Comparison between a linear ion trap and a triple quadruple MS in the sensitive detection of large peptides at femtomole amounts on column.

In addition to the importance of sample preparation and extract separation, MS detection is a key factor in the sensitive quantification of large undigested peptides. In this article, a linear ion trap MS (LIT-MS) and a triple quadrupole MS (TQ-MS) have been compared in the detection of large peptides at subnanomolar concentrations. Natural brain natriuretic peptide, C-peptide, substance P and D-Junk-inhibitor peptide, a full D-amino acid therapeutic peptide, were chosen. They were detected by ESI and simultaneous MS(1) and MS(2) acquisitions. With direct peptide infusion, MS(2) spectra revealed that fragmentation was peptide dependent, milder on the LIT-MS and required high collision energies on the TQ-MS to obtain high-intensity product ions. Peptide adsorption on surfaces was overcome and peptide dilutions ranging from 0.1 to 25 nM were injected onto an ultra high-pressure LC system with a 1 mm id analytical column and coupled with the MS instruments. No difference was observed between the two instruments when recording in LC-MS(1) acquisitions. However, in LC-MS(2) acquisitions, a better sensitivity in the detection of large peptides was observed with the LIT-MS. Indeed, with the three longer peptides, the typical fragmentation in the TQ-MS resulted in a dramatic loss of sensitivity (> or = 10x).

A LC-tandem MS assay for the simultaneous measurement of new antiretroviral agents: Raltegravir, maraviroc, darunavir, and etravirine.

Raltegravir (RAL), maraviroc (MVC), darunavir (DRV), and etravirine (ETV) are new antiretroviral agents with significant potential for drug interactions. This work describes a sensitive and accurate liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the determination of plasma drug levels. Single-step extraction of RAL, MVC, DRV, ETV and RTV from plasma (100 microl) is performed by protein precipitation using 600 microl of acetonitrile, after the addition of 100 microl darunavir-d(9) (DRV-d(9)) at 1000 ng/ml in MeOH/H(2)O 50/50 as internal standard (I.S.). The mixture is vortexed, sonicated for 10 min, vortex-mixed again and centrifuged. An aliquot of supernatant (150 microl) is diluted 1:1 with a mixture of 20 mM ammonium acetate/MeOH 40/60 and 10 microl is injected onto a 2.1 x 50 mm Waters Atlantis-dC18 3 microm analytical column. Chromatographic separations are performed using a gradient program with 2 mM ammonium acetate containing 0.1% formic acid and acetonitrile with 0.1% formic acid. Analytes quantification is performed by electrospray ionisation-triple quadrupole mass spectrometry using the selected reaction monitoring detection in the positive mode. The method has been validated over the clinically relevant concentrations ranging from 12.5 to 5000 ng/ml, 2.5 to 1000 ng/ml, 25 to 10,000 ng/ml, 10 to 4000 ng/ml, and 5 to 2000 ng/ml for RAL, MRV, DRV, ETV and RTV, respectively. The extraction recovery for all antiretroviral drugs is always above 91%. The method is precise, with mean inter-day CV% within 5.1-9.8%, and accurate (range of inter-day deviation from nominal values -3.3 to +5.1%). In addition our method enables the simultaneous assessment of raltegravir-glucuronide. This is the first analytical method allowing the simultaneous assay of antiretroviral agents targeted to four different steps of HIV replication. The proposed method is suitable for the Therapeutic Drug Monitoring Service of these new regimen combinations administered as salvage therapy to patients having experienced treatment failure, and for whom exposure, tolerance and adherence assessments are critical.

Ensenyar a llegir i escriure i més hores de castellà. Com ho farem?

La LOCE i els decrets que la complementen estableixen que en el primer cicle de primària, els cursos en què s'aprèn a llegir i escriure, s'han impartir quatre hores setmanals de castellà. En aquest article s'analitzen les repercussions d¿aquesta mesura en el procés d'aprenentatge de la lectura i l'escriptura i en la consecució de l'objectiu lingüístic final del sistema educatiu a Catalunya (garantir el coneixement de les dues llengües oficials). La discussió gira entorn de tres eixos: la diversitat de coneixements lingüístics de l'alumnat que aprèn a llegir i escriure en una mateixa aula, la integració de l'ensenyament de la lectura i l'escriptura en les activitats que es desenvolupen al llarg de la jornada escolar, i la constatació que els infants aprenen a llegir i escriure en les llengües que fan servir els adults quan interaccionen amb ells, encara que els nens no les parlin correctament.

Comparative study of the LC-MS/MS and UPLC-MS/MS for the multi-residue analysis of quinolones, penicillins and cephalosporins in cow milk, and validation according to the regulation 2002/657/EC

The aim of this study was to develop and validate an analytical method to simultaneously determine European Union-regulated beta-lactams (penicillins and cephalosporins) and quinolones in cow milk. The procedure involves a new solid phase extraction (SPE) to clean-up and pre-concentrate the three series of antibiotics before analysis by liquid chromatography¿tandem mass spectrometry (LC-MS/MS) and ultra-high-performance liquid chromatography¿tandem mass spectrometry (UPLC-MS/MS). LC-MS/MS and UPLC-MS/MS techniques were also compared. The method was validated according to the Directive 2002/657/EC and subsequently applied to 56 samples of raw cow milk supplied by the Laboratori Interprofessional Lleter de Catalunya (ALLIC) (Laboratori Interprofessional Lleter de Catalunya, Control Laboratory Interprofessional of Milk of Catalunya).

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.

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.

Perdas do nitrogênio da uréia no sistema solo-planta em dois ciclos de cana-de-açúcar

O objetivo deste trabalho foi quantificar as perdas de N do sistema solo-cana-de-açúcar, nos ciclos de cana-planta e de cana-soca. Desenvolveram-se dois experimentos em vasos de 220 L, contendo solo de classe textural arenosa. Os fatores de estudo do experimento com cana-planta foram dois tipos de restos culturais incorporados ao solo e quatro doses de N no plantio. No experimento com cana-soca, estudaram-se duas formas de aplicação da uréia em superfície: sobre a palha ou sobre o solo descoberto, ou na profundidade de 15 cm, e duas fontes de K: KCl ou vinhaça. Utilizou-se uréia marcada com 15N. O delineamento experimental foi o de blocos ao acaso, com três repetições. Em cana-planta, as perdas foram de 12% do N-uréia (recuperação de 88%), que ocorreram, principalmente, por desnitrificação no solo. Em cana-soca, a aplicação da uréia em profundidade resultou em 81% de recuperação do N-fertilizante, enquanto na superficial, somente em 50%. Perdas de 50% do N-uréia aplicado em superfície representam aquelas que ocorreram no solo, principalmente, por volatilização de amônia, e, também, pela parte aérea da cana-de-açúcar. Com aplicação em profundidade, as perdas foram de 19% e se deram pela parte aérea das plantas para a atmosfera, sendo a perda total de N (da uréia e de outras fontes) assimilado pela cultura da ordem de 90 kg ha-1.

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.

Perdas de solo, nutrientes, matéria orgânica e efeitos microestruturais em Argissolo Vermelho-Amarelo sob chuva simulada

Estudo experimental com simulador de chuva foi conduzido em área de Argissolo Vermelho-Amarelo caulinítico, em Viçosa, MG, com intensidade de precipitação de 60 mm h-1 e seis aplicações sucessivas, espaçadas de 12 horas. Caracterizou-se a evolução do selamento superficial e das perdas de nutrientes, solo e matéria orgânica em razão de diferentes porcentagens de cobertura (0, 20, 40, 80 e 100%) em cultivo morro abaixo (declividade média de 9,5%), em resposta à energia cinética decorrente da precipitação. As perdas totais de solo foram superiores a 11 t ha-1 nos tratamentos com porcentagem de cobertura entre 0 e 40%, reduzindo-se a pouco mais de 5 t ha-1 com 80% até zero no tratamento 100% coberto com Bidim. As perdas de nutrientes seguiram a ordem Ca>Mg>K>P e foram correlacionadas às perdas de matéria orgânica. O fracionamento de substâncias húmicas revelou a concentração residual de humina e perdas seletivas de formas mais solúveis (ácidos fúlvicos) com a enxurrada. A erosão causou heterogeneidade entre a parte superior e inferior das parcelas experimentais. A macroporosidade entre 10 e 20 cm é maior na parte superior da parcela, sugerindo a migração de argila dispersa e entupimento de macroporos nas condições de chuva simulada. Excetuando-se o tratamento com 100% de cobertura, todos os demais evidenciam crosta deposicional. Nos tratamentos com maior exposição houve presença de crosta erosional, ao fim do teste de campo.

¿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.