Adaptação e validação do Cardiac Patients Learnings Needs Inventory para pacientes brasileiros

OBJETIVOS: Adaptar culturalmente o Cardiac Patients'Leaning Needs Inventory para uso no Brasil e testar sua confiabilidade (consistência interna e estabilidade) em pacientes brasileiros com doença arterial coronariana. MÉTODOS: Participaram do estudo 65 pacientes com infarto agudo do miocárdio, internados em um hospital público do interior do Estado de São Paulo. Para a coleta dos dados, foram utilizados um instrumento para caracterização sociodemográfica e a versão em português do Cardiac Patients Leaning Needs Inventory. A consistência interna foi estimada com base no alfa de Cronbach. A estabilidade foi medida apoiada no teste-reteste e calculada pelo teste t de Student. O nível de significância adotado foi 0,05. RESULTADOS: Identificou-se consistência interna alta (0,96 na primeira medida e 0,78 na segunda). O domínio que apresentou melhor consistência interna foi Fatores de Risco (α= 0,91). CONCLUSÃO: A versão adaptada manteve as equivalências conceituais, semânticas e idiomáticas da versão original e apresentou confiabilidade e estabilidade adequadas.

Tributyltin in crustacean tissues: analytical performance and validation of method

The hermit crab Clibanarius vittatus is a typical organism from intertidal regions being considered as a good bioindicator of tributyltin presence at these environments. Thus this study presents the analytical performance and validation method for TBT quantification in tissues of C. vittatus by gas chromatography with pulsed flame photometric detector (GC-PFPD) after extraction with an apolar solvent (toluene) and Grignard derivatization. The limits of detection of the method (LOD) were 2.0 and 2.8 ng g-1 for TBT and DBT (dibutyltin), respectively, and its limits of quantification (LOQ) were 6.6 and 8.9 ng g-1 for TBT and DBT, respectively. The method was applied to samples from Santos Estuary, São Paulo State, Brazil. TBT and DBT concentrations ranged from 26.7 to 175.0 ng g-1 and from 46.2 to 156.0 ng g-1, respectively. These concentrations are worrisome since toxic effects (such as endocrine disruption) have been reported for other organisms even under lower levels of registred at this study.

Assessment of depression in medical patients: a systematic review of the utility of the beck depression inventory-II

To perform a systematic review of the utility of the Beck Depression Inventory for detecting depression in medical settings, this article focuses on the revised version of the scale (Beck Depression Inventory-II), which was reformulated according to the DSM-IV criteria for major depression. We examined relevant investigations with the Beck Depression Inventory-II for measuring depression in medical settings to provide guidelines for practicing clinicians. Considering the inclusion and exclusion criteria seventy articles were retained. Validation studies of the Beck Depression Inventory-II, in both primary care and hospital settings, were found for clinics of cardiology, neurology, obstetrics, brain injury, nephrology, chronic pain, chronic fatigue, oncology, and infectious disease. The Beck Depression Inventory-II showed high reliability and good correlation with measures of depression and anxiety. Its threshold for detecting depression varied according to the type of patients, suggesting the need for adjusted cut-off points. The somatic and cognitive-affective dimension described the latent structure of the instrument. The Beck Depression Inventory-II can be easily adapted in most clinical conditions for detecting major depression and recommending an appropriate intervention. Although this scale represents a sound path for detecting depression in patients with medical conditions, the clinician should seek evidence for how to interpret the score before using the Beck Depression Inventory-II to make clinical decisions

Psychometric properties of the Beck Depression Inventory-II: a comprehensive review

OBJECTIVE: To review the psychometric properties of the Beck Depression Inventory-II (BDI-II) as a self-report measure of depression in a variety of settings and populations. METHODS: Relevant studies of the BDI-II were retrieved through a search of electronic databases, a hand search, and contact with authors. Retained studies (k = 118) were allocated into three groups: non-clinical, psychiatric/institutionalized, and medical samples. RESULTS: The internal consistency was described as around 0.9 and the retest reliability ranged from 0.73 to 0.96. The correlation between BDI-II and the Beck Depression Inventory (BDI-I) was high and substantial overlap with measures of depression and anxiety was reported. The criterion-based validity showed good sensitivity and specificity for detecting depression in comparison to the adopted gold standard. However, the cutoff score to screen for depression varied according to the type of sample. Factor analysis showed a robust dimension of general depression composed by two constructs: cognitive-affective and somatic-vegetative. CONCLUSIONS: The BDI-II is a relevant psychometric instrument, showing high reliability, capacity to discriminate between depressed and non-depressed subjects, and improved concurrent, content, and structural validity. Based on available psychometric evidence, the BDI-II can be viewed as a cost-effective questionnaire for measuring the severity of depression, with broad applicability for research and clinical practice worldwide.

137Cs Inventory in sedimentary columns from continental shelf of São Paulo State

137Cs is an artificial radioactive isotope produced by 235U fission. This radionuclide has a high fission yield and a half-life of 30 years. It has been detected in the environment since 1945 and its principal contamination source has been nuclear tests in the atmosphere. There are other sources of 137Cs contamination in the environment, such as: release from nuclear and reprocessing plants, radioactive dumping and nuclear accidents (Chernobyl, for example). This paper presents an inventory of 137Cs on the Continental Shelf of São Paulo State, a region located between Cabo de Santa Marta Grande (Santa Catarina state) and Cabo Frio (Rio de Janeiro state). In this area, 9 cores were collected by the Instituto Oceanográfico da Universidade de São Paulo (São Paulo University Institute of Oceanography). The cores were sliced at every 2 cm; sub-samples were lyophilized, grinded and stored in plastic containers. 137Cs was determined by 661 keV photopeak using a gamma spectrometry detector (Ge hyperpure). The analysis was performed by efficiency and background in different counting times. 137Cs concentration activities varied from 0.3 to 3.6 Bq kg-1 with a mean value of 1.2±0.6 Bq kg-1. The inventory of 137Cs in this area was 13±7 Bq m-2. Values obtained are in agreement with the Southern Hemisphere, a region contaminated by atmospheric fallout due to past nuclear explosions.

Isocyanates and Amines – Sampling and Analytical Procedures

This thesis covers sampling and analytical procedures for isocyanates (R-NCO) and amines (R-NH2), two kinds of chemicals frequently used in association with the polymeric material polyurethane (PUR). Exposure to isocyanates may result in respiratory disorders and dermal sensitisation, and they are one of the main causes of occupational asthma. Several of the aromatic diamines associated with PUR production are classified as suspected carcinogens. Hence, the presence of these chemicals in different exposure situations must be monitored. In the context of determining isocyanates in air, the methodologies included derivatisation with the reagent di-n-butylamine (DBA) upon collection and subsequent determination using liquid chromatography (LC) and mass spectrometric detection (MS). A user-friendly solvent-free sampler for collection of airborne isocyanates was developed as an alternative to a more cumbersome impinger-filter sampling technique. The combination of the DBA reagent together with MS detection techniques revealed several new exposure situations for isocyanates, such as isocyanic acid during thermal degradation of PUR and urea-based resins. Further, a method for characterising isocyanates in technical products used in the production of PUR was developed. This enabled determination of isocyanates in air for which pure analytical standards are missing. Tandem MS (MS/MS) determination of isocyanates in air below 10-6 of the threshold limit values was achieved. As for the determination of amines, the analytical methods included derivatisation into pentafluoropropionic amide or ethyl carbamate ester derivatives and subsequent MS analysis. Several amines in biological fluids, as markers of exposure for either the amines themselves or the corresponding isocyanates, were determined by LC-MS/MS at amol level. In aqueous extraction solutions of flexible PUR foam products, toluene diamine and related compounds were found. In conclusion, this thesis demonstrates the usefulness of well characterised analytical procedures and techniques for determination of hazardous compounds. Without reliable and robust methodologies there is a risk that exposure levels will be underestimated or, even worse, that relevant compounds will be completely missed.

Variance Reduction in Analytical Chemistry : New Numerical Methods in Chemometrics and Molecular Simulation

This thesis is based on five papers addressing variance reduction in different ways. The papers have in common that they all present new numerical methods. Paper I investigates quantitative structure-retention relationships from an image processing perspective, using an artificial neural network to preprocess three-dimensional structural descriptions of the studied steroid molecules. Paper II presents a new method for computing free energies. Free energy is the quantity that determines chemical equilibria and partition coefficients. The proposed method may be used for estimating, e.g., chromatographic retention without performing experiments. Two papers (III and IV) deal with correcting deviations from bilinearity by so-called peak alignment. Bilinearity is a theoretical assumption about the distribution of instrumental data that is often violated by measured data. Deviations from bilinearity lead to increased variance, both in the data and in inferences from the data, unless invariance to the deviations is built into the model, e.g., by the use of the method proposed in paper III and extended in paper IV. Paper V addresses a generic problem in classification; namely, how to measure the goodness of different data representations, so that the best classifier may be constructed. Variance reduction is one of the pillars on which analytical chemistry rests. This thesis considers two aspects on variance reduction: before and after experiments are performed. Before experimenting, theoretical predictions of experimental outcomes may be used to direct which experiments to perform, and how to perform them (papers I and II). After experiments are performed, the variance of inferences from the measured data are affected by the method of data analysis (papers III-V).

Methodology to create a proxy climate index for environmental and Octopus vulgaris fishery studies at the Northwest Africa: analytical and mathematical analyses

Diploma de Estudios Avanzados y Tesis de Máster

Food safety in wine: optimization of analytical controls and evaluation of production technologies

This PhD thesis has been proposed to validate and then apply innovative analytical methodologies for the determination of compounds with harmful impact on human health, such as biogenic amines and ochratoxin A in wines. Therefore, the influence of production technology (pH, amino acids precursor and use of different malolactic starters) on biogenic amines content in wines was evaluated. An HPLC method for simultaneous determination of amino acids and amines with precolumnderivatization with 9-Fluorenyl-methoxycarbonyl chloride (FMOC-Cl) and UV detection was developed. Initially, the influence of pH, time of derivatization, gradient profile were studied. In order to improve the separation of amino acids and amines and reduce the time of analysis, it was decided to study the influence of different flows and the use of different columns in the chromatographic method. Firstly, a C18 Luna column was used and later two monolithic columns Chromolith in series. It appeared to be suitable for an easy, precise and accurate determination of a relatively large number of amino acids and amines in wines. This method was then applied on different wines produced in the Emilia Romagna region. The investigation permitted to discriminate between red and white wines. Amino acids content is related to the winemaking process. Biogenic amines content in these wines does not represent a possible toxicological problem for human health. The results of the study of influence of technologies and wine composition demonstrated that pH of wines and amino acids content are the most important factors. Particularly wines with pH > 3,5 show higher concentration of biogenic amines than wines with lower pH. The enrichment of wines by nutrients also influences the content of some biogenic amines that are higher in wines added with amino acids precursors. In this study, amino acids and biogenic amines are not statistically affected by strain of lactic acid bacteria inoculated as a starter for malolactic fermentation. An evaluation of different clean-up (SPE-MycoSep; IACs and LLE) and determination methods (HPLC and ELISA) of ochratoxin A was carried out. The results obtained proved that the SPE clean-up are reliable at the same level while the LLE procedures shows lowest recovery. The ELISA method gave a lower determination and a low reproducibility than HPLC method.

Innovative analytical methods for Central Nervous System Drug analysis in biological fluids

During recent years a consistent number of central nervous system (CNS) drugs have been approved and introduced on the market for the treatment of many psychiatric and neurological disorders, including psychosis, depression, Parkinson disease and epilepsy. Despite the great advancements obtained in the treatment of CNS diseases/disorders, partial response to therapy or treatment failure are frequent, at least in part due to poor compliance, but also genetic variability in the metabolism of psychotropic agents or polypharmacy, which may lead to sub-therapeutic or toxic plasma levels of the drugs, and finally inefficacy of the treatment or adverse/toxic effects. With the aim of improving the treatment, reducing toxic/side effects and patient hospitalisation, Therapeutic Drug Monitoring (TDM) is certainly useful, allowing for a personalisation of the therapy. Reliable analytical methods are required to determine the plasma levels of psychotropic drugs, which are often present at low concentrations (tens or hundreds of nanograms per millilitre). The present PhD Thesis has focused on the development of analytical methods for the determination of CNS drugs in biological fluids, including antidepressants (sertraline and duloxetine), antipsychotics (aripiprazole), antiepileptics (vigabatrin and topiramate) and antiparkinsons (pramipexole). Innovative methods based on liquid chromatography or capillary electrophoresis coupled to diode-array or laser-induced fluorescence detectors have been developed, together with the suitable sample pre-treatment for interference removal and fluorescent labelling in case of LIF detection. All methods have been validated according to official guidelines and applied to the analysis of real samples obtained from patients, resulting suitable for the TDM of psychotropic drugs.

Traces de terre, traces d'encre... La rappresentazione dello spazio nella letteratura caraibica. (Francofona e Anglofona)

This study concerns the representation of space in Caribbean literature, both francophone and Anglophone and, in particular, but not only, in the martinican literature, in the works of the authors born in the island. The analysis focus on the second half of the last century, a period in which the martinican production of novels and romances increased considerably, and where the representation and the rule of space had a relevant place. So, the thesis explores the literary modalities of this representation. The work is constituted of 5 chapters and the critical and methodological approaches are both of an analytical and comparative type. The first chapter “The caribbean space: geography, history and society” presents the geographic context, through an analysis of the historical and political major events occurred in the Caribbean archipelago, in particular of the French Antilles, from the first colonization until the départementalisation. The first paragraph “The colonized space: historical-political excursus” the explores the history of the European colonization that marked forever the theatre of the relationship between Europe, Africa and the New World. This social situation take a long and complex process of “Re-appropriation and renegotiation of the space”, (second paragraph) always the space of the Other, that interest both the Antillean society and the writers’ universe. So, a series of questions take place in the third paragraph “Landscape and identity”: what is the function of space in the process of identity construction? What are the literary forms and representations of space in the Caribbean context? Could the writing be a tool of cultural identity definition, both individual and collective? The second chapter “The literary representation of the Antillean space” is a methodological analysis of the notions of literary space and descriptive gender. The first paragraph “The literary space of and in the novel” is an excursus of the theory of such critics like Blanchot, Bachelard, Genette and Greimas, and in particular the recent innovation of the 20th century; the second one “Space of the Antilles, space of the writing” is an attempt to apply this theory to the Antillean literary space. Finally the last paragraph “Signs on the page: the symbolic places of the antillean novel landscape” presents an inventory of the most recurrent antillean places (mornes, ravines, traces, cachots, En-ville,…), symbols of the history and the past, described in literary works, but according to new modalities of representation. The third chapter, the core of the thesis, “Re-drawing the map of the French Antilles” focused the study of space representation on francophone literature, in particular on a selected works of four martinican writers, like Roland Brival, Édouard Glissant, Patrick Chamoiseau and Raphaël Confiant. Through this section, a spatial evolution comes out step by step, from the first to the second paragraph, whose titles are linked together “The novel space evolution: from the forest of the morne… to the jungle of the ville”. The virgin and uncontaminated space of the Antilles, prior to the colonisation, where the Indios lived in harmony with the nature, find a representation in both works of Brival (Le sang du roucou, Le dernier des Aloukous) and of Glissant (Le Quatrième siècle, Ormerod). The arrival of the European colonizer brings a violent and sudden metamorphosis of the originary space and landscape, together with the traditions and culture of the Caraïbes population. These radical changes are visible in the works of Chamoiseau (Chronique des sept misères, Texaco, L’esclave vieil homme et le molosse, Livret des villes du deuxième monde, Un dimanche au cachot) and Confiant (Le Nègre et l’Amiral, Eau de Café, Ravines du devant-jour, Nègre marron) that explore the urban space of the creole En-ville. The fourth chapter represents the “2nd step: the Anglophone novel space” in the exploration of literary representation of space, through an analytical study of the works of three Anglophone writers, the 19th century Lafcadio Hearn (A Midsummer Trip To the West Indies, Two Years in the French West Indies, Youma) and the contemporary authors Derek Walcott (Omeros, Map of the New World, What the Twilight says) and Edward Kamau Brathwaite (The Arrivants: A New World Trilogy). The Anglophone voice of the Caribbean archipelago brings a very interesting contribution to the critical idea of a spatial evolution in the literary representation of space, started with francophone production: “The spatial evolution goes on: from the Martiniques Sketches of Hearn… to the modern bards of Caribbean archipelago” is the new linked title of the two paragraphs. The fifth chapter “Extended look, space shared: the Caribbean archipelago” is a comparative analysis of the results achieved in the prior sections, through a dialogue between all the texts in the first paragraph “Francophone and Anglophone representation of space compared: differences and analogies”. The last paragraph instead is an attempt of re-negotiate the conventional notions of space and place, from a geographical and physical meaning, to the new concept of “commonplace”, not synonym of prejudice, but “common place” of sharing and dialogue. The question sets in the last paragraph “The “commonplaces” of the physical and mental map of the Caribbean archipelago: toward a non-place?” contains the critical idea of the entire thesis.

Numerical and analytical vibro-acoustic modelling of porous materials: the Cell Method for poroelasticity and the case of inclusions

Porous materials are widely used in many fields of industrial applications, to achieve the requirements of noise reduction, that nowadays derive from strict regulations. The modeling of porous materials is still a problematic issue. Numerical simulations are often problematic in case of real complex geometries, especially in terms of computational times and convergence. At the same time, analytical models, even if partly limited by restrictive simplificative hypotheses, represent a powerful instrument to capture quickly the physics of the problem and general trends. In this context, a recently developed numerical method, called the Cell Method, is described, is presented in the case of the Biot's theory and applied for representative cases. The peculiarity of the Cell Method is that it allows for a direct algebraic and geometrical discretization of the field equations, without any reduction to a weak integral form. Then, the second part of the thesis presents the case of interaction between two poroelastic materials under the context of double porosity. The idea of using periodically repeated inclusions of a second porous material into a layer composed by an original material is described. In particular, the problem is addressed considering the efficiency of the analytical method. A analytical procedure for the simulation of heterogeneous layers based is described and validated considering both conditions of absorption and transmission; a comparison with the available numerical methods is performed. ---------------- I materiali porosi sono ampiamente utilizzati per diverse applicazioni industriali, al fine di raggiungere gli obiettivi di riduzione del rumore, che sono resi impegnativi da norme al giorno d'oggi sempre più stringenti. La modellazione dei materiali porori per applicazioni vibro-acustiche rapprensenta un aspetto di una certa complessità. Le simulazioni numeriche sono spesso problematiche quando siano coinvolte geometrie di pezzi reali, in particolare riguardo i tempi computazionali e la convergenza. Allo stesso tempo, i modelli analitici, anche se parzialmente limitati a causa di ipotesi semplificative che ne restringono l'ambito di utilizzo, rappresentano uno strumento molto utile per comprendere rapidamente la fisica del problema e individuare tendenze generali. In questo contesto, un metodo numerico recentemente sviluppato, il Metodo delle Celle, viene descritto, implementato nel caso della teoria di Biot per la poroelasticità e applicato a casi rappresentativi. La peculiarità del Metodo delle Celle consiste nella discretizzazione diretta algebrica e geometrica delle equazioni di campo, senza alcuna riduzione a forme integrali deboli. Successivamente, nella seconda parte della tesi viene presentato il caso delle interazioni tra due materiali poroelastici a contatto, nel contesto dei materiali a doppia porosità. Viene descritta l'idea di utilizzare inclusioni periodicamente ripetute di un secondo materiale poroso all'interno di un layer a sua volta poroso. In particolare, il problema è studiando il metodo analitico e la sua efficienza. Una procedura analitica per il calcolo di strati eterogenei di materiale viene descritta e validata considerando sia condizioni di assorbimento, sia di trasmissione; viene effettuata una comparazione con i metodi numerici a disposizione.

Development of original analytical methods for the therapeutic drug monitoring of CNS druges: Antipsychotics, Antidepressants and Anxiolytics-hypnotics

Great strides have been made in the last few years in the pharmacological treatment of neuropsychiatric disorders, with the introduction into the therapy of several new and more efficient agents, which have improved the quality of life of many patients. Despite these advances, a large percentage of patients is still considered “non-responder” to the therapy, not drawing any benefits from it. Moreover, these patients have a peculiar therapeutic profile, due to the very frequent application of polypharmacy, attempting to obtain satisfactory remission of the multiple aspects of psychiatric syndromes. Therapy is heavily individualised and switching from one therapeutic agent to another is quite frequent. One of the main problems of this situation is the possibility of unwanted or unexpected pharmacological interactions, which can occur both during polypharmacy and during switching. Simultaneous administration of psychiatric drugs can easily lead to interactions if one of the administered compounds influences the metabolism of the others. Impaired CYP450 function due to inhibition of the enzyme is frequent. Other metabolic pathways, such as glucuronidation, can also be influenced. The Therapeutic Drug Monitoring (TDM) of psychotropic drugs is an important tool for treatment personalisation and optimisation. It deals with the determination of parent drugs and metabolites plasma levels, in order to monitor them over time and to compare these findings with clinical data. This allows establishing chemical-clinical correlations (such as those between administered dose and therapeutic and side effects), which are essential to obtain the maximum therapeutic efficacy, while minimising side and toxic effects. It is evident the importance of developing sensitive and selective analytical methods for the determination of the administered drugs and their main metabolites, in order to obtain reliable data that can correctly support clinical decisions. During the three years of Ph.D. program, some analytical methods based on HPLC have been developed, validated and successfully applied to the TDM of psychiatric patients undergoing treatment with drugs belonging to following classes: antipsychotics, antidepressants and anxiolytic-hypnotics. The biological matrices which have been processed were: blood, plasma, serum, saliva, urine, hair and rat brain. Among antipsychotics, both atypical and classical agents have been considered, such as haloperidol, chlorpromazine, clotiapine, loxapine, risperidone (and 9-hydroxyrisperidone), clozapine (as well as N-desmethylclozapine and clozapine N-oxide) and quetiapine. While the need for an accurate TDM of schizophrenic patients is being increasingly recognized by psychiatrists, only in the last few years the same attention is being paid to the TDM of depressed patients. This is leading to the acknowledgment that depression pharmacotherapy can greatly benefit from the accurate application of TDM. For this reason, the research activity has also been focused on first and second-generation antidepressant agents, like triciclic antidepressants, trazodone and m-chlorophenylpiperazine (m-cpp), paroxetine and its three main metabolites, venlafaxine and its active metabolite, and the most recent antidepressant introduced into the market, duloxetine. Among anxiolytics-hypnotics, benzodiazepines are very often involved in the pharmacotherapy of depression for the relief of anxious components; for this reason, it is useful to monitor these drugs, especially in cases of polypharmacy. The results obtained during these three years of Ph.D. program are reliable and the developed HPLC methods are suitable for the qualitative and quantitative determination of CNS drugs in biological fluids for TDM purposes.