It has long been held that processing at the single word level during reading is automatic. However, research has recently begun to emerge that challenges this view. The literature surrounding the processing of emotion while recognizing printed words is limited, but some findings in the processing of emotion in faces suggest that negative stimuli (especially threat stimuli) promote quick and accurate processing. The purpose of the present experiments is to investigate whether negative emotionally-laden words are afforded priority processing in visual word recognition compared to positive emotionally-laden words. Two experiments are reported that manipulated the lexicality and valence of the target and distractor stimuli (Experiments 1 & 2), the validity of a spatial pre-cue (Experiments 1 & 2), and the presence of a distractor item (Experiment 2). Participants were asked to determine whether the target stimulus spelled a word or not. Response times on valid trials were faster compared to invalid trials, response times to negative emotionally-laden words were slower compared to positive emotionally-laden words, and the presence of a distractor item encouraged better focus on the target stimuli in the absence of any evidence that the valence of the distractor itself was processed. These results are consistent with the hypothesis that visual word recognition is not automatic given that processing benefited from the accurate direction of spatial attention. Furthermore, negative emotionally-laden words benefited equally compared to positive emotionally-laden words and therefore provide no evidence of automatic processing.

To better understand the optical and electronic properties of thiophene- and pyrrole-based organic compounds on a molecular level, several aromatic compounds and their corresponding monocations were analyzed by a variety of solution-based spectroscopic techniques. The derivatives were initially synthesized using palladium-catalyzed amination reactions, condensation reactions, Horner-Emmons reactions, and Stille coupling reactions. Once isolated, the neutral compounds were analyzed by UV-visible-NIR absorption spectroscopy, fluorescence spectroscopy, cyclic voltammetry, and / or differential pulse voltammetry. Monocations were generated by chemical oxidation and were analyzed by visible-NIR absorption spectroscopy and electron paramagnetic resonance spectroscopy. By quantifying the extent of the electron-donor abilities of some chromophores and the electron delocalization of positive charge in the monocations, a more thorough understanding of the optical and electronic properties of the compounds was obtained.

Texte remanié de: T. doct.--Universidad de Valencia, 1987.

Thèse de doctorat--Sciences naturelles--Faculté des sciences de Paris, 1891. N°: 734.

Thesis (M.A.)--Miami University, Dept. of Psychology, 2007. / Title from first page of PDF document. Includes bibliographical references (p. 21-24).

Th.--Sci. hum.--Paris 7, 1986.

abstract: The present study of two hundred and seven university students examined the structural relation of future-orientation (both valence and instrumentality), career decision-making self-efficacy and career indecision (choice/commitment anxiety and lack of readiness). Structural equation modeling results indicated that while the overall proposed model fit the data well, my hypotheses were partially supported. Valence was not significantly related to career decision-making self-efficacy, choice/commitment anxiety and lack of readiness. However, instrumentality completely mediated the relation between valence and career decision-making self-efficacy, choice/commitment anxiety and lack of readiness. Instrumentality was significantly related to career decision-making self-efficacy and lack of readiness. Career decision-making self-efficacy completely mediated the relation between instrumentality and choice/commitment anxiety; however, it only partially mediated the relation between instrumentality and lack of readiness. Although the proposed model was invariant across gender, the findings indicate that women reported higher instrumentality and lower lack of readiness than did men. No differences were found for career decision-making self-efficacy and choice/commitment anxiety across gender. The findings suggest that psychologists, counselors, teachers, and career interventionists should consider the role future time perspective in university students' career development. / Dissertation/Thesis / Ph.D. Counseling Psychology 2014

The conformational energy differences have been determined for ethylene glycol, 2- chloroethanol, and 2,2- dichloroethanol in the neat liquid, DMSO, and H20 with Raman spectroscopy. Spectra in the 0-H valence region were utilized to determine the energy difference between interand intramolecularly hydrogen bonded species. It was found that the solvent effect on the relative stabilities of the gauche and trans rotamers of the alcohols differ significantly. The results also indicate that, unlike ethylene glycol, there is significant intramolecular hydrogen bond formation in the halogenated alcohols in the neat liquid phase. Stronger intramolecular hydrogen bond formation was observed in dichloroethanol than in 2-chloroethanol.

abstract: While discrete emotions like joy, anger, disgust etc. are quite popular, continuous emotion dimensions like arousal and valence are gaining popularity within the research community due to an increase in the availability of datasets annotated with these emotions. Unlike the discrete emotions, continuous emotions allow modeling of subtle and complex affect dimensions but are difficult to predict. Dimension reduction techniques form the core of emotion recognition systems and help create a new feature space that is more helpful in predicting emotions. But these techniques do not necessarily guarantee a better predictive capability as most of them are unsupervised, especially in regression learning. In emotion recognition literature, supervised dimension reduction techniques have not been explored much and in this work a solution is provided through probabilistic topic models. Topic models provide a strong probabilistic framework to embed new learning paradigms and modalities. In this thesis, the graphical structure of Latent Dirichlet Allocation has been explored and new models tuned to emotion recognition and change detection have been built. In this work, it has been shown that the double mixture structure of topic models helps 1) to visualize feature patterns, and 2) to project features onto a topic simplex that is more predictive of human emotions, when compared to popular techniques like PCA and KernelPCA. Traditionally, topic models have been used on quantized features but in this work, a continuous topic model called the Dirichlet Gaussian Mixture model has been proposed. Evaluation of DGMM has shown that while modeling videos, performance of LDA models can be replicated even without quantizing the features. Until now, topic models have not been explored in a supervised context of video analysis and thus a Regularized supervised topic model (RSLDA) that models video and audio features is introduced. RSLDA learning algorithm performs both dimension reduction and regularized linear regression simultaneously, and has outperformed supervised dimension reduction techniques like SPCA and Correlation based feature selection algorithms. In a first of its kind, two new topic models, Adaptive temporal topic model (ATTM) and SLDA for change detection (SLDACD) have been developed for predicting concept drift in time series data. These models do not assume independence of consecutive frames and outperform traditional topic models in detecting local and global changes respectively. / Dissertation/Thesis / Doctoral Dissertation Computer Science 2015

CoordenaÃÃo de AperfeiÃoamento de NÃvel Superior / Os compostos trans-[Co(cyclam)(SO3)(NCS)]Â4H2O, trans-[Ru(NH3)4(NCS)(SO4)] e trans-[(SO3)(cyclam)Co−NCS−Ru(NH3)4(NCS)](BF4), onde cyclam = 1,4,8,11-tetraazaciclotetradecano, foram sintetizados e caracterizados por difraÃÃes de raios-X, espectroscopias vibracional na regiÃo do infravermelho e eletrÃnica nas regiÃes do ultravioleta e visÃvel (UV-Vis) e por tÃcnicas eletroquÃmicas. O grau de comunicaÃÃo eletrÃnica entre os Ãtomos de Co e Ru do complexo binuclear foi avaliado por eletroquÃmica e espectroscopia eletrÃnica na regiÃo do infravermelho prÃximo. Apenas para o complexo trans-[Co(cyclam)(SO3)(NCS)]Â4H2O foi possÃvel a obtenÃÃo de cristais que permitiram a determinaÃÃo estrutural. Os dados obtidos indicam estrutura monoclÃnica com o ligante cyclam no plano equatorial e os ligantes SO32− e NCS− ocupando posiÃÃes trans e coordenados ao Ãtomo de Co atravÃs, respectivamente, dos Ãtomos de S e N. Este resultado à reforÃado atravÃs da observaÃÃo, no espectro vibracional, de bandas tipicamente atribuÃdas ao ligante cyclam quando este se encontra em uma geometria trans. Os resultados de voltametria cÃclica deste composto indicam um mecanismo eletroquÃmico-quÃmico-eletroquÃmico. De fato, os experimentos de espectroeletroquÃmica (potencial controlado em -0,80 V vs Ag/AgCl) indicam que este composto experimenta, apÃs reduÃÃo, reaÃÃo de substituiÃÃo das molÃculas SO32− e NCS− por molÃculas do solvente (L), formando compostos do tipo [Co(cyclam)(L)2]2+. A observaÃÃo, no espectro vibracional do complexo trans-[Ru(NH3)4(NCS)(SO4)], das bandas em 2132, 887 e 478 cm-1, atribuÃdas aos modos de νCN, νCS e δ(NCS), respectivamente, do ligante NCS−, indica a coordenaÃÃo deste grupo atravÃs do Ãtomo de nitrogÃnio. Estudos eletroquÃmicos e de espectroscopia eletrÃnica deste composto em meio aquoso indicam que a reduÃÃo do centro metÃlico induz a reaÃÃo de substituiÃÃo do ligante SO42− por uma molÃcula de H2O. A reaÃÃo para formaÃÃo do composto binuclear, portanto, foi realizada em condiÃÃes redutoras a fim de induzir a formaÃÃo do aquo-complexo de rutÃnio e, em seguida, a reaÃÃo de substituiÃÃo da molÃcula de H2O por um sÃtio de coordenaÃÃo do monÃmero trans- [Co(cyclam)(SO3)(NCS)]Â4H2O. Os resultados obtidos para o material isolado indicam que hà a formaÃÃo do complexo binuclear com o ligante NCS− ocupando a posiÃÃo ponte. A curva voltamÃtrica obtida para este composto apresenta dois pares de ondas redox com potenciais formais de meia-onda (E1/2) em −0,27 e 0,13 V vs Ag|AgCl atribuÃdos, respectivamente, aos centros metÃlicos de Co e Ru. Comparativamente aos monÃmeros, hà a observaÃÃo de um deslocamento positivo de potencial o que reflete a estabilizaÃÃo do estado reduzido para o Ãtomo de rutÃnio, RuII, e desestabilizaÃÃo do estado oxidado para o Ãtomo de cobalto, CoIII. Este resultado à atribuÃdo a coordenaÃÃo a um centro oxidado, CoIII, cuja carga nuclear efetiva aumenta a deslocalizaÃÃo de densidade eletrÃnica aumentando o carÃter retirador do ligante ponte NCS−. O valor da constante de comproporcionamento, Kc = 5,78 x 106, calculada a partir da diferenÃa entre os valores de E1/2, indica um forte grau de comunicaÃÃo entre os centros metÃlicos e classifica este complexo como um sistema de valÃncia mista de classe II. / Trans-[Co(cyclam)(SO3)(NCS)]Â4H2O, trans-[Ru(NH3)4(NCS)(SO4)], and trans-[(SO3)(cyclam)Co−NCS−Ru(NH3)4(NCS)](BF4) complexes, where cyclam = 1,4,8,11-tetraazacyclotetradecane, were synthesized and characterized by X-ray difraction, vibrational and electronic (ultraviolet, visible and near infrared) spectroscopies, and electrochemical techniques. The electronic communication between Co and Ru metal centers of the binuclear complex was evaluated by electrochemistry and electronic spectrocopy in the near infrared region. Crystals suitable for X-ray studies were only isolated for the trans-[Co(cyclam)(SO3)(NCS)]Â4H2O complex. The obtained results indicate a monoclic structure with cyclam ligand at the equatorial plane and SO32− and NCS− moieties occupying the axial positions being coordinated through, respectively, sulfur and nitrogen atoms. This result is reinforced by the observation, in the vibrational spectrum, of bands typically assigned to the cyclam ligand in a trans configuration. The cyclic voltammograms obtained for this compound indicate as Electrochemical-Chemical-Electrochemical mechanism. In fact, the spectroelectrochemical experiments obtained at -0.80 V vs Ag/AgCl show that this compound, upon reduction, suffers a substitution reaction in which the SO32− and NCS− moieties are replaced by solvent molecules (L) thus forming [Co(cyclam)(L)2]2+ type complexes. The observation in the vibrational spectrum of the trans-[Ru(NH3)4(NCS)(SO4)] complex of the 2132, 887 e 478 cm-1 bands assigned, respectively, to the νCN, νCS e δ(NCS) vibrational modes of the NCS− ligand indicates that this moiety is coordinated through the nitrogen atom. Electrochemical and spectroscopic studies of this compound in aqueous medium indicate that the reduction of the metal center induces the replacement of SO42− ligand by a water molecule. The synthesis of the binuclear compound, therefore, was made under reductive conditions aiming to produce the aquo-complex and, then, replace the water molecule by a coordination site of the trans-[Co(cyclam)(SO3)(NCS)]Â4H2O complex. The results obtained for the isolated material hints that the binuclear complex is formed with the NCS− fragment as the bridge ligand. The acquired cyclic voltammogram presents two redox process with the half-wave formal potentials (E1/2) observed at −0.27 and 0.13 V vs Ag|AgCl and being assigned to the Co and Ru metal centers, respectively. In comparison to the monomers, the positive potential shift reflects the stabilization of the reduced state of the ruthenium metal atom (RuII) and the destabilization of the cobalt metal center (CoIII). This result is assigned to the coordination to an oxidated metal center, CoIII, whose effective nuclear charge increased the electronic delocalization increasing the withdrawing character of the NCS− bridge ligand. The comproportionation constant, Kc = 5.78 x 106, was calculated from the difference between the E1/2 values. The Kc value indicates a strong electronic communication between the metal atoms and classifies this binuclear complex as a mixed valence system of class II.