Structure development in electrospun fibres of gelatin

Gelatin fibres have been successfully electrospun from water by heating a gelatin solution above the sol-gel transition temperature, and allowing cooling in a controlled environment as the fibres are produced. The development of structure with in these fibres is monitored using wide angle x-ray scattering, in this way the presence of the triple helix structure, which provides the physical cross-linkages in the gel could be probed. There is clear evidence that these structures are obtained in gelatin electrospun from aqueous solutions. In contrast fibres electrospun from a solution of gelatin in glacial acetic acid, showed no evidence of the triple helix structure.

Structure determination of an intercalating ruthenium dipyridophenazine complex which kinks DNA by semiintercalation of a tetraazaphenanthrene ligand

We describe a crystal structure, at atomic resolution (1.1 Å, 100 K), of a ruthenium polypyridyl complex bound to duplex DNA, in which one ligand acts as a wedge in the minor groove, resulting in the 51° kinking of the double helix. The complex cation Λ-[Ru(1,4,5,8-tetraazaphenanthrene)2(dipyridophenazine)]2+ crystallizes in a 1∶1 ratio with the oligonucleotide d(TCGGCGCCGA) in the presence of barium ions. Each complex binds to one duplex by intercalation of the dipyridophenazine ligand and also by semiintercalation of one of the orthogonal tetraazaphenanthrene ligands into a second symmetrically equivalent duplex. The result is noncovalent cross-linking and marked kinking of DNA.

Preferred orientation in an angled intercalation site of a chloro-substituted lambda- [Ru(TAP)2(dppz)]2+ complex bound to d(TCGGCGCCGA)2

The crystal structure of the ruthenium DNA ‘light-switch’ complex -[Ru(TAP)2(11-Cl-dppz)]2+ (TAP = tetraazaphenanthrene, dppz = dipyrido[3,2-a':2',3'-c]phenazine)) bound to the oligonucleotide duplex d(TCGGCGCCGA)2 is reported. The synthesis of the racemic ruthenium complex is described for the first time, and the racemate was used in this study. The crystal structure, at atomic resolution (1.0 Å), shows one ligand as a wedge in the minor groove, resulting in the 51 kinking of the double helix, as with the parent lambda-[Ru(TAP)2(dppz)]2+. Each complex binds to one duplex by intercalation of the dppz ligand and also by semi-intercalation of one of the orthogonal TAP ligands into a second symmetrically equivalent duplex. The 11-Cl substituent binds with the major component (66%) oriented with the 11-chloro substituent on the purine side of the terminal step of the duplex.

Enhanced activity of horseradish peroxidase in Langmuir-Blodgett films of phospholipids

The immobilization of enzymes in nanostructured films has potential applications, e.g. in biosensing, for which the activity may not only be preserved, but also enhanced if optimized conditions are identified. Optimization is not straightforward because several requirements must be fulfilled, including a suitable matrix and film-forming technique. In this study, we show that horseradish peroxidase (HRP) has its activity enhanced when immobilized in Langmuir-Blodgett (LB) films, in conjunction with dipalmitoylphosphaticlylglycerol (DPPG). Incorporation of HRP into a DPPG monolayer at the air-water interface was demonstrated with compression isotherms, and Polarization-Modulation Infrared Reflection Absorption Spectroscopy (PM-IRRAS). From the PM-IRRAS data, we inferred that HRP was not denatured when adsorbed on a pre-formed, low pressure DPPG monolayer. A change in orientation was induced by the phospholipid matrix, with the amide C=O and NH groups from HRP being oriented perpendicular to the surface, parallel to the DPPG acyl chains, i.e. the alpha-helix was inserted into the monolayer. The mixed DPPG-HRP monolayer could be transferred onto solid supports, to which HRP activity was ca. 23% higher than in solution. The control of molecular architecture and choice of a suitable phospholipid matrix allowed HRP-containing LB films to be used in sensing peroxide. (c) 2008 Elsevier B.V. All rights reserved.

Novel Zn(2+)-binding Sites in Human Transthyretin IMPLICATIONS FOR AMYLOIDOGENESIS AND RETINOL-BINDING PROTEIN RECOGNITION

Human transthyretin (TTR) is a homotetrameric protein involved in several amyloidoses. Zn(2+) enhances TTR aggregation in vitro, and is a component of ex vivo TTR amyloid fibrils. We report the first crystal structure of human TTR in complex with Zn(2+) at pH 4.6-7.5. All four structures reveal three tetra-coordinated Zn(2+)-binding sites (ZBS 1-3) per monomer, plus a fourth site (ZBS 4) involving amino acid residues from a symmetry-related tetramer that is not visible in solution by NMR.Zn(2+) binding perturbs loop E-alpha-helix-loop F, the region involved in holo-retinol-binding protein (holo-RBP) recognition, mainly at acidic pH; TTR affinity for holo-RBP decreases similar to 5-fold in the presence of Zn(2+). Interestingly, this same region is disrupted in the crystal structure of the amyloidogenic intermediate of TTR formed at acidic pH in the absence of Zn(2+). HNCO and HNCA experiments performed in solution at pH 7.5 revealed that upon Zn(2+) binding, although the alpha-helix persists, there are perturbations in the resonances of the residues that flank this region, suggesting an increase in structural flexibility. While stability of the monomer of TTR decreases in the presence of Zn(2+), which is consistent with the tertiary structural perturbation provoked by Zn(2+) binding, tetramer stability is only marginally affected by Zn(2+). These data highlight structural and functional roles of Zn(2+) in TTR-related amyloidoses, as well as in holo-RBP recognition and vitamin A homeostasis.

Accumulation of (5 ` S)-8,5 `-cyclo-2 `-deoxyadenosine in organs of Cockayne syndrome complementation group B gene knockout mice

Cockayne syndrome (CS) is a human genetic disorder characterized by sensitivity to UV radiation, neurodegeneration, premature aging among other phenotypes. CS complementation group B (CS-B) gene (csb) encodes the CSB protein (CSB) that is involved in base excision repair of a number of oxidatively induced lesions in genomic DNA in vivo. We hypothesized that CSB may also play a role in cellular repair of the DNA helix-distorting tandem lesion (5`S)-8,5`-cyclo-2`-deoxyadenosine (S-cdA). Among many DNA lesions. S-cdA is unique in that it represents a concomitant damage to both the sugar and base moieties of the same nucleoside. Because of the presence of the C8-C5` covalent bond, S-cdA is repaired by nucleotide excision repair unlike most of other oxidatively induced lesions in DNA, which are subject to base excision repair. To test our hypothesis, we isolated genomic DNA from brain, kidney and liver of wild type and csb knockout (csb(-/-)) mice. Animals were not exposed to any exogenous oxidative stress before the experiment. DNA samples were analysed by liquid chromatography/mass spectrometry with isotope-dilution. Statistically greater background levels of S-cdA were observed in all three organs of csb(-/-) mice than in those of wild type mice. These results suggest the in vivo accumulation of S-cdA in genomic DNA due to lack of its repair in csb(-/-) mice. Thus, this study provides, for the first time, the evidence that CSB plays a role in the repair of the DNA helix-distorting tandem lesion S-cdA. Accumulation of unrepaired S-cdA in vivo may contribute to the pathology associated with CS. Published by Elsevier B.V.

Oxindole-Schiff base copper(II) complexes interactions with human serum albumin: Spectroscopic, oxidative damage, and computational studies

CD and EPR were used to characterize interactions of oxindole-Schiff base copper(II) complexes with human serum albumin (HSA). These imine ligands form very stable complexes with copper, and can efficiently compete for this metal ion towards the specific N-terminal binding site of the protein, consisting of the amino acid sequence Asp-Ala-His. Relative stability constants for the corresponding complexes were estimated from CD data, using the protein as competitive ligand, with values of log K(CuL) in the range 15.7-18.1, very close to that of [Cu(HSA)] itself, with log K(CuHSA) 16.2. Some of the complexes are also able to interfere in the a-helix structure of the protein, while others seem not to affect it. EPR spectra corroborate those results, indicating at least two different metal species in solution, depending on the imine ligand. Oxidative damage to the protein after incubation with these copper(II) complexes, particularly in the presence of hydrogen peroxide, was monitored by carbonyl groups formation, and was observed to be more severe when conformational features of the protein were modified. Complementary EPR spin-trapping data indicated significant formation of hydroxyl and carbon centered radicals, consistent with an oxidative mechanism. Theoretical calculations at density functional theory (DFT) level were employed to evaluate Cu(II)-L binding energies, L -> Cu(II) donation, and Cu(II) -> L back-donation, by considering the Schiff bases and the N-terminal site of HSA as ligands. These results complement previous studies on cytotoxicity, nuclease and pro-apoptotic properties of this kind of copper(II) complexes, providing additional information about their possibilities of transport and disposition in blood plasma. (C) 2009 Elsevier Inc. All rights reserved.

Konstruktion och design av två glassförpackningar i kartongkvaliteten Frövi Light

This degree project was made in cooperation with AssiDomän Frövi and Charlotte Andersson and the main objectivehas been to create to ice cream pacbges from 250 gsm Frövi Light board. The paekages are intended to be easilyresealable while decreasing in size together with the ice cream. The project also describes the food packaging labelsand symbols currently present in the European common market.Both capsules utilize a separate lid for resealing. One of the paekages (Capsuie A) is indended to be cut along withthe ice cream and thereby decrease in size. The other one (Capsuie B) uses a series of flaps for contracting and expandingwhich enab1es adjusting of the size without cutting the package up.The design for Capsuie A is created both as a series of flavours with a super-hero theme intended for children andwith a colfee flavour for a maturer audience. For Capsule B, a design was created for a sorbet.

Essays on infrastructure in Brazil

A presente tese engloba cinco trabalhos sobre dois setores brasileiros de infraestrutura: setor de energia e de transportes. No primeiro trabalho, modela-se o lance dos leilões de linhas de transmissão de energia, buscando compreender porque os lances ganhadores têm se situado em níveis abaixo do que se espera. No segundo paper, estima-se a demanda de energia do Brasil e as elasticidades preço e renda que os consumidores apresentem em relação a essa demanda, usando uma técnica ainda não aplicada na literatura e incluindo o período da Crise do Racionamento – a qual pode ter mudado o padrão de consumo dos agentes. No terceiro trabalho, estuda-se a evolução do mercado de gás natural liquefeito (GNL) ao redor do mundo. O GNL pode ser o link que faltava entre os mercados de gás natural e essa hipótese é testada por meio de análises de séries de tempo e de cópulas. O quarto paper discute a entrada do GNL no sistema energético brasileiro e suas eventuais consequências. Por fim, o quinto paper analisa a experiência de leilões de rodovias no Brasil. O trabalho levanta relevantes insights a respeito do modelo de leilão utilizado e dos detalhes contratuais dessas licitações.

Ensaios sobre o poder judiciário no Brasil

A tese apresenta três ensaios empíricos sobre os padrões decisórios de magistrados no Brasil, elaborados à partir de bases de dados inéditas e de larga escala, que contém detalhes de dezenas de milhares de processos judiciais na primeira e na segunda instância. As bases de dados são coletadas pelo próprio autor através de programas-robô de coleta em massa de informações, aplicados aos "links" de acompanhamento processual de tribunais estaduais no Brasil (Paraná, Minas Gerais e Santa Catarina). O primeiro artigo avalia - com base em modelo estatístico - a importância de fatores extra-legais sobre os resultados de ações judiciais, na Justiça Estadual do Paraná. Isto é, se os juízes favorecem sistematicamente a parte hipossuficiente (beneficiária de Assistência Judiciária Gratuita). No segundo artigo, estuda-se a relação entre a duração de ações cíveis no primeiro grau e a probabilidade de reforma da sentença, utilizando-se dados da Justiça Estadual de Minas Gerais. O objetivo é avaliar se existe um dilema entre a duração e a qualidade das sentenças. Dito de outra forma, se existe um dilema entre a observância do direito ao devido processo legal e a celeridade processual. O último artigo teste a hipótese - no âmbito de apelações criminais e incidentes recursais no Tribunal de Justiça de Santa Catarina - de que as origens profissionais dos desembargadores influenciam seus padrões decisórios. Isto é, testa-se a hipótese de que desembargadores/relatores oriundos da carreira da advocacia são mais "garantistas" ( e desembargadores oriundos da carreira do Ministério Público são menos "garantistas") relativamente aos seus pares oriundos da carreira da magistratura. Testam-se as hipóteses com base em um modelo estatístico que explica a probabilidade de uma decisão recursal favorável ao réu, em função da origem de carreira do relator do recurso, além de um conjunto de características do processo e do órgão julgador.

A arquitetura jurídico-institucional de um ambiente de inovação brasileiro: o Parque Tecnológico de São José dos Campos.

O presente trabalho objetiva investigar a arquitetura jurídico-institucional de um ambiente inovativo denominado parque tecnológico. Este é um arranjo imobiliário que conta com os elementos da chamada tríplice hélice - academia, setor privado e Estado. Almeja a transformação do conhecimento em desenvolvimento, por meio de atividades fundadas em ciência, tecnologia e inovação (C&T&I). A pretensão é contribuir com a premissa de que esses arranjos são frutos da nova lógica econômica baseada no conhecimento e da atual concepção sistêmica de inovação que exige interdependência e interação dos seus agentes. Dentre esses destacamos, o Estado, por ser o ator mais paciente por resultados e o potencial idealizador, fomentador e articulador de processos inovativos sistemicamente pensados. A estratégia Estudo de Caso Único foi eleita para observar, em detalhes, a arquitetura jurídico-institucional do Parque Tecnológico de São José dos Campos, bem como para, a partir de um olhar jurídico-institucional, retirar aprendizados dessa experiência que possam ser aproveitados em novas modelagens de parques tecnológicos e de políticas públicas que focam a estruturação de ambientes inovativos sistêmicos. Foram priorizados exames qualitativos: (i) da sua fisiologia jurídico-institucional; (ii) dos agentes envolvidos e das respectivas amarrações jurídicas estabelecidas; (iii) da influência do Estado e das políticas públicas que o permeiam; (iv) do seu processo de implantação e desenvolvimento; e (v) dos desafios jurídico-formais e jurídico-institucionais que enfrenta. Compreendeu-se que parques tecnológicos são estruturados como arranjos híbridos, segundo a lógica da inovação em sistema, em que os elementos da tríplice hélice atuam em sinergia a partir da ativa atuação do Estado. Sua arquitetura jurídico-institucional decorre da aplicação de tecnologias de contratação e de regulação aplicadas em ambientes alicerçados em fatores institucionais específicos.

Sustentabilidade das empresas associadas à REDEPETRO-RN

The present study investigated the management of social, environmental and economic sustainability practices employed by 72 oil companies in Rio Grande do Norte state in Brazil associated to Joint Business Network for Enhancing the Competitive Ability of Suppliers of Goods and Services to the Gas and Oil Industry in Rio Grande do Norte (REDEPETRO-RN). Thus, our investigation aimed to determine the extent to which sustainability practices of companies associated to REDEPETRO-RN are developed through their own efforts or influenced by the Triple Helix interorganizational arrangement (governamental organizations, education and research institutions, and industries). The research instrument used was a questionnaire in order to map and characterize the sustainability practices. The research subjects were business owners and managers. The data collected supported the descriptive, correspondence and correlation analyzes. Were identified a greater emphasis of the companies surveyed in developing sustainability practices and greater economic influence of business organizations in the construction of sustainability status. It was concluded with confirmation of thesis of the REDEPETRO-RN arrangement exhibits the characteristics and functioning of a common Interorganizational Cooperative Arrangement, not those of a triple helix interorganizational arrangement, given that the influences exerted for the development of social, environmental and economical sustainability on the part of teaching and research institutions, and government and business organizations do not interact with one another sufficiently to create a virtuous circle of cooperation among the associated companies. By contrast, the Interorganizational Cooperative Arrangement plays an important role in strengthening the competitiveness of companies affiliated to REDEPETRO-RN, by combining different competencies in an attempt at supporting the adoption of sustainability practices, a role reinforced by the scope of PETROBRAS, which, due to its economic importance, has considerable weight in the managerial decisions of associated companies

As relações da tríplice hélice no setor da carcinicultura do Rio Grande do Norte: uma análise a partir das abordagens da imersão social e da dependência de recursos

This work consists in a study of the Shrimp Industry in the state of Rio Grande do Norte, whose central issue relates to the understanding of how the Triple Helix (University, Government and the productive sector) interrelationship limits or expands the industry s innovation process. The study aims to understand how the Triple Helix relationship interferes in the innovation process of shrimp in Rio Grande do Norte. As the knowledge becomes the resource key for production methods, the generation of new technologies, new products and processes which demands joint and integrated action of the institutions comprising the Triple Helix: University, Government and productive sector, which possess the essential resources to innovate the process and can be maximized from cooperative relationships between the referred Institutions. Thus, in this work, it was sharply used the pioneering studies of Sabato and Botana (1968) regarding the cooperation relationship between the scientific-technological sphere, the governmental and the productive base, and studies on the Triple Helix approach, proposed by Etzkowitz and Leydesdorff (2000), in which the university has a key role in the process of technological and innovative development of countries and regions, and under which it is assigned to the very University - the character of the entrepreneurial institution, through the concept of entrepreneurial University. Aiming to overcome the criticism of Cooke (2005), regarding the limitations of the Triple Helix approach, in this study it was used - as analytical perspectives - the perspective of social immersion (Granovetter, 1985, 2005) and the theory of resources dependence (PFEFFER; SALANCIK, 1978). The analytical perspectives presented in here, despite of the different assumptions, are essential to eliminate the bias that one only approach can lead (ASTLEY; VAN DE VEM; 2007). The authors arguments focus on the fact that the integration is possible if the researcher acknowledged that different perspectives may have different descriptions of the same phenomenon. As a research strategy, this study is characterized as a study case, along with the proposed objectives - the qualitative method was used as an approach and, depending on the gathering of the sector s historical, a sectional longitudinal view approach was applied (VIEIRA, 2004). The primary and secondary data were used in order to understand the sector s evolutionary process and its inter-institutional relations - regarding the shrimp culture in Rio Grande do Norte - to promote the development, as the content was used for the technical analysis (BARDIN, 1977). The approach of social immersion and resources addiction dependence made it possible to understand that relationships are established within and between each sphere (university, government and productive sector) characterizing a network of low density relationships and strongly internal and external dependence. Based on the speech of Etzkowitz and Mello (2006), a successful Triple Helix strategy of innovation requires not only the involvement and commitment of the parts, within the institutional sphere and among them, but also the development of mechanisms to coordinate the multiple and complex interactions and interfaces, focusing on promoting both environment and context for innovation and learning; it can be acknowledge from study results that the shrimp in the State of the RN, although there are several institutional mechanisms to promote greater integration and technological development, has been presented disjointed - both internally and between the spheres - and under no legitimate practice when facing the innovational promotion and integration institutions. Due to those factors, the central institutions of the network are crucial to the promotion of innovations, spreading through their direct contacts the importance factor of the sustainable competitive activity in the world market and on the national level. However, it may be concluded, from the data, that the Triple Helix relations are interfering in a negative way on what concerns the promotion of innovations in the shrimp industry in RN

A influência do modelo de triplice hélice no grau de maturidade de inovação: um estudo de caso em empresas participantes do projeto PRÓ-INOVA/NAGI no estado do RIO GRANDE DO NORTE

Public investments in the development of innovation in the country, either through the rigging of public universities, either through public announcements of the promotion, increased dramatically in recent years. To analyze the efficiency and effectiveness of the use of public resources is especially in times of austerity, essential for the development of a country. In this context, this research aims to identify the influence of public investments to promote innovation in the degree of maturity of innovative companies in the state of the RN. Another goal is to identify the regional influence from the installation site - capital or countryside, in the performance of the companies studied in the degree of innovation. The theoretical basis of the understanding of the scope of the concept of innovation and its determination for the purposes of this study. Typology, degree of innovation, evaluation methodologies and mechanisms to support innovation : Still on the theme of innovation additional concepts that help the reader to a greater understanding, such as are presented. Following is approached conceptualization of the triple helix, highlighting the concepts advocated by Etzkowitz and Leydesdorff, Salomon and Silva and Ipiranga, Freitas and Paiva, among others. With regard to methodological aspects, we propose a descriptive, exploratory and explanatory research quantitative and qualitative approach with the target audience group of companies served by INOVA PRO- NAGI design - multi-institutional action from a public resource called FINEP promotes the development of innovative companies in the State of Rio Grande do Norte - in 2013. The research should provide reflection and understanding of the influence of public investment in innovation, which by means of qualitative predictive variables associated with quantitative method to explain which variables are significant variations in the degree of maturity of enterprises studied

Transporte eletrônico e propriedades termodinâmicas de nanobiomoléculas

We use a tight-binding formulation to investigate the transmissivity and the currentvoltage (I_V) characteristics of sequences of double-strand DNA molecules. In order to reveal the relevance of the underlying correlations in the nucleotides distribution, we compare theresults for the genomic DNA sequence with those of arti_cial sequences (the long-range correlated Fibonacci and RudinShapiro one) and a random sequence, which is a kind of prototype of a short-range correlated system. The random sequence is presented here with the same _rst neighbors pair correlations of the human DNA sequence. We found that the long-range character of the correlations is important to the transmissivity spectra, although the I_V curves seem to be mostly inuenced by the short-range correlations. We also analyze in this work the electronic and thermal properties along an _-helix sequence obtained from an _3 peptide which has the uni-dimensional sequence (Leu-Glu-Thr- Leu-Ala-Lys-Ala)3. An ab initio quantum chemical calculation procedure is used to obtain the highest occupied molecular orbital (HOMO) as well as their charge transfer integrals, when the _-helix sequence forms two di_erent variants with (the so-called 5Q variant) and without (the 7Q variant) _brous assemblies that can be observed by transmission electron microscopy. The di_erence between the two structures is that the 5Q (7Q) structure have Ala ! Gln substitution at the 5th (7th) position, respectively. We estimate theoretically the density of states as well as the electronic transmission spectra for the peptides using a tight-binding Hamiltonian model together with the Dyson's equation. Besides, we solve the time dependent Schrodinger equation to compute the spread of an initially localized wave-packet. We also compute the localization length in the _nite _-helix segment and the quantum especi_c heat. Keeping in mind that _brous protein can be associated with diseases, the important di_erences observed in the present vi electronic transport studies encourage us to suggest this method as a molecular diagnostic tool