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1.
An Acad Bras Cienc ; 93(3): e20191229, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34076181

RESUMO

To evaluate the addition of antioxidants in extenders on post-thaw bovine semen quality and in vitro embryo production efficiency. Six semen samples were collected from five Holstein bulls. In the experiment I, the samples were diluted with AndroMed® and Bovimix® and added antioxidants glutathione (1.5 and 2.5 mM) and melatonin (0.5 and 1.0 mM). In the experiment II, the best treatments obtained in experiment I were used for in vitro fecundation. Glutathione did not improve sperm viability. Melatonin had a negative effect on semen characteristics. Andromed® showed better results in sperm kinetics parameters. Bovimix® was more efficient in maintaining cell integrity parameters. Significant correlation was found between sperm kinetics parameters and between cell integrity parameters. For in vitro embryo production, after oocyte selection, maturation, fertilization and cultivation were performed using the four treatments previously evaluated. Andromed® was more efficient in the cleavage rate, no effect of the addition of glutathione. However, the addition of 2.5 mM glutathione in the Bovimix® improved the cleavage rate. There was a significant moderate correlation between cleavage rate and sperm kinetic characteristics. Glutathione did not improve sperm viability. Melatonin reduced the maintenance of sperm characteristics. Andromed® was more efficient in in vitro embryo production and no effect of glutathione was found in this extender. Addition of 2.5 mM glutathione in the Bovimix® extender provided a higher cleavage rate.


Assuntos
Análise do Sêmen , Preservação do Sêmen , Animais , Antioxidantes/farmacologia , Bovinos , Criopreservação/veterinária , Crioprotetores , Humanos , Masculino , Análise do Sêmen/veterinária , Preservação do Sêmen/veterinária , Motilidade dos Espermatozoides , Espermatozoides
2.
Forensic Sci Int ; 318: 110588, 2021 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-33278694

RESUMO

Drugs of abuse are psychoactive substances illicitly distributed and used worldwide. In Rio de Janeiro, Brazil, they represent a public health issue and are directly related to several social problems. The recent increase in appearances of new psychoactive substances (NPS), derived from structural modifications of existing psychoactive substances, poses a threat to public health and forensic laboratories worldwide, as little is known about these substances. This study aimed to chemically and geographically map drugs of abuse from blotter papers seized by the Civil Police of Rio de Janeiro State (PCERJ) between 2006 and 2019. High-performance analytical techniques, such as gas chromatography-mass spectrometry (GC-MS) and Orbitrap mass spectrometry (Orbitrap-MS), combined with statistical analyses, were employed to characterize the seized samples. The most common chemical compounds in NPS found in this study were synthetic phenethylamines, i.e., molecules from the 25I-NBOH (2-(((4-iodo-2,5-dimethoxyphenethyl)amino)methyl)phenol) and 25I-NBOMe (2-(4-iodo-2,5-dimethoxyphenyl)-N-(2-methoxybenzyl)ethanamine) families. Prior to 2014, the majority of seized blotter papers contained lysergic acid diethylamide (LSD) and were concentrated in the Metropolitan region. An upsurge in blotter paper seizures was observed from 2014 to 2017; the most common substances during this time were from the NBOMe family. NBOH compounds emerged in 2016 in coastal regions with high tourism, reaching over 1300 items only in 2017. Only one synthetic cannabinoid was found among the blotter papers seized in Rio de Janeiro between 2006 and 2019. The assembled chemical data and statistical analyses allowed the mapping and monitoring of the chemical profiles of the seized blotter papers, providing a strong foundation for the understanding of the origins and movement of these drugs around the RJ State.


Assuntos
Tráfico de Drogas/estatística & dados numéricos , Controle de Medicamentos e Entorpecentes/estatística & dados numéricos , Papel , Psicotrópicos/química , Brasil , Canabinoides/química , Formas de Dosagem , Fentanila/análogos & derivados , Fentanila/química , Cromatografia Gasosa-Espectrometria de Massas , Humanos , Estrutura Molecular
3.
Curr Aging Sci ; 14(1): 32-38, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-32988360

RESUMO

BACKGROUND: A decrease in the physical activity level in old age is common, which results in an increase in the number of falls and chronic conditions. Associated with that occurs the decline in motor skills as a result of the deficit in the interaction of cognitive and motor processes. Physical activity levels can be associated differently with each motor domain. ; Objective: We analyzed the relationship between physical activity level and motor aptitude and to identify which motor domains were most sensitive to detect insufficiently active level in older adults. ; Methods: 385 elderly people of both sexes participated in the study. For the evaluation of the subjects, the International Questionnaire on Physical Activity and the Motor Scale for Older Adults were adopted. ; Results: The majority of the elderly were active. In comparing motor aptitude between active and insufficiently active (IAC) elders a significant difference was found in the Global Coordination, Balance, Body Scheme and General Motor Aptitude. From the analysis of the Area Under the Curve (AUC), we verified that these domains also were the ones that presented adequate diagnostic accuracy to identify IAC elderly. Besides that, active elderly have presented the General Motor Aptitude classified within normality while the IAC below the normal. ; Conclusion: Our data suggest that IAC older adults present lower motor aptitude than the active elderly, especially in the domains of Global Coordination, Balance, Body Scheme and General Motor Aptitude, and that these domains were sensitive to indicate IAC older adults.


Assuntos
Aptidão , Exercício Físico , Acidentes por Quedas , Idoso , Brasil , Feminino , Humanos , Masculino , Inquéritos e Questionários
4.
Drug Test Anal ; 13(1): 197-202, 2021 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-32808487

RESUMO

The treatment of a man who attempted suicide after experiencing symptoms of anxiety and aggressiveness associated with the use of androgenic-anabolic steroids (AAS) is described. This report includes 30 days of inpatient treatment and a 6-month follow-up. Regular use of fluoxetine apparently prevented the onset of anxiety, depression, aggressiveness, and suicide ideation, even with the concurrent use of AAS. The urinary concentration of androgens, metabolites of AAS, and fluoxetine were monitored through analysis of urinary samples by the Brazilian Laboratory of Doping Control. Our results are congruent with previous findings describing the risk of suicide prompted by AAS use as well as the efficacy of fluoxetine in the treatment of mood disorders associated with the use of anabolic steroids.


Assuntos
Agressão/efeitos dos fármacos , Antidepressivos de Segunda Geração/uso terapêutico , Ansiedade/prevenção & controle , Fluoxetina/uso terapêutico , Tentativa de Suicídio/prevenção & controle , Congêneres da Testosterona/efeitos adversos , Adulto , Ansiedade/induzido quimicamente , Depressão/prevenção & controle , Humanos , Masculino , Adulto Jovem
5.
Zebrafish ; 17(2): 104-111, 2020 04.
Artigo em Inglês | MEDLINE | ID: mdl-32096703

RESUMO

Testolactone is a potent steroid aromatase (CYP19A1) inhibitor, and its main effect is a reduction in estradiol and estrone and an increase in testosterone and androstenedione levels. In this work, we evaluated a zebrafish water tank (ZWT) as a model to investigate testolactone biotransformation and the possibility to increase knowledge regarding the applicability of the ZWT on steroid hormone elimination research, as well as on the impact of steroid hormones on the endogenous metabolism of zebrafish. High-resolution mass spectrometry combined with SIEVE software was used to discriminate the peaks of interest based on significant changes in the relative signal intensity of the m/z values between different ZWT experiments. The metabolites, 4,5-dihydrotestolactone and 1,2,4,5-tetrahydrotestolactone, the same metabolites as those described in humans, were detected in ZWT, both in quite similar proportions. The presence of testolactone in the ZWT caused a rise in testosterone and androstenedione in the water tank, similar to that in human serum. These data suggest that, while the concentration of testolactone was high enough to inhibit the aromatase enzyme, an accumulation of androgens in the water occurred, indicating that the ZWT can be considered a model to investigate the impact of steroids on live organisms.


Assuntos
Inibidores da Aromatase/metabolismo , Testolactona/metabolismo , Peixe-Zebra/metabolismo , Animais , Biotransformação , Hormônios Esteroides Gonadais , Testolactona/análogos & derivados
6.
An. acad. bras. ciênc ; 89(3): 1403-1415, July-Sept. 2017. tab, graf
Artigo em Inglês | LILACS | ID: biblio-886744

RESUMO

ABSTRACT This study presents the bioreduction of six β-ketoesters by whole cells of Kluyveromyces marxianus and molecular investigation of a series of 13 β-ketoesters by hologram quantitative structure-activity relationship (HQSAR) in order to relate with conversion and enantiomeric excess of β-stereogenic-hydroxyesters obtained by the same methodology. Four of these were obtained as (R)-configuration and two (S)-configuration, among them four compounds exhibited >99% enantiomeric excess. The β-ketoesters series LUMO maps showed that the β-carbon of the ketoester scaffold are exposed to undergo nucleophilic attack, suggesting a more favorable β-carbon side to enzymatic reduction based on adopted molecular conformation at the reaction moment. The HQSAR method was performed on the β-ketoesters derivatives separating them into those provided predominantly (R)- or (S)-β-hydroxyesters. The HQSAR models for both (R)- and (S)-configuration showed high predictive capacity. The HQSAR contribution maps suggest the importance of β-ketoesters scaffold as well as the substituents attached therein to asymmetric reduction, showing a possible influence of the ester group carbonyl position on the molecular conformation in the enzyme catalytic site, exposing a β-carbon side to the bioconversion to (S)- and (R)-enantiomers.


Assuntos
Kluyveromyces/metabolismo , Ésteres/química , Cetonas/química , Oxirredução , Biotransformação , Estrutura Molecular
7.
An Acad Bras Cienc ; 89(3): 1403-1415, 2017.
Artigo em Inglês | MEDLINE | ID: mdl-28793010

RESUMO

This study presents the bioreduction of six ß-ketoesters by whole cells of Kluyveromyces marxianus and molecular investigation of a series of 13 ß-ketoesters by hologram quantitative structure-activity relationship (HQSAR) in order to relate with conversion and enantiomeric excess of ß-stereogenic-hydroxyesters obtained by the same methodology. Four of these were obtained as (R)-configuration and two (S)-configuration, among them four compounds exhibited >99% enantiomeric excess. The ß-ketoesters series LUMO maps showed that the ß-carbon of the ketoester scaffold are exposed to undergo nucleophilic attack, suggesting a more favorable ß-carbon side to enzymatic reduction based on adopted molecular conformation at the reaction moment. The HQSAR method was performed on the ß-ketoesters derivatives separating them into those provided predominantly (R)- or (S)-ß-hydroxyesters. The HQSAR models for both (R)- and (S)-configuration showed high predictive capacity. The HQSAR contribution maps suggest the importance of ß-ketoesters scaffold as well as the substituents attached therein to asymmetric reduction, showing a possible influence of the ester group carbonyl position on the molecular conformation in the enzyme catalytic site, exposing a ß-carbon side to the bioconversion to (S)- and (R)-enantiomers.


Assuntos
Ésteres/química , Cetonas/química , Kluyveromyces/metabolismo , Biotransformação , Estrutura Molecular , Oxirredução
8.
Artigo em Inglês | MEDLINE | ID: mdl-28010923

RESUMO

Women are employed in increasing numbers as gasoline station attendants, a work category with risk of exposure to benzene. We have assessed the effect of gender on biomarkers of occupational benzene exposure. Gasoline station attendants (20 men and 20 women) and 40 control individuals (20 men and 20 women) with no history of occupational benzene exposure were evaluated. Benzene exposure was monitoring by environmental and biological measurements. Urinary trans,trans-muconic acid levels, well-known genetic and hematological alterations linked to benzene exposure, and non-cancer effects on the immune, hepatic, and renal systems were investigated. Our results suggest a potential effect of gender on some effects of occupational benzene exposure, particularly the hematological parameters and trans,trans-muconic acid levels. Despite limitations of our study, our findings provide important considerations about occupational exposure of women to benzene and may contribute to the development of occupational protection standards.


Assuntos
Benzeno/toxicidade , Monitoramento Ambiental/métodos , Gasolina , Exposição Ocupacional , Feminino , Humanos , Masculino
9.
Environ Sci Pollut Res Int ; 23(19): 19626-33, 2016 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-27392628

RESUMO

Petrochemical industries generate wastewaters containing pollutants that can severely impact the biological treatment systems. Some streams from specific production units may contain nonbiodegradable or toxic compounds that impair the performance of the wastewater treatment plant and should be segregated and treated by specific techniques. In this work, the utilization of chemical oxidation (H2O2/UV) was investigated for removing 4-vinylcyclohexene (VCH) from a liquid stream coming from the production of hydroxylated liquid polybutadiene (HLPB). Besides VCH, this stream also contains ethanol, hydrogen peroxide, and many other organic compounds. Experiments were carried out in a small-scale photochemical reactor (0.7 L) using a 25-W low-pressure mercury vapor lamp. The photochemical reactor was operated in batch, and the reaction times were comprised between 10 and 60 min. Assays were also performed with a synthetic medium containing VCH, H2O2, and ethanol to investigate the removal of these substances in a less complex aqueous matrix. By-products formed in the reaction were identified by gas chromatography and mass spectroscopy (GC-MS). VCH was significantly removed by the oxidation process, in most assays to undetectable levels. Ethanol removal varied from 16 to 23 % depending on the reaction conditions. Acetic acid, acetaldehyde, and diols were detected as by-products of the industrial wastewater stream oxidation. A drop on the toxicity of the industrial stream was also observed in assays using the organism Artemia salina.


Assuntos
Peróxido de Hidrogênio/química , Resíduos Industriais/análise , Raios Ultravioleta , Eliminação de Resíduos Líquidos/métodos , Águas Residuárias/química , Purificação da Água/métodos , Indústria de Petróleo e Gás , Oxirredução , Poluentes Químicos da Água/química
10.
Talanta ; 144: 627-35, 2015 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-26452870

RESUMO

Comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-TOFMS) was successfully applied to eight real Brazilian Fischer-Tropsch (FT) product samples for the quantitative analysis of O-containing compounds. It not only allowed identifying and quantifying simultaneously a large number of O-containing compounds but also resolved many co-eluting components, such as carboxylic acids, which co-elute in one-dimensional gas chromatography. The homologous series of alcohols and carboxylic acids as trimethylsilyl derivatives were detected and identified at trace levels. The absolute quantification of each compound was accomplished with reliability using analytical curves. Linear alcohols (from C5 to C19), branched alcohols (C6-C13) and carboxylic acids (C4 to C12) were obtained in the range of 1.58 mg g(-1) to 14.75 mg g(-1), 0.51 mg g(-1) to 1.12 mg g(-1) and 0.21 mg g(-1) to 1.63 mg g(-1) of FT product samples, respectively. GC×GC-TOFMS provided a linear range (from 0.3 ng µL(-1) to 10 ng µL(-1)), good precision (<8%), and excellent accuracy (recovery range of 77% to 118%) for quantification of individual O-containing compounds in FT product samples. The results can benefit the development of gas-to-liquid technologies from natural gas and guide the choice of an FT conversion process that generates clean products with higher added value.

11.
Drug Test Anal ; 7(10): 967-70, 2015 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-26112364

RESUMO

Glycerol is a naturally occurring polyol in the human body, essential for several metabolic processes. It is widely used in the food, pharmaceutical, and medical industries and in clinical practice as a plasma volume expander (PVE). Athletes, however, may use glycerol to mask the presence of forbidden substances or to enhance performance, inclusively through hyperhydration achieved by glycerol ingestion with added fluid. These practices are considered doping, and are prohibited by the World Anti-Doping Agency (WADA). Therefore, glycerol was introduced in the prohibited list. Doping through glycerol ingestion can readily be identified by detection of elevated glycerol concentrations in urine. In this paper, a protocol for the fast detection of glycerol in urine is proposed. It consists of a previous visual colourimetric screening, followed by a quantitative/qualitative confirmation analysis by mass spectrometry. The screening procedure involves a reaction in which polyhydric alcohols are oxidized by periodate to formic acid and formaldehyde, which is detected by the addition of a fuchsin solution. For the subsequent qualitative/quantitative confirmation analysis, a gas chromatography-mass spectrometry based approach with a non-deuterated internal standard and a drying step of only 10 min is proposed. The linear correlation was demonstrated within WADA´s threshold range. The calculated RSD were 2.1% for within-day precision and 2.8% for between-day precision. The uncertainty estimation was calculated, and a value of 2.7% was obtained. The procedure may also be used for the analysis of other polyols in urine, as for example the PVE mannitol.


Assuntos
Colorimetria/métodos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Glicerol/urina , Detecção do Abuso de Substâncias/métodos , Atletas , Dopagem Esportivo , Humanos , Limite de Detecção
12.
Anal Bioanal Chem ; 407(14): 4091-9, 2015 May.
Artigo em Inglês | MEDLINE | ID: mdl-25845527

RESUMO

This work evaluates the application of a thermodynamic model to comprehensive two-dimensional gas chromatography (GC × GC) coupled with time-of-flight mass spectrometry for anabolic agent investigation. Doping control deals with hundreds of drugs that are prohibited in sports. Drug discovery in biological matrices is a challenging task that requires powerful tools when one is faced with the rapidly changing designer drug landscape. In this work, a thermodynamic model developed for the prediction of both primary and secondary retention times in GC × GC has been applied to trimethylsilylated hydroxyl (O-TMS)- and methoxime-trimethylsilylated carbonyl (MO-TMS)-derivatized endogenous steroids. This model was previously demonstrated on a pneumatically modulated GC × GC system, and is applied for the first time to a thermally modulated GC × GC system. Preliminary one-dimensional experiments allowed the calculation of thermodynamic parameters (ΔH, ΔS, and ΔC p ) which were successfully applied for the prediction of the analytes' interactions with the stationary phases of both the first-dimension column and the second-dimension column. The model was able to predict both first-dimension and second-dimension retention times with high accuracy compared with the GC × GC experimental measurements. Maximum differences of -8.22 s in the first dimension and 0.4 s in the second dimension were encountered for the O-TMS derivatives of 11ß-hydroxyandrosterone and 11-ketoetiocholanolone, respectively. For the MO-TMS derivatives, the largest discrepancies were from testosterone (9.65 ) for the first-dimension retention times and 11-keto-etiocholanolone (0.4 s) for the second-dimension retention times.


Assuntos
Cromatografia Gasosa/métodos , Espectrometria de Massas/métodos , Esteroides/química , Termodinâmica
13.
J Chromatogr A ; 1298: 76-85, 2013 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-23746644

RESUMO

The detection of 11 sympathomimetic alkylamines in urine was presented with a focus on human doping control is proposed using liquid chromatography tandem mass spectrometry (LC-QqQ) and high resolution mass spectrometry (LC-HRMS) as a screening tool after a dilute-and-shoot (DS) approach. For the LC-HRMS analyses, several compounds exhibited better limits of detection (L.O.D.) than the LC-QqQ. However, due to their small differences in structure, co-elution among the alkylamines was observed. Therefore, the chemical conversion of the alkylamines into an appropriate derivative for the confirmation analyses using gas chromatography-mass spectrometry (GC-MS) was evaluated. Five derivatization approaches were evaluated in an attempt to increase the analytical response and the confidence of the identification. The choice of the appropriated derivative for each alkylamine makes their spectra more easily interpretable, fulfills the WADA's rather strict identification criteria and enables the unequivocal identification of alkylamines in urine.


Assuntos
Cromatografia Líquida/métodos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Simpatomiméticos/análise , Espectrometria de Massas em Tandem/métodos , Humanos
14.
J Dairy Res ; 79(3): 272-9, 2012 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-22444071

RESUMO

The test-day yields of milk, fat and protein were analysed from 1433 first lactations of buffaloes of the Murrah breed, daughters of 113 sires from 12 herds in the state of São Paulo, Brazil, born between 1985 and 2007. For the test-day yields, 10 monthly classes of lactation days were considered. The contemporary groups were defined as the herd-year-month of the test day. Random additive genetic, permanent environmental and residual effects were included in the model. The fixed effects considered were the contemporary group, number of milkings (1 or 2 milkings), linear and quadratic effects of the covariable cow age at calving and the mean lactation curve of the population (modelled by third-order Legendre orthogonal polynomials). The random additive genetic and permanent environmental effects were estimated by means of regression on third- to sixth-order Legendre orthogonal polynomials. The residual variances were modelled with a homogenous structure and various heterogeneous classes. According to the likelihood-ratio test, the best model for milk and fat production was that with four residual variance classes, while a third-order Legendre polynomial was best for the additive genetic effect for milk and fat yield, a fourth-order polynomial was best for the permanent environmental effect for milk production and a fifth-order polynomial was best for fat production. For protein yield, the best model was that with three residual variance classes and third- and fourth-order Legendre polynomials were best for the additive genetic and permanent environmental effects, respectively. The heritability estimates for the characteristics analysed were moderate, varying from 0·16±0·05 to 0·29±0·05 for milk yield, 0·20±0·05 to 0·30±0·08 for fat yield and 0·18±0·06 to 0·27±0·08 for protein yield. The estimates of the genetic correlations between the tests varied from 0·18±0·120 to 0·99±0·002; from 0·44±0·080 to 0·99±0·004; and from 0·41±0·080 to 0·99±0·004, for milk, fat and protein production, respectively, indicating that whatever the selection criterion used, indirect genetic gains can be expected throughout the lactation curve.


Assuntos
Búfalos/genética , Gorduras/análise , Lactação/genética , Proteínas do Leite/análise , Leite/química , Animais , Brasil , Búfalos/metabolismo , Feminino , Variação Genética , Modelos Estatísticos , Característica Quantitativa Herdável , Análise de Regressão
15.
J Dairy Res ; 79(1): 60-5, 2012 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-22054225

RESUMO

The objective of this study was to apply factor analysis to describe lactation curves in dairy buffaloes in order to estimate the phenotypic and genetic association between common latent factors and cumulative milk yield. A total of 31 257 monthly test-day milk yield records from buffaloes belonging to herds located in the state of São Paulo were used to estimate two common latent factors, which were then analysed in a multi-trait animal model for estimating genetic parameters. Estimates of (co)variance components for the two common latent factors and cumulated 270-d milk yield were obtained by Bayesian inference using a multiple trait animal model. Contemporary group, number of milkings per day (two levels) and age of buffalo cow at calving (linear and quadratic) as covariate were included in the model as fixed effects. The additive genetic, permanent environmental and residual effects were included as random effects. The first common latent factor (F1) was associated with persistency of lactation and the second common latent factor (F2) with the level of production in early lactation. Heritability estimates for F1 and F2 were 0·12 and 0·07, respectively. Genetic correlation estimates between F1 and F2 with cumulative milk yield were positive and moderate (0·63 and 0·52). Multivariate statistics employing factor analysis allowed the extraction of two variables (latent factors) that described the shape of the lactation curve. It is expected that the response to selection to increase lactation persistency is higher than the response obtained from selecting animals to increase lactation peak. Selection for higher total milk yield would result in a favourable correlated response to increase the level of production in early lactation and the lactation persistency.


Assuntos
Búfalos/genética , Búfalos/fisiologia , Lactação/fisiologia , Leite/fisiologia , Animais , Teorema de Bayes , Bases de Dados Factuais , Feminino
16.
Bioanalysis ; 3(2): 215-26, 2011 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-21250849

RESUMO

Plasma volume expanders comprise a heterogeneous group of substances used in medicine that are intravenously administered in cases of great blood loss owing to surgery or medical emergency. These substances, however, can also be used to artificially enhance performance of healthy athletes in sport activities, and to mask the presence of others substances. These practices are considered doping, and are therefore prohibited by the International Olympic Committee and the World Antidoping Agency. Consequently, drug testing procedures are essential. The present work provides an overview of plasma volume expanders, assembling pertinent data such as chemical characteristics, physiological aspects, adverse effects, doping and analytical detection methods, which are currently dispersed in the literature.


Assuntos
Dopagem Esportivo , Preparações Farmacêuticas/análise , Substitutos do Plasma/análise , Detecção do Abuso de Substâncias/métodos , Humanos
17.
Rapid Commun Mass Spectrom ; 24(22): 3297-302, 2010 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-20973004

RESUMO

Trimethylsilylation of anabolic agents and their metabolites is frequently achieved by using the derivatization mixture N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA)/NH(4)I/2-mercaptoethanol. Nevertheless, artifacts were formed when this mixture was employed in the monitoring of exemestane and its main metabolite 17ß-hydroxyexemestane prior to GC-MS analysis. These artifacts were identified as the N-methyltrifluoroacetamide (MTFA) and trimethylsiloxyethylmercapto products of the respective trimethylsilyl (TMS) derivatives. Furthermore, artifact formation was evaluated taking the structure (1,4-diene-3-keto-6-exomethylene) of the compounds into account. Although these artifacts are relevant for investigations regarding the derivatization process and may be of interest in many fields, they are detrimental to cope with the requirements of the World Anti-Doping Agency (WADA) in terms of the limits of detection (LODs) required. To overcome this issue, a method using an alternative derivatization was proposed: formation of methyloxime-TMS derivatives through double derivatization using O-methylhydroxylamine/pyridine and MSTFA/TMS imidazole after enzymatic hydrolysis and liquid-liquid extraction. Samples from an excretion study after administration of exemestane to healthy volunteers were analyzed by the proposed method and detection of both exemestane and its main metabolite was possible. This method showed excellent results for both analytes meeting the LODs required for antiestrogenic agents (50 ng/mL) established by WADA. The method was validated for the main metabolite, it was robust and cost-effective for qualitative and quantitative purposes, with LOD and LOQ of 10 ng/mL and 25 ng/mL, respectively.


Assuntos
Androstadienos/urina , Cromatografia Gasosa-Espectrometria de Massas/métodos , Acetamidas , Adulto , Androstadienos/química , Androstadienos/farmacocinética , Artefatos , Dopagem Esportivo , Fluoracetatos , Humanos , Masculino , Oximas/química , Reprodutibilidade dos Testes , Sensibilidade e Especificidade , Ácido Trifluoracético/química , Compostos de Trimetilsilil/química
18.
Drug Test Anal ; 2(11-12): 599-602, 2010.
Artigo em Inglês | MEDLINE | ID: mdl-21204291

RESUMO

Changes in the endogenous profile of androgenic anabolic steroids (AAS) may be interpreted as markers of doping. The objective of this study was to evaluate the endogenous profile of AAS in male athletes of the 2009 Brazilian National Soccer Championship, in normal conditions, particularly in the light of the revision of World Anti-Doping Agency's (WADA) Technical Document on the Interpretation of Endogenous AAS in athletes for doping control drafted in that year, as well as comparing these results to profiles already published in the literature. The upper limit of the 95% central reference interval of the following parameters for the studied population were estimated to be significantly higher than WADA's criteria, with a confidence of 90%: DHEA (about 2.3 times higher), Adiol (1.2 times higher), Bdiol (2.7 times higher), and Adiol/E (6 times higher). These findings seem to imply that WADA's criteria proposed in 2009 for DHEA, Adiol, Bdiol, and Adiol/E may not have been applicable to the studied population. Moreover, their comparison to previously published studies pointed to the need to evaluate in detail the appropriateness of adopting these criteria as universal, since there seems to be variations among different populations of athletes.


Assuntos
Anabolizantes/urina , Dopagem Esportivo , Cromatografia Gasosa-Espectrometria de Massas , Esteroides/urina , Atletas , Brasil , Humanos , Masculino , Valores de Referência , Futebol
19.
J Sci Med Sport ; 13(1): 13-5, 2010 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-18768354

RESUMO

The artificial colloid hydroxyethyl starch (HES) is among the most frequently used plasma volume expanders in the medical field. However, in 1998, its misuse by the athletic community was officially reported and since 2000, HES is prohibited by the International Olympic Committee (IOC). Therefore, several methods enabling the detection of HES in urine were developed, most based on gas chromatography-mass spectrometry (GC-MS). In the present work, a simple and low-cost screening method, intended to reduce the number of samples to be analysed by GC-MS, was developed. The method is based on the acid hydrolysis of HES and detection of the resulting glucose and hydroxyethyl glucose derivatives by Benedict's reaction (reduction of copper sulfate to brick-red cuprous oxide by glucose and/or derivatives). Samples considered suspect were submitted to GC-MS analysis for identification of HES. The method was successfully applied for screening of HES in 2627 urine samples from 1346 Brazilian soccer players and 1281 athletes from the Pan-American Games (Rio de Janeiro, 2007); 71 (2.7%) samples, considered suspect, were submitted to GC-MS, but no positive results were found. Moreover, a thin layer chromatography (TLC) method was adapted for visualisation of the characteristic band pattern of HES hydrolysis products. The results indicate that the methods are efficient and useful for the screening of HES in urine.


Assuntos
Dopagem Esportivo , Cromatografia Gasosa-Espectrometria de Massas/métodos , Derivados de Hidroxietil Amido/urina , Substitutos do Plasma/análise , Brasil , Humanos , Futebol , Esportes
20.
Oecologia ; 153(2): 353-64, 2007 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-17453251

RESUMO

Plant architecture is considered to affect herbivory intensity, but it is one of the least studied factors in plant-insect interactions, especially for gall-inducing insects. This study aimed to investigate the influence of plant architecture on the speciose fauna of gall-inducing insects associated with 17 species of Baccharis. Five architectural variables were evaluated: plant height, number of fourth-level shoots, biomass, average level and number of ramifications. The number of galling species associated with each host plant species was also determined. To test the effects of plant architecture on gall richness at the individual level, we used another data set where the number of fourth-level shoots and gall richness were determined for B. concinna, B. dracunculifolia, and B. ramosissima every 3 weeks during 1 year. The average similarity between host species based on gall fauna was low (9%), but plants with the same architectural pattern tended to support similar gall communities. The most important architectural trait influencing gall richness at the species level was the number of fourth-level shoots, which is indicative of the availability of plant meristems, a fundamental tissue for gall induction and development. This variable also showed a positive correlation with gall richness at the individual level. We propose that variations in gall richness among host species are driven by interspecific differences in plant architecture via availability of young, undifferentiated tissue, which is genetically controlled by the strength of the apical dominance. Plant architecture should have evolutionary consequences for gall communities, promoting insect radiation among architecturally similar plants through host shift and sympatric speciation. We also discuss the role of plant architecture in the global biogeography of gall-inducing insects.


Assuntos
Baccharis/parasitologia , Biodiversidade , Insetos , Meristema/fisiologia , Tumores de Planta/parasitologia , Animais , Baccharis/anatomia & histologia , Baccharis/fisiologia
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