Facile synthesis of polymer-peptide conjugates via direct amino acid coupling chemistry

Polymer-peptide conjugates (also known as biohy-brids) are attracting considerable attention as injectable materials owing to the self-assembling behavior of the peptide and the ability to control the material properties using the polymer component. To this end, a simple method for preparing poly(ethylene oxide)-oligophenylalanine polymer-peptide conjugates (mPEOm-F n-OEt) using isobutylchloroformate as the activating reagent has been identified and developed. The synthetic approach reported employs an industrially viable route to produce conjugates with high yield and purity. Moreover, the approach allows judicious selection of the precursor building blocks to produce libraries of polymer-peptide conjugates with complete control over the molecular composition. Control over the molecular make-up of the conjugates allows fine control of the physicochemical properties, which will be exploited in future studies into the prominent self-assembling behavior of such materials. © 2013 Wiley Periodicals, Inc.

Base-free, one-pot chemocatalytic conversion of glycerol to methyl lactate using supported gold catalysts

We report an efficient one-pot conversion of glycerol (GLY) to methyl lactate (MLACT) in methanol in good yields (73 % at 95 % GLY conversion) by using Au nanoparticles on commercially available ultra-stable zeolite-Y (USY) as the catalyst (160 °C, air, 47 bar pressure, 0.25 M GLY, GLY-to-Au mol ratio of 1407, 10 h). The best results were obtained with zeolite USY-600, a catalyst that has both Lewis and Brønsted sites. This methodology provides a direct chemo-catalytic route for the synthesis of MLACT from GLY. MLACT is stable under the reaction conditions, and the Au/USY catalyst was recycled without a decrease in the activity and selectivity. From glycerol to green building blocks and solvents! An efficient, base-free conversion of glycerol to methyl lactate in methanol is reported, achieving good yields (73 % at 95 % glycerol conversion) using Au/ultra-stable zeolite-Y (USY) as the catalyst and environmentally benign oxygen as the oxidant by combining two separate reaction steps efficiently in a one pot procedure. The Au/USY catalyst can be recycled without a decrease in the activity and selectivity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Early spatial vision:a view through two eyes

Simple features such as edges are the building blocks of spatial vision, and so I ask: how arevisual features and their properties (location, blur and contrast) derived from the responses ofspatial filters in early vision; how are these elementary visual signals combined across the twoeyes; and when are they not combined? Our psychophysical evidence from blur-matchingexperiments strongly supports a model in which edges are found at the spatial peaks ofresponse of odd-symmetric receptive fields (gradient operators), and their blur B is givenby the spatial scale of the most active operator. This model can explain some surprisingaspects of blur perception: edges look sharper when they are low contrast, and when theirlength is made shorter. Our experiments on binocular fusion of blurred edges show that singlevision is maintained for disparities up to about 2.5*B, followed by diplopia or suppression ofone edge at larger disparities. Edges of opposite polarity never fuse. Fusion may be served bybinocular combination of monocular gradient operators, but that combination - involvingbinocular summation and interocular suppression - is not completely understood.In particular, linear summation (supported by psychophysical and physiological evidence)predicts that fused edges should look more blurred with increasing disparity (up to 2.5*B),but results surprisingly show that edge blur appears constant across all disparities, whetherfused or diplopic. Finally, when edges of very different blur are shown to the left and righteyes fusion may not occur, but perceived blur is not simply given by the sharper edge, nor bythe higher contrast. Instead, it is the ratio of contrast to blur that matters: the edge with theAbstracts 1237steeper gradient dominates perception. The early stages of binocular spatial vision speak thelanguage of luminance gradients.

State–society relations in a dynamic framework: The case of the Far East and Sub-Saharan Africa.

According to the textbook approach, the developmental states of the Far East have been considered as strong and autonomous entities. Although their bureaucratic elites have remained isolated from direct pressures stemming from society, the state capacity has also been utilised in order to allocate resources in the interest of the whole society. Yet, society – by and large –has remained weak and subordinated to the state elite. On the other hand, the general perception of Sub-Saharan Africa (SSA) has been just the opposite. The violent and permanent conflict amongst rent-seeking groups for influence and authority over resources has culminated in a situation where states have become extremely weak and fragmented, while society – depending on the capacity of competing groups for mobilising resources to organise themselves mostly on a regional or local level (resulting in local petty kingdoms) – has never had the chance to evolve as a strong player. State failure in the literature, therefore, – in the context of SSA – refers not just to a weak and captured state but also to a non-functioning, and sometimes even non-existent society, too. Recently, however, the driving forces of globalisation might have triggered serious changes in the above described status quo. Accordingly, our hypothesis is the following: globalisation, especially the dynamic changes of technology, capital and communication have made the simplistic “strong state–weak society” (in Asia) and “weak state–weak society” (in Africa) categorisation somewhat obsolete. While our comparative study has a strong emphasis on the empirical scrutiny of trying to uncover the dynamics of changes in state–society relations in the two chosen regions both qualitatively and quantitatively, it also aims at complementing the meaning and essence of the concepts and methodology of stateness, state capacity and state-society relations, the well-known building blocks of the seminal works of Evans (1995), Leftwich (1995), Migdal (1988) or Myrdal (1968).

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.

Szimulációk és érzékenységvizsgálatok a magyar gazdaság egy középméretű makromodelljével = Simulations and sensitivity analyses with a medium-sized macro model of the Hungarian economy

A tanulmányban a Pénzügyminisztérium gazdaságpolitikai főosztálya és az MTA Közgazdaságtudományi Intézete által kifejlesztett középméretű negyedéves makrogazdasági modell segítségével elemezzük a magyar gazdaság legfontosabb mechanizmusait. A modellezés során követett alapelvek és a modell blokkjainak bemutatása után egy forgatókönyv-elemzés keretében vizsgáljuk a makrogazdasági és költségvetési folyamatokat befolyásoló főbb faktorok hatásait. A - tágan értelmezett - "bizonytalansági tényezőket" három csoportba soroljuk: megkülönböztetjük a külső környezet (például árfolyam) változását, a gazdasági szereplők viselkedésében rejlő bizonytalanságokat (például a bérigazodás sebességének vagy a fogyasztássimítás mértékének bizonytalanságát), valamint a gazdaságpolitikai lépéseket (például állami bérek emelését). Megmutatjuk, hogy e kockázatok makrokövetkezményei nem függetlenek egymástól, például egy árfolyamváltozás hatását befolyásolja a bérigazodás sebessége. ______ This paper analyses the most important mechanisms of the Hungarian economy using a medium-sized quarterly macroeconomic model developed jointly by the Economic Policy Department of the Ministry of Finance and the Institute of Economics of the Hungarian Academy of Sciences. After introducing the fundamental principles of modelling and the building blocks of the model investigated, within a scenario analysis, the authors present the effects of the main factors behind the macroeconomic and budgetary processes. The sources of uncertainty - defined in a broad sense - are categorized in three groups: change in the external environment (e.g. the exchange rate), uncertainties in the behav-iour of economic agents (e.g. in speed of wage adjustment or extent of consumption smoothing), and economic policy decisions (e.g. the increase in public sector wages). The macroeconomic consequences of these uncertainties are shown not to be independent of each other. For instance, the effects of an exchange rate shock are influenced by the speed of wage adjustment.

A reliability centered maintenance decision system for a discrete part manufacturing facility

This thesis develops and validates the framework of a specialized maintenance decision support system for a discrete part manufacturing facility. Its construction utilizes a modular approach based on the fundamental philosophy of Reliability Centered Maintenance (RCM). The proposed architecture uniquely integrates System Decomposition, System Evaluation, Failure Analysis, Logic Tree Analysis, and Maintenance Planning modules. It presents an ideal solution to the unique maintenance inadequacies of modern discrete part manufacturing systems. Well established techniques are incorporated as building blocks of the system's modules. These include Failure Mode Effect and Criticality Analysis (FMECA), Logic Tree Analysis (LTA), Theory of Constraints (TOC), and an Expert System (ES). A Maintenance Information System (MIS) performs the system's support functions. Validation was performed by field testing of the system at a Miami based manufacturing facility. Such a maintenance support system potentially reduces downtime losses and contributes to higher product quality output. Ultimately improved profitability is the final outcome. ^

Ionized cluster beam deposition: Modeling, cluster size measurement and applications

Clusters are aggregations of atoms or molecules, generally intermediate in size between individual atoms and aggregates that are large enough to be called bulk matter. Clusters can also be called nanoparticles, because their size is on the order of nanometers or tens of nanometers. A new field has begun to take shape called nanostructured materials which takes advantage of these atom clusters. The ultra-small size of building blocks leads to dramatically different properties and it is anticipated that such atomically engineered materials will be able to be tailored to perform as no previous material could.^ The idea of ionized cluster beam (ICB) thin film deposition technique was first proposed by Takagi in 1972. It was based upon using a supersonic jet source to produce, ionize and accelerate beams of atomic clusters onto substrates in a vacuum environment. Conditions for formation of cluster beams suitable for thin film deposition have only recently been established following twenty years of effort. Zinc clusters over 1,000 atoms in average size have been synthesized both in our lab and that of Gspann. More recently, other methods of synthesizing clusters and nanoparticles, using different types of cluster sources, have come under development.^ In this work, we studied different aspects of nanoparticle beams. The work includes refinement of a model of the cluster formation mechanism, development of a new real-time, in situ cluster size measurement method, and study of the use of ICB in the fabrication of semiconductor devices.^ The formation process of the vaporized-metal cluster beam was simulated and investigated using classical nucleation theory and one dimensional gas flow equations. Zinc cluster sizes predicted at the nozzle exit are in good quantitative agreement with experimental results in our laboratory.^ A novel in situ real-time mass, energy and velocity measurement apparatus has been designed, built and tested. This small size time-of-flight mass spectrometer is suitable to be used in our cluster deposition systems and does not suffer from problems related to other methods of cluster size measurement like: requirement for specialized ionizing lasers, inductive electrical or electromagnetic coupling, dependency on the assumption of homogeneous nucleation, limits on the size measurement and non real-time capability. Measured ion energies using the electrostatic energy analyzer are in good accordance with values obtained from computer simulation. The velocity (v) is measured by pulsing the cluster beam and measuring the time of delay between the pulse and analyzer output current. The mass of a particle is calculated from m = (2E/v$\sp2).$ The error in the measured value of background gas mass is on the order of 28% of the mass of one N$\sb2$ molecule which is negligible for the measurement of large size clusters. This resolution in cluster size measurement is very acceptable for our purposes.^ Selective area deposition onto conducting patterns overlying insulating substrates was demonstrated using intense, fully-ionized cluster beams. Parameters influencing the selectivity are ion energy, repelling voltage, the ratio of the conductor to insulator dimension, and substrate thickness. ^

Blood-brain barrier in vitro model: A tissue engineering approach and validation

This dissertation evaluated the feasibility of using commercially available immortalized cell lines in building a tissue engineered in vitro blood-brain barrier (BBB) co-culture model for preliminary drug development studies. Mouse endothelial cell line and rat astrocyte cell lines purchased from American Type Culture Collections (ATCC) were the building blocks of the co-culture model. An astrocyte derived acellular extracellular matrix (aECM) was introduced in the co-culture model to provide a novel in vitro biomimetic basement membrane for the endothelial cells to form endothelial tight junctions. Trans-endothelial electrical resistance (TEER) and solute mass transport studies were engaged to quantitatively evaluate the tight junction formation on the in-vitro BBB models. Immuno-fluorescence microscopy and Western Blot analysis were used to qualitatively verify the in vitro expression of occludin, one of the earliest discovered tight junction proteins. Experimental data from a total of 12 experiments conclusively showed that the novel BBB in vitro co-culture model with the astrocyte derived aECM (CO+aECM) was promising in terms of establishing tight junction formation represented by TEER values, transport profiles and tight junction protein expression when compared with traditional co-culture (CO) model setups and endothelial cells cultured alone. Experimental data were also found to be comparable with several existing in vitro BBB models built from various methods. In vitro colorimetric sulforhodamine B (SRB) assay revealed that the co-cultured samples with aECM resulted in less cell loss on the basal sides of the insert membranes than that from traditional co-culture samples. The novel tissue engineering approach using immortalized cell lines with the addition of aECM was proven to be a relevant alternative to the traditional BBB in vitro modeling.

Material Synthesis and Characterization on Low-Dimensional Cobaltates

In this thesis, results of the investigation of a new low-dimensional cobaltates Ba2-xSrxCoO 4 are presented. The synthesis of both polycrystalline and single crystalline compounds using the methods of conventional solid state chemical reaction and floating-zone optical furnace is first introduced. Besides making polycrystalline powders, we successfully, for the first time, synthesized large single crystals of Ba2CoO4. Single crystals were also obtained for Sr doped Ba2-xSrxCoO 4. Powder and single crystal x-ray diffraction results indicate that pure Ba2CoO4 has a monoclinic structure at room temperature. With Sr doping, the lattice structure changes to orthorhombic when x ≥ 0.5 and to tetragonal when x = 2.0. In addition, Ba2CoO4 and Sr2CoO4, have completely different basic building blocks in the structure. One is CoO4 tetrahedron and the later is CoO6 octahedron, respectively. Electronic and magnetic properties were characterized and discussed. The magnetic susceptibility, specific heat and thermal conductivity show that Ba2CoO4 has an antiferromagnetic (AF) ground state with an AF ordering temperature TN = 25 K. However, the magnitude of the Néel temperature TN is significantly lower than the Curie-Weiss temperature (:&thetas;: ∼ 110 K), suggesting either reduced-dimensional magnetic interactions and/or the existence of magnetic frustration. The AF interaction persists in all the samples with different doping concentrations. The Néel temperature doesn't vary much in the monoclinic structure regime but decreases when the system enters orthorhombic. Magnetically, Ba2CoO4 has an AF insulating ground state while Sr2CoO4 has a ferromagnetic (FM) metallic ground state. Neutron powder refinement results indicate a magnetic structure with the spin mostly aligned along the a-axis. The result from a μ-spin rotation/relaxation (μ+SR) experiment agrees with our refinement. It confirms the AF order in the ab -plane. We also studied the spin dynamics and its anisotropy in the AF phase. The results from inelastic neutron scattering show that spin waves have a clear dispersion along a-axis but not along c-axis, indicating spin anisotropy. This work finds the strong spin-lattice coupling in this novel complex material. The interplay between the two degrees of freedom results an interesting phase diagram. Further research is needed when large single crystal samples are available.

Theoretical investigations of intercellular communication in the microcirculation: Conducted responses, myoendothelial projections and endothelium derived hyperpolarizing factor

The contractile state of microcirculatory vessels is a major determinant of the blood pressure of the whole systemic circulation. Continuous bi-directional communication exists between the endothelial cells (ECs) and smooth muscle cells (SMCs) that regulates calcium (Ca2+) dynamics in these cells. This study presents theoretical approaches to understand some of the important and currently unresolved microcirculatory phenomena. ^ Agonist induced events at local sites have been shown to spread long distances in the microcirculation. We have developed a multicellular computational model by integrating detailed single EC and SMC models with gap junction and nitric oxide (NO) coupling to understand the mechanisms behind this effect. Simulations suggest that spreading vasodilation mainly occurs through Ca 2+ independent passive conduction of hyperpolarization in RMAs. Model predicts a superior role for intercellular diffusion of inositol (1,4,5)-trisphosphate (IP3) than Ca2+ in modulating the spreading response. ^ Endothelial derived signals are initiated even during vasoconstriction of stimulated SMCs by the movement of Ca2+ and/or IP3 into the EC which provide hyperpolarizing feedback to SMCs to counter the ongoing constriction. Myoendothelial projections (MPs) present in the ECs have been recently proposed to play a role in myoendothelial feedback. We have developed two models using compartmental and 2D finite element methods to examine the role of these MPs by adding a sub compartment in the EC to simulate MP with localization of intermediate conductance calcium activated potassium channels (IKCa) and IP3 receptors (IP 3R). Both models predicted IP3 mediated high Ca2+ gradients in the MP after SMC stimulation with limited global spread. This Ca 2+ transient generated a hyperpolarizing feedback of ∼ 2–3mV. ^ Endothelium derived hyperpolarizing factor (EDHF) is the dominant form of endothelial control of SMC constriction in the microcirculation. A number of factors have been proposed for the role of EDHF but no single pathway is agreed upon. We have examined the potential of myoendothelial gap junctions (MEGJs) and potassium (K+) accumulation as EDHF using two models (compartmental and 2D finite element). An extra compartment is added in SMC to simulate micro domains (MD) which have NaKα2 isoform sodium potassium pumps. Simulations predict that MEGJ coupling is much stronger in producing EDHF than alone K+ accumulation. On the contrary, K+ accumulation can alter other important parameters (EC V m, IKCa current) and inhibit its own release as well as EDHF conduction via MEGJs. The models developed in this study are essential building blocks for future models and provide important insights to the current understanding of myoendothelial feedback and EDHF.^

Illustrating Cognitive Connections between Math and Language in Pre-Service Teachers’ Perceptions of Common or Everyday Terms

This paper introduces a new construct that we term Math Mediated Language (MML) focusing on the notion that common or everyday terms with mathematical meanings are important building blocks for students’ mathematical reasoning. A survey given to 96 pre-service early childhood educators indicated clear patterns of perceptions of these terms.

Uma investigação das sequências de fase Hebbianas descritas como grafos de assembleias neuronais

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 neuronal assemblies correspond to primitive building blocks of representation, nearly unchanged in 10 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

Economia criativa e estratégia como prática social: uma abordagem teórico-empírico-conceitual a partir de ambientes criativos de grupos musicais

This study seeks to identify how creative environments of musical groups are configured in the Strategy as Practice perspective as theoretical, empirical and conceptual models. It develops within the theoretical framework, discussions on the context of the Creative Economy, Creative Industries, creative environment, organizational paradigm of Creative Economy, music as a creative environment and business, design and dynamics of Strategy as Practice and conjecture about the contextualism and other epistemological currents. The study is shaped as an exploratory and descriptive research, utilizing the qualitative method and being characterized as a Grounded Theory. A total of four musical groups of different styles, markets and areas of operation with over ten years of activity were surveyed. The Grounded Theory and simple observation methods were used for both data collection and analysis. The software ATLAS.ti. was used to help with the analysis. The research shows that the bands perceive the specialized expertise in the virtual social media as a strategic differentiator. It also shows that the groups nourish individuation and the differentiation in their relationship with the individual. Finally, it validates that these organizations get teams involved and value the dynamic design of their routines in strategic decision making, paying attention to a strategic social bias. Strategy and Creative Practice is the main category that emerged from the data. This category is explained through the three aforementioned results. It shows that organizations that are part of the Creative Economy perform simultaneously and dynamically creative and strategic making at both artistic and managerial levels.The theory created is validated by the principles of degree of coherence, functionality, relevance, flexibility, density and integration, and it is inserted in the contextualism principle, which points the knowledge as related to the context in which it is placed and discussed.

Utilização de pulsos de radiofrequência fortemente modulados no processamento de informação quântica via ressonância magnética nuclear

Nesta dissertação apresentamos um trabalho de desenvolvimento e utilização de pulsos de radiofreqüência modulados simultaneamente em freqüência, amplitude e fase (pulsos fortemente modulados, SMP, do inglês Strongly Modulated Pulses) para criar estados iniciais e executar operações unitárias que servem como blocos básicos para processamento da informação quântica utilizando Ressonância Magnética Nuclear (RMN). As implementações experimentais foram realizas em um sistema de 3 q-bits constituído por spins nucleares de Césio 133 (spin nuclear 7/2) em uma amostra de cristal líquido em fase nemática. Os pulsos SMP´s foram construídos teoricamente utilizando um programa especialmente desenvolvido para esse fim, sendo o mesmo baseado no processo de otimização numérica Simplex Nelder-Mead. Através deste programa, os pulsos SMP foram otimizados de modo a executarem as operações lógicas desejadas com durações consideravelmente menores que aquelas realizadas usando o procedimento usual de RMN, ou seja, seqüências de pulsos e evoluções livres. Isso tem a vantagem de reduzir os efeitos de descoerência decorrentes da relaxação do sistema. Os conceitos teóricos envolvidos na criação dos SMPs são apresentados e as principais dificuldades (experimentais e teóricas) que podem surgir devido ao uso desses procedimentos são discutidas. Como exemplos de aplicação, foram produzidos os estados pseudo-puros usados como estados iniciais de operações lógicas em RMN, bem como operações lógicas que foram posteriormente aplicadas aos mesmos. Utilizando os SMP\'s também foi possível realizar experimentalmente os algoritmos quânticos de Grover e Deutsch-Jozsa para 3 q-bits. A fidelidade das implementações experimentais foi determinadas utilizando as matrizes densidade experimentais obtidas utilizando um método de tomografia da matriz densidade previamente desenvolvido.