91 resultados para Multimodal timbre characterization


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RESUMO: Introdução: O conhecimento acerca da influência das características dos indivíduos com dor cervical crónica (DCC) no prognóstico dos resultados alcançados com a Fisioterapia é ainda inconsistente, sendo escassos os estudos desenvolvidos neste âmbito. Objetivo: Este relatório pretende determinar se um modelo baseado em fatores de prognóstico é capaz de prever os resultados de sucesso da Fisioterapia, a curto prazo, em utentes com DCC, ao nível da incapacidade funcional, intensidade da dor e perceção global de melhoria. Metodologia: Trata-se de estudo de coorte prospetivo com 112 participantes. Os utentes foram avaliados na primeira semana de tratamento e sete semanas após o início da intervenção. Os instrumentos utilizados foram o Neck Disability Index–Versão Portuguesa (NDI-PT) e a Escala Numérica da Dor (END) nos dois momentos de avaliação, um Questionário de Caracterização Sociodemográfica e Clínica da Amostra na baseline e a Patient Global Impression Change Scale–Versão Portuguesa (PGIC-PT) no follow-up. As características sociodemográficas e clínicas foram incluídas como potenciais fatores de prognóstico e estes foram definidos com base nas diferenças mínimas clinicamente importantes (DMCI) dos instrumentos NDIPT (DMCI≥6) e END (DMCI≥2) e no critério de pontuação ≥5 na PGIC-PT. A análise dos dados foi realizada através do método de regressão logística (backward conditional procedure) para identificar as associações entre os indicadores e as variáveis de resultado (p<0.05). Resultados: Dos 112 participantes incluídos no estudo, 108 completaram o follow-up (média de idade: 51.76±10.19). No modelo multivariado relativo à incapacidade funcional, os resultados de sucesso encontram-se associados a elevados níveis de incapacidade na baseline (OR=1.123; 95% IC 1.056–1.194) e a duração da dor inferior a 12 meses (OR=2.704; 95% IC 1.138–6.424). Este modelo explica 30.0% da variância da melhoria da funcionalidade e classifica corretamente 74.1% dos utentes (sensibilidade: 75.9%; especificidade: 72.0%). O modelo relativo à intensidade da dor identificou apenas a associação do outcome com níveis elevados de intensidade da dor na baseline (OR=1.321; 95% IC 1.047–1.668), explicando 7.5% da variância da redução da mesma e classificando corretamente 68.2% dos utentes (sensibilidade: 94.4%; especificidade: 16.7%). O modelo final referente à perceção global de melhoria apresentou uma associação com a intensidade da dor na baseline (OR=0.621; 95% IC 0.465–0.829), com a presença de cefaleias e/ou tonturas (OR=2.538; 95% IC 0.987–6.526) e com a duração da dor superior a 12 meses (OR=0.279; 95% IC 0.109–0.719). Este modelo explica 27.5% da variância dos resultados de sucesso para este outcome e classifica corretamente 73.1% dos utentes (sensibilidade: 81.8%; especificidade: 59.5%). Conclusões: Utentes com DCC com elevada incapacidade na baseline e queixas de dor há menos de 12 meses apresentam maior probabilidade de obter melhorias ao nível da incapacidade funcional. Elevados níveis de intensidade da dor na baseline predizem resultados de sucesso na redução da dor após sete semanas de tratamento. Utentes com DCC com baixos níveis de dor na baseline, com cefaleias e/ou tonturas e com queixas de dor há mais de 12 meses apresentam maior probabilidade de obter uma melhor perceção de melhoria.--------------- ABSTRACT:Introduction: The influence of the characteristics of individuals with chronic neck pain (CNP) on the prognosis of physiotherapy outcomes is still inconsistent, there being few studies developed in this context. Aim: This study seeks to determine whether a model based on prognostic factors can predict the short-term physiotherapy successful outcomes in CNP patients, regarding functional disability, pain intensity and perceived recovery. Methodology: This is a prospective cohort study with 112 participants. Patients were assessed during the first week of treatment and seven weeks after the start of the intervention. The instruments used were the Neck Disability Index–Portuguese Version (NDI-PT) and the Numerical Rating Scale (NRS) at both moments of assessment, a Sample Sociodemographic and Clinical Characterization Questionnaire at baseline and Patient Global Impression Change Scale–Portuguese Version (PGIC-PT) at the follow-up. The sociodemographic and clinical characteristics were included as potential predictors of successful outcomes, and these were defined on the basis of minimal clinically important differences (MCID) of NDI-PT (MCID≥6) and END (MCID≥2) and the criteria score ≥5 on the PGIC-PT. Data analysis was performed using logistic regression (backward conditional procedure) to identify associations between predictors and outcomes (p<0.05). Results: Of the 112 participants included in the study, 108 completed the follow-up (mean age: 51.76±10.19). In the multivariate model of functional disability, the successful outcomes are associated with high levels of disability at baseline (OR = 1.123; 95% CI 1.056-1.194), and pain duration shorter than 12 months (OR=2.704; 95% CI 1.138–6.424). This model explains 30.0% of the variance of improved functional capacity and correctly classifies 74.1% of the patients (sensitivity: 75.9%, specificity: 72.0%). The model for pain intensity solely identified an outcome association with high pain intensity at baseline (OR=1.321; 95% CI 1.047-1.668), explaining 7.5% of the variance of pain reduction and correctly classifying 68.2% of the patients (sensitivity: 94.4%, specificity: 16.7%). The final model of perceived recovery showed an association with pain intensity at baseline (OR=0.621; 95% CI 0465-0829), with the presence of headache and/or dizziness (OR=2.538; 95% CI 0.987-6.526) and the duration of pain over 12 months (OR=0.279; 95% CI 0.109-0.719). This model explains 27.5% of the variance of successful outcomes and correctly classifies 73.1% of the patients (sensitivity: 81.8%, specificity: 59.5%). Conclusions: Patients with CNP with high disability at baseline and complaints of pain for less than 12 months are more likely to obtain improvements in functional disability. High levels of pain intensity at baseline predict successful outcomes in pain reduction after seven weeks of treatment. Patients with CNP with low levels of pain at baseline, with headache and/or dizziness and with pain complaints for more than 12 months are more likely to get a better perceived recovery.

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Inorganica Chimica Acta 356 (2003) 215-221

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This work describes the synthesis and characterization of a series of new α-diimine and P,O, β-keto and acetamide phosphines ligands, and their complexation to Ni(II), Co(II),Co(III) and Pd(II) to obtain a series of new compounds aiming to study their structural characteristics and to test their catalytic activity. All the compounds synthesized were characterized by the usual spectroscopic and spectrometric techniques: Elemental Analysis, MALDI-TOF-MS spectrometry, IR, UV-vis, 1H, 13C and 31P NMR spectroscopies. Some of the paramagnetic compounds were also characterized by EPR. For the majority of the compounds it was possible to solve their solid state structure by single crystal X-ray diffraction. Tests for olefin polymerization were performed in order to determine the catalytic activity of the Co(II) complexes. Chapter I presents a brief introduction to homogenous catalysis, highlighting the reactions catalyzed by the type of compounds described in this thesis, namely olefin polymerization and oligomerization and reactions catalyzed by the complexes bearing α-diimines and P,O type ligands. Chapter II is dedicated to the description of the synthesis of new α-diimines cobalt (II) complexes, of general formula [CoX2(α-diimine)], where X = Cl or I and the α-diimines are bis(aryl)acenaphthenequinonediimine) (Ar-BIAN) and 1,4-diaryl-2,3-dimethyl-1,4-diaza-1,3-butadiene (Ar-DAB). Structures solved by single crystal X-ray diffraction were obtained for all the described complexes. For some of the compounds, X-band EPR measurements were performed on polycrystalline samples, showing a high-spin Co(II) (S = 3/2) ion, in a distorted axial environment. EPR single crystal experiments on two of the compounds allowed us to determine the g tensor orientation in the molecular structure. In Chapter III we continue with the synthesis and characterization of more cobalt (II)complexes bearing α-diimines of general formula [CoX2(α-diimine)], with X = Cl or I and α-diimines are bis(aryl)acenaphthenequinonediimine) (Ar-BIAN) and 1,4-diaryl-2,3-dimethyl- 1,4-diaza-1,3-butadiene (Ar-DAB). The structures of three of the new compounds synthesized were determined by single crystal X-ray diffraction. A NMR paramagnetic characterization of all the compounds described is presented. Ethylene polymerization tests were done to determine the catalytic activity of several of the Co(II) complexes described in Chapter II and III and their results are shown. In Chapter IV a new rigid bidentate ligand, bis(1-naphthylimino)acenaphthene, and its complexes with Zn(II) and Pd(II), were synthesized. Both the ligand and its complexes show syn and anti isomers. Structures of the ligand and the anti isomer of the Pd(II) complex were solved by single crystal X-ray diffraction. All the compounds were characterized by elemental analysis, MALDI-TOF-MS spectrometry, and by IR, UV-vis, 1H, 13C, 1H-1H COSY, 1H-13C HSQC, 1H-13C HSQC-TOCSY and 1H-1H NOESY NMR when necessary. DFT studies showed that both conformers of [PdCl2(BIAN)] are isoenergetics and can be obtain experimentally. However, we can predict that the isomerization process is not available in square-planar complex, but is possible for the free ligand. The molecular geometry is very similar in both isomers, and only different orientations for naphthyl groups can be expected. Chapter V describes the synthesis of new P, O type ligands, β-keto phosphine, R2PCH2C(O)Ph, and acetamide phosphine R2PNHC(O)Me, as well as a series of new cobalt(III) complexes namely [(η5-C5H5)CoI2{Ph2PCH2C(O)Ph}], and [(η5- C5H5)CoI2{Ph2PNHC(O)Me}]. Treating these Co(III) compounds with an excess of Et3N, resulted in complexes η2-phosphinoenolate [(η5-C5H5)CoI{Ph2PCH…C(…O)Ph}] and η2- acetamide phosphine [(η5-C5H5)CoI{Ph2PN…C(…O)Me}]. Nickel (II) complexes were also obtained: cis-[Ni(Ph2PN…C(…O)Me)2] and cis-[Ni((i-Pr)2PN…C(…O)Me)2]. Their geometry and isomerism were discussed. Seven structures of the compounds described in this chapter were determined by single crystal X-ray diffraction. The general conclusions of this work can be found in Chapter VI.

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A study about the physical appearance of pre-photographic, photomechanical, photographic and digital positive reflective prints was made, relating the obtained images with the history, materials and technology used to create them. The studied samples are from the Image Permanence Institute (IPI) study collection. The digital images were obtained using a digital SLR on a copystand and a compound light microscope, with different lighting angles (0º, 45ºand 90º) and magnifications from overall views on the copystand down to a 20x objective lens on the microscope. Most of these images were originally created by IPI for www.digitalsamplebook.org, a web tool for teaching print identification, and will be used on the www.graphicsatlas.org website, along with textual information on identification, technology and history information about these reproduction processes.

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Shape Memory Alloy (SMA) Ni-Ti films have attracted much interest as functional and smart materials due to their unique properties. However, there are still important issues unresolved like formation of film texture and its control as well as substrate effects. Thus, the main challenge is not only the control of the microstructure, including stoichiometry and precipitates, but also the identification and control of the preferential orientation since it is a crucial factor in determining the shape memory behaviour. The aim of this PhD thesis is to study the optimisation of the deposition conditions of films of Ni-Ti in order to obtain the material fully crystallized at the end of the deposition, and to establish a clear relationship between the substrates and texture development. In order to achieve this objective, a two-magnetron sputter deposition chamber has been used allowing to heat and to apply a bias voltage to the substrate. It can be mounted into the six-circle diffractometer of the Rossendorf Beamline (ROBL) at the European Synchrotron Radiation Facility (ESRF), Grenoble, France, enabling an in-situ characterization by X-ray diffraction(XRD) of the films during their growth and annealing. The in-situ studies enable us to identify the different steps of the structural evolution during deposition with a set of parameters as well as to evaluate the effect of changing parameters on the structural characteristics of the deposited film. Besides the in-situ studies, other complementary ex-situ characterization techniques such as XRD at a laboratory source, Rutherford backscattering spectroscopy(RBS), Auger electron spectroscopy (AES), cross-sectional transmission electron microscopy (X-TEM), scanning electron microscopy (SEM), and electrical resistivity (ER) measurements during temperature cycling have been used for a fine structural characterization. In this study, mainly naturally and thermally oxidized Si(100) substrates, TiN buffer layers with different thicknesses (i.e. the TiN topmost layer crystallographic orientation is thickness dependent) and MgO(100) single crystals were used as substrates. The chosen experimental procedure led to a controlled composition and preferential orientation of the films. The type of substrate plays an important role for the texture of the sputtered Ni-Ti films and according to the ER results, the distinct crystallographic orientations of the Ni-Ti films influence their phase transformation characteristics.

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This paper characterizes work accidents at Portuguese industrial cleaning companies, operating in the service sector, through the application of ESAW methodology. Data was codified based on the analysis of 748 accident claims to insurance companies (number of days lost 1 working day) in 3 large industrial cleaning companies for the period 2001-2003. Slipping and falling in the same level was the main deviation from the normal working process in the moment of the accident (in 25% of the accidents); uncoordinated movements was the second cause of accidents (14%); falls of persons to a lower level was the third cause of accidents (~10%), including falls from stairs (~7%) and falls from ladders and mobile ladders (~2%); globally, body movement under or with physical stress, including lifting, carrying, putting down, bending down, twisting, turning, trading badly, twisting leg or ankle and slipping without falling, were the cause in 17% of the accidents. Lower limbs were injured in ~25% of the accidents, hand and fingers in ~14%, the eye in ~4% and the back in ~9% of the accidents. An incidence rate of 3,580 accidents/100,000 employees was found to the sector (2003 data).

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Pine forests constitute some of the most important renewable resources supplying timber, paper and chemical industries, among other functions. Characterization of the volatiles emitted by different Pinus species has proven to be an important tool to decode the process of host tree selection by herbivore insects, some of which cause serious economic damage to pines. Variations in the relative composition of the bouquet of semiochemicals are responsible for the outcome of different biological processes, such as mate finding, egg-laying site recognition and host selection. The volatiles present in phloem samples of four pine species, P. halepensis, P. sylvestris, P. pinaster and P. pinea, were identified and characterized with the aim of finding possible host-plant attractants for native pests, such as the bark beetle Tomicus piniperda. The volatile compounds emitted by phloem samples of pines were extracted by headspace solid-phase micro extraction, using a 2 cm 50/30 mm divinylbenzene/carboxen/polydimethylsiloxane table flex solid-phase microextraction fiber and its contents analyzed by high-resolution gas chromatography, using flame ionization and a non polar and chiral column phases. The components of the volatile fraction emitted by the phloem samples were identified by mass spectrometry using time-of-flight and quadrupole mass analyzers. The estimated relative composition was used to perform a discriminant analysis among pine species, by means of cluster and principal component analysis. It can be concluded that it is possible to discriminate pine species based on the monoterpenes emissions of phloem samples.

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Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para a obtenção do grau de Mestre em Engenharia do Ambiente, perfil Sanitária

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A novel two-component enzyme system from Escherichia coli involving a flavorubredoxin (FlRd) and its reductase was studied in terms of spectroscopic, redox, and biochemical properties of its constituents. FlRd contains one FMN and one rubredoxin (Rd) center per monomer. To assess the role of the Rd domain, FlRd and a truncated form lacking the Rd domain (FlRd¢Rd), were characterized. FlRd contains 2.9 ( 0.5 iron atoms/subunit, whereas FlRd¢Rd contains 2.1 ( 0.6 iron atoms/subunit. While for FlRd one iron atom corresponds to the Rd center, the other two irons, also present in FlRd¢Rd, are most probably due to a di-iron site. Redox titrations of FlRd using EPR and visible spectroscopies allowed us to determine that the Rd site has a reduction potential of -140 ( 15 mV, whereas the FMN undergoes reduction via a red-semiquinone, at -140 ( 15 mV (Flox/Flsq) and -180 ( 15 mV (Flsq/Flred), at pH 7.6. The Rd site has the lowest potential ever reported for a Rd center, which may be correlated with specific amino acid substitutions close to both cysteine clusters. The gene adjacent to that encoding FlRd was found to code for an FAD-containing protein, (flavo)rubredoxin reductase (FlRd-reductase), which is capable of mediating electron transfer from NADH to DesulfoVibrio gigas Rd as well as to E. coli FlRd. Furthermore, electron donation was found to proceed through the Rd domain of FlRd as the Rd-truncated protein does not react with FlRd-reductase. In vitro, this pathway links NADH oxidation with dioxygen reduction. The possible function of this chain is discussed considering the presence of FlRd homologues in all known genomes of anaerobes and facultative aerobes.

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α3/4-Fucosyltransferases (α3/4-FUTs) are glycosyltransferases (GTs) that catalyze the transfer of fucose in an α3/4-linkage onto the N-acetylglucosamine residue from acceptors containing the type II or type I (Galβ4/3GlcNAc, respectively) structures, thus synthesizing the fucosylated Lewis (Le) carbohydrate determinants. Fucosyltransferase IX (FUT9), the most recently identified member of the family, presents the higher divergence from the other FUTs and its sequence is the only highly conserved among species. FUT9 synthesizes the Lewisx (Lex) epitope (Galβ4(Fucα3)GlcNAc). Recent evidence has suggested that it is the enzyme responsible for the synthesis of Lex in the mouse brain. Lex expression has been described in glycoproteins, proteoglycans and glycolipids from the central nervous system (CNS) of diverse species, including rodents and humans.

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Ovarian cancer is within the most lethal gynecological malignancies in woman. Therefore, many investigators study its biological aspects with the purpose of discovering more rapid diagnostic methods and efficient treatment. Resembling many other tumors, in ovarian cancer, aberrant glycosylation occurs with the appearance of novel or altered carbohydrate structures. These can be terminal motifs, such as the Lewis determinants, or entire carbohydrate sequences, which have been related to tumorigenesis and its outcome.(...)