Sample pre-treatment and analytical methodology for the simultaneous determination of pharmaceuticals and personal care products in sewage sludge.

This work describes the design, optimization and validation of an analytical method for the simultaneous determination of 14 pharmaceuticals and personal care products (PPCPs) in sewage sludge. A thorough optimization of the sample pre-treatment was carried out. As a result, microwave-assisted extraction (MAE) was combined with an in-situ clean-up stage and a filtration step. A combination of MilliQ® water/MeOH 95:5 (v/v) adjusted to pH 9 turned out to be the optimal solvent mixture for extraction. The instrumental part of the method presents a significant novelty based on a fully automated sample preparation for the analysis of PPCPs. It consisted of a direct immersion solid phase microextraction followed by on-fiber derivatization, online coupled to gas chromatography - mass spectrometry (DI-SPME-On-fiber derivatization - GC-MS). An isotope dilution approach was used for quantifying, which conferred high reliability to the method. This methodology was validated for 10 compounds with good analytical performance, limit of detection below 20 ng g-1 and absolute recovery in the range of 30-70% for most of the compounds. It supposes an ecological analytical alternative for many routine analysis laboratories around the world. The developed method was applied to different real samples generated in both a pilot-scale thermal hydrolysis treatment plant and an anaerobic digester operated in mesophilic conditions. Salicylic acid and naproxen were found at concentrations above 1000 ng g-1.

Tailoring metal-dielectric nanocomposite materials with ultrashort laser pulses for dichroic color control.

Metal-dielectric nanocomposites are multiphase material systems containing nanostructures, whose size and arrangement determine the optical properties of the material, enabling the production of new materials with custom-designed response. In this paper, we exploit a femtosecond laser-based strategy to fabricate nanocomposites based on silver nanoparticles (Ag NPs) with tunable optical spectral response. We demonstrate how the spectral response, specifically color and dichroic response, is linked to Ag NPs growth and self-organization processes that are controlled locally by the choice of the laser irradiation parameters, such as scan speed and laser light polarization. When the scan speed increases, the Ag NPs are formed at larger depths below the film surface and give rise to the formation of embedded NPs gratings. As a result, the effective optical properties of the films are strongly modified enabling the display of a broad range of solid colors in the visible region. Furthermore, the choice of the laser light polarization allows to fabricate films either with iridescent or dichroic properties (linear polarization) or with non-diffractive and non-dichroic colors (circular polarization). Finally, the high spatial control over the transformed areas achieved with the laser processing, allows the building of hybrid nanostructures by means of interlacing structures with different optical responses. These results demonstrate the high potential of fs-laser technology to process Ag-based nanocomposites to fabricate coatings with a designed reflectivity, transmission, diffraction, as well as polarization anisotropy response. The Ag nanocomposites investigated in this work hold great promise for a broad range of applications especially for coloring, for enhanced visual effects, and for smart information encoding for security applications.

Analytical methodologies for the determination of pharmaceuticals and personal care products (PPCPs) in sewage sludge: A critical review.

Several analytical approaches have been developed for the determination of emerging pollutants (EPs), including pharmaceuticals and personal care products (PPCPs) in environmental matrices. This paper reviews the sample preparation and instrumental methods proposed in the last few years (2012-2018) to assess PPCPs in sewage sludge. Three main steps are examined: extraction, clean-up and analysis. Sample preparation is critical as target compounds are normally found at low concentrations in complex matrices. Most procedures include sewage sludge pretreatment mostly through ultrasound-assisted extraction (UAE) although other novel techniques such as QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) or MSPD (matrix solid-phase dispersion) have been also employed. In one report, no differences in extraction efficiency were detected among the most commonly used extraction techniques such as ultrasound, microwave and pressurized liquid. Clean-up usually involves a conventional method such as solid phase extraction (SPE). This step is needed to appreciably reduce matrix suppression, and is followed by an instrumental analysis using techniques of preference such as gas chromatography (GC) or liquid chromatography (LC), mostly coupled to mass spectrometry (MS). A fully automated on-line system that includes extraction, chromatographic separation, and mass spectrometry in one-stage is here presented as a novel way of determining PPCPs in sewage sludge. This review also discusses the advantages and limitations of the different techniques used. Miniaturizing analytical techniques and the use of novel solid and liquid phase materials are emerging as efficient options that fulfill the principles of so-called "green chemistry".

Femtosecond laser writing of photonic devices in borate glasses compositionally designed to be laser writable.

The design and performance of borate glass samples compositionally pre-designed to be femtosecond laser writable via laser-induced ion migration is reported in this Letter. It is demonstrated that borate glasses modified on purpose with small amounts of La2O3 and Na2O can be straightforwardly used to produce high-index contrast (Δn) waveguides by femtosecond-laser-assisted ion migration. The positive Δn of the waveguides is caused by the local enrichment of La2O3 in the guiding region with a slope of 8·10-3(mol.%)-1. The value of this is consistent with numerical aperture measurements of the waveguides and local compositional measurements at the guiding region performed by energy-dispersive x-ray micro-analysis. The maximum achievable Δn values can be controlled through the initial La2O3 content of the glass. Maximum Δn values >10-2 for samples with just 5.5 mol. % of La2O3 have been produced. This compositional design approach could be potentially used to produce highly efficient femtosecond laser writeable glasses in other glass families.

Memristive behaviour of Si-Al oxynitride thin films: the role of oxygen and nitrogen vacancies in the electroforming process.

The resistive switching properties of silicon-aluminium oxynitride (SiAlON) based devices have been studied. Electrical transport mechanisms in both resistance states were determined, exhibiting an ohmic behaviour at low resistance and a defect-related Poole-Frenkel mechanism at high resistance. Nevertheless, some features of the Al top-electrode are generated during the initial electroforming, suggesting some material modifications. An in-depth microscopic study at the nanoscale has been performed after the electroforming process, by acquiring scanning electron microscopy and transmission electron microscopy images. The direct observation of the devices confirmed features on the top electrode with bubble-like appearance, as well as some precipitates within the SiAlON. Chemical analysis by electron energy loss spectroscopy has demonstrated that there is an out-diffusion of oxygen and nitrogen ions from the SiAlON layer towards the electrode, thus forming silicon-rich paths within the dielectric layer and indicating vacancy change to be the main mechanism in the resistive switching.

SiGe layer thickness effect on the structural and optical properties of well-organized SiGe/SiO2 multilayers.

In this work, we report on the production of regular (SiGe/SiO2)20 multilayer structures by conventional RF-magnetron sputtering, at 350 °C. Transmission electron microscopy, scanning transmission electron microscopy, raman spectroscopy, and x-ray reflectometry measurements revealed that annealing at a temperature of 1000 °C leads to the formation of SiGe nanocrystals between SiO2 thin layers with good multilayer stability. Reducing the nominal SiGe layer thickness (t SiGe) from 3.5-2 nm results in a transition from continuous SiGe crystalline layer (t SiGe ∼ 3.5 nm) to layers consisting of isolated nanocrystals (t SiGe ∼ 2 nm). Namely, in the latter case, the presence of SiGe nanocrystals ∼3-8 nm in size, is observed. Spectroscopic ellipsometry was applied to determine the evolution of the onset in the effective optical absorption, as well as the dielectric function, in SiGe multilayers as a function of the SiGe thickness. A clear blue-shift in the optical absorption is observed for t SiGe ∼ 2 nm multilayer, as a consequence of the presence of isolated nanocrystals. Furthermore, the observed near infrared values of n = 2.8 and k = 1.5 are lower than those of bulk SiGe compounds, suggesting the presence of electronic confinement effects in the nanocrystals. The low temperature (70 K) photoluminescence measurements performed on annealed SiGe/SiO2 nanostructures show an emission band located between 0.7-0.9 eV associated with the development of interface states between the formed nanocrystals and surrounding amorphous matrix.

Flat-on lamellae in spin-coated, stable films of poly(propylene azelate).

Thin films (5-500 nm thick) of the linear aliphatic polyester (3,7) poly(propylene azelate) (PPAz) were prepared by spin-coating of CHCl(3) polymer solutions with different polymer concentrations. The morphology and structure of the spin-coated thin films were investigated by atomic force microscopy (AFM) and by grazing incidence wide-angle X-ray scattering (GIWAXS) techniques. AFM revealed the continuous nature of the flat, spherulitic films which are stable against dewetting even for polymer coatings as thin as 15 nm. GIWAXS patterns revealed a high crystal orientation of the films. A sharp reflection on the meridian whose spacing is related to the polymer chain unit length (c-axis) supports the presence of flat-on lamellae morphology in the whole range of film thicknesses investigated. The flat-on lamellae morphology is also supported by AFM images. A triclinic unit cell with the c*-axis perpendicular to the substrate is proposed for PPAz. The repulsion of the long aliphatic spacer by the Si-substrate is invoked as the main reason for the flat-on morphology observed.

Critical separation for efficient Tm3+ -Tm3+ energy transfer evidenced in nanostructured Tm3+: Al2O3 thin films.

Nanostructured amorphous Al oxide (a-Al2O3) thin films doped with Tm3+ were synthesized by alternate pulsed laser deposition. The Tm3+ ions have been deposited in layers with in-depth separation ranging from 0.75 to 6 nm. The films show two broad emission bands originated from the Tm3+ 3H4-->3F4 and 3F4-->3H6 transitions. Their intensity increases at a similar rate and the lifetimes are not modified as the layer separation decreases down to 1.5 nm, suggesting that there is no concentration quenching. At the critical value of 1.5 nm the onset of Tm3+ -Tm3+ energy transfer is evidenced by a sharp decrease of the emission intensity and lifetime. Below this critical value, the rate at which the intensity increases for the 3F4-->3H6 transition is much higher than that for the 3H4-->3F4 transition, evidencing quenching of the 3H4-->3F4 transition through a cross-relaxation mechanism. The control of the Tm3+ ions in the nanometer scale allows evidencing the onset of energy transfer processes among ions and offers a route to optimize compact photonic gain integrated devices.

Size-dependent thermo-optical properties of embedded Bi nanostructures.

The thermally induced optical transmission changes upon melting and solidification of Bi nanostructures embedded in amorphous Al(2)O(3) thin films have been studied as a function of characteristic sizes in the range 7-35 nm. The results show a repeatable optical transmission-temperature hysteresis loop with sharp changes at the melting and solidification temperatures. Both temperatures decrease linearly when the mean size of the nanostructures decreases and they are respectively higher and lower than that of the bulk melting temperature of Bi. The optical transmission shows a significant contrast that increases up to 16% as the mean size of the nanostructures increases. The results show that in addition to the usual decrease of melting temperature as the size of the nanostructures decreases, the melting temperatures for all samples are higher than that of the bulk. This unexpected result is associated to the contraction of Bi upon melting and to matrix effects related to the balance of surface energies between the solid and liquid Bi and the matrix. The solidification process shows a weaker dependence on the nanostructure size, and thus it is consistent with a mainly volume controlled process. It is shown that by controlling the characteristic dimensions of the Bi nanostructures the temperature operability of the Bi nanostructures embedded in amorphous Al(2)O(3) as a thermally driven optical switch can be tuned over 73 K.

sexual en personas menores de edad. A propósito del estudio de tres casos. sexual en personas menores de edad. A propósito del estudio de tres casos / Valoración médica de la sospecha de abuso. Medical evaluation of sexual abuse suspicion in children. Report of three cases

El diagnóstico, la valoración y el tratamiento de menores que pueden haber sido víctimas de alguna forma de abuso sexual, constituye un problema emergente de salud que tiene implicaciones legales y sociales. Por la complejidad y diversidad de los factores que intervienen, su abordaje tiene que ser llevado a cabo con la colaboración de diferentes especialistas, profesionales de distintas disciplinas y por instituciones de varios sectores. A través de la revisión de tres casos se pretende expresar las dificultades que puede ofrecer el diagnóstico de abuso sexual en personas menores de edad, que como otros síndromes, se establece con un rango de probabilidad, basado en un proceso de valoración médica, psicológica y social; lo que no debe poner en cuestión el propio diagnóstico del abuso. Como conclusión fundamental se extrae que no siempre es posible obtener indicadores de certeza, y que no siempre coincidirán la valoración médica con la psicológica o con la social, o que las actuaciones judiciales no habrán de ser en todos los casos determinantes para que la entidad pública pueda adoptar medidas de protección

The diagnostic, valuation and treatment of children that could have been victims of any form of sexual abuse, is an emergent health problem with important legal and social implications. Because of the complexity and diversity of the factors that can be related to this issue, its study has to be done with the cooperation of a wide range of specialists, professionals of different disciplines and also institutions belonging to several sectors. Through the revision of three different cases our aim is to express the obstacles that can be created by the diagnostic of sexual abuse in minors. Such a diagnostic is established after a medical, psychological and social process, always in a probabilistic rank, still this fact must never create doubts about the diagnostic. As a conclusion just to insist in the fact that not always it is going to be possible to obtain certainty indicators, and also that the medical impression will not always coincide with the psychological or social one, as well as not always it is necessary to have the permission of the Court to obtain a response of the Public Administration

Optical evidence for reactive processes when embedding Cu nanoparticles in Al(2)O(3) by pulsed laser deposition.

The optical response of nanocomposite thin films formed by Cu nanoparticles (NPs) embedded in amorphous aluminium oxide (Al(2)O(3)) prepared by pulsed laser deposition (PLD) in vacuum is studied in order to investigate the possible existence of reactive processes on the Cu NPs during their covering with Al(2)O(3). The study is performed as a function of the laser fluence on the Al(2)O(3) target (0.6-4.6 J cm(-2)), while the laser fluence for Cu ablation is kept constant (1.8 J cm(-2)). The structural analysis of the films shows that they are formed by a high density of NPs with average dimensions in the 4.9-5.9 nm range. The optical response of the films has been followed in situ by real-time reflectivity measurements at 633 nm and after deposition by transmission measurements as a function of wavelength around the surface plasmon resonance (SPR). For low laser fluences on the Al(2)O(3) target, the absorption spectrum is dominated by a well-defined SPR absorption band at 1.9 eV. As the laser fluence is increased, the intensity of the absorption band associated with the SPR decreases and shifts to 2.1 eV. The films deposited at low fluences contain metallic Cu NPs and, as the laser fluence increases sputtering of Cu from the NPs and mixing of the species from the Al(2)O(3) deposition with the Cu from the NPs surface takes place. The latter process leads to the formation of an Al-Cu oxide cover on the Cu NPs. The present results provide evidence for mixing of species from the host and Cu at the surface of the NPs, and it is shown how the degree of mixing depends on the laser fluence used to ablate the Al(2)O(3) host target.

Accuracy of endometrial biopsy with the Cornier pipelle for diagnosis of endometrial cancer and atypical hyperplasia.

OBJECTIVE: To establish the accuracy of endometrial biopsy with the Cornier pipelle in the diagnosis of endometrial cancer and atypical endometrial hyperplasia in our milieu. MATERIAL AND METHOD: We reviewed 1,535 anatomopathologic reports on endometrial biopsies taken from outpatients using the Cornier pipelle between 1997 and 2000, in pre- and postmenopausal patients with abnormal vaginal bleeding. In 168 patients (10.9%), curettage and/or hysterectomy was subsequently carried out. In these cases, the anatomopathologic reports were compared to determine sensitivity, specificity, positive predictive value (PPV), negative predictive value (NPV) and likelihood ratio (LR). RESULTS: Sensitivity was 84.2%, specificity was 99.1%, accuracy was 96.9%, PPV was 94.1%, NPV was 93.7% and LR was 93.5. In 249 cases (16.09%) the material was insufficient for study. CONCLUSION: We determined that endometrial biopsy taken with the Cornier pipelle is, as we practice it, an accurate method for diagnosis of endometrial cancer and its precursor, atypical hyperplasia.

El cerclaje de urgencia en la incompetencia istimicocervical con membranas protruyentes. Nuestra experiencia / Emergency cerclage of the incompetent cervicalisthmus with bulging membranes. Our experience

Presentamos nuestra experiencia en el cerclaje cervical en gestantes con cérvix uterino dilatado y membranas protruyentes. Nuestra supervivencia fetal es del 25 por ciento. La ecografía transvaginal es la técnica aceptada para la valoración de la competencia cervical durante el embarazo. Existe evidencia para afirmar que el cerclaje de urgencia en casos con dilatación avanzada proporciona mayor supervivencia fetal que el tratamiento médico con reposo en cama. Persiste la controversia en los casos con cambios cervicales tempranos diagnosticados mediante ecografía, en los que el cerclaje cervical no ha demostrado ser superior al tratamiento conservador en los trabajos realizados (AU)

Structural studies of pulsed-laser deposited nanocomposite metal-oxide films.

Pulsed laser deposition in vacuum has been used to develop metal-oxide nanocomposite films with well controlled structural quality. Results for the copper-aluminium oxide (Cu:Al2O3) system are used to illustrate the main morphological and structural features of these films. High resolution transmission electron microscopy (TEM) analysis shows that the films consist of Cu nanocrystals with average dimensions that can be controlled between 2 nm and 10 nm embedded in an amorphous Al2O3 matrix. It is observed that the in-plane shape of the nanocrystals evolves from circular to elongated, and the number of nanocrystals per unit area decreases as their size increases. This evolution is explained in terms of nucleation at the substrate surface and coalescence during the later stages of growth. The thermal stability of the films has been studied by in situ TEM annealing and no transformation could be observed up to about 800 degrees C when partial crystallization of the Al2O3 starts.

Occurrence of angioimmunoblastic T cell lymphoma in a patient with chronic myelomonocytic leukemia features.

In a patient with recently diagnosed chronic myelomonocytic leukemia features, the biopsy of a peripheral lymphadenopathy seven months later revealed disorganised lymphoid tissue with a few large EBER (+) LMP1 (+) B-lymphocytes before any treatment was given. At this time, a clonal TCR gamma rearrangement and very faint clonal IgH rearrangement were demonstrated, and the diagnosis of angioimmunoblastic T-cell lymphoma was made. Treatment with MOPP was started, followed by Hydroxycarbamide and CHOP but the outcome was fatal. During the evolution, there was no blastic transformation of the chronic myelomonocytic leukemia. The T-cell lymphoma extended to abdominal lymph nodes, Waldeyer ring and bone marrow and the percentage of large LMPI EBER (+) B-cells increased in the lymph nodes. These findings do not support a common stem cell abnormality leading to myelodysplasia in the bone marrow and lymphoma in peripheral lymph nodes. The lack of a clearcut light chain restriction in the EBV infected B-cell is suggestive of a persistant EBV infection in polyclonal or oligoclonal activated B-cells as described in immunodepressed patients. The association of CMML features and an angioimmunoblastic T-cell lymphoma is discussed.

Re-evaluation of a programmed method to teach generalized identity matching to sample.

Programmed training in identity matching to sample was given to six participants who had severe mental retardation, mental age-equivalent scores of 3.0 years or less, and histories of failures in prior assessments and training attempts with standard procedures. An intermediate goal of the training program was to establish one-trial discrimination learning (OTDL), where new discriminations are acquired after a single training trial, OTDL was included because an analysis of the task requirements for identity matching suggested that it could be a prerequisite skill. One participant was eliminated from the experiment when stimulus control by prompting procedures broke down relatively early in training. Only one of the remaining participants achieved OTDL. When the program was modified to eliminate OTDL as an intermediate goal, for participants completed it and passed tests for generalized identity matching with high accuracy scores. The program was partially successful with the sixth participant in that it established highly accurate and reliable identity matching when different stimuli were displayed on every trial (nonconditional-function matching), but not when the same set of comparison stimuli was displayed on every trial (conditional-function matching). The results showed that (a) one-trial discrimination learning appears to be sufficient but not necessary for identify matching, and (b) the program successfully established identity matching in a majority of difficult-to-teach students who had well-documented failures to learn by standard teaching methods.

Blank-comparison assessment of stimulus-stimulus relations in individuals with mental retardation: a methodological note.

Matching to sample is commonly used in research and practice to assess relational learning of persons with mental retardation. However, forced-choice matching tasks are not always appropriate. In this paper we have illustrated blank-comparison matching to sample, a selection-based "yes/no" method requiring no verbal skills. Participants select a comparison stimulus if it is judged to be related to the sample (analogous to "yes") but select a black square (blank) if it is not so judged ("no"). In the first experiment the method was used to explore bases for emergent symbolic "mapping" performances. In the second experiment we assessed similarity judgments between form stimuli. Both experiments confirmed the feasibility and utility of the method for making unambiguous inferences as to whether pairs of stimuli were or were not related.

Assessing same/different judgments in individuals with severe intellectual disabilities: a status report.

This report summarizes state-of-the-art approaches for assessing visual stimulus same/different judgments in individuals with severe intellectual disabilities. Methods are described that permit one to conduct assessments on a population-wide basis, excluding few if any participants due to failure to acquire necessary baseline performances. Methodological investigations summarized here indicate that one can obtain reliable same/different judgments with a variety of stimuli in virtually anyone for whom a basal score on the Peabody Picture Vocabulary Test can be obtained. This approach includes judgments involving not only familiar, readily nameable stimuli, but also abstract two-dimensional forms of the type commonly used to minimize extraexperimental influences on performance. Taken together, recent findings lead to the conclusion that past studies have significantly under-estimated the capacity of participants with low MA scores to make same/different judgments. They also suggest a more general methodological approach that can potentially lead to more sensitive assessment of other behavioral capacities in this difficult-to-test population.