Rapid sample pre-treatment prior to GC-MS and GC-MS/MS urinary toxicological screening.

Drug screening is an important issue in clinical and forensic toxicology. Gas chromatography coupled to mass spectrometry (GC-MS) remains the gold standard technique for the screening of unknown compounds in urine samples. However, this technique requires substantial sample preparation, which is time consuming. Moreover, some common drugs such as cannabis cannot be easily detected in urine using general procedures. In this work, a sample preparation protocol for treating 200 μL of urine in less than 30 min is described. The enzymatic hydrolysis of glucuro-conjugates was performed in 5 min thanks to the use of microwaves. The use of a deconvolution software allowed reducing the GC-MS run to 10 min, without impairing the quality of the compound identifications. Comparing the results from 139 authentic urine samples to those obtained using the current routine analysis indicated this method performed well. Moreover, additional 5-min GC-MS/MS programs are described, enabling a very sensitive target screening of 54 drugs, including THC-COOH or buprenorphine, without further sample preparation. These methods appeared as an interesting alternative to immuno-assays based screening. The analytical strategy presented in this article proved to be a promising approach for systematic toxicological analysis (STA) of drugs in urine.

Vitamin D deficiency: A forgotten treatable cause of motor delay and proximal myopathy.

We report a four-year-old African boy referred for proximal muscle weakness, fatigability and episodic limb pain. Classical causes of structural and metabolic myopathy were initially considered before clinical and biological features of vitamin D deficiency rickets were identified. Prompt treatment with vitamin D and calcium supplementation led to a complete reversal of the muscle symptoms. Rickets-associated myopathy should be included in the differential diagnosis of proximal myopathy, especially in at-risk individuals. Vitamin D deficiency and its prevention remain important health issues in industrialized countries.

L’alguer de Posidonia oceanica de les illes Medes: més de trenta anys d’estudi

Fins on hem pogut esbrinar, el primer estudi publicat en una revista científica sobre la praderia o alguer de Posidonia oceanica de les illes Medes és el de De Haro (1965). En aquella època, la investigació delsfons marins estava als seus inicis i probablement la praderia de les illes Medes va ser un dels primers llocs en què, amb mitjans força precaris i a càrrec d’uns joves estudiants, es van efectuar prospeccions en immersió, tècnica que tot just començava però que molt ràpidament havia de substituir les dragues ialtres artefactes menys fiables. Amb el Programa de Bentos, entre 1972-1974 (Ros, 1982) –precisament aquest autor (vegeu el capítol 1) era un d’aquells «joves estudiants»; l’altre era en Jordi Camp, actualment investigador del CSIC–, la recerca bentònica va agafar un primer impuls i l’escafandre autònom es va incorporar plenament com a eina d’observació i mostreig. Durant aquest programa, es va situar una de les estacions de treball a les illes Medes, i l’alguer de Posidonia va ser un dels hàbitats objecte d’estudi, tot i que més aviat amb un objectiu faunístic i biocenòtic que estrictament ecològic.

Los adhesivos empleados en el entelado de carteles modernos. Uso de la Espectrometría de Masas de Ionización/Desorción por Láser asistida por Matriz y analizador de Tiempo de Vuelo (MALDI-TOF-MS) para la identificación de éteres de celulosa

"XVIII Congreso Internacional de Conservación y Restauración de Bienes Culturales - 18th International Meeting on Heritage Conservation", Granada 9 al 11 novembre de 2011

Influência da época de semeadura no comportamento de cultivares de arroz irrigado por aspersão em Selvíria, MS

Este trabalho teve por objetivo avaliar os efeitos da época da semeadura no comportamento de diferentes cultivares de arroz (Oryza sativa L.) de sequeiro (IAC 201, Carajás, Guarani, IAC 202, CNA 7800, CNA 7801, Caiapó, Rio Paranaíba e Araguaia) irrigados por aspersão, quanto à produção e qualidade dos grãos. As sementes foram semeadas no início da segunda quinzena dos meses de setembro, outubro, novembro, dezembro, janeiro e fevereiro. Os experimentos foram instalados no Município de Selvíria, MS, durante os anos agrícolas 1995/96 e 1996/97. O delineamento experimental utilizado foi o de blocos casualizados, com quatro repetições. O controle da irrigação foi realizado por meio de tensiômetros, e a suplementação hídrica foi realizada quando o potencial matricial atingiu -0,033 MPa, durante a fase reprodutiva e -0,058 MPa, nas demais fases. De acordo com os resultados obtidos, pode-se concluir que as cultivares CNA 7801, Carajás, IAC 201, CNA 7800 e IAC 202 apresentaram comportamento superior; a semeadura realizada em novembro propiciou produtividade mais elevada; semeaduras antecipadas (setembro-outubro) ou retardada (fevereiro) resultaram em menores índices de acamamento; as cultivares IAC 202, CNA 7800 e CNA 7801 apresentaram ausência ou baixo índice de acamamento, nas diferentes épocas de semeadura e, a semeadura retardada (fevereiro) proporcionou a obtenção de maior rendimento de inteiros.

Tire traces: discrimination and classification of pyrolysis-GC/MS profiles

Tire traces can be observed on several crime scenes as vehicles are often used by criminals. The tread abrasion on the road, while braking or skidding, leads to the production of small rubber particles which can be collected for comparison purposes. This research focused on the statistical comparison of Py-GC/MS profiles of tire traces and tire treads. The optimisation of the analytical method was carried out using experimental designs. The aim was to determine the best pyrolysis parameters regarding the repeatability of the results. Thus, the pyrolysis factor effect could also be calculated. The pyrolysis temperature was found to be five time more important than time. Finally, a pyrolysis at 650 °C during 15 s was selected. Ten tires of different manufacturers and models were used for this study. Several samples were collected on each tire, and several replicates were carried out to study the variability within each tire (intravariability). More than eighty compounds were integrated for each analysis and the variability study showed that more than 75% presented a relative standard deviation (RSD) below 5% for the ten tires, thus supporting a low intravariability. The variability between the ten tires (intervariability) presented higher values and the ten most variant compounds had a RSD value above 13%, supporting their high potential of discrimination between the tires tested. Principal Component Analysis (PCA) was able to fully discriminate the ten tires with the help of the first three principal components. The ten tires were finally used to perform braking tests on a racetrack with a vehicle equipped with an anti-lock braking system. The resulting tire traces were adequately collected using sheets of white gelatine. As for tires, the intravariability for the traces was found to be lower than the intervariability. Clustering methods were carried out and the Ward's method based on the squared Euclidean distance was able to correctly group all of the tire traces replicates in the same cluster than the replicates of their corresponding tire. Blind tests on traces were performed and were correctly assigned to their tire source. These results support the hypothesis that the tested tires, of different manufacturers and models, can be discriminated by a statistical comparison of their chemical profiles. The traces were found to be not differentiable from their source but differentiable from all the other tires present in the subset. The results are promising and will be extended on a larger sample set.

Identificació de les competències més valorades en l'entorn professional i adequació del pla d'estudis de grau en enginyeria informàtica

L'execució d'aquest projecte ha volgut reflectir quines són les capacitats professionals més valorades actualment, poder entendre quines són les condicions actuals i reflexionar sobre quina és la cobertura que els plans educatius actuals -en l'àmbit de l'enginyeria informàtica- brinden a aquesta evolució, contribuint amb aquest estudi a l'objectiu general de l'àrea de competències professionals d'apropar el món acadèmic al laboral.

¿Y después del trabajo, qué? Más allá de la integración laboral de las personas con discapacidad = What happens after work? Going further than labour integration for disabled people

La actividad profesional es fundamental en la vida de cualquier persona y en el caso de las que padecen una discapacidad tiene una gran importancia para contribuir a configurar su identidad adulta. En este sentido, la finalidad del artículo es valorar la importancia del trabajo en los procesos de participación social y de calidad de vida de las personas con discapacidad. Por ello, en el artículo se pone de manifiesto la relación que se establece entre la dimensión laboral y la integración social de los individuos con discapacidad mediante el análisis de investigaciones desarrolladas en nuestro contexto, entre las que figuran diversos estudios realizados por nuestro grupo de investigación durante los últimos años. Con la voluntad de conocer con más detalle esta cuestión, se presenta una investigación reciente realizada por nuestro equipo. En ella desarrollamos un estudio de casos centrado en personas con discapacidad psíquica que han participado en experiencias de integración laboral en el mercado ordinario, con el objetivo de obtener información sobre la incidencia de la inserción laboral en diferentes dimensiones de la vida de los trabajadores con discapacidad. Los resultados nos permiten valorar que la experiencia genera cambios positivos, sobre todo a nivel personal (expectativas personales, potenciación del proyecto de vida, mejora de competencias…). Sin embargo, a pesar de que se aprecian mejoras en la dimensión social, el estudio plantea la necesidad de emprender acciones alternativas para potenciar la participación comunitaria de las personas implicadas en la investigación. El artículo concluye con algunas propuestas orientadas a mejorar los procesos de inserción social del colectivo

Optimization of HS-SPME/GC-MS analysis and its use in the profiling of illicit ecstasy tablets (Part 1)

A headspace solid-phase microextraction procedure (HS-SPME) was developed for the profiling of traces present in 3,4-methylenedioxymethylampethamine (MDMA). Traces were first extracted using HS-SPME and then analyzed by gas chromatography-mass spectroscopy (GC-MS). The HS-SPME conditions were optimized using varying conditions. Optimal results were obtained when 40 mg of crushed MDMA sample was heated at 80 °C for 15 min, followed by extraction at 80 °C for 15 min with a polydimethylsiloxane/divinylbenzene coated fibre. A total of 31 compounds were identified as traces related to MDMA synthesis, namely precursors, intermediates or by-products. In addition some fatty acids used as tabletting materials and caffeine used as adulterant, were also detected. The use of a restricted set of 10 target compounds was also proposed for developing a screening tool for clustering samples having close profile. 114 seizures were analyzed using an SPME auto-sampler (MultiPurpose Samples MPS2), purchased from Gerstel GMBH & Co. (Germany), and coupled to GC-MS. The data was handled using various pre-treatment methods, followed by the study of similarities between sample pairs based on the Pearson correlation. The results show that HS-SPME, coupled with the suitable statistical method is a powerful tool for distinguishing specimens coming from the same seizure and specimens coming from different seizures. This information can be used by law enforcement personnel to visualize the ecstasy distribution network as well as the clandestine tablet manufacturing.

Diagnostic delay in Crohn's disease is associated with a complicated disease course and increased operation rate.

OBJECTIVES: The impact of diagnostic delay (a period from appearance of first symptoms to diagnosis) on the clinical course of Crohn's disease (CD) is unknown. We examined whether length of diagnostic delay affects disease outcomes. METHODS: Data from the Swiss IBD cohort study were analyzed. Patients were recruited from university centers (68%), regional hospitals (14%), and private practices (18%). The frequencies of occurrence of bowel stenoses, internal fistulas, perianal fistulas, and CD-related surgery (intestinal and perianal) were analyzed. RESULTS: A total of 905 CD patients (53.4% female, median age at diagnosis 26 (20-36) years) were stratified into four groups according to the quartiles of diagnostic delay (0-3, 4-9, 10-24, and ≥25 months, respectively). Median diagnostic delay was 9 (3-24) months. The frequency of immunomodulator and/or antitumor necrosis factor drug use did not differ among the four groups. The length of diagnostic delay was positively correlated with the occurrence of bowel stenosis (odds ratio (OR) 1.76, P=0.011 for delay of ≥25 months) and intestinal surgery (OR 1.76, P=0.014 for delay of 10-24 months and OR 2.03, P=0.003 for delay of ≥25 months). Disease duration was positively associated and non-ileal disease location was negatively associated with bowel stenosis (OR 1.07, P<0.001, and OR 0.41, P=0.005, respectively) and intestinal surgery (OR 1.14, P<0.001, and OR 0.23, P<0.001, respectively). CONCLUSIONS: The length of diagnostic delay is correlated with an increased risk of bowel stenosis and CD-related intestinal surgery. Efforts should be undertaken to shorten the diagnostic delay.

On-line desorption of dried blood spot: A novel approach for the direct LC/MS analysis of micro-whole blood samples.

The aim of this work is to present a new concept, called on-line desorption of dried blood spots (on-line DBS), allowing the direct analysis of a dried blood spot coupled to liquid chromatography mass spectrometry device (LC/MS). The system is based on an inox cell which can receive a blood sample (10 microL) previously spotted on a filter paper. The cell is then integrated into LC/MS system where the analytes are desorbed out of the paper towards a column switching system ensuring the purification and separation of the compounds before their detection on a single quadrupole MS coupled to atmospheric pressure chemical ionisation (APCI) source. The described procedure implies that no pretreatment is necessary in spite the analysis is based on whole blood sample. To ensure the applicability of the concept, saquinavir, imipramine, and verapamil were chosen. Despite the use of a small sampling volume and a single quadrupole detector, on-line DBS allowed the analyses of these three compounds over their therapeutic concentrations from 50 to 500 ng/mL for imipramine and verapamil and from 100 to 1000 ng/mL for saquinavir. Moreover, the method showed good repeatability with relative standard deviation (RSD) lower than 15% based on two levels of concentration (low and high). Function responses were found to be linear over the therapeutic concentration for each compound and were used to determine the concentrations of real patient samples for saquinavir. Comparison of the founded values with those of a validated method used routinely in a reference laboratory showed a good correlation between the two methods. Moreover, good selectivity was observed ensuring that no endogenous or chemical components interfered with the quantitation of the analytes. This work demonstrates the feasibility and applicability of the on-line DBS procedure for bioanalysis.

The data treatment dependent variability of U-Pb zircon ages obtained using mono-collector, sector field, laser ablation ICP-MS

U-Pb dating of zircons by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) is a widely used analytical technique in Earth Sciences. For U-Pb ages below 1 billion years (1 Ga), Pb-206/U-238 dates are usually used, showing the least bias by external parameters such as the presence of initial lead and its isotopic composition in the analysed mineral. Precision and accuracy of the Pb/U ratio are thus of highest importance in LA-ICPMS geochronology. We consider the evaluation of the statistical distribution of the sweep intensities based on goodness-of-fit tests in order to find a model probability distribution fitting the data to apply an appropriate formulation for the standard deviation. We then discuss three main methods to calculate the Pb/U intensity ratio and its uncertainty in the LA-ICPMS: (1) ratio-of-the-mean intensities method, (2) mean-of-the-intensity-ratios method and (3) intercept method. These methods apply different functions to the same raw intensity vs. time data to calculate the mean Pb/U intensity ratio. Thus, the calculated intensity ratio and its uncertainty depend on the method applied. We demonstrate that the accuracy and, conditionally, the precision of the ratio-of-the-mean intensities method are invariant to the intensity fluctuations and averaging related to the dwell time selection and off-line data transformation (averaging of several sweeps); we present a statistical approach how to calculate the uncertainty of this method for transient signals. We also show that the accuracy of methods (2) and (3) is influenced by the intensity fluctuations and averaging, and the extent of this influence can amount to tens of percentage points; we show that the uncertainty of these methods also depends on how the signal is averaged. Each of the above methods imposes requirements to the instrumentation. The ratio-of-the-mean intensities method is sufficiently accurate provided the laser induced fractionation between the beginning and the end of the signal is kept low and linear. We show, based on a comprehensive series of analyses with different ablation pit sizes, energy densities and repetition rates for a 193 nm ns-ablation system that such a fractionation behaviour requires using a low ablation speed (low energy density and low repetition rate). Overall, we conclude that the ratio-of-the-mean intensities method combined with low sampling rates is the most mathematically accurate among the existing data treatment methods for U-Pb zircon dating by sensitive sector field ICPMS.