In this work, the combination of dispersive micro solid-phase extraction (DµSPE) with laser-induced breakdown spectroscopy (LIBS) was evaluated for simultaneous preconcentration and detection of Zn, ...Cd, Mn, Ni, Cr and Pb in aqueous samples. Two adsorbent materials were tested in the microextraction step, namely graphene oxide and activated carbon. In both cases, the microextraction process consisted in the dispersion of a small quantity of adsorbent in the sample solution containing the analytes. However, while the use of activated carbon required a previous chelation of the metals, this step was avoided with the use of graphene oxide. After extraction, the analytes retained in the adsorbents were analysed by LIBS. Several experimental factors affecting the extraction of the metals (adsorbent amount, pH and extraction time) were optimized by means of the traditional univariate approach. Under optimum microextraction conditions, the analytical features of the proposed DµSPE-LIBS methods were assessed, leading to limits of detection below 100 µg kg−1 and 50 µg kg−1 with the use of activated carbon and graphene oxide, respectively, as adsorbents in the DµSPE process. Trueness evaluation of the most sensitive procedure was carried out by spike and recovery experiments in a real sample of tap water, leading to recovery values in the range 98–110%.
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•DµSPE-LIBS, using graphene oxide as sorbent, has been evaluated for the first time.•Several metals in liquid samples has been detected at µg Kg−1 level by LIBS.•Metal chelation step has been avoided with the use of graphene oxide.•Graphene oxide provides superior analytical capabilities than activated carbon.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
The combination of electrospray deposition with laser-induced breakdown spectroscopy (ESD-LIBS) was investigated as a potential approach to the detection and quantification of Zn, Cd, Cr and Ni, at ...trace levels, in aqueous samples. In this analytical procedure, the aqueous samples were first converted into solids in an electrospray system. To this end, micro-volumes of liquids were electro-sprayed onto a heated substrate, leading to the generation of solid residues. Afterwards, the as-obtained residues were analysed by LIBS. Three calibration methodologies were tested with the proposed ESD-LIBS methodology, namely external calibration, conventional standard addition calibration and on-line standard addition calibration. In all cases, the analytical features of the ESD-LIBS method were assessed. The obtained limits of detection ranged from 9 μg kg
−1
to 57 μg kg
−1
, depending on the element and on the calibration modality used. Method trueness, evaluated from the analysis of a real sample of tap water, was highly dependent on the calibration method. The use of external calibration led to recovery values in the range of 18-123%, indicating the existence of strong matrix effects. This drawback was overcome with the application of conventional standard addition and on-line standard addition calibration modalities, for which recovery values were improved to the ranges 91-110% and 90-105%, respectively. Among them, the use of on-line standard addition provides a sensitive and accurate methodology with possibilities of automation.
Hyphenation of electrospray deposition with laser-induced breakdown spectroscopy as an alternative approach for sensitive elemental analysis of liquids with high possibilities of automation.
Alors que les approches de métabolomique sont de plus en plus utilisées pour identifier de nouveaux biomarqueurs associés à des risques de développer certaines pathologies, les valeurs de référence ...de nombreux métabolites plasmatiques restent encore à établir. L’objectif de cette étude est de définir le métabolome normal dans une population d’individus sains. Huit cent quatre-vingt-cinq volontaires sains âgés de 18 à 86 ans ont été inclus, avec un ratio hommes/femmes proche de 1, sans traitement médicamenteux, et considérés sains sur la base de leur histoire médicale, d’examens cliniques, de leur IMC et de dosages biologiques de routine. Nous avons quantifié 185 métabolites dont les acides aminés, 18 amines biogènes, 40 acyclcarnitines, 76 phosphatidylcholines, 15 sphingomyélines et les hexoses, par spectrométrie de masse en tandem. Nous avons établi les valeurs de référence pour chacun des 185 métabolites mesurés. Par analyse en composante principale, nous avons identifié trois facteurs majeurs expliquant la variabilité du métabolome : le cholestérol plasmatique total, le genre et l’âge. Les individus avec les concentrations de cholestérol total les plus élevées avaient de plus fortes concentrations de sphingomyélines et de phosphatidylcholines. Les hommes avaient de plus fortes concentrations de créatinine, d’acides aminés ramifiés, et de lysophosphatidylcholines, mais de plus faibles concentrations de sphingomyélines et de phosphatidylcholines que les femmes. Les sujets âgés avaient de plus fortes concentrations de sphingomyélines et de phosphatidylcholines que les sujets jeunes. Cette étude descriptive menée sur une large population de sujets sains constitue un outil essentiel pour l’interprétation de nombreuses situations pathologiques.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
An analytical methodology based in the combination of Thin Film Microextraction with Laser-induced Breakdown Spectroscopy (TFME-LIBS) was investigated, for the first time, for detection of Cu, Cr, Ni ...and Pb in aqueous solutions. In this methodology, the analytes were extracted in a thin film of adsorbent material deposited on a solid support, which was introduced in the sample to analyse. After extraction, the analytes retained in the adsorbent were analysed by LIBS. In order to obtain adsorbent films useful for the microextraction step, two different experimental procedures for film generation, denoted as Drop Casting Deposition and Mould Deposition, were evaluated. In both cases, graphene oxide was used as adsorbent material. The mould deposition procedure was found to produce more homogeneous graphene oxide layers, leading to more uniform distribution of the adsorbed analytes on the graphene oxide surface. Experimental parameters affecting the TFME procedure, such as the adsorbent amount and extraction time, were studied. Under optimum microextraction conditions, the analytical figures of merit of the proposed TFME-LIBS method were evaluated, leading to limits of detection ranging from 41 μg kg−1 and 52 μg kg−1. Method trueness, evaluated from the analysis of a real sample of bottle water, led to recovery values about 70%, indicating the existence of strong matrix effects probably due to the presence of major cations in the bottle water. After 50% dilution of the sample with deionized water, recoveries values improved to 100%–108%.
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•TFME-LIBS, using graphene oxide as adsorbent, has been evaluated for the first time.•Thin Film microextraction is an easily automated procedure reducing the sample handling.•Several metals in liquid samples has been detected at μg kg−1 level by LIBS.•Metal chelation step has been avoided with the use of graphene oxide.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
In this work, a solid phase microextraction procedure, denoted as Thin Film Microextraction (TFME), was combined with Laser-induced Breakdown Spectroscopy for the detection of several analytes in ...aqueous solutions (Cu, Cr, Ni and Pb). The adsorbent films, consisting of a thin layer of graphene oxide deposited on glass substrates, were generated by using the electrospray deposition technique (ESD). Several parameters affecting the quality and shape of the films resulting from the ESD process were studied, and the morphology and adsorption capacity of the films were evaluated. The generated films were used for extraction of the target analytes from aqueous solutions and, after extraction, the analytes-enriched adsorbents were analysed by LIBS without the need of any desorption or elution step. In order to assess the analytical capability of the TFME-LIBS procedure, different analytical figures of merit of the proposed TFME-LIBS methodology were evaluated. The obtained limits of detection were 14 μg kg−1 for Pb and 15 μg kg−1 for the rest of the tested analytes. Measurement repeatability was better than 4% RSD at low concentration level (20 μg kg−1) but deteriorated by increasing the concentration level at 100 μg kg−1, with %RSD ranging from 3.6% (Cr) to 24% (Pb). Method trueness, evaluated from the analysis of a real sample of bottled water, led to recovery values in the range 85%–106%.
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•TFME is an easily automated procedure reducing the sample handling.•ESD is able to generate homogeneous and reproducible graphene oxide thin films.•With ESD-generated GO films, TFME-LIBS combination allows μg kg−1 level detection.•The developed TFME-LIBS method has possibilities for automation.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
A new method to tag the barium daughter in the double-beta decay of ^{136}Xe is reported. Using the technique of single molecule fluorescent imaging (SMFI), individual barium dication (Ba^{++}) ...resolution at a transparent scanning surface is demonstrated. A single-step photobleach confirms the single ion interpretation. Individual ions are localized with superresolution (∼2 nm), and detected with a statistical significance of 12.9σ over backgrounds. This lays the foundation for a new and potentially background-free neutrinoless double-beta decay technology, based on SMFI coupled to high pressure xenon gas time projection chambers.
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CMK, CTK, FMFMET, IJS, NUK, PNG, UL, UM
The partition of the energy release rate of beam-like geometries is analyzed here. Several methods for partitioning mode I and II energy release rates are presented and critically compared. A ...Timoshenko beam theory with Dugdale cohesive stress is applied and results show a mixed mode energy release rate dependence on the interface fracture toughness. A geometry is proposed that eliminates this dependence, offering a method to characterize the fracture properties of interfaces between dissimilar materials.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Purpose
The aim of this study was to evaluate the clinical outcome at 5-year follow-up of a one-step procedure combining anterior cruciate ligament (ACL) reconstruction and partial meniscus ...replacement using a polyurethane scaffold for the treatment of symptomatic patients with previously failed ACL reconstruction and partial medial meniscectomy. Moreover, the implanted scaffolds have been evaluated by MRI protocol in terms of morphology, volume, and signal intensity.
Methods
Twenty patients with symptomatic knee laxity after failed ACL reconstruction and partial medial meniscectomy underwent ACL revision combined with polyurethane-based meniscal scaffold implant. Clinical assessment at 2- and 5-year follow-ups included VAS, Tegner Activity Score, International Knee Documentation Committee (IKDC), Western Ontario and McMaster Universities Osteoarthritis Index (WOMAC), and the Lysholm Score. MRI evaluation of the scaffold was performed according to the Genovese scale with quantification of the scaffold’s volume at 1- and 5-year follow-ups.
Results
All scores revealed clinical improvement as compared with the preoperative values at the 2- and 5-year follow-ups. However, a slight, but significant reduction of scores was observed between 2 and 5 years. Concerning the MRI assessment, a significant reduction of the scaffold’s volume was observed between 1 and 5 years. Genovese Morphology classification at 5 years included two complete resorptions (Type 3) and all the remaining patients had irregular morphology (Type 2). With regard to the Genovese Signal at the 5-year follow-up, three were classified as markedly hyperintense (Type 1), 15 as slightly hyperintense (Type 2), and two as isointense (Type 1).
Conclusion
Simultaneous ACL reconstruction and partial meniscus replacement using a polyurethane scaffold provides favourable clinical outcomes in the treatment of symptomatic patients with previously failed ACL reconstruction and partial medial meniscectomy at 5 years. However, MRI evaluation suggests that integration of the scaffold is not consistent.
Level of evidence
Level IV.
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EMUNI, FSPLJ, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
This work aims at the characterization of a modern concrete material. For this purpose, we perform two experimental series of inverse planar plate impact (PPI) tests with the ultra-high performance ...concrete B4Q, using two different witness plate materials. Hugoniot data in the range of particle velocities from 180 to 840 m/s and stresses from 1.1 to 7.5 GPa is derived from both series. Within the experimental accuracy, they can be seen as one consistent data set. Moreover, we conduct corresponding numerical simulations and find a reasonably good agreement between simulated and experimentally obtained curves. From the simulated curves, we derive numerical Hugoniot results that serve as a homogenized, mean shock response of B4Q and add further consistency to the data set. Additionally, the comparison of simulated and experimentally determined results allows us to identify experimental outliers. Furthermore, we perform a parameter study which shows that a significant influence of the applied pressure dependent strength model on the derived equation of state (EOS) parameters is unlikely. In order to compare the current results to our own partially reevaluated previous work and selected recent results from literature, we use simulations to numerically extrapolate the Hugoniot results. Considering their inhomogeneous nature, a consistent picture emerges for the shock response of the discussed concrete and high-strength mortar materials. Hugoniot results from this and earlier work are presented for further comparisons. In addition, a full parameter set for B4Q, including validated EOS parameters, is provided for the application in simulations of impact and blast scenarios.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
Marine planktonic protists are critical components of ocean ecosystems and are highly diverse. Molecular sequencing methods are being used to describe this diversity and reveal new associations and ...metabolisms that are important to how these ecosystems function. We describe here the use of the single cell genomics approach to sample and interrogate the diversity of the smaller (pico- and nano-sized) protists from a range of oceanic samples. We created over 900 single amplified genomes (SAGs) from 8 Tara Ocean samples across the Indian Ocean and the Mediterranean Sea. We show that flow cytometric sorting of single cells effectively distinguishes plastidic and aplastidic cell types that agree with our understanding of protist phylogeny. Yields of genomic DNA with PCR-identifiable 18S rRNA gene sequence from single cells was low (15% of aplastidic cell sorts, and 7% of plastidic sorts) and tests with alternate primers and comparisons to metabarcoding did not reveal phylogenetic bias in the major protist groups. There was little evidence of significant bias against or in favor of any phylogenetic group expected or known to be present. The four open ocean stations in the Indian Ocean had similar communities, despite ranging from 14°N to 20°S latitude, and they differed from the Mediterranean station. Single cell genomics of protists suggests that the taxonomic diversity of the dominant taxa found in only several hundreds of microliters of surface seawater is similar to that found in molecular surveys where liters of sample are filtered.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
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