A comparative study of ballpoint ink ageing parameters using GC/MS

For more than a decade scientists tried to develop methods capable of dating ink by monitoring the loss of phenoxyethanol (PE) over time. While many methods were proposed in the literature, few were really used to solve practical cases and they still raise much concern within the scientific community. In fact, due to the complexity of ink drying processes it is particularly difficult to find a reliable ageing parameter to reproducibly follow ink ageing. Moreover, systematic experiments are required in order to evaluate how different factors actually influence the results over time. Therefore, this work aimed at evaluating the capacity of four different ageing parameters to reliably follow ink ageing over time: (1) the quantity of solvent PE in an ink line, (2) the relative peak area (RPA) normalising the PE results using stable volatile compounds present in the ink formulation, (3) the solvent loss ratio (R%) calculated from PE results obtained by the analyses of naturally and artificially aged samples, (4) a modified solvent loss ratio version (R%*) calculated from RPA results. After the determination of the limits of reliable measurements of the analytical method, the repeatability of the different ageing parameters was evaluated over time, as well as the influence of ink composition, writing pressure and storage conditions on the results. Surprisingly, our results showed that R% was not the most reliable parameter, as it showed the highest standard deviation. Discussion of the results in an ink dating perspective suggests that other proposed parameters, such as RPA values, may be more adequate to follow ink ageing over time.

LC-MS/MS based assay and reference intervals in children and adolescents for oxysterols elevated in Niemann-Pick diseases.

BACKGROUND: Niemann-Pick type C (NP-C) is a rare progressive neurodegenerative lipid storage disorder with heterogeneous clinical presentation and challenging diagnostic procedures. Recently oxysterols have been reported to be specific biomarkers for NP-C but knowledge on the intra-individual variation and on reference intervals in children and adolescents are lacking. METHODS: We established a LC-MS/MS assay to measure Cholestane-3β, 5α, 6β-triol (C-triol) and 7-Ketocholesterol (7-KC) following Steglich esterification. To assess reference intervals and intra-individual variation we determined oxysterols in 148 children and adolescents from 0 to 18 years and repeat measurements in 19 of them. RESULTS: The reported method is linear (r>0.99), sensitive (detection limit of 0.03 ng/mL [0.07 nM] for C-triol, and 0.54 ng/mL [1.35 nM] for 7-KC) and precise, with an intra-day imprecision of 4.8% and 4.1%, and an inter-day imprecision of 7.0% and 11.0% for C-triol (28 ng/ml, 67 nM) and 7-KC (32 ng/ml, 80 nM), respectively. Recoveries for 7-KC and C-triol range between 93% and 107%. The upper reference limit obtained for C-triol is 40.4 ng/mL (95% CI: 26.4-61.7 ng/mL, 96.0 nM, 95% CI: 62.8-146.7 nM) and 75.0 ng/mL for 7-KC (95% CI: 55.5-102.5 ng/mL, 187.2 nM, 95% CI: 138.53-255.8 nM), with no age or gender dependency. Both oxysterols have a broad intra-individual variation of 46%±23% for C-triol and 52%±29% for 7-KC. Nevertheless, all Niemann-Pick patients showed increased C-triol levels including Niemann-Pick type A and B patients. CONCLUSIONS: The LC-MS/MS assay is a robust assay to quantify C-triol and 7-KC in plasma with well documented reference intervals in children and adolescents to screen for NP-C in the pediatric population. In addition our results suggest that especially the C-triol is a biomarker for all three Niemann-Pick diseases.

High Throughput Purification of Combinatorial Libraries by Preparative LC/MS

Viime vuosien nopea kehitys on kiihdyttänyt uusien lääkkeiden kehittämisprosessia. Kombinatorinen kemia on tehnyt mahdolliseksi syntetisoida suuria kokoelmia rakenteeltaan toisistaan poikkeavia molekyylejä, nk. kombinatorisia kirjastoja, biologista seulontaa varten. Siinä molekyylien rakenteeseen liittyvä aktiivisuus tutkitaan useilla erilaisilla biologisilla testeillä mahdollisten "osumien" löytämiseksi, joista osasta saatetaan myöhemmin kehittää uusia lääkeaineita. Jotta biologisten tutkimusten tulokset olisivat luotettavia, on syntetisoitujen komponenttien oltava mahdollisimman puhtaita. Tämän vuoksi tarvitaan HTP-puhdistusta korkealaatuisten komponenttien ja luotettavan biologisen tiedon takaamiseksi. Jatkuvasti kasvavat tuotantovaatimukset ovat johtaneet näiden puhdistustekniikoiden automatisointiin ja rinnakkaistamiseen. Preparatiivinen LC/MS soveltuu kombinatoristen kirjastojen nopeaan ja tehokkaaseen puhdistamiseen. Monet tekijät, esimerkiksi erotuskolonnin ominaisuudet sekä virtausgradientti, vaikuttavat preparatiivisen LC/MS puhdistusprosessin tehokkuuteen. Nämä parametrit on optimoitava parhaan tuloksen saamiseksi. Tässä työssä tutkittiin emäksisiä komponentteja erilaisissa virtausolosuhteissa. Menetelmä kombinatoristen kirjastojen puhtaustason määrittämiseksi LC/MS-puhdistuksen jälkeen optimoitiin ja määritettiin puhtaus joillekin komponenteille eri kirjastoista ennen puhdistusta.

Un món amb més de mil sexes

En els animals i les plantes, hi ha espècies en què la sexualitat és molt complexa, fins al punt que trenquen amb la divisió en dos sexes que regna en la biologia dels éssers humans

Descripción del ms. 80 de la Zawiyya Hamzawiyya

La Zawiya Hamzawiya forma parte de las bibliotecas marroquíes descritas en les bibliothéques au Maro por Latifa Benjelloun-Larouil. Anteriormente, Mutrammad al-Mannünt había publicado un inventario de los fondos de la biblioteca entre los que se hace referencia al manuscrito 80 aunque sin especificar todo su contenido. En este mismo artículo introducía un resumen de la historia de la ZÁvwya haciendo hincapié en los principales copistas que trabajaron en ella, así como en las expediciones locales y extranjeras que consultaron sus manuscritos.

Més noticies a l'entorn del període americà de Josep Pijoan Soteras (1881-1963)

[cat]El coneixement de la trajectòria dels catalans exiliats, com és el cas de Josep Pijoan Soteras, Francesc Cambó Batlle i Josep Gudiol Ricart, entre altres, és fascinant perquè permet comprendre i valorar el seu itinerari personal, alhora que projecta un dramàtic resplendor sobre la cultura catalana de l"època. En aquest article es plantegen dues qüestions. La primera se centra en Pijoan com a agent d"art, aspecte molt poc conegut fi ns ara; mentre que en la segona part tracta de Pijoan com a escriptor d"art i la problemàtica que es va produir amb motiu de la seva intervenció en el llibre Les pintures romàniques de Catalunya dins la «Monumenta Cataloniae», col·lecció patrocinada per Francesc Cambó. [eng]Knowledge of the pathways of Catalan exiles -as in the case of Jose Pijoan Soteras, Francesc Cambó Batlle and Jose Gudiol Ricart, among others- is fascinating because it permits understanding and evaluation of their personal itineraires while at the same time casting a dramatic light on Catalan culture of the epoch. In this article two questions are presented: the first is centered on Pijoan as an art dealer, an aspect very little known until now, while the second deals with Pijoan as a writer on art and the problems raised by his participation in the book on Romanesque painters of Catalonia in the «Monumenta Cataloniae», the collection of whitch Francesc Cambó was patron.

Determination and characterization of quinolones in foodstuffs of animal origin by CE-UV, LC-UV, LC-Fl, LC-MS and LC-MS/MS

In this work methods for the multiresidue determination of the series of quinolones include in the European regulation in food of animal origin are de veloped and validated in line with Commission Decision 2002/657/EC in terms of linearity, decision limit, capability detection, precision and stability. Mult iresidue methods were established to allow the determination of quinolones covered by EU legislation in 2377/90/EC in muscle of chicken, turkey, pig and cow, plasma of cow and pig, liver of pig and milk of cow. First an extraction step was optimized and a SPE step was applied to clean!up and preconcentrate quinolones prior to their separation by CE or LC and determination by CE!UV, LC!UV, LC!Fl, LC!MS with different ion sources (ESI ,ApCI) and different mass analyser (Q, ToF) and LC!E SI!QqQ tandem mass spectrometry. The limits of quantification obtained are always lower than Maxim um Residue Limit (MRL) established by EU for quinolones in animal products and they can be applied to the control of quinolones in foodstuffs of animal origin . Finally the proposed methods were applied to determine quinolones in samples of turkey and pig muscle, pig plasma and milk of cow. Excellent quality parameters and reduced time of analysis were obtained when LC!ESI!MS/MS is used, although the others techniques presented too satisfactory results.

Disgenesia do corpo caloso e más-formações associadas: achados de tomografia computadorizada e ressonância magnética

O termo disgenesia do corpo caloso refere-se a uma má-formação deste com origem na embriogênese do telencéfalo. O relato analisa os achados de tomografia computadorizada e ressonância magnética em 11 pacientes com disgenesia calosa e em um caso de corpo caloso normal com lipoma associado. Esta pode ser distinguida em três grupos: agenesia total (três casos), agenesia parcial (seis casos) e hipoplasia (dois casos). Anomalias associadas foram observadas em nove casos, incluindo má-formação de Chiari tipo II (um caso), esquizencefalia (um caso), cisto inter-hemisférico (dois casos), heterotopia nodular (um caso), cisto de Dandy-Walker (um caso) e lipoma do corpo caloso (quatro casos). Este artigo demonstra um espectro destes distúrbios, auxiliando na sua interpretação diagnóstica.

El sentit de l'humor més agut s'amaga al cervell

Un estudi indica que les persones amb més matèria grisa en certes regions del cervell tenen una capacitat humorística més aguda i desenvolupada

El cervell bilingüe pren decisions més depressa

Diferents estudis mostren que les persones que parlen dues llengües són més àgils a l"hora de resoldre conflictes en què cal valorar diferents informacions de manera simultània

De Andrew Carnegie a OverDrive, Amazon y ¿algo más? Biblioteca pública y préstamo de libros digitales en Estados Unidos

Ressenya de: 2012 survey of ebook usage in U.S. public libraries: third annual survey. LJ/SLJ Library Research Syndicate (LRS). [New York, N.Y.]: Library Journal, 2012. 108 p. Disponible en línia a: [Consulta: 27 feb. 2013].

DogsON : Aplicació mòbil Android per descobrir les àrees canines més properes i conèixer els gossos que hi ha en temps real

Aquest projecte final de postgrau tracta sobre el desenvolupament de DogsON, una aplicació mòbil per ajudar a les persones que tenen gossos a evitar que el seu gos estigui sol durant les seves hores d'esplai en les àrees canines i parcs habilitats.

(MA)LDI MS Imaging at High Specificity and Sensitivity

(Matrix-assisted) laser desorption/ionization ((MA)LDI) mass spectrometry imaging (MSI) has been driven by remarkable technological developments in the last couple of years. Although molecular information of a wide range of molecules including peptides, lipids, metabolites, and xenobiotics can be mapped, (MA)LDI MSI only leads to the detection of the most abundant soluble molecules in the cells and, consequently, does not provide access to the least expressed species, which can be very informative in the scope of disease research. Within a short period of time, numerous protocols and concepts have been developed and introduced in order to increase MSI sensitivity, including in situ tissue chemistry and solvent-free matrix depositions. In this chapter, we will discuss some of the latest developments in the field of high-sensitivity MSI using solvent-free matrix depositions and will detail protocols of two methods with their capability of enriching molecular MSI signal as demonstrated within our laboratory.

Longitudinal monitoring of endogenous steroids in human serum by UHPLC-MS/MS as a tool to detect testosterone abuse in sports.

The detection of testosterone abuse in sports is routinely achieved through the 'steroidal module' of the Athlete Biological Passport by GC-MS(/MS) quantification of selected endogenous anabolic androgenic steroids (EAAS) from athletes' urines. To overcome some limitations of the "urinary steroid profile" such as the presence of confounding factors (ethnicity, enzyme polymorphism, bacterial contamination, and ethanol), ultrahigh performance liquid chromatography (UHPLC) measurements of blood concentrations of testosterone, its major metabolites, and precursors could represent an interesting and complementary strategy. In this work, two UHPLC-MS/MS methods were developed for the quantification of testosterone and related compounds in human serum, including major progestogens, corticoids, and estrogens. The validated methods were then used for the analyses of serum samples collected from 19 healthy male volunteers after oral and transdermal testosterone administration. Results from unsupervised multiway analysis allowed variations of target analytes to be assessed simultaneously over a 96-h time period. Except for alteration of concentration values due to the circadian rhythm, which concerns mainly corticosteroids, DHEA, and progesterone, significant variations linked to the oral and transdermal testosterone administration were observed for testosterone, DHT, and androstenedione. As a second step of analysis, the longitudinal monitoring of these biomarkers using intra-individual thresholds showed, in comparison to urine, significant improvements in the detection of testosterone administration, especially for volunteers with del/del genotype for phase II UGT2B17 enzyme, not sensitive to the main urinary marker, T/E ratio. A substantial extension of the detection window after transdermal testosterone administration was also observed in serum matrix. The longitudinal follow-up proposed in this study represents a first example of 'blood steroid profile' in doping control analysis, which can be proposed in the future as a complement to the 'urinary module' for improving steroid abuse detection capabilities.

Mantenimiento de catéteres venosos periféricos durante más de 4 dias. En busca de la mejor evidencia

Antecedentes: Desde 1981, los Centers for Disease Control and Prevention (CDC) recomiendan sustituir los catéteres venosos periféricos cada 3-4 días para disminuir el riesgo de flebitis, infección y bacteriemia de catéter. Objetivo: El objetivo de esta revisión sistemática es determinar la efectividad de esta intervención mediante la evaluación de la evidencia científica disponible. Material y método: Se realizó una exploración de diferentes bases de datos electrónicas y se revisaron manualmente varios índices desde 1981 a 200l. Para identificar los trabajos más relevantes y descartar los de menor calidad se empleó un sistema de evaluación cualitativa que permitió la discriminación de tres grupos de estudios, de mayor a menor calidad metodológica y, por tanto, de riesgo de sesgo. Resultados y conclusiones: De los originales captados, 12 fueron sometidos a valoración crítica. Un 33% se clasificó como metodológicamente insuficiente y un 41% obtuvo una puntuación intermedia, con lo que sus resultados debían interpretarse con cautela. Los trabajos cualitativamente más significativos no demuestran que sea necesario sustituir de forma rutinaria los catéteres venosos periféricos, como recomiendan los CDC.