Structural Characterization of Photopolymerizable Binary Liposomes Containing Diacetylenic and Saturated Phospholipids

The use of liposomes to encapsulate materials has received widespread attention for drug delivery, transfection, diagnostic reagent, and as immunoadjuvants. Phospholipid polymers form a new class of biomaterials with many potential applications in medicine and research. Of interest are polymeric phospholipids containing a diacetylene moiety along their acyl chain since these kinds of lipids can be polymerized by Ultra-Violet (UV) irradiation to form chains of covalently linked lipids in the bilayer. In particular the diacetylenic phosphatidylcholine 1,2-bis(10,12-tricosadiynoyl)- sn-glycero-3-phosphocholine (DC8,9PC) can form intermolecular cross-linking through the diacetylenic group to produce a conjugated polymer within the hydrocarbon region of the bilayer. As knowledge of liposome structures is certainly fundamental for system design improvement for new and better applications, this work focuses on the structural properties of polymerized DC8,9PC:1,2-dimyristoyl-sn-glycero-3-phusphocholine (DMPC) liposomes. Liposomes containing mixtures of DC8,9PC and DMPC, at different molar ratios, and exposed to different polymerization cycles, were studied through the analysis of the electron spin resonance (ESR) spectra of a spin label incorporated into the bilayer, and the calorimetric data obtained from differential scanning calorimetry (DSC) studies. Upon irradiation, if all lipids had been polymerized, no gel-fluid transition would be expected. However, even samples that went through 20 cycles of UV irradiation presented a DSC band, showing that around 80% of the DC8,9PC molecules were not polymerized. Both DSC and ESR indicated that the two different lipids scarcely mix at low temperatures, however few molecules of DMPC are present in DC8,9PC rich domains and vice versa. UV irradiation was found to affect the gel fluid transition of both DMPC and DC8,9PC rich regions, indicating the presence of polymeric units of DC8,9PC in both areas, A model explaining lipids rearrangement is proposed for this partially polymerized system.

A closer look at the influence of tubular initial conditions on two-particle correlations

In a recent paper, the hydrodynamic code NEXSPheRIO was used in conjunction with STAR analysis methods to study two-particle correlations as a function of Delta(eta) and Delta phi. The various structures observed in the data were reproduced. In this work, we discuss the origin of these structures as well as present new results.

Influence of different solvents on the structural, optical and morphological properties of CdS nanoparticles

CdS is one of the most important II-VI semiconductors, with applications in solar cells, optoelectronics and electronic devices. CdS nanoparticles were synthesized via microwave-assisted solvothermal technique. Structural and morphological characterization revealed the presence of crystalline structures presenting single phase with different morphologies such as ""nanoflowers"" and nanoplates depending on the solvent used. Optical characterization was made by diffuse reflectance and photoluminescence spectroscopy, revealing the influence of the different solvents on the optical properties due to structural defects generated during synthesis. It is proposed that these defects are related to sulfur vacancies, with higher concentration of defects for the sample synthesized in ethylene glycol in comparison with the one synthesized in ethylene diamine. (C) 2011 Elsevier B.V. All rights reserved.

On the efficiency of data representation on the modeling and characterization of complex networks

Specific choices about how to represent complex networks can have a substantial impact on the execution time required for the respective construction and analysis of those structures. In this work we report a comparison of the effects of representing complex networks statically by adjacency matrices or dynamically by adjacency lists. Three theoretical models of complex networks are considered: two types of Erdos-Renyi as well as the Barabasi-Albert model. We investigated the effect of the different representations with respect to the construction and measurement of several topological properties (i.e. degree, clustering coefficient, shortest path length, and betweenness centrality). We found that different forms of representation generally have a substantial effect on the execution time, with the sparse representation frequently resulting in remarkably superior performance. (C) 2011 Elsevier B.V. All rights reserved.

Study of the spectroscopic properties and first hyperpolarizabilities of disperse azo dyes derived from 2-amino-5-nitrothiazole

The solvatochromism and other spectroscopic and photophysical characteristics of four azo disperse dyes, derived from 2-amino-5-nitrothiazole, were evaluated and interpreted with the aid of experimental data and quantum mechanical calculations. For the non-substituted compound two conformers, E and Z, were proposed for the isolated molecules, being the second one considerably less stable. The optimization of these structures in combination with a SCRF methodology (IEFPCM, Simulating the molecules in a continuum dielectric with characteristics of methanol), suggests that the Z form is not stable in solution. This same behaviour is expected for the substituted compounds, which is corroborated by experimental data presented in previous investigations [A.E.H. Machado, L.M. Rodrigues, S. Gupta, A.M.F. Oliveira-Campos, A.M.S. Silva, J. Mol. Struct. 738 (2005) 239-245]. For the substituted compounds, two forms derived from E conformer (A and R) are possible. Quantum mechanical data suggest for the isolated molecules, that the low energy absorption hand of the E conformers involve at least two close electronic states. having the low-lying excited state a (1)(n,pi*) nature, and being the S-2 state attributed to a (1)(pi,pi*) transition. The data also suggest a small energy gap between the absorption peaks of A and B, related to the easy conversion between these forms. For the structures optimized in combination with the applied SCRF methodology, an states inversion is observed for the Substituted compounds, with a considerable diminish of the energy gap between A and B absorption peaks. The electronic spectra of these compounds are quite sensitive to changes in the solvent polarity. The positive solvatochromism is more evident in aprotic solvents, probably due to the polarization induced by the solute. These compounds do not fluoresce at 298 K, but present a small but perceptible fluorescence at 77 K, which seems to be favoured by the nature of the group in the 2 `-position of the phenyl ring. Moreover, such compounds present expressive values for first hyperpolarizability, which implies in good non-linear optics (NLO) responses and photoswitching capability. (C) 2008 Elsevier B.V. All rights reserved.

Enhanced visualization of histological samples with an adjustable RGB contrast system with application for tissue used in photodynamic therapy

The analysis of histological sections has long been a valuable tool in the pathological studies. The interpretation of tissue conditions, however, relies directly on visual evaluation of tissue slides, which may be difficult to interpret because of poor contrast or poor color differentiation. The Chromatic Contrast Visualization System (CCV) combines an optical microscope with electronically controlled light-emitting diodes (LEDs) in order to generate adjustable intensities of RGB channels for sample illumination. While most image enhancement techniques rely on software post-processing of an image acquired under standard illumination conditions, CCV produces real-time variations in the color composition of the light source itself. The possibility of covering the entire RGB chromatic range, combined with the optical properties of the different tissues, allows for a substantial enhancement in image details. Traditional image acquisition methods do not exploit these visual enhancements which results in poorer visual distinction among tissue structures. Photodynamic therapy (PDT) procedures are of increasing interest in the treatment of several forms of cancer. This study uses histological slides of rat liver samples that were induced to necrosis after being exposed to PDT. Results show that visualization of tissue structures could be improved by changing colors and intensities of the microscope light source. PDT-necrosed tissue samples are better differentiated when illuminated with different color wavelengths, leading to an improved differentiation of cells in the necrosis area. Due to the potential benefits it can bring to interpretation and diagnosis, further research in this field could make CCV an attractive technique for medical applications.

Investigation by Combined Solid-State NMR and SAXS Methods of the Morphology and Domain Size in Polystyrene-b-Polyethylene Oxide-b-Polystyrene Triblock Copolymers

The microphase structure of a series of polystyrene-b-polyethylene oxide-b-polystyrene (SEOS) triblock copolymers with different compositions and molecular weights has been studied by solid-state NMR, DSC, wide and small angle X-ray scattering (WAXS and SAXS). WAXS and DSC measurements were used to detect the presence of crystalline domains of polyethyleneoxide (PEO) blocks at room temperature as a function of the copolymer chemical composition. Furthermore, DSC experiments allowed the determination of the melting temperatures of the crystalline part of the PEO blocks. SAXS measurements, performed above and below the melting temperature of the PEO blocks, revealed the formation of periodic structures, but the absence or the weakness of high order reflections peaks did not allow a clear assessment of the morphological structure of the copolymers. This information was inferred by combining the results obtained by SAXS and (1)H NMR spin diffusion experiments, which also provided an estimation of the size of the dispersed phases of the nanostructured copolymers. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48:55-64,2010

The CATH Hierarchy Revisited-Structural Divergence in Domain Superfamilies and the Continuity of Fold Space

This paper explores the structural continuum in CATH and the extent to which superfamilies adopt distinct folds. Although most superfamilies are structurally conserved, in some of the most highly populated superfamilies (4% of all superfamilies) there is considerable structural divergence. While relatives share a similar fold in the evolutionary conserved core, diverse elaborations to this core can result in significant differences in the global structures. Applying similar protocols to examine the extent to which structural overlaps occur between different fold groups, it appears this effect is confined to just a few architectures and is largely due to small, recurring super-secondary motifs (e.g., alpha beta-motifs, alpha-hairpins). Although 24% of superfamilies overlap with superfamilies having different folds, only 14% of nonredundant structures in CATH are involved in overlaps. Nevertheless, the existence of these overlaps suggests that, in some regions of structure space, the fold universe should be seen as more continuous.

Multiple stages of detergent-erythrocyte membrane interaction-A spin label study

The various stages of the interaction between the detergent Triton X-100 (TTX-100) and membranes of whole red blood cells (RBC) were investigated in a broad range of detergent concentrations. The interaction was monitored by RBC hemolysis-assessed by release of intracellular hemoglobin (Hb) and inorganic phosphate- and by analysis of EPR spectra of a fatty acid spin probe intercalated in whole RBC suspensions, as well as pellets and supernatants obtained upon centrifugation of detergent-treated cells. Hemolysis finished at ca. 0.9 mM TTX-100. Spectral analysis and calculation of order parameters (S) indicated that a complex sequence of events takes place, and allowed the characterization of various structures formed in the different stages of detergent-membrane interaction. Upon reaching the end of cell lysis, essentially no pellet was detected, the remaining EPR signal being found almost entirely in the supernatants. Calculated order parameters revealed that whole RBC suspensions, pellets, and supernatants possessed a similar degree of molecular packing, which decreased to a small extent up to 2.5 mM detergent. Between 3.2 and 10 mM TTX-100, a steep decrease in S was observed for both whole RBC suspensions and supernatants. Above 10 mM detergent, S decreased in a less pronounced manner and the EPR spectra approached that of pure TTX-100 micelles. The data were interpreted in terms of the following events: at the lower detergent concentrations, an increase in membrane permeability occurs: the end of hemolysis coincides with the lack of pellet upon centrifugation. Up to 2.5 mM TTX-100 the supernatants consist of a (very likely) heterogeneous population of membrane fragments with molecular packing similar to that of whole cells. As the detergent concentration increases, mixed micelles are formed containing lipid and/or protein, approaching the packing found in pure TTX-100 micelles. This analysis is in agreement with the models proposed by Lasch (Biochim. Biophys Acta 1241 (1995) 269-292) and by Le Maire and coworkers (Biochim. Biophys. Acta 1508 (2000) 86-111). (C) 2010 Elsevier B.V. All rights reserved.

Russian Arctic Ports : Problems with the development and management of tourist flows

The potential changes to the territory of the Russian Arctic open up unique possibilities for the development of tourism. More favourable transport opportunities along the Northern Sea Route (NSR) create opportunities for tourism development based on the utilisation of the extensive areas of sea shores and river basins. A major challenge for the Russian Arctic sea and river ports is their strong cargo transport orientation originated by natural resource extraction industries. A careful assessment of the prospects of current and future tourism development is presented here based on the development of regions located along the shores of the Arctic ocean (including Murmansk and Arkhangelsk oblast, Nenets Autonomous okrug (AO), Yamal-Nenets AO, Taymyr AO, Republic of Sakha, Chykotsky AO). An evaluation of the present development of tourism in maritime cities suggests that a considerable qualitative and quantitative increase of tourism activities organised by domestic tourism firms is made virtually impossible. There are several factors contributing to this. The previously established Soviet system of state support for the investments into the port facilities as well as the sea fleet were not effectively replaced by creation of new structures. The necessary investments for reconstruction could be contributed by the federal government but the priorities are not set towards the increased passenger transportation. Having in mind, increased environmental pressures in this highly sensitive area it is especially vital to establish a well-functioning monitoring and rescue system in the situation of ever increasing risks which come not only from the increased transports along the NSR, but also from the exploitation of the offshore oil and gas reserves in the Arctic seas. The capacity and knowledge established in Nordic countries (Norway, Finland) concerning cruise tourism should not be underestimated and the already functioning cooperation in Barents Region should expand towards this particular segment of the tourism industry. The current stage of economic development in Russia makes it clear that tourism development is not able to compete with the well-needed increase in the cargo transportation, which means that Russia’s fleet is going to be utilised by other industries. However, opening up this area to both local and international visitors could contribute to the economic prosperity of these remote areas and if carefully managed could sustain already existing maritime cities along the shores of the Arctic Ocean.

Sculptural abstraction of landscape

The purpose of my Senior Scholar project was to create a series of sculptures that are based on the interaction of natural forms within a selected landscape setting. I hope to convey a sense of how I view and interpret the landscape and to create works that stimulate a sense of wonder in the mind of the viewer. This fascination, perhaps even obsession, with the power of the landscape has kept me going throughout the year. As a source of ideas and imagery, the landscape can never be depleted. There will always be new combinations of landscape elements, different light conditions, and changing seasons to provide me with fresh ideas. Research for the project took me to many different places, be it my trip to Monhegan Island or driving to New York City to study the cityscape. I began the year working in steel and plaster, combining the two in works that explore the interaction between living tree roots and inanimate rocks. This led to a series entitled Landscape Recollections, comprised of welded steel forms housed in protective wooden boxes and lit from inside. After visiting New York City, architecture began to playa role in my work, as seen in the two Roadcut pieces and the Cathedral Woods series. Roadcut #1 and Roadcut #2 explore the relationship between a man-made road and the landscape that lies beneath and around it. The Cathedral Woods pieces incorporate architecture in a more abstract manner, using imagery derived from Gothic cathedrals to convey a sense of quiet peacefulness. The soaring verticality of Gothic architecture integrates with the tall tree forms in each piece, enabling me to intertwine these two elements into one another and create a harmonious relationship between architecture and nature. Throughout the year I have kept a sketchbook in which I draw from life, jot down ideas, and take notes on how the project is progressing. I have also completed several large charcoal drawings of my sculptures in which I explore different ways of viewing the steel forms. I am grateful to have had the opportunity to undertake this project, as it has been a very difficult but rewarding process of observing, interpreting, and manifesting the landscape according to my personal vision and experiences.

Of Law, Lawlessness, and Sovereignty : Multinational Peacekeeping and International Law

Laws of war have been carefully defined by individual nations’ own codes of law as well as by supranational bodies. Yet the international scene has seen an increasing movement away from traditionally declared war toward multinational peacekeeping missions geared at containing local conflicts when perceived as potential threats to their respective regions’ political stability. While individual nations’ laws governing warfare presuppose national sovereignty, the multinational nature of peacekeeping scenarios can blur the lines of command structures, soldiers’ national loyalties, occupational jurisdiction, and raise profound questions as to which countries’ moral sense/governmental system is to be the one upheld. Historically increasingly complex international relations have driven increasingly detailed internationally drafted guidelines for countries’ interactions while at war, yet there are operational, legislative, and moral issues arising in multinational peacekeeping situations which these laws do not address at all. The author analyzes three unique peacekeeping operations in light of these legislative voids and suggests systematic points to consider to the end of protecting the peacekeepers, the national interests of the countries involved, operational matters, and clearly delineating both the objective and logical boundaries of a given multinational peacekeeping mission.

About DAPP: Meet the Department of Public Policy Analysis

The Department of Public Policy Analysis of Getulio Vargas Foundation (DAPP-FGV) is a research boutique concerned with the innovation of state structures and the relations between these and Civil Society, based on an interdisciplinary approach of applied social science, together with Information and Communication Technologies.

Windows of opportunities and knowledge networks: implications for the catch-up in developing countries

This document represents a doctoral thesis held under the Brazilian School of Public and Business Administration of Getulio Vargas Foundation (EBAPE/FGV), developed through the elaboration of three articles. The research that resulted in the articles is within the scope of the project entitled “Windows of opportunities and knowledge networks: implications for catch-up in developing countries”, funded by Support Programme for Research and Academic Production of Faculty (ProPesquisa) of Brazilian School of Public and Business Administration (EBAPE) of Getulio Vargas Foundation.

Processing of hierarchical syntactic strusture in music

Hierarchical structure with nested nonlocal dependencies is a key feature of human language and can be identified theoretically in most pieces of tonal music. However, previous studies have argued against the perception of such structures in music. Here, we show processing of nonlocal dependencies in music. We presented chorales by J. S. Bach and modified versions inwhich the hierarchical structure was rendered irregular whereas the local structure was kept intact. Brain electric responses differed between regular and irregular hierarchical structures, in both musicians and nonmusicians. This finding indicates that, when listening to music, humans apply cognitive processes that are capable of dealing with longdistance dependencies resulting from hierarchically organized syntactic structures. Our results reveal that a brain mechanism fundamental for syntactic processing is engaged during the perception of music, indicating that processing of hierarchical structure with nested nonlocal dependencies is not just a key component of human language, but a multidomain capacity of human cognition.