Posta a punt, automatització i validació d’una tècnica analítica per a la determinació de crom (VI) en continu mitjançant espectroscòpia d’absorció molecular

La determinació de Cr(VI) en l’aigua per espectroscòpia d’absorció molecular a la regió visible es realitza mitjançant una tècnica colorimètrica per reacció amb un reactiu cromogènic. El Cr(VI) reacciona amb la 1,5-Difenilcarbacida formant un complex de color vermell-violeta que absorbeix radiació a la longitud d’ona de 540 nm. Tradicionalment, la determinació de Cr(VI) per colorimetria es realitza de forma manual i discontínua, essent un mètode repetitiu i laboriós que té implícit un cost de mà d’obra i de temps considerable, tant pel que es refereix a la preparació de les mostres i dels patrons, com al propi acte de la mesura a l’aparell. Aquest projecte s’ha realitzat sota la idea que les determinacions de Cr(VI) per colorimetria, poden complir els requisits bàsics operacionals dels mètodes d’anàlisi de flux en continu. Partint d’aquesta base, s’ha desenvolupat un nou equip de mesura per realitzar les determinacions de Cr(VI) amb una presa de mostres automatitzada, i un règim de treball en continu. L’objectiu d’aquest projecte és la posta a punt, automatització, i validació de la tècnica d’anàlisi instrumental de determinació de crom (VI) en continu per espectroscòpia molecular visible

Anàlisi de models d'intervenció pedagògica i psicologia a les escoles. 'Análisis de modelos de intervención pedagógica y psicológica en las escuelas'.

Analizar los ECR. A/ Encuadre conceptual referencial operativo y los instrumentos de intervención pedagógica y psicológica en las escuelas así como las funciones de los maestros, alumnos y psicólogos en la Institución escolar. 8 escuelas: 4 privadas, 4 laicas, 7 privadas y 1 estatal seleccionadas según los criterios: tener un psicólogo o un equipo psicológico en las escuelas y posibilidad de encuadrarse en dos grupos diferentes en cuanto al modelo pedagógico. Lleva a cabo un estudio empírico centrado en el análisis y comparación de los modelos de intervención pedagógica y psicológica en las escuelas. Cuantifica los datos mediante la definición de unas dimensiones y la creación de unos indicadores e ítems para cada aspecto diferenciador de los modelos constructivista y de transmisión de adquisición del conocimiento. Analiza los datos configuradores de ambos modelos en las 8 escuelas mediante análisis descriptivo y concluye con un análisis comparativo de los dos grupos de escuelas. Observación directa. Encuestas individuales a los alumnos de primero y octavo. Entrevistas a los profesores o tutores y a los psicólogos. Estadística descriptiva. Dos escuelas se vinculan con el modelo constructivista e interactivo de intervención pedagógica. Los instrumentos que se movilizan son las actividades comunicativas del alumno con el medio. Otras dos se encuadran en el modelo de transmisión del conocimiento. Estos dependen del maestro y sólo obtienen conocimiento de aquello que le transmite el maestro. Otras dos se enmarcan en una posición intermedia. Respecto a la intervención psicológica, se observan dos directrices básicas: psicopedagógico contextualizador y psicopedagógico descontextualizador: intervención puntual. No tiene en cuenta el medio de donde sale el fracaso escolar. Las funciones de alumnos y maestros están en consonancia con los ECRO e instrumentos de nivel instrumental-ideológico de las escuelas. En todas las escuelas se observa una convergencia entre los tres aspectos analizados con uno de los modelos de intervención pedagógica definidos.

The impact of institutional, instrumental and interpersonal underpinnings on network dynamics and outcomes

Networks form a key part of the infrastructure of contemporary governance arrangements and, as such, are likely to continue for some time. Networks can take many forms and be formed for many reasons. Some networks have been explicitly designed to generate a collective response to an issue; some arise from a top down perspective through mandate or coercion; while others rely more heavily on interpersonal relations and doing the right thing. In this paper, these three different perspectives are referred to as the “3I”s: Instrumental, Institutional or Interpersonal. It is proposed that these underlying motivations will affect the process dynamics within the different types of networks in different ways and therefore influence the type of outcomes achieved. This proposition is tested through a number of case studies. An understanding of these differences will lead to more effective design, management and clearer expectations of what can be achieved through networks.

Characterisation of soils with the use of instrumental techniques : a multivariate forensic study

The value of soil evidence in the forensic discipline is well known. However, it would be advantageous if an in-situ method was available that could record responses from tyre or shoe impressions in ground soil at the crime scene. The development of optical fibres and emerging portable NIR instruments has unveiled a potential methodology which could permit such a proposal. The NIR spectral region contains rich chemical information in the form of overtone and combination bands of the fundamental infrared absorptions and low-energy electronic transitions. This region has in the past, been perceived as being too complex for interpretation and consequently was scarcely utilized. The application of NIR in the forensic discipline is virtually non-existent creating a vacancy for research in this area. NIR spectroscopy has great potential in the forensic discipline as it is simple, nondestructive and capable of rapidly providing information relating to chemical composition. The objective of this study is to investigate the ability of NIR spectroscopy combined with Chemometrics to discriminate between individual soils. A further objective is to apply the NIR process to a simulated forensic scenario where soil transfer occurs. NIR spectra were recorded from twenty-seven soils sampled from the Logan region in South-East Queensland, Australia. A series of three high quartz soils were mixed with three different kaolinites in varying ratios and NIR spectra collected. Spectra were also collected from six soils as the temperature of the soils was ramped from room temperature up to 6000C. Finally, a forensic scenario was simulated where the transferral of ground soil to shoe soles was investigated. Chemometrics methods such as the commonly known Principal Component Analysis (PCA), the less well known fuzzy clustering (FC) and ranking by means of multicriteria decision making (MCDM) methodology were employed to interpret the spectral results. All soils were characterised using Inductively Coupled Plasma Optical Emission Spectroscopy and X-Ray Diffractometry. Results were promising revealing NIR combined with Chemometrics is capable of discriminating between the various soils. Peak assignments were established by comparing the spectra of known minerals with the spectra collected from the soil samples. The temperature dependent NIR analysis confirmed the assignments of the absorptions due to adsorbed and molecular bound water. The relative intensities of the identified NIR absorptions reflected the quantitative XRD and ICP characterisation results. PCA and FC analysis of the raw soils in the initial NIR investigation revealed that the soils were primarily distinguished on the basis of their relative quartz and kaolinte contents, and to a lesser extent on the horizon from which they originated. Furthermore, PCA could distinguish between the three kaolinites used in the study, suggesting that the NIR spectral region was sensitive enough to contain information describing variation within kaolinite itself. The forensic scenario simulation PCA successfully discriminated between the ‘Backyard Soil’ and ‘Melcann® Sand’, as well as the two sampling methods employed. Further PCA exploration revealed that it was possible to distinguish between the various shoes used in the simulation. In addition, it was possible to establish association between specific sampling sites on the shoe with the corresponding site remaining in the impression. The forensic application revealed some limitations of the process relating to moisture content and homogeneity of the soil. These limitations can both be overcome by simple sampling practices and maintaining the original integrity of the soil. The results from the forensic scenario simulation proved that the concept shows great promise in the forensic discipline.

Property : an instrumental institution for environmental governance

Property in an elusive concept. In many respects it has been regarded as a source of authority to use, develop and make decisions about whatever is the subject matter of this right of ownership. This is true whether the holder of this right of ownership is a private entity or a public entity. Increasingly a right of ownership of this kind has been recognised not only as a source of authority but also as a mechanism for restricting or limiting and perhaps even prohibiting existing or proposed activities that impact upon the environment. It is increasingly therefore an instrument of control as much as an instrument of authorisation. The protection and conservation of the environment are ultimately a matter of the public interest. This is not to suggest that the individual holders of rights of ownership are not interested in protecting the environment. It is open to them to do so in the exercise of a right of ownership as a source of authorisation. However a right of ownership – whether private or public – has become increasingly the instrument according to which the environment is protected and conserved. This article addresses these issues from a doctrinal as well as a practical perspective about how the environment is managed. It does so in five ways: ●considering briefly property as a concept ●reviewing property in its historical context ●analysing property as a human right ●examining property in natural resources ●reviewing judicial approaches to property in natural resources.

Influence of environmental and instrumental variables on the non-invasive prediction of Brix in pineapple using near infrared spectroscopy

The Brix content of pineapple fruit can be non-invasively predicted from the second derivative of near infrared reflectance spectra. Correlations obtained using a NIRSystems 6500 spectrophotometer through multiple linear regression and modified partial least squares analyses using a post-dispersive configuration were comparable with that from a pre-dispersive configuration in terms of accuracy (e.g. coefficient of determination, R2, 0.73; standard error of cross validation, SECV, 1.01°Brix). The effective depth of sample assessed was slightly greater using the post-dispersive technique (about 20 mm for pineapple fruit), as expected in relation to the higher incident light intensity, relative to the pre-dispersive configuration. The effect of such environmental variables as temperature, humidity and external light, and instrumental variables such as the number of scans averaged to form a spectrum, were considered with respect to the accuracy and precision of the measurement of absorbance at 876 nm, as a key term in the calibration for Brix, and predicted Brix. The application of post-dispersive near infrared technology to in-line assessment of intact fruit in a packing shed environment is discussed.

Signifying Angels : Analyses and Interpretations of Rautavaara s Instrumental Compositions

The subject of doctoral thesis is the analysis and interpretation of instrumental pieces composed by Einojuhani Rautavaara (b. 1928) that have been given angelic titles: Archangel Michael Fighting the Antichrist from the suite Icons (1955)/Before the Icons (2006), Angels and Visitations (1978), the Double Bass Concerto Angel of Dusk (1980), Playgrounds for Angels (1981)and the Seventh Symphony Angel of Light (1994). The aim of the work is to find those musical elements common to these pieces that distinguish them from Rautavaara s other works and to determine if they could be thought of as a series. I prove that behind the common elements and titles stands the same extramusical idea the figure of an angel that the composer has described in his commentaries. The thesis is divided into three parts. Since all of the compositions possess titles that refer to the spiritual symbol of an angel, the first part offers a theoretical background to demonstrate the significant role played by angels in various religions and beliefs, and the means by which music has attempted to represent this symbol throughout history. This background traces also Rautavaara s aesthetic attitude as a spiritual composer whose output can be studied with reference to his extramusical interests including literature, psychology, painting, philosophy and myths. The second part focuses on the analysis of the instrumental compositions with angelic titles, without giving consideration to their commentaries and titles. The analyses concentrate in particular on those musical features that distinguish these pieces from Rautavaara s other compositions. In the third part these musical features are interpreted as symbols of the angel through comparison with vocal and instrumental pieces which contain references to the character of an angel, structures of mythical narration, special musical expressions, use of instruments and aspects of brightness. Finally I explore the composer s interpretative codes, drawing on Rilke s cycle of poems Ten Duino Elegies and Jung s theory of archetypes, and analyze the instrumental pieces with angelic titles in the light of the theory of musical ekphrasis.

Capillary electrochromatography: a versatile instrumental technique for nanodomain interaction studies

This doctoral thesis describes the development of a miniaturized capillary electrochromatography (CEC) technique suitable for the study of interactions between various nanodomains of biological importance. The particular focus of the study was low-density lipoprotein (LDL) particles and their interaction with components of the extracellular matrix (ECM). LDL transports cholesterol to the tissues through the blood circulation, but when the LDL level becomes too high the particles begin to permeate and accumulate in the arteries. Through binding sites on apolipoprotein B-100 (apoB-100), LDL interacts with components of the ECM, such as proteoglycans (PGs) and collagen, in what is considered the key mechanism in the retention of lipoproteins and onset of atherosclerosis. Hydrolytic enzymes and oxidizing agents in the ECM may later successively degrade the LDL surface. Metabolic diseases such as diabetes may provoke damage of the ECM structure through the non-enzymatic reaction of glucose with collagen. In this work, fused silica capillaries of 50 micrometer i.d. were successfully coated with LDL and collagen, and steroids and apoB-100 peptide fragments were introduced as model compounds for interaction studies. The LDL coating was modified with copper sulphate or hydrolytic enzymes, and the interactions of steroids with the native and oxidized lipoproteins were studied. Lipids were also removed from the LDL particle coating leaving behind an apoB-100 surface for further studies. The development of collagen and collagen decorin coatings was helpful in the elucidation of the interactions of apoB-100 peptide fragments with the primary ECM component, collagen. Furthermore, the collagen I coating provided a good platform for glycation studies and for clarification of LDL interactions with native and modified collagen. All methods developed are inexpensive, requiring just small amounts of biomaterial. Moreover, the experimental conditions in CEC are easily modified, and the analyses can be carried out in a reasonable time frame. Other techniques were employed to support and complement the CEC studies. Scanning electron microscopy and atomic force microscopy provided crucial visual information about the native and modified coatings. Asymmetrical flow field-flow fractionation enabled size measurements of the modified lipoproteins. Finally, the CEC results were exploited to develop new sensor chips for a continuous flow quartz crystal microbalance technique, which provided complementary information about LDL ECM interactions. This thesis demonstrates the potential of CEC as a valuable and flexible technique for surface interaction studies. Further, CEC can serve as a novel microreactor for the in situ modification of LDL and collagen coatings. The coatings developed in this study provide useful platforms for a diversity of future investigations on biological nanodomains.

Comprehensive Two-Dimensional Gas Chromatography: Instrumental and Methodological Development

Comprehensive two-dimensional gas chromatography (GC×GC) offers enhanced separation efficiency, reliability in qualitative and quantitative analysis, capability to detect low quantities, and information on the whole sample and its components. These features are essential in the analysis of complex samples, in which the number of compounds may be large or the analytes of interest are present at trace level. This study involved the development of instrumentation, data analysis programs and methodologies for GC×GC and their application in studies on qualitative and quantitative aspects of GC×GC analysis. Environmental samples were used as model samples. Instrumental development comprised the construction of three versions of a semi-rotating cryogenic modulator in which modulation was based on two-step cryogenic trapping with continuously flowing carbon dioxide as coolant. Two-step trapping was achieved by rotating the nozzle spraying the carbon dioxide with a motor. The fastest rotation and highest modulation frequency were achieved with a permanent magnetic motor, and modulation was most accurate when the motor was controlled with a microcontroller containing a quartz crystal. Heated wire resistors were unnecessary for the desorption step when liquid carbon dioxide was used as coolant. With use of the modulators developed in this study, the narrowest peaks were 75 ms at base. Three data analysis programs were developed allowing basic, comparison and identification operations. Basic operations enabled the visualisation of two-dimensional plots and the determination of retention times, peak heights and volumes. The overlaying feature in the comparison program allowed easy comparison of 2D plots. An automated identification procedure based on mass spectra and retention parameters allowed the qualitative analysis of data obtained by GC×GC and time-of-flight mass spectrometry. In the methodological development, sample preparation (extraction and clean-up) and GC×GC methods were developed for the analysis of atmospheric aerosol and sediment samples. Dynamic sonication assisted extraction was well suited for atmospheric aerosols collected on a filter. A clean-up procedure utilising normal phase liquid chromatography with ultra violet detection worked well in the removal of aliphatic hydrocarbons from a sediment extract. GC×GC with flame ionisation detection or quadrupole mass spectrometry provided good reliability in the qualitative analysis of target analytes. However, GC×GC with time-of-flight mass spectrometry was needed in the analysis of unknowns. The automated identification procedure that was developed was efficient in the analysis of large data files, but manual search and analyst knowledge are invaluable as well. Quantitative analysis was examined in terms of calibration procedures and the effect of matrix compounds on GC×GC separation. In addition to calibration in GC×GC with summed peak areas or peak volumes, simplified area calibration based on normal GC signal can be used to quantify compounds in samples analysed by GC×GC so long as certain qualitative and quantitative prerequisites are met. In a study of the effect of matrix compounds on GC×GC separation, it was shown that quality of the separation of PAHs is not significantly disturbed by the amount of matrix and quantitativeness suffers only slightly in the presence of matrix and when the amount of target compounds is low. The benefits of GC×GC in the analysis of complex samples easily overcome some minor drawbacks of the technique. The developed instrumentation and methodologies performed well for environmental samples, but they could also be applied for other complex samples.

Refletindo criticamente sobre as necessidades do aluno de inglês instrumental à luz da condição pós-método

O Inglês para Fins Específicos é a abordagem de ensino que ancora o trabalho feito no instituto federal no qual trabalho. Ele tem como premissa básica o ensino focado em uma análise de necessidades, ou seja, tudo o que é ensinado/aprendido está em alinhamento com o que os aprendizes necessitam em seu ambiente acadêmico e profissional. Por causa de mitos e dogmas enraizados ao longo das décadas, porém, a abordagem transformou-se exclusivamente no ensino de leitura e originou distorções na proposta original. O estudo parte da pergunta de pesquisa: O que o aluno participante desta pesquisa vê como prioridade em sua aprendizagem de inglês na escola? Outras perguntas surgiram após conversar com os dados coletados: Por que os alunos participantes querem um ensino e a escola propicia outro?; O que falta na sala de aula para amenizar essa lacuna entre o desejo dos alunos-participantes e a oferta da escola?; e, O que nós, professores, podemos fazer em relação às propostas pedagógicas para preencher esse espaço, à luz dos dados coletados e da revisão de literatura? Investigo então o posionamento de 65 aprendizes do 3 ano do ensino médio da escola na qual trabalho, através de questionários e entrevista nos moldes de um grupo focal com 5 participantes, sobre o que eles veem como prioridade na aprendizagem de inglês na escola e reflito sobre práticas pedagógicas que poderiam atender às necessidades apontadas pelos participantes. Dentro do espírito (in)disciplinar da Linguística Aplicada e dentro de um paradigma qualitativo, a análise das respostas pautou-se na recorrência de temas nas respostas às perguntas do questionário e participação no grupo focal. Temas que recorreram com frequência alta formaram categorias que serviram de base para a discussão. Selecionei duas perguntas do questionário para a análise: a pergunta (9) como você espera que seja o ensino de inglês no Ensino Médio? e a (10) quais habilidades vocês gostariam de desenvolver?, por sua relação direta com o objetivo da pesquisa. A categoria que emergiu das menções mais recorrentes nos proferimentos dos alunos foi comunicação oral, em um total de 62 menções. Outras oito categorias emergiram do corpus. Considerei frequência alta, e por isso categórica, a quantidade de 17 menções. A partir desses resultados, defendo neste trabalho que a voz do aluno (que grita urgência ao aprendizado da comunicação oral) seja ouvida nesse processo, e que uma nova pedagogia pós-metodológica seja implantada no ensino-aprendizagem de línguas no ensino médio e técnico

Human pavlovian-instrumental transfer.

The vigor with which a participant performs actions that produce valuable outcomes is subject to a complex set of motivational influences. Many of these are believed to involve the amygdala and the nucleus accumbens, which act as an interface between limbic and motor systems. One prominent class of influences is called pavlovian-instrumental transfer (PIT), in which the motivational characteristics of a predictor influence the vigor of an action with respect to which it is formally completely independent. We provide a demonstration of behavioral PIT in humans, with an audiovisual predictor of the noncontingent delivery of money inducing participants to perform more avidly an action involving squeezing a handgrip to earn money. Furthermore, using functional magnetic resonance imaging, we show that this enhanced motivation was associated with a trial-by-trial correlation with the blood oxygenation level-dependent (BOLD) signal in the nucleus accumbens and a subject-by-subject correlation with the BOLD signal in the amygdala. Our data dovetails well with the animal literature and sheds light on the neural control of vigor.