Spectroscopic Study on the Structural Differences of Thermally Induced Cross-Linking Segments in Emeraldine Salt and Base Forms of Polyaniline

This paper reports the spectroscopic study on the structural differences of thermally induced cross-linking segments in polyaniline in its emeraldine salt (PANI-ES) and base (PANI-EB) forms. Casting films of PANI-ES (ES-film) and PANI-EB (EB-film) were prepared and heated at 150 degrees C under atmospheric air for 30 min. Raman spectra excited at 632.8 nm of heated ES-film presented the characteristic bands of phenazine-like structures at 1638, 1392, and 575 cm(-1), whereas EB-film showed lower relative intensities for these bands. The lower content of phenazine-like segments in heated EB-film is related to residual polaronic segments from preparation procedures, as revealed by Raman. This statement was confirmed by a sequence of thermal and doping experiments in both films. Quantum-chemical calculations by density functional theory (DFT) and time-dependent density functional theory (TD-DFT) showed that the phenazine-like structure presents the intense Raman band at 1350 cm(-1) due to heterocycle breathing mode, and the non-phenazine-like structure (substituted hydrophenazine-type) presents higher energy for HOMO-LUMO transition, indicating the lack of conjugation in the heterocycle compared with the phenazine-like structure. According to experimental and theoretical data reported here, it is proposed that only thermally treated PANI-ES presents phenazine-like rings, whereas PANI-EB presents heterocyclic non-aromatic structures.

Morphological priming in Spanish verb forms: an ERP repetition priming study

The ERP repetition priming paradigm has been shown to be sensitive to the processing differences between regular and irregular verb forms in English and German. The purpose of the present study is to extend this research to a language with a different inflectional system, Spanish. The design (delayed visual repetition priming) was adopted from our previous study on English, and the specific linguistic phenomena we examined are priming relations between different kinds of stem (or root) forms. There were two experimental conditions: In the first condition, the prime and the target shared the same stem form, e.g., "ando-andar" [I walk-to walk], whereas in the second condition, the prime contained a marked (alternated) stem, e.g., "duermo-dormir" [I sleep-to sleep]. A reduced N400 was found for unmarked (nonalternated) stems in the primed condition, whereas marked stems showed no such effect. Moreover, control conditions demonstrated that the surface form properties (i.e., the different degree of phonetic and orthographic overlap between primes and targets) do not explain the observed priming difference. The ERP priming effect for verb forms with unmarked stems in Spanish is parallel to that found for regularly inflected verb forms in English and German. We argue that effective priming is possible because prime target pairs such as "ando-andar" access the same lexical entry for their stems. By contrast, verb forms with alternated stems (e.g., "duermo") constitute separate lexical entries, and are therefore less powerful primes for their corresponding base forms.

Optimisation de la concentration en électrolytes au sein des matrices à base de HASCA pour la libération prolongée

Le sel sodique du carboxyméthylamidon à haute teneur en amylose, HASCA (Amylose 60%-amylopectine 40%), est un polymère hydrophile ionique utilisé pour obtenir des comprimés matriciels à libération prolongée. Il est caractérisé par la formation d'un hydrogel lors de la mise en contact avec le milieu de dissolution. La libération du principe actif (PA) à travers ce polymère est principalement contrôlée par la diffusion fickienne et la relaxation du réseau polymérique. De plus, la solubilité du PA est un facteur qui permet de moduler la libération, cependant, la solubilité d’un médicament dépend de la forme utilisée et du pH. Les bases ou les acides libres présentent une solubilité moins élevée que leurs sels. Nous proposons d’étudier l’effet d’une combinaison entre le sel et la forme acide ou le sel et la forme alcaline dans le même comprimé matriciel d’HASCA. Comme objectif de ce travail, nous étudions l’influence de la nature du polymère sur le profil de libération de PA dans un milieu aqueux en gradient de pH à cause de la nature des matrices à base d’HASCA caractérisées par la présence de groupement carboxyliques, ionisés ou non selon l’acidité du milieu de dissolution. Nous étudions également l’influence de la nature du PA (base libre ou son sel vs acide libre ou son sel) sur le profil de libération, ceci en sélectionnant des PAs modèles représentatifs de chaque catégorie. L’influence de changement de proportions entre la forme libre (acide ou base) et son sel sur le profil de libération est aussi investiguée. Pour ce, des comprimés à base de HASCA avec des proportions différentes de, soit le naproxène acide et le naproxène de sodium (PA acide et son sel), soit la tétracycline et le chlorhydrate de tétracycline (PA alcalin et son sel) ont été utilisés. Ceux-ci sont évalués lors des tests de dissolution dans un milieu simulant le milieu gastro-intestinal, selon les normes de l’USP (spectrophotométrie UV). Nous avons également menés des études de vitesse de dissolution intrinsèque sur les PAs purs, afin de déterminer leur solubilité et vitesse de libération dans les même pH de dissolution étudiés. Nous avons réussit d’obtenir des comprimés matriciels à base de HASCA convenables à être administrés une fois par jour en utilisant une combinaison du naproxène acide et son sel comme PA. Tandis que les résultats ont montré qu’en utilisant la tétracycline et son sel, les temps de libération étaient trop élevés pour permettre la réalisation d’une formulation convenable pour une administration quotidienne unique

Photoinduced electron transfer and electronic energy transfer in naphthyl-appended cyclams

A series of novel macrocyclic tetraaza ligands that incorporate a naphthalene moiety as a photoactive chromophore have been prepared and structurally characterized as their Cu(II) complexes. Variable-temperature photophysical studies have concluded that the luminescence quenching evident in the Cu(H) complexes is due to intramolecular electronic energy transfer (EET). In their free-base forms, these ligands undergo reductive luminescence quenching via photoinduced electron transfer (PET) reactions, with proximate amine lone pairs acting as electron donors. Consequently, the emission behavior can be modulated by variations in pH and/or the presence of other Lewis acids such as Zn(H).

Intramolecular electronic energy transfer in bichromophoric macrocyclic complexes

Efficient intramolecular electronic energy transfer (EET) has been demonstrated for three novel bichromophoric compounds utilizing a macrocyclic spacer as the bridge between the electronic energy donor and acceptor fragments. As their free base forms, emission from the electronically excited donor is absent and the acceptor emission is reductively quenched via photoinduced oxidation of proximate amine lone pairs. As their Zn(II) complexes, excitation of the donor results in sensitization of the electronic acceptor emission.

Processing of zero-derived words in English: an fMRI investigation

Derivational morphological processes allow us to create new words (e.g. punish (V) to noun (N) punishment) from base forms. The number of steps from the basic units to derived words often varies (e.g., nationalitybridge-V) i.e., zero-derivation ( Aronoff, 1980). We compared the processing of one-step (soakingforms of words (soaking, bridging) in a lexical decision task. Although the surface derived -ing forms can be contextually participles, gerunds, or even nouns, they are all derived from verbs since the suffix -ing can only be attached to verb roots. Crucially, the verb root is the basic form for the one-step words, whereas for the two-step words the verb root is zero derived from a basic noun. Significantly increased brain activity was observed for complex (one-step and two-step) versus simple (zero-step) forms in regions involved in morphological processing, such as the left inferior frontal gyrus (LIFG). Critically, activation was also more pronounced for two-step compared to one-step forms. Since both types of derived words have the same surface structure, our findings suggest that morphological processing is based on underlying morphological complexity, independent of overt affixation. This study is the first to provide evidence for the processing of zero derivation, and demonstrates that morphological processing cannot be reduced to surface form-based segmentation.

Structural and vibrational characterization of polyaniline nanofibers prepared from interfacial polymerization

This work deals with the structural and vibrational characterization of PANI nanofibers prepared through interfacial polymerization using different concentrations of HCl aqueous solution. The results were compared to those obtained by PANI prepared through the conventional route. X-ray diffraction and small-angle X-ray scattering techniques showed that high concentrations of HCl solutions used in the preparation of the PANI nanofibers reduce their crystallinity. The increase of regions with granular morphology was also observed in the scanning electron microscopy images. The changes in the resonance Raman spectra from 200 to 500 cm(-1), FTIR spectra, and the EPR data of the PANI nanofibers reveal an increase in the torsion angles of C-ring-N-C-ring segments owing the formation of bipolarons in the PANI backbone higher than the PANI samples prepared by conventional route.

Studies on the resonance Raman spectra of polyaniline obtained with near-IR excitation

The effects of near-IR (NIR) laser power over the Raman spectra of poly(aniline) emeraldine salt (PANIES) and base (PANI-EB) were investigated. The reasons for the existence of several bands from 1324 to 1500 cm-1 in the Raman spectra of poly(aniline) obtained at NIR region were also studied. The bands from 1324 to 1375 cm-` were associated to vC-N of polarons with different conjugation lengths and the bands from 1450 to 1500 cm-1 in Raman spectra of PANI emeraldine and pernigraniline base forms were correlated to vC=N modes associated with quinoid units having different conjugation lengths. The increase of laser power at 1064.0 run causes the deprotonation of PANI-ES and the formation of cross-linking segments having phenazine and/or oxazine rings. For PANI-EB only a small spectral change is observed when the laser power is increased, owing to the low absorption of this form in the NIR region. Copyright (c) 2007 John Wiley & Sons, Ltd.

O faz-de-conta como atividade promotora de desenvolvimento infantil e algumas contribuições acerca de suas implicações para aprender a ler e escrever

Pós-graduação em Educação - FFC

Tense, aspect and modality in first and second language

Time after time… and aspect and mood. Over the last twenty five years, the study of time, aspect and - to a lesser extent - mood acquisition has enjoyed increasing popularity and a constant widening of its scope. In such a teeming field, what can be the contribution of this book? We believe that it is unique in several respects. First, this volume encompasses studies from different theoretical frameworks: functionalism vs generativism or function-based vs form-based approaches. It also brings together various sub-fields (first and second language acquisition, child and adult acquisition, bilingualism) that tend to evolve in parallel rather than learn from each other. A further originality is that it focuses on a wide range of typologically different languages, and features less studied languages such as Korean and Bulgarian. Finally, the book gathers some well-established scholars, young researchers, and even research students, in a rich inter-generational exchange, that ensures the survival but also the renewal and the refreshment of the discipline. The book at a glance The first part of the volume is devoted to the study of child language acquisition in monolingual, impaired and bilingual acquisition, while the second part focuses on adult learners. In this section, we will provide an overview of each chapter. The first study by Aviya Hacohen explores the acquisition of compositional telicity in Hebrew L1. Her psycholinguistic approach contributes valuable data to refine theoretical accounts. Through an innovating methodology, she gathers information from adults and children on the influence of definiteness, number, and the mass vs countable distinction on the constitution of a telic interpretation of the verb phrase. She notices that the notion of definiteness is mastered by children as young as 10, while the mass/count distinction does not appear before 10;7. However, this does not entail an adult-like use of telicity. She therefore concludes that beyond definiteness and noun type, pragmatics may play an important role in the derivation of Hebrew compositional telicity. For the second chapter we move from a Semitic language to a Slavic one. Milena Kuehnast focuses on the acquisition of negative imperatives in Bulgarian, a form that presents the specificity of being grammatical only with the imperfective form of the verb. The study examines how 40 Bulgarian children distributed in two age-groups (15 between 2;11-3;11, and 25 between 4;00 and 5;00) develop with respect to the acquisition of imperfective viewpoints, and the use of imperfective morphology. It shows an evolution in the recourse to expression of force in the use of negative imperatives, as well as the influence of morphological complexity on the successful production of forms. With Yi-An Lin’s study, we concentrate both on another type of informant and of framework. Indeed, he studies the production of children suffering from Specific Language Impairment (SLI), a developmental language disorder the causes of which exclude cognitive impairment, psycho-emotional disturbance, and motor-articulatory disorders. Using the Leonard corpus in CLAN, Lin aims to test two competing accounts of SLI (the Agreement and Tense Omission Model [ATOM] and his own Phonetic Form Deficit Model [PFDM]) that conflicts on the role attributed to spellout in the impairment. Spellout is the point at which the Computational System for Human Language (CHL) passes over the most recently derived part of the derivation to the interface components, Phonetic Form (PF) and Logical Form (LF). ATOM claims that SLI sufferers have a deficit in their syntactic representation while PFDM suggests that the problem only occurs at the spellout level. After studying the corpus from the point of view of tense / agreement marking, case marking, argument-movement and auxiliary inversion, Lin finds further support for his model. Olga Gupol, Susan Rohstein and Sharon Armon-Lotem’s chapter offers a welcome bridge between child language acquisition and multilingualism. Their study explores the influence of intensive exposure to L2 Hebrew on the development of L1 Russian tense and aspect morphology through an elicited narrative. Their informants are 40 Russian-Hebrew sequential bilingual children distributed in two age groups 4;0 – 4;11 and 7;0 - 8;0. They come to the conclusion that bilingual children anchor their narratives in perfective like monolinguals. However, while aware of grammatical aspect, bilinguals lack the full form-function mapping and tend to overgeneralize the imperfective on the principles of simplicity (as imperfective are the least morphologically marked forms), universality (as it covers more functions) and interference. Rafael Salaberry opens the second section on foreign language learners. In his contribution, he reflects on the difficulty L2 learners of Spanish encounter when it comes to distinguishing between iterativity (conveyed with the use of the preterite) and habituality (expressed through the imperfect). He examines in turn the theoretical views that see, on the one hand, habituality as part of grammatical knowledge and iterativity as pragmatic knowledge, and on the other hand both habituality and iterativity as grammatical knowledge. He comes to the conclusion that the use of preterite as a default past tense marker may explain the impoverished system of aspectual distinctions, not only at beginners but also at advanced levels, which may indicate that the system is differentially represented among L1 and L2 speakers. Acquiring the vast array of functions conveyed by a form is therefore no mean feat, as confirmed by the next study. Based on the prototype theory, Kathleen Bardovi-Harlig’s chapter focuses on the development of the progressive in L2 English. It opens with an overview of the functions of the progressive in English. Then, a review of acquisition research on the progressive in English and other languages is provided. The bulk of the chapter reports on a longitudinal study of 16 learners of L2 English and shows how their use of the progressive expands from the prototypical uses of process and continuousness to the less prototypical uses of repetition and future. The study concludes that the progressive spreads in interlanguage in accordance with prototype accounts. However, it suggests additional stages, not predicted by the Aspect Hypothesis, in the development from activities and accomplishments at least for the meaning of repeatedness. A similar theoretical framework is adopted in the following chapter, but it deals with a lesser studied language. Hyun-Jin Kim revisits the claims of the Aspect Hypothesis in relation to the acquisition of L2 Korean by two L1 English learners. Inspired by studies on L2 Japanese, she focuses on the emergence and spread of the past / perfective marker ¬–ess- and the progressive – ko iss- in the interlanguage of her informants throughout their third and fourth semesters of study. The data collected through six sessions of conversational interviews and picture description tasks seem to support the Aspect Hypothesis. Indeed learners show a strong association between past tense and accomplishments / achievements at the start and a gradual extension to other types; a limited use of past / perfective marker with states and an affinity of progressive with activities / accomplishments and later achievements. In addition, - ko iss– moves from progressive to resultative in the specific category of Korean verbs meaning wear / carry. While the previous contributions focus on function, Evgeniya Sergeeva and Jean-Pierre Chevrot’s is interested in form. The authors explore the acquisition of verbal morphology in L2 French by 30 instructed native speakers of Russian distributed in a low and high levels. They use an elicitation task for verbs with different models of stem alternation and study how token frequency and base forms influence stem selection. The analysis shows that frequency affects correct production, especially among learners with high proficiency. As for substitution errors, it appears that forms with a simple structure are systematically more frequent than the target form they replace. When a complex form serves as a substitute, it is more frequent only when it is replacing another complex form. As regards the use of base forms, the 3rd person singular of the present – and to some extent the infinitive – play this role in the corpus. The authors therefore conclude that the processing of surface forms can be influenced positively or negatively by the frequency of the target forms and of other competing stems, and by the proximity of the target stem to a base form. Finally, Martin Howard’s contribution takes up the challenge of focusing on the poorer relation of the TAM system. On the basis of L2 French data obtained through sociolinguistic interviews, he studies the expression of futurity, conditional and subjunctive in three groups of university learners with classroom teaching only (two or three years of university teaching) or with a mixture of classroom teaching and naturalistic exposure (2 years at University + 1 year abroad). An analysis of relative frequencies leads him to suggest a continuum of use going from futurate present to conditional with past hypothetic conditional clauses in si, which needs to be confirmed by further studies. Acknowledgements The present volume was inspired by the conference Acquisition of Tense – Aspect – Mood in First and Second Language held on 9th and 10th February 2008 at Aston University (Birmingham, UK) where over 40 delegates from four continents and over a dozen countries met for lively and enjoyable discussions. This collection of papers was double peer-reviewed by an international scientific committee made of Kathleen Bardovi-Harlig (Indiana University), Christine Bozier (Lund Universitet), Alex Housen (Vrije Universiteit Brussel), Martin Howard (University College Cork), Florence Myles (Newcastle University), Urszula Paprocka (Catholic University of Lublin), †Clive Perdue (Université Paris 8), Michel Pierrard (Vrije Universiteit Brussel), Rafael Salaberry (University of Texas at Austin), Suzanne Schlyter (Lund Universitet), Richard Towell (Salford University), and Daniel Véronique (Université d’Aix-en-Provence). We are very much indebted to that scientific committee for their insightful input at each step of the project. We are also thankful for the financial support of the Association for French Language Studies through its workshop grant, and to the Aston Modern Languages Research Foundation for funding the proofreading of the manuscript.

Quadratic and Symmetric Bilinear Forms on Modules with Unique Base Over a Semiring

27 pages

Quadratic and symmetric bilinear forms on modules with unique base over a semiring

Peer reviewed

Validade científica de conhecimento epidemiológico gerado com base no estudo Saúde Bucal Brasil 2003

Problematiza-se a afirmação de que não são válidas as estimativas sobre as condições de saúde bucal da população brasileira geradas pelo SB Brasil 2003. Criticam-se os elementos que pretendem sustentar esse ponto de vista com base apenas em conceitos estatísticos, sem prova empírica. Identificam-se reduções decorrentes da abordagem epistemocêntrica que recusa peremptoriamente outras formas de conhecimento e não reconhece o caráter multidisciplinar da epidemiologia. Reconstituem-se informações sobre a realização do levantamento e seu impacto na produção de conhecimento. Faz-se uma analogia entre ciência e arte, argumentando-se que, nas imagens obtidas por ambas, os saberes gerados a partir do objeto cognoscível assumem feições variadas e, portanto, o reconhecimento de sua validade requer amplo domínio do objeto e operações com adequados critérios de valor. Conclui-se pela cientificidade, validade e relevância da produção acadêmica desenvolvida a partir da base de dados do levantamento SB Brasil 2003.

Structures of free and complexed forms of Escherichia coli xanthine-guanine phosphoribosyltransferase

Structures of free, substrate-bound and product-bound forms of Escherichia coli xanthine-guanine phosphoribosyltransferase (XGPRT) have been determined by X-ray crystallography. These are compared with the previously determined structure of magnesium and sulphate-bound XPRT. The structure of free XGPRT at 2.25 Angstrom resolution confirms the flexibility of residues in and around a mobile loop identified in other PRTases and shows that the cis-peptide conformation of Arg37 at the active site is maintained in the absence of bound ligands. The structures of XGPRT complexed with the purine base substrates guanine or xanthine in combination with cPRib-PP, an analog of the second substrate PRib-PP, have been solved to 2.0 Angstrom resolution. In these two structures the disordered phosphate-binding loop of uncomplexed XGPRT becomes ordered through interactions with the 5'-phosphate group of cPRib-PP. The cyclopentane ring of cPRib-PP has the C3 exo pucker conformation, stabilised by the cPRib-PP-bound Mg2+. The purine base specificity of XGPRT appears to be due to water-mediated interactions between the 2-exocyclic groups of guanine or xanthine and side-chains of Glu136 and Asp140, as well as the main-chain oxygen atom of Ile135. Asp92, together with Lys115, could help stabilise the N7-protonated tautomer of the incoming base and could act as a general base to remove the proton from N7 .when the nucleotide product is formed. The 2.6 Angstrom resolution structure of XGPRT complexed with product GMP is similar to the substrate-bound complexes. However, the ribose ring of GMP is rotated by similar to 24 degrees compared with the equivalent ring in cPRib-PP. This rotation results in the loss of all interactions between the ribosyl group and the enzyme in the product complex. (C) 1998 Academic Press.

Utilização de PAM's e Medicamentos e/ou Produtos à base de Plantas pela População do Concelho de Bragança

Introdução: Entende-se por fitoterapia a terapêutica caracterizada pelo uso de plantas medicinais nas diferentes formas farmacêuticas com finalidade terapêutica, usada assim para prevenir, atenuar ou curar um estado patológico. Objetivos: Caracterizar a utilização de plantas aromáticas e medicinais (PAM´s), medicamentos e produtos à base de plantas pela população do concelho de Bragança, conhecer a fonte de indicação deste tipo de produtos, apurar a relação entre a fonte de indicação e o estado de saúde após a utilização, verificar a sua correta utilização relativa à indicação terapêutica, modo e frequência de utilização, identificar potenciais interacções medicamentosas, averiguar se os utentes informam o médico do seu uso, investigar a ocorrência de efeitos adversos e apurar a relação entre os efeitos adversos ocorridos e o género dos inquiridos. Métodos: Trata-se de um estudo observacional analítico-transversal. Nele participaram 404 indivíduos de ambos os géneros e com idades compreendidas entre os 18 e os 89 anos. A recolha de dados foi realizada entre os meses de abril e junho de 2014, através de um questionário estruturado de autopreenchimento, formado por 30 perguntas. Após a recolha dos dados procedeu-se à leitura óptica dos questionários, sendo os dados posteriormente exportados para SPSS permitindo assim o tratamento dos mesmos. Para análise estatística utilizou-se o teste do qui-quadrado considerando o nível de significância p <0,05. Resultados: Verificou-se que 53,7% dos inquiridos recorre terapeuticamente a PAM´s que inclui principalmente o uso de cidreira e camomila enquanto 33,8% faz uso de medicamentos e/ou produtos àbase de plantas nomeadamente Valdispert e Daflon. A utilização de PAM,s é motivada por autoconhecimento e indicação de familiares, amigos e vizinhos. Já os medicamentos e/ou produtos à base de plantas são utilizados maioritariamente por prescrição médica e indicação na farmácia. A ocorrência de efeitos indesejáveis foi sentida unicamente com a utilização de PAM´s e em pequena escala. Conclusão: O recurso a este tipo de produtos é uma prática bastante comum entre os moradores do concelho de Bragança, que utilizam uma grande diversidade de plantas e produtos à base de plantas para um variado leque de indicações terapêuticas, apontando a percentagem de respostas para um conhecimento dos seus efeitos terapêuticos.