basic ideological dilemma in a wider discursive context of governance in our time. 

The Purely Reflected Self

Belief in the concept of the self causes suffering. Unfortunately, although conceptual constructions like this may help to define our goal—the casting off of the belief in the self—this is a much more difficult thing to actualize and attain in daily practice. Our building blocks can form a neat tower, and we can climb to the top and gaze at the horizon, but they will topple, leaving us once again over our heads in the hedgerow. Buddha describes his teachings as a raft to ford the river of suffering in order to reach the far off bank of enlightenment: as one does not take the raft after crossing the river, so we must not lean on his teachings to make our way through life. So I intend here to abandon the raft for other accounts of existence written by other thinkers, and in this my purpose is twofold: First, in reading other interpretations we can gain new tools with which to study the architecture of the concept of the self, and second, in studying the history of the concept of self as it progresses through history we can better understand the non-inherentness of this problematic construct. I intend to examine the philosophies of self in the Chinese and European traditions, and their subsequent deconstructive traditions in order to achieve this goal.

Uma história do pensamento em marketing

Estudar a evolução de uma disciplina, sua história, pode auxiliar em um entendimento melhor desta disciplina, de forma mais ampla e profunda.. Considerando uma disciplina como a acumulação de conhecimento científico dentro de uma área de conhecimento estabelecida através de um processo de construção evolutiva, este estudo procura estabelecer e apresentar o processo evolutivo do Marketing. Assume-se neste trabalho que os building blocks da construção de uma disciplina se dá através dos artigos acadêmicos aceitos e publicados em Journals que são veículos de associações de classe, ou apresentados em congressos, ambos promovidos por associações de classe que reflitam os interesses de uma escola de pensamento. Assim, neste trabalho, são apresentadas as evoluções das principais escolas de pensamento da disciplina Marketing juntamente com os artigos de autores mais representativos.

A Framework supporting collaboration on the distributed design of integrated systems

The work described in this thesis aims to support the distributed design of integrated systems and considers specifically the need for collaborative interaction among designers. Particular emphasis was given to issues which were only marginally considered in previous approaches, such as the abstraction of the distribution of design automation resources over the network, the possibility of both synchronous and asynchronous interaction among designers and the support for extensible design data models. Such issues demand a rather complex software infrastructure, as possible solutions must encompass a wide range of software modules: from user interfaces to middleware to databases. To build such structure, several engineering techniques were employed and some original solutions were devised. The core of the proposed solution is based in the joint application of two homonymic technologies: CAD Frameworks and object-oriented frameworks. The former concept was coined in the late 80's within the electronic design automation community and comprehends a layered software environment which aims to support CAD tool developers, CAD administrators/integrators and designers. The latter, developed during the last decade by the software engineering community, is a software architecture model to build extensible and reusable object-oriented software subsystems. In this work, we proposed to create an object-oriented framework which includes extensible sets of design data primitives and design tool building blocks. Such object-oriented framework is included within a CAD Framework, where it plays important roles on typical CAD Framework services such as design data representation and management, versioning, user interfaces, design management and tool integration. The implemented CAD Framework - named Cave2 - followed the classical layered architecture presented by Barnes, Harrison, Newton and Spickelmier, but the possibilities granted by the use of the object-oriented framework foundations allowed a series of improvements which were not available in previous approaches: - object-oriented frameworks are extensible by design, thus this should be also true regarding the implemented sets of design data primitives and design tool building blocks. This means that both the design representation model and the software modules dealing with it can be upgraded or adapted to a particular design methodology, and that such extensions and adaptations will still inherit the architectural and functional aspects implemented in the object-oriented framework foundation; - the design semantics and the design visualization are both part of the object-oriented framework, but in clearly separated models. This allows for different visualization strategies for a given design data set, which gives collaborating parties the flexibility to choose individual visualization settings; - the control of the consistency between semantics and visualization - a particularly important issue in a design environment with multiple views of a single design - is also included in the foundations of the object-oriented framework. Such mechanism is generic enough to be also used by further extensions of the design data model, as it is based on the inversion of control between view and semantics. The view receives the user input and propagates such event to the semantic model, which evaluates if a state change is possible. If positive, it triggers the change of state of both semantics and view. Our approach took advantage of such inversion of control and included an layer between semantics and view to take into account the possibility of multi-view consistency; - to optimize the consistency control mechanism between views and semantics, we propose an event-based approach that captures each discrete interaction of a designer with his/her respective design views. The information about each interaction is encapsulated inside an event object, which may be propagated to the design semantics - and thus to other possible views - according to the consistency policy which is being used. Furthermore, the use of event pools allows for a late synchronization between view and semantics in case of unavailability of a network connection between them; - the use of proxy objects raised significantly the abstraction of the integration of design automation resources, as either remote or local tools and services are accessed through method calls in a local object. The connection to remote tools and services using a look-up protocol also abstracted completely the network location of such resources, allowing for resource addition and removal during runtime; - the implemented CAD Framework is completely based on Java technology, so it relies on the Java Virtual Machine as the layer which grants the independence between the CAD Framework and the operating system. All such improvements contributed to a higher abstraction on the distribution of design automation resources and also introduced a new paradigm for the remote interaction between designers. The resulting CAD Framework is able to support fine-grained collaboration based on events, so every single design update performed by a designer can be propagated to the rest of the design team regardless of their location in the distributed environment. This can increase the group awareness and allow a richer transfer of experiences among them, improving significantly the collaboration potential when compared to previously proposed file-based or record-based approaches. Three different case studies were conducted to validate the proposed approach, each one focusing one a subset of the contributions of this thesis. The first one uses the proxy-based resource distribution architecture to implement a prototyping platform using reconfigurable hardware modules. The second one extends the foundations of the implemented object-oriented framework to support interface-based design. Such extensions - design representation primitives and tool blocks - are used to implement a design entry tool named IBlaDe, which allows the collaborative creation of functional and structural models of integrated systems. The third case study regards the possibility of integration of multimedia metadata to the design data model. Such possibility is explored in the frame of an online educational and training platform.

An evaluation of the Business Model Canvas by technology-oriented startups in Brazil : a qualitative study about the usage of the tool by Brazilian entrepreneurs

The following paper was conducted with the support of several entrepreneurs and startups from Brazil. The aim of the research was to find out which impact the Business Model Canvas, further abbreviated as BMC, has on technology-oriented startups in Brazil. The first step of the study was identify some general concepts of entrepreneurship, as well as the conditions and environment of the country. Afterwards, it was focused on defining and comparing different business model tools and concepts to the BMC. After the literature review and meeting with several professionals in the area of entrepreneurship and startups, a questionnaire was formulated in order to conduct the qualitative study and identify the main impact of the tool. The questionnaire was answered by ten startups. In order to check the validity and credibility of the research outcomes, theory and investigator triangulation was used. As a result, the usage of the BMC could be evaluated by obtaining the outcomes and the theory, which showed that Brazilian tech startups are using Osterwalder’s model for the reason of idea creation and testing, validating and pivoting their business model. Interestingly, the research revealed that the entrepreneurs are using the tool often not in the traditional way of printing it, but rather applying it as a thinking approach. Besides, the entrepreneurs are focusing mostly on developing a strong Value Proposition, Customer Segment and sustainable Revenue Streams, while afterwards the remaining building blocks are built. Moreover, the research showed that the startups are using also other concepts, such as the Customer Development Process or Build-Measure-Learn Feedback Loop. These methodologies are often applied together with the BMC and helps to identify the most sustainable components of the business idea. Keywords: Business

An investigation of Hebbian phase sequences as assembly graphs

Hebb proposed that synapses between neurons that fire synchronously are strengthened, forming cell assemblies and phase sequences. The former, on a shorter scale, are ensembles of synchronized cells that function transiently as a closed processing system; the latter, on a larger scale, correspond to the sequential activation of cell assemblies able to represent percepts and behaviors. Nowadays, the recording of large neuronal populations allows for the detection of multiple cell assemblies. Within Hebb's theory, the next logical step is the analysis of phase sequences. Here we detected phase sequences as consecutive assembly activation patterns, and then analyzed their graph attributes in relation to behavior. We investigated action potentials recorded from the adult rat hippocampus and neocortex before, during and after novel object exploration (experimental periods). Within assembly graphs, each assembly corresponded to a node, and each edge corresponded to the temporal sequence of consecutive node activations. The sum of all assembly activations was proportional to firing rates, but the activity of individual assemblies was not. Assembly repertoire was stable across experimental periods, suggesting that novel experience does not create new assemblies in the adult rat. Assembly graph attributes, on the other hand, varied significantly across behavioral states and experimental periods, and were separable enough to correctly classify experimental periods (Naïve Bayes classifier; maximum AUROCs ranging from 0.55 to 0.99) and behavioral states (waking, slow wave sleep, and rapid eye movement sleep; maximum AUROCs ranging from 0.64 to 0.98). Our findings agree with Hebb's view that assemblies correspond to primitive building blocks of representation, nearly unchanged in the adult, while phase sequences are labile across behavioral states and change after novel experience. The results are compatible with a role for phase sequences in behavior and cognition.

Compositional analysis for an unbiased measure of soil aggregation

Soil aggregation is an index of soil structure measured by mean weight diameter (MWD) or scaling factors often interpreted as fragmentation fractal dimensions (D-f). However, the MWD provides a biased estimate of soil aggregation due to spurious correlations among aggregate-size fractions and scale-dependency. The scale-invariant D-f is based on weak assumptions to allow particle counts and sensitive to the selection of the fractal domain, and may frequently exceed a value of 3, implying that D-f is a biased estimate of aggregation. Aggregation indices based on mass may be computed without bias using compositional analysis techniques. Our objective was to elaborate compositional indices of soil aggregation and to compare them to MWD and D-f using a published dataset describing the effect of 7 cropping systems on aggregation. Six aggregate-size fractions were arranged into a sequence of D-1 balances of building blocks that portray the process of soil aggregation. Isometric log-ratios (ilrs) are scale-invariant and orthogonal log contrasts or balances that possess the Euclidean geometry necessary to compute a distance between any two aggregation states, known as the Aitchison distance (A(x,y)). Close correlations (r>0.98) were observed between MWD, D-f, and the ilr when contrasting large and small aggregate sizes. Several unbiased embedded ilrs can characterize the heterogeneous nature of soil aggregates and be related to soil properties or functions. Soil bulk density and penetrater resistance were closely related to A(x,y) with reference to bare fallow. The A(x,y) is easy to implement as unbiased index of soil aggregation using standard sieving methods and may allow comparisons between studies. (C) 2012 Elsevier B.V. All rights reserved.

Compósito para fabricação de blocos para construção de casas: estudos térmico e de materiais

We present two models of blocks made of composite material obtained from the use of cement, plaster, EPS crushed, shredded tire, mud, sand and water, for the construction of popular housing. Were made metal molds for the manufacture of blocks to be used in the construction of a residence for low-income families. Performed tests of compressive strength of the composite for various formulations that met the specific standard for blocks used in construction. To study the thermal conductivity of the composite for further study of thermal comfort generated in a residence built with the proposed composite. We also determined the mass-specific and water absorption for each formulation studied. Using a home already built with another composite material, made up the closing of a window with the building blocks and found the thermal insulation, measuring external and internal temperatures of the blocks. The blocks had made good thermal insulation of the environment, resulting in differences of up to 12.6°C between the outer and inner faces. It will be shown the feasibility of using composite for the end proposed and chosen the most appropriate wording

Theoretical study of the structure and stability of NbxOy, and NbxOy+ (x = 1-3; y = 2-5, 7, 8) clusters

Geometric, thermodynamic and electronic properties of cluster neutrals NbxOy and cations NbxOy+ (x = 1-3; y = 2-5, 7, 8) have been characterized theoretically. A DFT calculation using a hybrid combination of B3LYP with contracted Huzinaga basis sets. Numerical results of the relative stabilities, ionization potentials and band gaps of different clusters are in agreement with experiment. Analysis of dissociation channels supports the more stable building blocks as formed by NbO2, NbO2+ NbO3 and NbO3+ stoichiometries. The net atomic charges suggest that oxygen donor molecules can interact more favorably on central niobium atoms of cluster cations, while the interaction with oxygen acceptor molecules is more favorable on the terminal oxygen atoms of neutral clusters. A topological analysis of the electron localization function gradient field indicates that the clusters may be described as having a strong ionic interaction between Nb and O atoms. Published by Elsevier B.V. B.V.