839 resultados para ESI-FTICRMS


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Örömmel és büszkeséggel adjuk közre a Budapesti Corvinus Egyetem Fenntarthatósági Indikátorok Kutatóközpontjának első kötetét, amely az ökológiai lábnyomhoz kapcsolódó kutatásainkat foglalja össze. Az ökológiai lábnyomot lehet szeretni vagy kritizálni, de kevés kutató közömbös iránta. Jellemzően nagy lelkesedéssel vagy kritikai dühvel közelít hozzá a tudomány és a szakpolitika, és csak ritkán teszik fel azt a kérdést, hogy melyek azok a kérdések, amelyek jól megválaszolhatóak a segítségével, és melyek azok a kérdések, ahol alkalmazása sarlatánság vagy bűn. Lelkesedést és kritikát félretéve objektíven állíthatjuk, hogy az ökológiai lábnyom mind a laikusok között, mind pedig a tudományos világban terjed. Épp olyan népszerű a Google-on és Facebookon, mint a tudományos világban − A Web of Science-en vagy a Google-on végzett felméréseink azt mutatják, hogy míg több kompozit indikátor napja –HDI, ISEW GPI, ESI ¬− leáldozóban van, addig az ökológiai lábnyomra történő hivatkozások száma rendületlenül nő, még a legigényesebb, impakt faktoros tudományos közleményekben is. Ha többet nem is, de azt mindenképpen igazolja népszerűsége, hogy ez az indikátor „tud” valamit, amit az elődei nem tudtak, versenytársaihoz képest használhatóbbnak mutatkozott egyes problémák megválaszolására. Lehet tehát szeretni vagy nem szeretni, az igazi kérdés az, mely problémákat célszerű e mutató felhasználásával megközelíteni. E kötet reményeink szerint ebbe az irányba mutat. A kötet tanulmányainak túlnyomó része egy 1000 fős reprezentatív felmérés eredményeire támaszkodva mutatja be a magyar lakosság ökológiai lábnyomát, és annak összefüggéseit különböző gazdasági, társadalmi és pszichológiai tényezőkkel. Ezeket mintegy három elméleti fejezet fogja keretbe, melyek az ökológiai lábnyom elméletével és kritikájával, az energialábnyom csökkentése során tapasztalható visszapattanó hatással, illetve az ökológiai lábnyom−eltartóképesség dinamikájával foglalkoznak a Meadows-modellekből vett asszociációra támaszkodva. A kutatás „mellékterméke” egy ökológiai lábnyom kalkulátor, amely összhangban van a Global Footprint Network adataival és metodikájával, a reprezentatív felmérés eredményeire támaszkodva hoztuk létre, és konzisztens a KSH fogyasztási statisztika adataival is. Ebben a minőségében az országban egyedülálló.

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Existing instrumental techniques must be adaptable to the analysis of novel explosives if science is to keep up with the practices of terrorists and criminals. The focus of this work has been the development of analytical techniques for the analysis of two types of novel explosives: ascorbic acid-based propellants, and improvised mixtures of concentrated hydrogen peroxide/fuel. In recent years, the use of these explosives in improvised explosive devices (IEDs) has increased. It is therefore important to develop methods which permit the identification of the nature of the original explosive from post-blast residues. Ascorbic acid-based propellants are low explosives which employ an ascorbic acid fuel source with a nitrate/perchlorate oxidizer. A method which utilized ion chromatography with indirect photometric detection was optimized for the analysis of intact propellants. Post-burn and post-blast residues if these propellants were analyzed. It was determined that the ascorbic acid fuel and nitrate oxidizer could be detected in intact propellants, as well as in the post-burn and post-blast residues. Degradation products of the nitrate and perchlorate oxidizers were also detected. With a quadrupole time-of-flight mass spectrometer (QToFMS), exact mass measurements are possible. When an HPLC instrument is coupled to a QToFMS, the combination of retention time with accurate mass measurements, mass spectral fragmentation information, and isotopic abundance patterns allows for the unequivocal identification of a target analyte. An optimized HPLC-ESI-QToFMS method was applied to the analysis of ascorbic acid-based propellants. Exact mass measurements were collected for the fuel and oxidizer anions, and their degradation products. Ascorbic acid was detected in the intact samples and half of the propellants subjected to open burning; the intact fuel molecule was not detected in any of the post-blast residue. Two methods were optimized for the analysis of trace levels of hydrogen peroxide: HPLC with fluorescence detection (HPLC-FD), and HPLC with electrochemical detection (HPLC-ED). Both techniques were extremely selective for hydrogen peroxide. Both methods were applied to the analysis of post-blast debris from improvised mixtures of concentrated hydrogen peroxide/fuel; hydrogen peroxide was detected on variety of substrates. Hydrogen peroxide was detected in the post-blast residues of the improvised explosives TATP and HMTD.

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Arsenic has been classified as a group I carcinogen. It has been ranked number one in the CERCLA priority list of hazardous substances due to its frequency, toxicity and potential for human exposure. Paradoxically, arsenic has been employed as a successful chemotherapeutic agent for acute promyelocytic leukemia and has found some success in multiple myeloma. Since arsenic toxicity and efficacy is species dependent, a speciation method, based on the complementary use of reverse phase and cation exchange chromatography, was developed. Inductively coupled plasma mass spectrometer (ICP-MS), as an element specific detector, and electrospray ionization mass spectrometer (ESI-MS), as a molecule specific detector, were employed. Low detection limits in the µg. L−1 range on the ICP-MS and mg. L−1 range on the ESI-MS were obtained. The developed methods were validated against each other through the use of a Deming plot. With the developed speciation method, the effects of both pH on the stability of As species and reduced glutathione (GSH) concentration on the formation and stability of arsenic glutathione complexes were studied. To identify arsenicals in multiple myeloma (MM) cell lines post arsenic trioxide (ATO) and darinaparsin (DAR) incubation, an extraction method based on the use of ultrasonic probe was developed. Extraction tools and solvents were evaluated and the effect of GSH concentration on the quantitation of arsenic glutathione (As-GSH) complexes in MM cell extracts was studied. The developed method was employed for the identification of metabolites in DAR incubated cell lines where the effect of extraction pH, DAR incubation concentration and incubation time on the relative distribution of the As metabolites was assessed. A new arsenic species, dimethyarsinothioyl glutathione (DMMTA V-GS), a pentavalent thiolated arsenical, was identified in the cell extracts through the use of liquid chromatography tandem mass spectrometry. The formation of the new metabolite in the extracts was dependent on the decomposition of s-dimethylarsino glutathione (DMA(GS)). These results have major implications in both the medical and toxicological fields of As because they involve the metabolism of a chemotherapeutic agent and the role sulfur compounds play in this mechanism.

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This dissertation utilized electrospray ion mobility mass spectrometry (ESI-IMS-MS) to develop methods necessary for the separation of chiral compounds of forensic interest. The compounds separated included ephedrines and pseudoephedrines, that occur as impurities in confiscated amphetamine type substances (ATS) in an effort to determine the origin of these substances. The ESI-IMS-MS technique proved to be faster and more cost effective than traditional chromatographic methods currently used to conduct chiral separations such as gas and liquid chromatography. Both mass spectrometric and computational analysis revealed the separation mechanism of these chiral interactions allowing for further development to separate other chiral compounds by IMS. Successful separation of chiral compounds was achieved utilizing a variety of modifiers injected into the IMS drift tube. It was found that the modifiers themselves did not need to be chiral in nature and that achiral modifiers were sufficient in performing the required separations. The ESI-IMS-MS technique was also used to detect thermally labile compounds which are commonly found in explosive substances. The methods developed provided mass spectrometric identification of the type of ionic species being detected from explosive analytes as well as the appropriate solvent that enhances detection of these analytes in either the negative or positive ion mode. An application of the developed technique was applied to the analysis of a variety of low explosive smokeless powder samples. It was found that the developed ESI-IMS-MS technique not only detected the components of the smokeless powders, but also provided data that allowed the classification of the analyzed smokeless powders by manufacturer or make. ^

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The goal of this project was to develop a rapid separation and detection method for analyzing organic compounds in smokeless powders and then test its applicability on gunshot residue (GSR) samples. In this project, a total of 20 common smokeless powder additives and their decomposition products were separated by ultra performance liquid chromatography (UPLC) and confirmed by tandem mass spectrometry (MS/MS) using multiple reaction monitoring mode (MRM). Some of the targeted compounds included diphenylamines, centralites, nitrotoluenes, nitroglycerin, and various phthalates. The compounds were ionized in the MS source using simultaneous positive and negative electrospray ionization (ESI) with negative atmospheric pressure chemical ionization (APCI) in order to detect all compounds in a single analysis. The developed UPLC/MS/MS method was applied to commercially available smokeless powders and gunshot residue samples recovered from the hands of shooters, spent cartridges, and smokeless powder retrieved from unfired cartridges. Distinct compositions were identified for smokeless powders from different manufacturers and from separate manufacturing lots. The procedure also produced specific chemical profiles when tested on gunshot residues from different manufacturers. Overall, this thesis represents the development of a rapid and reproducible procedure capable of simultaneously detecting the widest possible range of components present in organic gunshot residue.^

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Existing instrumental techniques must be adaptable to the analysis of novel explosives if science is to keep up with the practices of terrorists and criminals. The focus of this work has been the development of analytical techniques for the analysis of two types of novel explosives: ascorbic acid-based propellants, and improvised mixtures of concentrated hydrogen peroxide/fuel. In recent years, the use of these explosives in improvised explosive devices (IEDs) has increased. It is therefore important to develop methods which permit the identification of the nature of the original explosive from post-blast residues. Ascorbic acid-based propellants are low explosives which employ an ascorbic acid fuel source with a nitrate/perchlorate oxidizer. A method which utilized ion chromatography with indirect photometric detection was optimized for the analysis of intact propellants. Post-burn and post-blast residues if these propellants were analyzed. It was determined that the ascorbic acid fuel and nitrate oxidizer could be detected in intact propellants, as well as in the post-burn and post-blast residues. Degradation products of the nitrate and perchlorate oxidizers were also detected. With a quadrupole time-of-flight mass spectrometer (QToFMS), exact mass measurements are possible. When an HPLC instrument is coupled to a QToFMS, the combination of retention time with accurate mass measurements, mass spectral fragmentation information, and isotopic abundance patterns allows for the unequivocal identification of a target analyte. An optimized HPLC-ESI-QToFMS method was applied to the analysis of ascorbic acid-based propellants. Exact mass measurements were collected for the fuel and oxidizer anions, and their degradation products. Ascorbic acid was detected in the intact samples and half of the propellants subjected to open burning; the intact fuel molecule was not detected in any of the post-blast residue. Two methods were optimized for the analysis of trace levels of hydrogen peroxide: HPLC with fluorescence detection (HPLC-FD), and HPLC with electrochemical detection (HPLC-ED). Both techniques were extremely selective for hydrogen peroxide. Both methods were applied to the analysis of post-blast debris from improvised mixtures of concentrated hydrogen peroxide/fuel; hydrogen peroxide was detected on variety of substrates. Hydrogen peroxide was detected in the post-blast residues of the improvised explosives TATP and HMTD.

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Thiosalt species are unstable, partially oxidized sulfur oxyanions formed in sulfur-rich environments but also during the flotation and milling of sulfidic minerals especially those containing pyrite (FeS₂) and pyrrhotite (Fe₍₁₋ₓ₎S, x = 0 to 0.2). Detecting and quantifying the major thiosalt species such as sulfate (SO₄²⁻), thiosulfate (S₂O₃²⁻), trithionate (S₃O₆²⁻), tetrathionate (S₄O₆²⁻) and higher polythionates (SₓO₆²⁻, where 3 ≤ x ≤ 10) in the milling process and in the treated tailings is important to understand how thiosalts are generated and provides insight into potential treatment. As these species are unstable, a fast and reliable analytical technique is required for their analysis. Three capillary zone electrophoresis (CZE) methods using indirect UV-vis detection were developed for the simultaneous separation and determination of five thiosalt anions: SO₄²⁻, S₂O₃²⁻, S₃O₆²⁻, S₄O₆²⁻ and S₅O₆²⁻. Both univariate and multivariate experimental design approaches were used to optimize the most critical factors (background electrolyte (BGE) and instrumental conditions) to achieve fast separation and quantitative analysis of the thiosalt species. The mathematically predicted responses for the multivariate experiments were in good agreement with the experimental results. Limits of detection (LODs) (S/N = 3) for the methods were between 0.09 and 0.34 μg/mL without a sample stacking technique and nearly four-fold increase in LODs with the application of field-amplified sample stacking. As direct analysis of thiosalts by mass spectrometry (MS) is limited by their low m/z values and detection in negative mode electrospray ionization (ESI), which is typically less sensitive than positive ESI, imidazolium-based (IP-L-Imid and IP-T-Imid) and phosphonium-based (IP-T-Phos) tricationic ion-pairing reagents were used to form stable high mass ions non-covalent +1 ion-pairs with these species for ESI-MS analysis and the association constants (Kassoc) determined for these ion-pairs. Kassoc values were between 6.85 × 10² M⁻¹ and 3.56 × 10⁵ M⁻¹ with the linear IP-L-Imid; 1.89 ×10³ M⁻¹ and 1.05 × 10⁵ M⁻¹ with the trigonal IP-T-Imid ion-pairs; and 7.51×10² M⁻¹ and 4.91× 10⁴ M⁻¹ with the trigonal IP-T-Phos ion-pairs. The highest formation constants were obtained for S₃O₆²⁻ and the imidazolium-based linear ion-pairing reagent (IP-L-Imid), whereas the lowest were for IP-L-Imid: SO₄²⁻ ion-pair.

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The chemical structure of refractory marine dissolved organic matter (DOM) is still largely unknown. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) was used to resolve the complex mixtures of DOM and provide valuable information on elemental compositions on a molecular scale. We characterized and compared DOM from two sharply contrasting aquatic environments, algal-derived DOM from the Weddell Sea (Antarctica) and terrigenous DOM from pore water of a tropical mangrove area in northern Brazil. Several thousand molecular formulas in the mass range of 300-600 Da were identified and reproduced in element ratio plots. On the basis of molecular elemental composition and double-bond equivalents (DBE) we calculated an average composition for marine DOM. O/C ratios in the marine samples were lower (0.36 ± 0.01) than in the mangrove pore-water sample (0.42). A small proportion of chemical formulas with higher molecular mass in the marine samples were characterized by very low O/C and H/C ratios probably reflecting amphiphilic properties. The average number of unsaturations in the marine samples was surprisingly high (DBE = 9.9; mangrove pore water: DBE = 9.4) most likely due to a significant contribution of carbonyl carbon. There was no significant difference in elemental composition between surface and deep-water DOM in the Weddell Sea. Although there were some molecules with unique marine elemental composition, there was a conspicuous degree of similarity between the terrigenous and algal-derived end members. Approximately one third of the molecular formulas were present in all marine as well as in the mangrove samples. We infer that different forms of microbial degradation ultimately lead to similar structural features that are intrinsically refractory, independent of the source of the organic matter and the environmental conditions where degradation took place.

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El concepto de Proteómica, acuñado en analogía al de Genómica, fue usado por primera vez por Marc Wilkins a mediados de los años 90 para describir al conjunto total de proteínas que se expresan por los genes de una célula, tejido u organismo. Anteriormente, a finales de los 80, el desarrollo de las técnicas de ionización suave, como la Ionización por Electrospray, ESI (Electrospray Ionization) o la Desorción Suave por Láser, SLD (Soft Laser Desorption), permitió ionizar grandes biomoléculas como los péptidos y proteínas manteniéndolas relativamente intactas. Esto sentó las bases de la espectrometría de masas aplicada a la proteómica. En la proteómica shotgun (el término inglés está muy asentado), el primer paso del experimento generalmente consiste en la digestión de las proteínas de la muestra en péptidos por acción de una enzima proteolítica como la tripsina. Esto incrementa notablmente el rendimiento en términos de número de proteínas que pueden ser identificadas en un sólo experimento comparado con los experimentos basados en gel. Sin embargo, tiene el coste asociado de provocar una gran complejidad de la mezcla de péptidos y el problema añadido de la inferencia de las proteínas originarias. Los péptidos son separados por cromatografía líquida e ionizados para entrar a continuación en el espectrómetro de masas donde son separados en función de la proporción entre su masa y su carga (m/z) y los valores obtenidos son registrados en un espectro MS1. En la espectrometría de masas en tándem (MS/MS), los péptidos con mayor intensidad son seleccionados para ser fragmentados de modo que se generan espectros MS/MS, colecciones de valores m/z y de intensidad para cada precursor y sus fragmentos...

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With the increasing fungi resistance compared with existing drugs on the market and the side effects reported by some compounds with antioxidant properties and enzymatic inhibitors, in particular against α-amylase and α-glucosidase, the discovery of new compounds with biological potential, becomes a need. In this context, natural products can be an important source for the discovery of new active molecular architectures. Then, this study aimed to evaluate the antioxidant activity, the enzymatic inhibitory activity of α-amylase and α-glucosidase, the antifungal and cytotoxic activities of ethanolic extract (EE) the leaves of Banisteriopsis argyrophylla (Malpighiaceae) and their fractions, obtained by liquid-liquid extraction using solvents of increasing polarity. The antioxidant activity was evaluated by the free radical DPPH scavenging method (2,2-diphenyl-1-picrylhydrazyl) and the ethyl acetate fractions (FAE) and n-butanol (FB) were the most active, confirmed by the peak current and the oxidation potential obtained by differential pulse voltammetry (DPV). The inhibitory activity of the α-amylase and α-glucosidase was analyzed considering the reactions between substrates α-(2-chloro-4-nitrophenyl)-β-1,4-galactopiranosilmaltoside (Gal-α-G2-CNP) and 4-nitrophenyl-α-D-glucopyranoside (p-NPG), respectively. Initially, it was found that the EE showed considerable activity against α-amylase (EC50 = 2.89±0.1 μg m L–1) compared to the acarbose used as positive control (EC50 = 0.08±0.1 μg mL–1) and that did not showed promising activity against the α-glucosidase. After this observation we evaluated the inhibitory activity of α-amylase fractions, with FAE (EC50 = 2.33±0.1 μg mL–1) and FB (EC50 = 2.57 ± 0.1 μg mL–1) showing the best inhibitions. The antifungal activity was evaluated against Candida species, and the FAE had better antifungal potential (MIC's between 93.75 and 11.72 μg mL–1) compared with amphotericin as positive standard (MIC = 1.00 and 2.00 μg L–1 for C. parapsilosis and C. krusei used as controls, respectively). The EE (CC50 = 360.00 ± 12 μg mL–1) and fractions (CC50's> 270.00 μg mL–1) were considerably less toxic to Vero cells than the cisplatin used as positive control (CC50 = 7.01 ± 0 6 μg mL–1). The FAE showed the best results for the activities studied, this fraction was submitted to ultra performance liquid chromatography coupled with mass spectrometry (UPLC-MS)), and the following flavonoids have been identified: (±)-catechin, quercetin-3-O-β-D-Glc/ quercetin-3-O-β-D-Gal, quercetin-3-O-β-L-Ara, quercetin-3-O-β-D-Xyl, quercetin-3-O-α-L-Rha, kaempferol-3-O-α-L-Rha, quercetin-3-O-(2''-galoil)-α-L-Rha, quercetin-3-O-(3''-galoil)-α-L-Rha and kaempferol-3-O-(3''-galoil)-α-L-Rha,. FAE was submitted to column chromatography using C18 phase, and (±)-catechin was isolated (FAE-A1, 73 mg) and three fractions consisting of a mixture of flavonoids were obtained (FAE-A2, FAE-A3 and FAE-A4). These compounds were identified by thin layer chromatography (TLC) and (–)-ESI-MS. The (±)-catechin fraction showed an MIC = 2.83 μg ml–1 in assay using C. glabrata, with amphotericin as positive control. The fractions FAE-A2, FAE-A3, FAE-A4, showed less antifungal potential in tested concentrations. The identified flavonoids are described in the literature, regarding their antioxidant capacity and (±)-catechin, quercetin-3-O-Rha and kaempferol-3-O-Rha are described as α-amylase inhibitors. Thus, B. argyrophylla is an important species that produces compounds with antioxidant potential that can be related to the traditional use as anti-inflammatory and also has antifungal compounds and inhibitors of α-amylase. Therefore, these leaves are promising resources for the production of new drugs.

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Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

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Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

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The presence of harmful algal blooms (HAB) is a growing concern in aquatic environments. Among HAB organisms, cyanobacteria are of special concern because they have been reported worldwide to cause environmental and human health problem through contamination of drinking water. Although several analytical approaches have been applied to monitoring cyanobacteria toxins, conventional methods are costly and time-consuming so that analyses take weeks for field sampling and subsequent lab analysis. Capillary electrophoresis (CE) becomes a particularly suitable analytical separation method that can couple very small samples and rapid separations to a wide range of selective and sensitive detection techniques. This paper demonstrates a method for rapid separation and identification of four microcystin variants commonly found in aquatic environments. CE coupled to UV and electrospray ionization time-of-flight mass spectrometry (ESI-TOF) procedures were developed. All four analytes were separated within 6 minutes. The ESI-TOF experiment provides accurate molecular information, which further identifies analytes.

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En la actualidad se observa como la categoría género se ha instalado no solo como categoría social sino como categoría teórica, esta última como normativa, legitimando prejuicios y estereotipos que entran en tensión con las nuevas prácticas sociales y las normativas que acompañan a estos nuevos procesos civilizadores desde una perspectiva de géneros que atiende a la diversidad y al mismo tiempo a la igualdad en el acceso a los derechos. Adentrando a que somos iguales por ser diferentes e irrumpiendo en que habrá tantas femineidades, masculinidades y sexualidades como sujetos haya. En esta línea de pensamiento, éste escrito pretende describir normativas que promueven y legitiman nuevos conceptos paradigmáticos de ser sujeto/a de derecho, como lo son: Los Nuevos Diseños Curriculares de la Provincia de Buenos Aires, La ?ESI?: Ley Nacional N°26.150 de Enseñanza Sexual Integral, Declaración Conjunta N°04/13, resolución N° 2476/13 pautas nuevas condiciones para la organización de la clase de Educación Física, (sobre enseñanza secundaria mixta). Describir reflexiones sobre esta tensión de lo escrito, de lo hecho y los discursos que llevan a cabo en sus prácticas los/las profesoras para facilitar algunas aproximaciones a las contradicciones de promover prácticas en perspectiva de géneros sexistas

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En la actualidad se observa como la categoría género se ha instalado no solo como categoría social sino como categoría teórica, esta última como normativa, legitimando prejuicios y estereotipos que entran en tensión con las nuevas prácticas sociales y las normativas que acompañan a estos nuevos procesos civilizadores desde una perspectiva de géneros que atiende a la diversidad y al mismo tiempo a la igualdad en el acceso a los derechos. Adentrando a que somos iguales por ser diferentes e irrumpiendo en que habrá tantas femineidades, masculinidades y sexualidades como sujetos haya. En esta línea de pensamiento, éste escrito pretende describir normativas que promueven y legitiman nuevos conceptos paradigmáticos de ser sujeto/a de derecho, como lo son: Los Nuevos Diseños Curriculares de la Provincia de Buenos Aires, La ?ESI?: Ley Nacional N°26.150 de Enseñanza Sexual Integral, Declaración Conjunta N°04/13, resolución N° 2476/13 pautas nuevas condiciones para la organización de la clase de Educación Física, (sobre enseñanza secundaria mixta). Describir reflexiones sobre esta tensión de lo escrito, de lo hecho y los discursos que llevan a cabo en sus prácticas los/las profesoras para facilitar algunas aproximaciones a las contradicciones de promover prácticas en perspectiva de géneros sexistas