Análise de glicocorticosteróides por CG-EM: uma nova abordagem de derivatização para o controle de dopagem no esporte

Glucocorticosteroids (CT) show a powerful anti-inflammatory effect. In view of this, they are extensively used in sports medicine, but their misuse (systemic administration) can lead to severe injuries on athletes and has been restricted by the IOC in recent years. For GC-MS analysis, a derivatization step is necessary in order to convert them to a stable form, thus preventing thermal breakdown with the loss of the ketone side chain. Derivatization of CT is reviewed and a new approach of silylation is presented for screening of CT in urine.

The dielectric suppress and the control of semiconductor non-Ohmic feature of CaCu3Ti4O12 by means of tin doping

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Treinta años del control del doping en los hipódromos españoles: 1983-2014

El deseo de lograr la victoria con el menor esfuerzo o la garantía de la derrota segura del rival, es un sentimiento tan antiguo como la historia del deporte, para conseguirlo a lo largo del tiempo los métodos, las formas, las sustancias para alterar el rendimiento físico han evolucionado, aunque la intención se mantiene de forma invariable. En nuestros días el doping está presente en la mayoría de los deportes y las carreras de caballos no son una excepción. Por esta razón con el fin de salvaguardar el bienestar animal, la limpieza del deporte y la protección del juego en los hipódromos españoles se realiza “el control del doping”, se practica a los caballos PSI de carreras, hasta ahora, siguiendo las directrices del “Código de la Sociedad Fomento de la Cría Caballar en España” (SFCCE), de esta forma tratamos de impedir el uso fraudulento de sustancias dopantes o el abuso de las sustancias medicamentosas. El control del doping en los hipódromos españoles empezó en 1960, gracias a un acuerdo entre la SFCCE y la Cátedra de Farmacología y Toxicología de la Facultad de Veterinaria de la Universidad Complutense, de lo sucedido en estos primeros años incluimos en nuestro trabajo un estudio crítico. En 1983 la SFCCE se modernizó y delegó la responsabilidad de los análisis de orina y sangre a un laboratorio homologado por la International Federation of Horseracing Authorities (IFHA). Por esta razón, en nuestro trabajo aportamos los datos correspondientes al control del doping de los caballos de carreras en España desde 1983 y hasta diciembre de 2014...

Pore structure tailoring of pillared clays with cation doping techniques

Techniques and mechanism of doping controlled amounts of various cations into pillared clays without causing precipitation or damages to the pillared layered structures are reviewed and discussed. Transition metals of great interest in catalysis can be doped in the micropores of pillared clay in ionic forms by a two-step process. The micropore structures and surface nature of pillared clays are altered by the introduced cations, and this results in a significant improvement in adsorption properties of the clays. Adsorption of water, air components and organic vapors on cation-doped pillared clays were studied. The effects of the amount and species of cations on the pore structure and adsorption behavior are discussed. It is demonstrated that the presence of doped Ca2+ ions can effectively aides the control of modification of the pillared clays of large pore openings. Controlled cation doping is a simple and powerful tool for improving the adsorption properties of pillared clay.

Controlled doping of transition metal cations in alumina pillared clays

A two-step method of loading controlled amounts of transition metal cations into alumina pillared clays (Al-PILCs) is proposed. First, calcined Al-PILC was dispersed into an aqueous solution of sodium or ammonium ions. Increasing the pH of the dispersion resulted in an increase in the amount of cations loaded into the clay. The ion-doped Al-PILC was then exchanged with an aqueous solution of transition metal salt at a pH of similar to 4.5 to replace Na+ or NH4+ ions by transition metal cations. Analytical techniques such as atomic absorption spectroscopy, X-ray diffraction, diffuse reflectance-ultraviolet-visible spectroscopy, as well as N-2 adsorption were used to characterize the PILC products with and without the loading of metal ions. The introduced transition metal species exist in the forms of hydrated ions in the PILC hosts. The content of transition metal ions in the final product increased with the amount of Na+ or NH4+ loaded in the first step so that by controlling the pH of the dispersion in the first step, one can control the doping amounts of transition metal cations into Al-PILCs. A sample containing 0.125 mmol/g of nickel was thus obtained, which is similar to 3 times of that obtained by directly exchanging Al-PILC with Ni(NO3)(2) solution, while the pillared layered structures of the Al-PILC remained. The porosity analysis using N-2 adsorption data indicated that most of the doped transition metal ions dispersed homogeneously in the micropores of the Al-PILC, significantly affecting the micropore structure.

Phase growth control in low temperature PLD Co: TiO2 films by pressure

This paper reports on the structural and optical properties of Co-doped TiO2 thin films grown onto (0001)Al2O3 substrates by non-reactive pulsed laser deposition (PLD) using argon as buffer gas. It is shown that by keeping constant the substrate temperature at as low as 310 degrees C and varying only the background gas pressure between 7 Pa and 70 Pa, it is possible to grow either epitaxial rutile or pure anatase thin films, as well as films with a mixture of both polymorphs. The optical band gaps of the films are red shifted in comparison with the values usually reported for undoped TiO2, which is consistent with n-type doping of the TiO2 matrix. Such band gap red shift brings the absorption edge of the Co-doped TiO2 films into the visible region, which might favour their photocatalytic activity. Furthermore, the band gap red shift depends on the films' phase composition, increasing with the increase of the Urbach energy for increasing rutile content. (C) 2012 Elsevier B.V. All rights reserved.

Total hemoglobin mass--a new parameter to detect blood doping?

PURPOSE: All kinds of blood manipulations aim to increase the total hemoglobin mass (tHb-mass). To establish tHb-mass as an effective screening parameter for detecting blood doping, the knowledge of its normal variation over time is necessary. The aim of the present study, therefore, was to determine the intraindividual variance of tHb-mass in elite athletes during a training year emphasizing off, training, and race seasons at sea level. METHODS: tHb-mass and hemoglobin concentration ([Hb]) were determined in 24 endurance athletes five times during a year and were compared with a control group (n = 6). An analysis of covariance was used to test the effects of training phases, age, gender, competition level, body mass, and training volume. Three error models, based on 1) a total percentage error of measurement, 2) the combination of a typical percentage error (TE) of analytical origin with an absolute SD of biological origin, and 3) between-subject and within-subject variance components as obtained by an analysis of variance, were tested. RESULTS: In addition to the expected influence of performance status, the main results were that the effects of training volume (P = 0.20) and training phases (P = 0.81) on tHb-mass were not significant. We found that within-subject variations mainly have an analytical origin (TE approximately 1.4%) and a very small SD (7.5 g) of biological origin. CONCLUSION: tHb-mass shows very low individual oscillations during a training year (<6%), and these oscillations are below the expected changes in tHb-mass due to Herythropoetin (EPO) application or blood infusion (approximately 10%). The high stability of tHb-mass over a period of 1 year suggests that it should be included in an athlete's biological passport and analyzed by recently developed probabilistic inference techniques that define subject-based reference ranges.

Procedures for monitoring recombinant erythropoietin and analogs in doping.

Hemoglobin concentration is one of the principal factors of aerobic power and, consequently, of performance in many types of physical activities. The use of recombinant human erythropoietin is, therefore, particularly powerful for improving the physical performances of patients, and, more generally, improving their quality of life. This article discusses procedures for monitoring recombinant erythropoietin and its analogues in doping for athletic performance.

Validation and performance comparison of two carbon isotope ratio methods to control the misuse of androgens in humans.

Carbon isotope ratio of androgens in urine specimens is routinely determined to exclude an abuse of testosterone or testosterone prohormones by athletes. Increasing application of gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) in the last years for target and systematic investigations on samples has resulted in the demand for rapid sample throughput as well as high selectivity in the extraction process particularly in the case of conspicuous samples. For that purpose, we present herein the complimentary use of an SPE-based assay and an HPLC fractionation method as a two-stage strategy for the isolation of testosterone metabolites and endogenous reference compounds prior to GC/C/IRMS analyses. Assays validation demonstrated acceptable performance in terms of intermediate precision (range: 0.1-0.4 per thousand) and Bland-Altman analyses revealed no significant bias (0.2 per thousand). For further validation of this two-stage analyses strategy, all the specimens (n=124) collected during a major sport event were processed.

Enhancement of the photoelectrochemical properties of Cl-doped ZnO nanowires by tuning their coaxial doping profile

Arrays of vertically aligned ZnO:Cl/ZnO core-shell nanowires were used to demonstrate that the control of the coaxial doping profile in homojunction nanostructures can improve their surface charge carrier transfer while conserving potentially excellent transport properties. It is experimentally shown that the presence of a ZnO shell enhances the photoelectrochemical properties of ZnO:Cl nanowires up to a factor 5. Likewise, the ZnO shell promotes the visible photoluminescence band in highly conducting ZnO:Cl nanowires. These lines of evidence are associated with the increase of the nanowires" surface depletion layer

Time for change: a roadmap to guide the implementation of the World Anti-Doping Code 2015

A medical and scientific multidisciplinary consensus meeting was held from 29 to 30 November 2013 on Anti-Doping in Sport at the Home of FIFA in Zurich, Switzerland, to create a roadmap for the implementation of the 2015 World Anti-Doping Code. The consensus statement and accompanying papers set out the priorities for the antidoping community in research, science and medicine. The participants achieved consensus on a strategy for the implementation of the 2015 World Anti-Doping Code. Key components of this strategy include: (1) sport-specific risk assessment, (2) prevalence measurement, (3) sport-specific test distribution plans, (4) storage and reanalysis, (5) analytical challenges, (6) forensic intelligence, (7) psychological approach to optimise the most deterrent effect, (8) the Athlete Biological Passport (ABP) and confounding factors, (9) data management system (Anti-Doping Administration & Management System (ADAMS), (10) education, (11) research needs and necessary advances, (12) inadvertent doping and (13) management and ethics: biological data. True implementation of the 2015 World Anti-Doping Code will depend largely on the ability to align thinking around these core concepts and strategies. FIFA, jointly with all other engaged International Federations of sports (Ifs), the International Olympic Committee (IOC) and World Anti-Doping Agency (WADA), are ideally placed to lead transformational change with the unwavering support of the wider antidoping community. The outcome of the consensus meeting was the creation of the ad hoc Working Group charged with the responsibility of moving this agenda forward.

Analytical progresses of the International Olympic Committee and World Anti-Doping Agency Olympic laboratories.

The Summer Olympic Games constitute the biggest concentration of human sports and activities in a particular place and time since 776 BCE, when the written history of the Olympic Games in Olympia began. Summer and Winter Olympic anti-doping laboratories, accredited by the International Olympic Committee in the past and the World Anti-Doping Agency in the present times, acquire worldwide interest to apply all new analytical advancements in the fight against doping in sports, hoping that this major human event will not become dirty by association with this negative phenomenon. This article summarizes the new analytical progresses, technologies and knowledge used by the Olympic laboratories, which for the vast majority of them are, eventually, incorporated into routine anti-doping analysis.