In vivo NMR and MRI using injection delivery of laser-polarized xenon

Because xenon NMR is highly sensitive to the local environment, laser-polarized xenon could be a unique probe of living tissues. Realization of clinical and medical science applications beyond lung airspace imaging requires methods of efficient delivery of laser-polarized xenon to tissues, because of the short spin-lattice relaxation times and relatively low concentrations of xenon attainable in the body. Preliminary results from the application of a polarized xenon injection technique for in vivo 129Xe NMR/MRI are extrapolated along with a simple model of xenon transit to show that the peak local concentration of polarized xenon delivered to tissues by injection may exceed that delivered by respiration by severalfold.

Propriedades magnéticas de trímeros de FexCo1-x depositados em Pt(111)

Quais propriedades magnéticas são modificadas quando se agrupam átomos de Fe/Co para formar estruturas quasi-2D, se comparadas aos nanofios (quasi-1D) de FexCo1-x? E como estas propriedades reagem com a variação da proporção de Fe/Co nos aglomerados? A fim de responder a estas questões, trímeros de FexCo1-x depositados em Pt(111) são investigados utilizando o método de primeiros princípios Real Space-Linear Muffin-Tin Orbital-Atomic Sphere Approximation (RS-LMTO-ASA) no âmbito da Teoria do Funcional da Densidade (DFT). Diferentes configurações de trímeros triangulares são consideradas, variando-se as posições e a concentração dos átomos de Fe/Co. Neste trabalho, demonstra-se a ocorrência de uma tendência não-linear estritamente decrescente dos momentos orbitais médios como função da concentração de Fe, distinta do encontrado tanto para os nanofios de FexCo1-x (dependência linear) quanto para a monocamada correspondente (dependência não-linear). Os resultados obtidos mostram ainda que os momentos orbitais variam com o ambiente local e com a direção de magnetização, especialmente quando associados aos átomos de Co, em concordância com publicações anteriores. A mudança de dimensionalidade quasi-1D (nanofios) para quasi-2D (trímeros compactos) não afeta o comportamento dos momentos de spin, que permanecem descritos por uma função linear com respeito à proporção de Fe/Co. Ambos o formato e a concentração de Fe nos sistemas apresentam um papel importante nos valores de energia de anisotropia magnética. Em adição, observou-se que o subtrato de Pt opera ativamente na definição das propriedades magnéticas dos aglomerados. Embora todas as configurações lineares e compactas dos aglomerados de FexCo1-x sejam estáveis e exibam interações fortemente ferromagnéticas entre os primeiros vizinhos, nem todas revelaram o ordenamento colinear como estado fundamental, apresentando uma interação de Dzyaloshinskii-Moriya não-desprezível induzida pelo acoplamento spin-órbita. Estes casos específicos são: o trímero triangular de Co puro e o trímero linear (nanofio) de Fe puro, para o qual foi verificado o acoplamento do tipo Ruderman-Kittel-Kasuya-Yosida entre os átomos de Fe constituintes. Os resultados obtidos contribuem para o entendimento de quais mecanismos definem o magnetismo nos trímeros de FexCo1-x/Pt(111), e discutem as questões presentes atualmente na literatura no contexto destes sistemas.

Abundance and characteristics of Polychaeta taxa and associated sediment during POLARSTERN campaign ANT-XXII/3 (ANDEEP-IIII)

During the austral summer of 2005, the Weddell deep sea and adjacent basins were sampled in the course of the ANDEEP III project. In this study, 19 epibenthic-sledge stations are analyzed, with a focus on species diversity and distribution patterns of polychaetes. The polychaete fauna of the deep Southern Ocean has been found to be similarly speciose and diverse compared with deep-sea basins worldwide. Also, in depths below 2,000 m many polychaete species do not seem to be endemic for certain areas but are rather far spread within the Southern Ocean and beyond. Therefore, ongoing faunal exchanges between adjacent basins, even beyond the Antarctic convergence, are strongly suggested, ruling out a general isolation of the Southern Ocean deep-sea benthos. Driving forces behind species distribution patterns were investigated. The findings indicate that polychaete species' distribution in the Southern Ocean deep sea is rather dependent on local environment than depths.

Better prediction of protein contact number using a support vector regression analysis of amino acid sequence

Background: Protein tertiary structure can be partly characterized via each amino acid's contact number measuring how residues are spatially arranged. The contact number of a residue in a folded protein is a measure of its exposure to the local environment, and is defined as the number of C-beta atoms in other residues within a sphere around the C-beta atom of the residue of interest. Contact number is partly conserved between protein folds and thus is useful for protein fold and structure prediction. In turn, each residue's contact number can be partially predicted from primary amino acid sequence, assisting tertiary fold analysis from sequence data. In this study, we provide a more accurate contact number prediction method from protein primary sequence. Results: We predict contact number from protein sequence using a novel support vector regression algorithm. Using protein local sequences with multiple sequence alignments (PSI-BLAST profiles), we demonstrate a correlation coefficient between predicted and observed contact numbers of 0.70, which outperforms previously achieved accuracies. Including additional information about sequence weight and amino acid composition further improves prediction accuracies significantly with the correlation coefficient reaching 0.73. If residues are classified as being either contacted or non-contacted, the prediction accuracies are all greater than 77%, regardless of the choice of classification thresholds. Conclusion: The successful application of support vector regression to the prediction of protein contact number reported here, together with previous applications of this approach to the prediction of protein accessible surface area and B-factor profile, suggests that a support vector regression approach may be very useful for determining the structure-function relation between primary sequence and higher order consecutive protein structural and functional properties.

Simulation of glassy state relaxations in polymers: A static analysis of methyl group and methoxy group rotation in poly(vinyl methyl ether)

We show that the simple quasi-static technique, also called the adiabatic mapping technique, can be used to determine the energetics of rotation of methyl and methoxy groups in amorphous poly(vinyl methyl ether) even though the latter process is too slow to be amenable to direct molecular dynamics simulation. For the methyl group rotation, we find that the mean and standard deviation of the simulated rotational barrier heights agree well with experimental data from quasi-elastic neutron scattering. In the case of the methoxy groups we find that just 4% of the groups contribute more than 90% of the observed dielectric relaxation strength. The groups which make the most contribution are those which, by virtue of their particular conformation and local environment, have two alternative positions of similar energy.

Using the Internet for Physical Activity Promotion in a Regional Community: Feasibility Study Findings

New communication technologies (websites and email) are believed to hold promise for delivering population health interventions. However, studies on internet-delivered physical activity (PA) programs have encountered difficulties in engaging and retaining participants. Recent PA research has focused on peoples’ perceptions of the local environment and how this relates to PA participation. This study investigated the potential of: 1) reaching people living in a regional community via a locally-based Internet Service Provider (ISP), and 2) using data on the local environment to design a PA intervention relevant to the individual. An online survey was conducted via the ISP’s website over 12 days. ISP clients (approximately 9,000) were invited to participate in the survey via electronic newsletter and direct email. Data on motivational readiness and environmental correlates of PA were collected. 820 surveys were completed, of which 797 were valid (response rate = 9%). Participants had a mean BMI 27.6±8.3, were 55% male, 56% aged >45 years, 57% worked fulltime, and 36% were in the early stages of motivational readiness for PA. Most reported positive perceptions of the local environment in terms of aesthetics, convenience, access, traffic and safety. However, over half did not know about or use local PA facilities. Over 70% were somewhat to extremely interested in having access to a PA promotion website. These data suggest that promoting PA via a locally based ISP is feasible and appealing to some people living in a regional community, but also highlight some of the challenges of using this technology to deliver population health interventions.

A Matriz Filosófica do Presbiterianismo no Brasil

Os missionários protestantes presbiterianos que vieram para o Brasil no início da segunda metade do século XIX trouxeram uma interpretação calvinista da bíblia, pois permaneceram fieis à formação princetoniana que efetivou uma síntese entre ortodoxia calvinista e pietismo. Estes pricetonianos tinham como base epistemológica a filosofia de Thomas Reid, conhecida como o Realismo do Senso Comum. Essa filosofia é utilizada como uma epistemologia reformada, ou calvinista. Ela é compreendida em sua formação escocesa e consequentemente americana, via Princeton, como a Epistemologia Providencial. Desta forma, quando ela é assimilada pelos brasileiros por meio da pregação e da formação teológica, a mesma se torna parte do perfil presbiteriano brasileiro como doutrina filosófica. A Filosofia do Senso Comum se gesta como crítica à filosofia empirista de David Hume que, para Reid, convergiria para um possível aniquilamento da religião e para uma visão pessimista da ciência, afetando o empirismo, por conseguinte, causando uma nova formulação mais próxima do ceticismo. Por isso, Reid formulou a filosofia que para ele contrapõe-se a Locke e Berkeley e depois a David Hume, afirmando que a realidade é independente de nossa apreensão. Ou seja, na percepção do mundo exterior não há interferência do sujeito cognoscente sobre o objeto do conhecimento. A nossa relação com os objetos é direta e não deve ser desvirtuada por intermediações. Na implantação do protestantismo no Brasil, via missionários de Princeton, não houve uma defesa intransigente dos princípios calvinistas por parte de missionários como Fletcher e Simonton e sim uma continuidade da leitura das escrituras sagradas pelo viés calvinista, como era feito no Seminário de Princeton. Não havia uma ênfase acentuada na defesa da ortodoxia porque o tema do liberalismo teológico, ou do conflito entre modernismo e fundamentalismo não se fazia necessário na conjuntura local, onde predominava a preocupação pela evangelização em termos práticos. O conceitos da Filosofia do Senso Comum eram próximos do empirismo mitigado de Silvestre Pinheiro e do Ecletismo de Victor Cousin. Por isso, no Brasil, o local em que mais se vê a utilização da filosofia do Senso Comum é nos debates entre intelectuais, em três pontos interessantes: 1ª) O Senso Comum ficou restrito ao espaço acadêmico, na formação de novos pastores, sendo que as obras de Charles Hodge e A. A. Hodge são as principais fontes de implantação desta mentalidade ratificadora da experiência religiosa e, desta forma, delineiam o rosto do protestantismo entre presbiterianos, uma das principais denominações protestantes do final do século XIX; 2ª) Nos debates entre clérigos católicos e protestantes em polêmicas teológicas;. 3º) No aproveitamento utilitarista da assimilação cultural estrangeira pelos protestantes nacionais, não por último, facilitada pela simpatia dos liberais brasileiros pelo protestantismo, ao mesmo tempo que mantinham uma linha filosófica mais próxima do empirismo mitigado e do ecletismo. Assim, nossa hipótese pretende demonstrar que os protestantes trouxeram em seu bojo as formulações epistemológicas que foram passadas para um grupo de intelectuais, que formaram o quadro dos primeiros pastores presbiterianos da história desta denominação. Eles foram convertidos e assimilaram melhor as novas doutrinas por meio de mais do que simples pregações, mas pela sua forma filosófica de encarar os objetos estudados, e que tais informações vêm por meio da base epistemológica do Realismo do Senso Comum, que encontra espaço nos ideais republicanos brasileiros do século XIX.

The structure and dynamics of 2-dimensional fluids in swelling clays

The interlayer pores of swelling 2:1 clays provide an ideal 2-dimensional environment in which to study confined fluids. In this paper we discuss our understanding of the structure and dynamics of interlayer fluid species in expanded clays, based primarily on the outcome of recent molecular modelling and neutron scattering studies. Counterion solvation is compared with that measured in bulk solutions, and at a local level the cation-oxygen coordination is found to be remarkably similar in these two environments. However, for the monovalent ions the contribution to the first coordination shell from the clay surfaces increases with counterion radius. This gives rise to inner-sphere (surface) complexes in the case of potassium and caesium. In this context, the location of the negative clay surface charge (i.e. arising from octahedral or tetrahedral substitution) is also found to be of major importance. Divalent cations, such as calcium, eagerly solvate to form outer-sphere complexes. These complexes are able to pin adjacent clay layers together, and thereby prevent colloidal swelling. Confined water molecules form hydrogen bonds to each other and to the clays' surfaces. In this way their local environment relaxes to close to the bulk water structure within two molecular layers of the clay surface. Finally, we discuss the way in which the simple organic molecules methane, methanol and ethylene glycol behave in the interlayer region of hydrated clays. Quasi-elastic neutron scattering of isotopically labelled interlayer CH 3OD and (CH2OD)2 in deuterated clay allows us to measure the diffusion of the CH3- and CH2-groups in both clay and liquid environments. We find that in both the one-layer methanol solvates and the two-layer glycol solvates the diffusion of the most mobile organic molecules is close to that in the bulk solution.

Flt1 acts as a negative regulator of tip cell formation and branching morphogenesis in the zebrafish embryo

Endothelial tip cells guide angiogenic sprouts by exploring the local environment for guidance cues such as vascular endothelial growth factor (VegfA). Here we present Flt1 (Vegf receptor 1) loss- and gain-of-function data in zebrafish showing that Flt1 regulates tip cell formation and arterial branching morphogenesis. Zebrafish embryos expressed soluble Flt1 (sFlt1) and membrane-bound Flt1 (mFlt1). In Tg(flt1(BAC):yfp) × Tg(kdrl:ras-cherry)(s916) embryos, flt1:yfp was expressed in tip, stalk and base cells of segmental artery sprouts and overlapped with kdrl:cherry expression in these domains. flt1 morphants showed increased tip cell numbers, enhanced angiogenic behavior and hyperbranching of segmental artery sprouts. The additional arterial branches developed into functional vessels carrying blood flow. In support of a functional role for the extracellular VEGF-binding domain of Flt1, overexpression of sflt1 or mflt1 rescued aberrant branching in flt1 morphants, and overexpression of sflt1 or mflt1 in controls resulted in short arterial sprouts with reduced numbers of filopodia. flt1 morphants showed reduced expression of Notch receptors and of the Notch downstream target efnb2a, and ectopic expression of flt4 in arteries, consistent with loss of Notch signaling. Conditional overexpression of the notch1a intracellular cleaved domain in flt1 morphants restored segmental artery patterning. The developing nervous system of the trunk contributed to the distribution of Flt1, and the loss of flt1 affected neurons. Thus, Flt1 acts in a Notch-dependent manner as a negative regulator of tip cell differentiation and branching. Flt1 distribution may be fine-tuned, involving interactions with the developing nervous system.

An examination of the determinants of entrepreneurship at the regional level:the case of East Midlands region

Despite the importance of new firms to the economy, determinants of start-ups have mainly been examined at a country level and discussion of regional entrepreneurial activity has received less attention. Since there are significant variations in entrepreneurship rates across and within countries, such an investigation at a regional level would help in gaining an in depth understanding of the impact of the individual level resource endowments and neighbourhood characteristics on an individual’s decision to engage in entrepreneurial activity. The main aim of the thesis is to explore various theories of entrepreneurship and develop integrated frameworks for examining the determinants of entrepreneurial activity at a neighbourhood level in the East Midlands region in England. The specific objectives of the thesis are to examine how the individual level resources and the neighbourhood characteristics: (i) combine to influence an individual to engage in the different stages of the entrepreneurial process, (ii) influence natives and migrants to engage in start up activity and (iii) influence women and men to become self-employed and ambitious entrepreneurs. In terms of the methodology, the empirical analysis is based on two databases combined: 2006 to 2009 GEM East Midlands region and the English Index of Multiple Deprivation dataset. Based on the critical review of the literature on entrepreneurship the thesis develop theoretical frameworks which led to formulate hypotheses related to the differentiated impact of both individual and neighbourhood level factors on the propensity of an individual to be involved in entrepreneurial activity. The findings indicate that the determinants of entrepreneurial activity vary with human, financial and the local environment factors affecting the entrepreneurial process. Finally, the thesis calls for caution when developing and applying generic and specific policy measures aimed at promoting entry into entrepreneurship.

Automatic Discovery of Word Semantic Relations

In this paper, we propose an unsupervised methodology to automatically discover pairs of semantically related words by highlighting their local environment and evaluating their semantic similarity in local and global semantic spaces. This proposal di®ers from previous research as it tries to take the best of two different methodologies i.e. semantic space models and information extraction models. It can be applied to extract close semantic relations, it limits the search space and it is unsupervised.

Functionalized carbon nanotube nanoelectrodes for biomolecular recognition

The objective of this research is to develop nanoscale ultrasensitive transducers for detection of biological species at molecular level using carbon nanotubes as nanoelectrodes. Rapid detection of ultra low concentration or even single DNA molecules are essential for medical diagnosis and treatment, pharmaceutical applications, gene sequencing as well as forensic analysis. Here the use of functionalized single walled carbon nanotubes (SWNT) as nanoscale detection platform for rapid detection of single DNA molecules is demonstrated. The detection principle is based on obtaining electrical signal from a single amine terminated DNA molecule which is covalently bridged between two ends of an SWNT separated by a nanoscale gap. The synthesis, fabrication, chemical functionalization of nanoelectrodes and DNA attachment were optimized to perform reliable electrical characterization these molecules. Using this detection system fundamental study on charge transport in DNA molecule of both genomic and non genomic sequences is performed. We measured an electrical signal of about 30 pA through a hybridized DNA molecule of 80 base pair in length which encodes a portion of sequence of H5N1 gene of avian Influenza A virus. Due the dynamic nature of the DNA molecules the local environment such as ion concentration, pH and temperature significantly influence its physical properties. We observed a decrease in DNA conductance of about 33% in high vacuum conditions. The counterion variation was analyzed by changing the buffer from sodium acetate to tris(hydroxymethyl) aminomethane, which resulted in a two orders of magnitude increase in the conductivity of the DNA. The fabrication of large array of identical SWNT nanoelectrodes was achieved by using ultralong SWNTs. Using these nanoelectrode array we have investigated the sequence dependent charge transport in DNA. A systematic study performed on PolyG - PolyC sequence with varying number of intervening PolyA - PolyT pairs showed a decrease in electrical signal from 180 pA (PolyG - PolyC) to 30 pA with increasing number of the PolyA - PolyT pairs. This work also led to the development of ultrasensitive nanoelectrodes based on enzyme functionalized vertically aligned high density multiwalled CNTs for electrochemical detection of cholesterol. The nanoelectrodes exhibited selectively detection of cholesterol in the presence of common interferents found in human blood.

Assessment of the occurrence and potential risks of antibiotics and their metabolites in South Florida waters using liquid chromatography tandem mass spectrometry

An automated on-line SPE-LC-MS/MS method was developed for the quantitation of multiple classes of antibiotics in environmental waters. High sensitivity in the low ng/L range was accomplished by using large volume injections with 10-mL of sample. Positive confirmation of analytes was achieved using two selected reaction monitoring (SRM) transitions per antibiotic and quantitation was performed using an internal standard approach. Samples were extracted using online solid phase extraction, then using column switching technique; extracted samples were immediately passed through liquid chromatography and analyzed by tandem mass spectrometry. The total run time per each sample was 20 min. The statistically calculated method detection limits for various environmental samples were between 1.2 and 63 ng/L. Furthermore, the method was validated in terms of precision, accuracy and linearity. ^ The developed analytical methodology was used to measure the occurrence of antibiotics in reclaimed waters (n=56), surface waters (n=53), ground waters (n=8) and drinking waters (n=54) collected from different parts of South Florida. In reclaimed waters, the most frequently detected antibiotics were nalidixic acid, erythromycin, clarithromycin, azithromycin trimethoprim, sulfamethoxazole and ofloxacin (19.3-604.9 ng/L). Detection of antibiotics in reclaimed waters indicates that they can't be completely removed by conventional wastewater treatment process. Furthermore, the average mass loads of antibiotics released into the local environment through reclaimed water were estimated as 0.248 Kg/day. Among the surface waters samples, Miami River (reaching up to 580 ng/L) and Black Creek canal (up to 124 ng/L) showed highest concentrations of antibiotics. No traces of antibiotics were found in ground waters. On the other hand, erythromycin (monitored as anhydro erythromycin) was detected in 82% of the drinking water samples (n.d-66 ng/L). The developed approach is suitable for both research and monitoring applications.^ Major metabolites of antibiotics in reclaimed wates were identified and quantified using high resolution benchtop Q-Exactive orbitrap mass spectrometer. A phase I metabolite of erythromycin was tentatively identified in full scan based on accurate mass measurement. Using extracted ion chromatogram (XIC), high resolution data-dependent MS/MS spectra and metabolic profiling software the metabolite was identified as desmethyl anhydro erythromycin with molecular formula C36H63NO12 and m/z 702.4423. The molar concentration of the metabolite to erythromycin was in the order of 13 %. To my knowledge, this is the first known report on this metabolite in reclaimed water. Another compound acetyl-sulfamethoxazole, a phase II metabolite of sulfamethoxazole was also identified in reclaimed water and mole fraction of the metabolite represent 36 %, of the cumulative sulfamethoxazole concentration. The results were illustrating the importance to include metabolites also in the routine analysis to obtain a mass balance for better understanding of the occurrence, fate and distribution of antibiotics in the environment. ^ Finally, all the antibiotics detected in reclaimed and surface waters were investigated to assess the potential risk to the aquatic organisms. The surface water antibiotic concentrations that represented the real time exposure conditions revealed that the macrolide antibiotics, erythromycin, clarithromycin and tylosin along with quinolone antibiotic, ciprofloxacin were suspected to induce high toxicity to aquatic biota. Preliminary results showing that, among the antibiotic groups tested, macrolides posed the highest ecological threat, and therefore, they may need to be further evaluated with, long-term exposure studies considering bioaccumulation factors and more number of species selected. Overall, the occurrence of antibiotics in aquatic environment is posing an ecological health concern.^

Fiber Scaffolds of Poly (glycerol-dodecanedioate) and its Derivative via Electrospinning for Neural Tissue Engineering

Peripheral nerves have demonstrated the ability to bridge gaps of up to 6 mm. Peripheral Nerve System injury sites beyond this range need autograft or allograft surgery. Central Nerve System cells do not allow spontaneous regeneration due to the intrinsic environmental inhibition. Although stem cell therapy seems to be a promising approach towards nerve repair, it is essential to use the distinct three-dimensional architecture of a cell scaffold with proper biomolecule embedding in order to ensure that the local environment can be controlled well enough for growth and survival. Many approaches have been developed for the fabrication of 3D scaffolds, and more recently, fiber-based scaffolds produced via the electrospinning have been garnering increasing interest, as it offers the opportunity for control over fiber composition, as well as fiber mesh porosity using a relatively simple experimental setup. All these attributes make electrospun fibers a new class of promising scaffolds for neural tissue engineering. Therefore, the purpose of this doctoral study is to investigate the use of the novel material PGD and its derivative PGDF for obtaining fiber scaffolds using the electrospinning. The performance of these scaffolds, combined with neural lineage cells derived from ESCs, was evaluated by the dissolvability test, Raman spectroscopy, cell viability assay, real time PCR, Immunocytochemistry, extracellular electrophysiology, etc. The newly designed collector makes it possible to easily obtain fibers with adequate length and integrity. The utilization of a solvent like ethanol and water for electrospinning of fibrous scaffolds provides a potentially less toxic and more biocompatible fabrication method. Cell viability testing demonstrated that the addition of gelatin leads to significant improvement of cell proliferation on the scaffolds. Both real time PCR and Immunocytochemistry analysis indicated that motor neuron differentiation was achieved through the high motor neuron gene expression using the metabolites approach. The addition of Fumaric acid into fiber scaffolds further promoted the differentiation. Based on the results, this newly fabricated electrospun fiber scaffold, combined with neural lineage cells, provides a potential alternate strategy for nerve injury repair.

A Cultural Historical Study of Land Use in Dade County, Florida

Humans have used the land within the area currently defined as Dade County, Florida since around 11,000 B.P., but did not significantly alter the local environment until less than one hundred years ago. These recent changes greatly affected many critical ecological factors, thereby reducing the sustainability of many types of life, including humans. This study explains how land use evolved from earlier sustainable systems for satisfying human needs into the current menacing patterns. This is done by examining the environmental, technological, social, and cognitive contexts of land use through time. Changes in all these areas have followed a general trend leading to increasing intensity of land use and environmental change driven by population growth and technological innovation.