Highly dispersed Ptδ+ on TixCe(1−x)O2 as an active phase in preferential oxidation of CO

Structure–activity relationships for 1 wt.% Pt catalysts were investigated for a series of TixCe(1−x)O2 (x = 1, 0.98, 0.9, 0.5, 0.2 and 0) supports prepared by the sol–gel method. The catalysts prepared by impregnation were characterized in detail by applying a wide range of techniques as N2-isotherms, XRF, XRD, Raman, XPS, H2-TPR, Drifts, UV–vis, etc. and tested in the preferential oxidation of CO in the presence of H2. Also several reaction conditions were deeply analyzed. A strong correlation between catalyst performance and the electronic properties let us to propose, based in all the experimental results, a plausible reaction mechanism where several redox cycles are involved.

Materials design for ambipolar devices: tuning orbital energetics in oligothiophene-naphthalimides semiconductors

Ambipolar organic field-effect transistors (OFETs), which can efficiently transport both holes and electrons, using a single type of electrode, are currently of great interest due to their possible applications in complementary metal oxide semiconductor (CMOS)-like circuits, sensors, and in light-emitting transistors. Several theoretical and experimental studies have argued that most organic semiconductors should be able to transport both types of carrier, although typically unipolar behavior is observed. One factor that can compromise ambipolar transport in organic semiconductors is poor solid state overlap between the HOMO (p-type) or LUMO (n-type) orbitals of neighboring molecules in the semiconductor thin film. In the search of low-bandgap ambipolar materials, where the absence of skeletal distortions allows closer intermolecular π-π stacking and enhanced intramolecular π-conjugation, a new family of oligothiophene-naphthalimide assemblies have been synthesized and characterized, in which both donor and acceptor moieties are directly conjugated through rigid linkers. In previous works we found that oligothiophene-napthalimide assemblies connected through amidine linkers (NDI derivates) exhibit skeletal distortions (50-60º) arising from steric hindrance between the carbonyl group of the arylene core and the sulphur atom of the neighbored thiophene ring (see Figure 1). In the present work we report novel oligo- and polythiophene–naphthalimide analogues NAI-3T, NAI-5T and poly-NAI-8C-3T, in which the connections of the amidine linkage have been inverted in order to prevent steric interactions. Thus, the nitrogen atoms are directly connected to the naphthalene moiety in NAI derivatives while they were attached directly to the thiophene moiety in the previously investigated NDI-3T and NDI-5T. In Figure 1 is depicted the calculated molecular structure of NAI-3T together with that of NDI-3T showing how the steric interactions are not present in the novel NAI derivative. The planar skeletons in these new family induce higher degree of crystallinity and the carrier charge transport can be switched from n-type to ambipolar behaviour. The highest FET performance is achieved for vapor-deposited films of NAI-3T with mobilities of 1.95x10-4cm2V-1s-1 and 2.00x10-4cm2V-1s-1 for electrons and holes, respectively. Finally, these planar semiconductors are compared with their NDI derivates analogues, which exhibit only n-type mobility, in order to understand the origin of the ambipolarity in this new series of molecular semiconductors.

Tools For Spatiotemporally Specific Proteomic Analysis In Multicellular Organisms

The emergence of mass spectrometry-based proteomics has revolutionized the study of proteins and their abundances, functions, interactions, and modifications. However, in a multicellular organism, it is difficult to monitor dynamic changes in protein synthesis in a specific cell type within its native environment. In this thesis, we describe methods that enable the metabolic labeling, purification, and analysis of proteins in specific cell types and during defined periods in live animals. We first engineered a eukaryotic phenylalanyl-tRNA synthetase (PheRS) to selectively recognize the unnatural L-phenylalanine analog p-azido-L-phenylalanine (Azf). Using Caenorhabditis elegans, we expressed the engineered PheRS in a cell type of choice (i.e. body wall muscles, intestinal epithelial cells, neurons, pharyngeal muscles), permitting proteins in those cells -- and only those cells -- to be labeled with azides. Labeled proteins are therefore subject to "click" conjugation to cyclooctyne-functionalized affnity probes, separation from the rest of the protein pool and identification by mass spectrometry. By coupling our methodology with heavy isotopic labeling, we successfully identified proteins -- including proteins with previously unknown expression patterns -- expressed in targeted subsets of cells. While cell types like body wall or pharyngeal muscles can be targeted with a single promoter, many cells cannot; spatiotemporal selectivity typically results from the combinatorial action of multiple regulators. To enhance spatiotemporal selectivity, we next developed a two-component system to drive overlapping -- but not identical -- patterns of expression of engineered PheRS, restricting labeling to cells that express both elements. Specifically, we developed a split-intein-based split-PheRS system for highly efficient PheRS-reconstitution through protein splicing. Together, these tools represent a powerful approach for unbiased discovery of proteins uniquely expressed in a subset of cells at specific developmental stages.

New bodipy dyads for two-photons fluorescence imaging in cells

Fluorescent probes are essential tools for studying biological systems. The last decade has witnessed particular interest in the development of two-photon excitable probes, due to their advantageous features in tissue imaging compared to the corresponding one-photon probes [1]. Recently, we have designed and synthetized an aminonaphthalimide–BODIPY derivative as energy transfer cassettes and were found to show very fast and efficient BODIPY fluorescence sensitization [2]. This was observed upon one- and two-photon excitation, which extends the application range of the investigated bichromophoric dyads in terms of accessible excitation wavelengths. In order to increase the two-photon absorption of the system aminonaphthalimide fluorophore was replace with a Prodan analog (BODIPY dyad 1), which presents found a variety of applications as probes and labels in biology [3]. The two-photon absorption cross-section  of the dyads is significantly incremented by the presence of the 6-acetyl-2-naphthylamine donor group. The emission maximum of a BODIPY fluorophore can significantly be red-shifted in comparison to their precursors by conjugation with aromatic aldehydes. [4] We use a synthetic strategy to obtain BODIPY dyad 2 that incorporates an imidazole ring. This molecule can be used in biological media as a near-neutral pH indicator based on one- and two-photon excitable BODIPY acceptor.

ArmA methyltransferase in a monophasic Salmonella enterica isolate from food

The 16S rRNA methyltransferase ArmA is a worldwide emerging determinant that confers high-level resistance to most clinically relevant aminoglycosides. We report here the identification and characterization of a multidrug-resistant Salmonella enterica subspecies I.4,12:i:- isolate recovered from chicken meat sampled in a supermarket on February 2009 in La Reunion, a French island in the Indian Ocean. Susceptibility testing showed an unusually high-level resistance to gentamicin, as well as to ampicillin, expanded-spectrum cephalosporins and amoxicillin-clavulanate. Molecular analysis of the 16S rRNA methyltransferases revealed presence of the armA gene, together with bla(TEM-1), bla(CMY-2), and bla(CTX-M-3). All of these genes could be transferred en bloc through conjugation into Escherichia coli at a frequency of 10(-5) CFU/donor. Replicon typing and S1 pulsed-field gel electrophoresis revealed that the armA gene was borne on an ~150-kb broad-host-range IncP plasmid, pB1010. To elucidate how armA had integrated in pB1010, a PCR mapping strategy was developed for Tn1548, the genetic platform for armA. The gene was embedded in a Tn1548-like structure, albeit with a deletion of the macrolide resistance genes, and an IS26 was inserted within the mel gene. To our knowledge, this is the first report of ArmA methyltransferase in food, showing a novel route of transmission for this resistance determinant. Further surveillance in food-borne bacteria will be crucial to determine the role of food in the spread of 16S rRNA methyltransferase genes worldwide.

Multiresistance in Pasteurella multocida is mediated by coexistence of small plasmids

In most gram-negative bacteria, acquired multiresistance is conferred by large plasmids compiling numerous antimicrobial resistance genes. Here, we show an evolutionary alternative strategy used by Pasteurella multocida to become resistant to multiple clinically relevant antibiotics. Thirteen beta-lactam-resistant clinical isolates, concomitantly resistant to tetracyclines and/or streptomycin as well as to sulfonamides, were studied. Pulsed-field gel electrophoresis analysis revealed different profiles among the isolates, showing that clonal dissemination was not the sole event responsible for the spread of multiresistance. Each P. multocida strain carried two or three small plasmids between 4 and 6 kb in size. A direct association between resistance profile and plasmid content was found. Complete nucleotide sequencing of all plasmids revealed seven different replicons, six of them belonging to the ColE1 superfamily. All plasmids carried one, or a maximum of two, antimicrobial resistance determinants. Plasmids pB1000 and pB1002 bore bla(ROB-1), pB1001 carried tet(B), pB1003 and pB1005 carried sul2 and strA, pB1006 harbored tet(O), and p9956 bore the tet(H) gene. All plasmids except pB1002 and pB1006 were successfully transformed into Escherichia coli. pB1000, also involved in beta-lactam resistance in Haemophilus parasuis (A. San Millan et al., Antimicrob. Agents Chemother. 51:2260-2264, 2007), was mobilized in E. coli using the conjugation machinery of an IncP plasmid. Stability experiments proved that pB1000 was stable in P. multocida but highly unstable in E. coli. In conclusion, bla(ROB-1) is responsible for beta-lactam resistance in P. multocida in Spain. Coexistence and the spread of small plasmids are used by P. multocida to become multiresistant.

Prevalence of hepatitis E virus antibodies in workers occupationally exposed to swine in Portugal

The concept of zoonotic hepatitis E in industrialized countries has emerged with the discovery of swine strains of hepatitis E virus (HEV) genotype 3, closely related to human HEV. Different routes of zoonotic HEV transmission have been recognized, including contact with infected pigs. Workers occupationally exposed to swine (WOES) have been considered a risk group for HEV infection, but contradictory results have been reported. In the present study, we searched for anti-HEV IgG in WOES (butchers, slaughterhouse workers, veterinarians and pig farmers; n = 114) and in the general population (n = 804) in order to investigate the potential occupational risk of zoonotic HEV infection in this work group. A significantly higher (p = 0.008) anti-HEV IgG seroprevalence was found in WOES (30.7 %) when compared with the general population (19.9 %). Multivariate analysis showed that having professions with exposure to pigs for more than 16.5 years was a risk factor for being positive for anti-HEV IgG (aOR of 5.4, 95 % CI 1.9-15.6, p = 0.002). To our knowledge, this is the first study on the prevalence of anti-HEV IgG in WOES in Portugal, also showing increased probability for infection in this group.

IMPACTS OF ENHANCED TEMPERATURE AND SNOW DEPOSITION ON SENESCENCE DATE, VEGETATION COVER, AND CO2 EXCHANGE IN A CANADIAN HIGH ARCTIC MESIC ECOSYSTEM

Arctic regions are expected to experience an increase in both temperature and precipitation over the coming decades, which is likely to impact vegetation dynamics and greenhouse gas exchange. To test this response, an experiment was installed at the Cape Bounty Arctic Watershed Observatory, on Melville Island, NU, in 2008 as part of the International Tundra Experiment (ITEX). Snow fences and open top chambers (OTCs) were used to manipulate snow depth and air temperature, respectively. Unlike most ITEX sites to date, enhanced temperature and snowfall were combined here in a factorial design with eight replicates. As an added control, four plots were established well outside the enhanced snow area. Senescence date was recorded at the end of the season, and at the peak of the growing season a vegetation survey was conducted within each plot in order to determine the total percent cover of each plot, as well as the percent cover of individual species. Carbon dioxide (CO2) exchange was also measured within each plot throughout the growing season. The date of senescence occurred significantly earlier in plots which had not been manipulated in any way, compared to all other treatments for all species. Salix arctica showed the greatest increase in cover over time at the species level. Lichen cover increased significantly in the deepened snow plots, and in general there were significant increases in percent cover in some functional groups over time. During June and into July the net CO2 flux was to the atmosphere. It was not until July 27 that these ecosystems became net carbon sinks. However, warming alone resulted in the ecosystem acting as a significant net carbon sink for the entire growing season. Plots exposed to warming alone were estimated to have removed approximately 19.94 g C m-2 from the atmosphere, whereas all other treatments were very similar to one another and estimated to have added approximately 3.12 g C m-2 to the atmosphere. Active layer depth and soil temperatures suggest that plots within the ambient snow zone may be receiving some additional snow due to their proximity to the fences. CO2 fluxes measured within the outer control plots suggest that the effect of warming alone could lead to this ecosystem being an even stronger net C sink under truly ambient snow conditions.

A Grammar of Tajio. A Language Spoken in Central Sulawesi

This work is a description of Tajio, a Western Malayo-Polynesian language spoken in Central Sulawesi, Indonesia. It covers the essential aspects of Tajio grammar without being exhaustive. Tajio has a medium sized phoneme inventory consisting of twenty consonants and five vowels. The language does not have lexical (word) stress; rather, it has a phrasal accent. This phrasal accent regularly occurs on the penultimate syllable of an intonational phrase, rendering this syllable auditorily prominent through a pitch rise. Possible syllable structures in Tajio are (C)V(C). CVN structures are allowed as closed syllables, but CVN syllables in word-medial position are not frequent. As in other languages in the area, the only sequence of consonants allowed in native Tajio words are sequences of nasals followed by a homorganic obstruent. The homorganic nasal-obstruent sequences found in Tajio can occur word-initially and word-medially but never in word-final position. As in many Austronesian languages, word class classification in Tajio is not straightforward. The classification of words in Tajio must be carried out on two levels: the morphosyntactic level and the lexical level. The open word classes in Tajio consist of nouns and verbs. Verbs are further divided into intransitive verbs (dynamic intransitive verbs and statives) and dynamic transitive verbs. Based on their morphological potential, lexical roots in Tajio fall into three classes: single-class roots, dual-class roots and multi-class roots. There are two basic transitive constructions in Tajio: Actor Voice and Undergoer Voice, where the actor or undergoer argument respectively serves as subjects. It shares many characteristics with symmetrical voice languages, yet it is not fully symmetric, as arguments in AV and UV are not equally marked. Neither subjects nor objects are marked in AV constructions. In UV constructions, however, subjects are unmarked while objects are marked either by prefixation or clitization. Evidence from relativization, control and raising constructions supports the analysis that AV and UV are in fact transitive, with subject arguments and object arguments behaving alike in both voices. Only the subject can be relativized, controlled, raised or function as the implicit subject of subjectless adverbial clauses. In contrast, the objects of AV and UV constructions do not exhibit these features. Tajio is a predominantly head-marking language with basic A-V-O constituent order. V and O form a constituent, and the subject can either precede or follow this complex. Thus, basic word order is S-V-O or V-O-S. Subject, as well as non-subject arguments, may be omitted when contextually specified. Verbs are marked for voice and mood, the latter of which is is obligatory. The two values distinguished are realis and non-realis. Depending on the type of predicate involved in clause formation, three clause types can be distinguished: verbal clauses, existential clauses and non-verbal clauses. Tajio has a small number of multi-verbal structures that appear to qualify as serial verb constructions. SVCs in Tajio always include a motion verb or a directional.

Sulfur transfer and activation by ubiquitin-like modifier system Uba4•Urm1 link protein urmylation and tRNA thiolation in yeast

Urm1 is a unique dual-function member of the ubiquitin protein family and conserved from yeast to man. It acts both as a protein modifier in ubiquitin-like urmylation and as a sulfur donor for tRNA thiolation, which in concert with the Elongator pathway forms 5-methoxy-carbonyl-methyl-2-thio (mcm5s2) modified wobble uridines (U34) in anticodons. Using Saccharomyces cerevisiae as a model to study a relationship between these two functions, we examined whether cultivation temperature and sulfur supply previously implicated in the tRNA thiolation branch of the URM1 pathway also contribute to proper urmylation. Monitoring Urm1 conjugation, we found urmylation of the peroxiredoxin Ahp1 is suppressed either at elevated cultivation temperatures or under sulfur starvation. In line with this, mutants with sulfur transfer defects that are linked to enzymes (Tum1, Uba4) required for Urm1 activation by thiocarboxylation (Urm1-COSH) were found to maintain drastically reduced levels of Ahp1 urmylation and mcm5s2U34 modification. Moreover, as revealed by site specific mutagenesis, the Stransfer rhodanese domain (RHD) in the E1-like activator (Uba4) crucial for Urm1-COSH formation is critical but not essential for protein urmylation and tRNA thiolation. In sum, sulfur supply, transfer and activation chemically link protein urmylation and tRNA thiolation. These are features that distinguish the ubiquitin-like modifier system Uba4•Urm1 from canonical ubiquitin family members and will help elucidate whether, in addition to their mechanistic links, the protein and tRNA modification branches of the URM1 pathway may also relate in function to one another.

Early Literacy in Library Storytimes: A Study of Measures of Effectiveness

Across the nation, librarians work with caregivers and children to encourage engagement in their early literacy programs. However, these early literacy programs that libraries provide have been left mostly undocumented by research, especially through quantitative methods. Valuable Initiatives in Early Learning that Work Successfully (VIEWS2) was designed to test new ways to measure the effectiveness of these early literacy programs for young children (birth to kindergarten), leveraging a mixed methods, quasi-experimental design. Using two innovative tools, researchers collected data at 120 public library storytimes in the first year of research, observing approximately 1,440 children ranging from birth to 60 months of age. Analysis of year-one data showed a correlation between the early literacy content of the storytime program and children’s outcomes in terms of early literacy behaviors. These findings demonstrate that young children who attend public library storytimes are responding to the early literacy content in the storytime programs.

The subjunctive mood in Late Middle English adverbial clauses: the interaction of form and function

This thesis focuses on the history of the inflexional subjunctive and its functional substitutes in Late Middle English. To explore why and how the inflexional subjunctive declined in the history of English language, I analysed 2653 examples of three adverbial clauses introduced by if (1882 examples), though (305 examples) and lest (466 examples). Using a corpus-based approach, this thesis argues that linguistic change in subjunctive constructions did not happen suddenly but rather gradually, and the way it changed was varied , and that different constructions changed at different speeds in different environments. It is well known that the inflexional subjunctive declined in the history of English, mainly because of inflexional loss. Strangely however this topic has been comparatively neglected in the scholarly literature, especially with regard to the Middle English period, probably due to the limitations of data and also because study of this development requires very cumbersome textual research. This thesis has derived and analysed the data from three large corpora in the public domain: the Middle English Grammar Corpus (MEG-C for short), the Innsbruck Computer Archive of Machine-Readable English Texts (ICAMET for short), and some selected texts from The Corpus of Middle English Prose and Verse, part of the Middle English Compendium that also includes the Middle English Dictionary. The data were analysed from three perspectives: 1) clausal type, 2) dialect, and 3) textual genre. The basic methodology for the research was to analyse the examples one by one, with special attention being paid to the peculiarities of each text. In addition, this thesis draw on some complementary – indeed overlapping -- linguistic theories for further discussion: 1) Biber’s multi-dimensional theory, 2) Ogura and Wang’s (1994) S-curve or ‘diffusion’ theory, 3) Kretzchmar’s (2009) linguistics of speech, and 4) Halliday’s (1987) notion of language as a dynamic open system. To summarise the outcomes of this thesis: 1) On variation between clausal types, it was shown that the distributional tendencies of verb types (sub, ind, mod) are different between the three adverbial clauses under consideration. 2) On variation between dialects, it has been shown that the northern area, i.e. the so-called Great Scandinavian Belt, displays an especially high comparative ratio of the inflexional subjunctive construction compared to the other areas. This thesis suggests that this result was caused by the influence of Norse, relating the finding to the argument of Samuels (1989) that the present tense -es ending in the northern dialect was introduced by the influence of the Scandinavians. 3) On variation between genres, those labelled Science, Documents and Religion display relatively high ratio of the inflexional subjunctive, while Letter, Romance and History show relatively low ratio of the inflexional subjunctive. This results are explained by Biber’s multi-dimensional theory, which shows that the inflexional subjunctive can be related to the factors ‘informational’, ‘non-narrative’, ‘persuasive’ and ‘abstract’. 4) Lastly, on the inflexional subjunctive in Late Middle English, this thesis concludes that 1) the change did not happen suddenly but gradually, and 2) the way language changes varies. Thus the inflexional subjunctive did not disappear suddenly from England, and there was a time lag among the clausal types, dialects and genres, which can be related to Ogura and Wang’s S-curve (“diffusion”) theory and Kretzchmars’s view of “linguistic continuum”. This thesis has shown that the issues with regard to the inflexional subjunctive are quite complex, so that research in this area requires not only textual analysis but also theoretical analysis, considering both intra- and extra- linguistic factors.

Spirituality in the Undergraduate Curricula of Nursing Schools in Portugal and São Paulo-Brazil

Spirituality is considered a dimension of nursing care, which is often recognized as being neglected, mainly due to a lack of education. Several studies have addressed nursing students’ perceptions and skills for providing spiritual care, but there is little evidence on how spirituality is addressed in undergraduate nursing curricula. This study comprised Portuguese and Brazilian nursing schools (from São Paulo) and describes how spirituality is addressed in undergraduate nursing curricula. It is descriptive and the survey research was performed in 2014–2015. The questionnaire was composed of closed and open-ended questions and was sent by e-mail. A total of 129 answers were obtained, mostly from Portugal. Results indicated that several curricular units include spirituality, although having different contents. The learning outcomes are consistent with improving nursing students’ integral education, developing the clinical reasoning regarding spirituality, and improving the assessment of the patient across the life span. Nevertheless, it seems that spirituality is poorly addressed in clinical practice. Few nursing schools have courses or curricular units specifically dealing with spirituality, but they do provide some form of teaching on the subject. No standard curriculum exists, but teachers believe that it is a very important subject that should be included in the courses taught.

Using syntactic and semantic features for classifying mo- dal values in the portuguese language

This paper presents a study made in a field poorly explored in the Portuguese language – modality and its automatic tagging. Our main goal was to find a set of attributes for the creation of automatic tag- gers with improved performance over the bag-of-words (bow) approach. The performance was measured using precision, recall and F1. Because it is a relatively unexplored field, the study covers the creation of the corpus (composed by eleven verbs), the use of a parser to extract syntac- tic and semantic information from the sentences and a machine learning approach to identify modality values. Based on three different sets of attributes – from trigger itself and the trigger’s path (from the parse tree) and context – the system creates a tagger for each verb achiev- ing (in almost every verb) an improvement in F1 when compared to the traditional bow approach.

Sinthesys of heteroleptic zinc complexes for imaging in living cells

This thesis arose from an interest in luminescence heteroleptic bis(dipyrrinato) Zn (II) complexes and their application in cell imaging, due to their attractive and fascinating characteristics. Among imaging technologies, near-infrared fluorescence imaging has been dedicated immense attention owing to its low absorption and autofluorescence from surrounding organism and tissues in this specific spectral region, which minimize background interference and improve tissue depth penetration. An ideal near-infrared probe should be equipped with excellence chemical and photophysical properties. The target of this work is the synthesis of new heteroleptic bis(dipyrrinato) Zn (II) complexes having two main features: the emission in the near-infrared region and water-solubility. In order to purse these intentions, the low-energy emission was achieved by expansion of π-conjugation of simple dipyrrins using Knoevenagel condensation106 and tri(ethylene)glycol chain was introduced to increase the water solubility of the final complex. Photophysical and luminescent properties of the new complexes were investigated. Finally, with a view to a potential biological use of these new complexes in biological environments, their biocompatibility was tested using a cell viability assay: (3-(4,5-dimethylthiazol-2-yl)-2’-5’-diphenyltetrazolium bromide (MTT) assay.