Evidence of human impact in Antarctic region by studying atmospheric aerosols.

Air quality is a global concerning topic because of its great impact on the environment and health. Because of that, the study of atmospheric aerosols looking for harmful pollutants is rising, as well as the interest in the origin of the contaminants. Depending on the nature and size of the aerosols, some elements can be detected at a great distance from the emission source, even in Antarctica, where this study is conducted. Several samples of PM filters from 2018 to 2019 (Deception Island) and 2019-2020 (Livingston Island) campaigns have been analyzed by three powerful spectroscopic techniques: FESEM (Field Emission Scanning Electron Microscopy), LIBS (Laser Induced Breakdown Spectroscopy), and ICP-MS (Inductively Coupled Plasma Mass Spectrometry). These techniques have allowed us to find some heavy metals in the air of the Antarctic region (Al, Fe, Ti, Ni, Cr, and Mn). Deeper studies on ICP-MS results have confirmed those results and have also provided information on their potential sources. Thus, while Al, Fe, Ti and Mn concentrations can be explained by crustal origin, Ni and Cr presented high values only coherent with important human contribution. The results point out that the Antarctic region is no longer a clean and isolated environment from human pollution.

Characterization of atmospheric aerosols in the Antarctic region using Raman Spectroscopy and Scanning Electron Microscopy.

The non-destructive spectroscopic characterization of airborne particulate matter (PM) was performed to gain better knowledge of the internal structures of atmospheric aerosols at the particle level in the Antarctic region, along with their potential sources. PM and soil samples were collected during the 2016-2017 austral summer season at the surroundings of the Spanish Antarctic Research Station "Gabriel de Castilla" (Deception Island, South Shetland Islands). PM was deposited in a low-volume sampler air filter. Raman spectroscopy (RS) and Scanning Electron Microscopy with Energy-Dispersive X-ray Spectroscopy (SEM-EDS) were used to determine the elemental and molecular composition of the individual aerosol and soil particles. Filter spectra measured by these techniques revealed long-range atmospheric transport of organic compounds (polystyrene and bacteria), local single and cluster particles made of different kinds of black carbon (BC), exotic minerals (polyhalite, arcanite, niter, ammonium nitrate, syngenite and nitrogen, phosphorus, and potassium (NPK) fertilizer), and natural PM (sea salts, silicates, iron oxides, etc.). In addition to the filter samples, forsterite and plagioclase were discovered in the soil samples together with magnetite. This is the first report of the presence of a microplastic fiber in the Antarctic air. This fact, together with the presence of other pollutants, reflects that even pristine and remote regions are influenced by anthropogenic activities.

Aerosol analysis by micro laser-induced breakdown spectroscopy: A new protocol for particulate matter characterization in filters.

Atmospheric aerosols (particulate matter - PM) affect the air quality and climate, even in remote areas, such as the Antarctic Region. Current techniques for continuous PM monitoring are usually complex, costly, time consuming and do not provide real-time measurements. In this work, based on micro laser-induced breakdown spectroscopy (LIBS), an innovative method with an optical design and multi-elemental scanning imaging, is presented to characterize PM collected in filters from Antarctica. After following a simple protocol and under atmospheric pressure, the new approach allows to obtain a global visualization of the elemental PM composition of the filters with a minimum sample destruction and preparation. For the first time, we were able to map the localization of pollutants in filters at high spatial resolution and speed. This recent method offers a new insight on the characterization of PM, particularly in isolated areas, where no complex equipment and real time measurements are demanded.

The Immunobiogram, a Novel In Vitro Assay to Evaluate Treatment Resistance in Patients Receiving Immunosuppressive Therapy.

Immunosuppressive drugs are widely used to treat several autoimmune disorders and prevent rejection after organ transplantation. However, intra-individual variations in the pharmacological response to immunosuppressive therapy critically influence its efficacy, often resulting in poor treatment responses and serious side effects. Effective diagnostic tools that help clinicians to tailor immunosuppressive therapy to the needs and immunological profile of the individual patient thus constitute a major unmet clinical need. In vitro assays that measure immune cell responses to immunosuppressive drugs constitute a promising approach to individualized immunosuppressive therapy. Here, we present the Immunobiogram, a functional pharmacodynamic immune cell-based assay for simultaneous quantitative measurement of a patient's immune response to a battery of immunosuppressive drugs. Peripheral blood mononuclear cells collected from patients are immunologically stimulated to induce activation and proliferation and embedded in a hydrogel mixture in which they are exposed to a concentration gradient of the immunosuppressants of interest. Analysis of samples from kidney transplant patients using this procedure revealed an association between the sensitivity of individual patients to the immunosuppressive regimen and their immunological risk of transplant rejection. Incorporation of the Immunobiogram assay into clinical settings could greatly facilitate personalized optimization and monitoring of immunosuppressive therapy, and study of the mechanisms underlying resistance to immunosuppressants.

Statistical Tools for Air Pollution Assessment: Multivariate and Spatial Analysis Studies in the Madrid Region.

The present work reports the distribution of pollutants in the Madrid city and province from 22 monitoring stations during 2010 to 2017. Statistical tools were used to interpret and model air pollution data. The data include the annual average concentrations of nitrogen oxides, ozone, and particulate matter (PM10), collected in Madrid and its suburbs, which is one of the largest metropolitan places in Europe, and its air quality has not been studied sufficiently. A mapping of the distribution of these pollutants was done, in order to reveal the relationship between them and also with the demography of the region. The multivariate analysis employing correlation analysis, principal component analysis (PCA), and cluster analysis (CA) resulted in establishing a correlation between different pollutants. The results obtained allowed classification of different monitoring stations on the basis of each of the four pollutants, revealing information about their sources and mechanisms, visualizing their spatial distribution, and monitoring their levels according to the average annual limits established in the legislation. The elaboration of contour maps by the geostatistical method, ordinary kriging, also supported the interpretation derived from the multivariate analysis demonstrating the levels of NO2 exceeding the annual limit in the centre, south, and east of the Madrid province.

Serum Malondialdehyde Concentration and Glutathione Peroxidase Activity in a Longitudinal Study of Gestational Diabetes.

AIMS: The main goal of this study was to evaluate the presence of oxidative damage and to quantify its level in gestational diabetes. METHODS: Thirty-six healthy women and thirty-six women with gestational diabetes were studied in the three trimesters of pregnancy regarding their levels of oxidative stress markers. These women were diagnosed with diabetes in the second trimester of pregnancy. Blood glucose levels after 100g glucose tolerance test were higher than 190, 165 or 145 mg/dl, 1, 2 or 3 hours after glucose intake. RESULTS: The group of women with gestational diabetes had higher serum malondialdehyde levels, with significant differences between groups in the first and second trimester. The mean values of serum glutathione peroxidase activity in the diabetic women were significantly lower in the first trimester. In the group of women with gestational diabetes there was a negative linear correlation between serum malondialdehyde concentration and glutathione peroxidase activity in the second and third trimester. CONCLUSIONS: In this observational and longitudinal study in pregnant women, the alterations attributable to oxidative stress were present before the biochemical detection of the HbA1c increase. Usual recommendations once GD is detected (adequate metabolic control, as well as any other normally proposed to these patients) lowered the concentration of malondialdehyde at the end of pregnancy to the same levels of the healthy controls. Serum glutathione peroxidase activity in women with gestational diabetes increased during the gestational period.

Two-dimensional liquid chromatography for direct chiral separations: a review.

Separation of enantiomers remains a challenge owing to their identical physical and chemical properties in an achiral environment, and research on specialized separation techniques such as multidimensional achiral-chiral liquid chromatography continues to resolve individual enantiomers in complex samples. Recent advances in application of multidimensional liquid chromatography applied to chiral analysis are reviewed. For this reason, benefits of achiral-chiral coupling are shown, with emphasis in applications on biological and pharmaceutical fields as well as pesticide analysis. A description of standard instrumental setup in both heart-cut and comprehensive multidimensional liquid chromatography is shown. The most broadly used chiral stationary phases for multidimensional liquid chromatography are summarized. An extensive overview of different interface designs applied to complex samples is presented.

Determination of salbutamol by direct chiral reversed-phase HPLC using teicoplanin as stationary phase and its application to natural water analysis.

A direct chiral LC-UV method was optimized for the determination of salbutamol (SAL) ß2 -agonist in environmental water. Two commercially available columns were evaluated: teicoplanin Chirobiotic-T™ (150 × 2.1 mm i.d., 5 µm) and vancomycin Chirobiotic-V™ (150 × 2.1 mm i.d., 5 µm). Finally, teicoplanin chiral stationary phase was selected for SAL enantiomer resolution. In order to preserve its integrity and maintain the column performance for longer time, the use of additives such as triethylamine (TEA) in the mobile phase was avoided. Experimental design was applied to simultaneously evaluate the influence of several parameters involved in enantiomer separation and to establish the conditions for acceptable resolution and performance in short analysis time. Optimum mobile phase was methanol-20 mM ammonium acetate buffer at pH 4.5 (98:2, v/v). A solid-phase extraction procedure for sample pre-concentration and clean-up allowed the determination of chiral SAL residues in natural water samples spiked at low concentrations in the range 1.0-20 ng mL(-1) . Reproducible recoveries, between 77 and 98%, were obtained and matrix effect was negligible. Injection of sample solutions at low elution strength permitted the SAL enantioresolution in the natural water complex matrix with satisfactory sensitivity and precision.

Direct chiral determination of free amino acid enantiomers by two-dimensional liquid chromatography: application to control transformations in E-beam irradiated foodstuffs.

Changes in free amino acids content and its potential racemization in ready-to-eat foods treated with E-beam irradiation between 1 and 8 kGy for sanitation purposes were studied. A simple heart cut two-dimensional high performance liquid chromatographic method (LC-LC) for the simultaneous enantiomeric determination of three pairs of amino acids used as markers (tyrosine, phenylalanine, and tryptophan) is presented. The proposed method involves the use of two chromatographs in an LC-LC achiral-chiral coupling. Amino acids and their decomposition products were firstly separated in a primary column (C(18)) using a mixture of ammonium acetate buffer (20 mM, pH 6) (94%) and methanol (6%) as the mobile phase. Then, a portion of each peak was transferred by heart cutting through a switching valve to a teicoplanin-chiral column. Methanol (90%)/water (10%) was used as the mobile phase. Ultraviolet detection was at 260 nm. Detection limits were between 0.16 and 3 mg L(-1) for each enantiomer. Recoveries were in the range 79-98%. The LC-LC method combined with the proposed sample extraction procedure is suitable for complex samples; it involves an online cleanup, and it prevents degradation of protein, racemization of L-enantiomers, and degradation of tryptophan. Under these conditions, D-amino acids were not found in any of the analyzed samples at detection levels of the proposed method.

The variant rs1867277 in FOXE1 gene confers thyroid cancer susceptibility through the recruitment of USF1/USF2 transcription factors.

In order to identify genetic factors related to thyroid cancer susceptibility, we adopted a candidate gene approach. We studied tag- and putative functional SNPs in genes involved in thyroid cell differentiation and proliferation, and in genes found to be differentially expressed in thyroid carcinoma. A total of 768 SNPs in 97 genes were genotyped in a Spanish series of 615 cases and 525 controls, the former comprising the largest collection of patients with this pathology from a single population studied to date. SNPs in an LD block spanning the entire FOXE1 gene showed the strongest evidence of association with papillary thyroid carcinoma susceptibility. This association was validated in a second stage of the study that included an independent Italian series of 482 patients and 532 controls. The strongest association results were observed for rs1867277 (OR[per-allele] = 1.49; 95%CI = 1.30-1.70; P = 5.9x10(-9)). Functional assays of rs1867277 (NM_004473.3:c.-283G>A) within the FOXE1 5' UTR suggested that this variant affects FOXE1 transcription. DNA-binding assays demonstrated that, exclusively, the sequence containing the A allele recruited the USF1/USF2 transcription factors, while both alleles formed a complex in which DREAM/CREB/alphaCREM participated. Transfection studies showed an allele-dependent transcriptional regulation of FOXE1. We propose a FOXE1 regulation model dependent on the rs1867277 genotype, indicating that this SNP is a causal variant in thyroid cancer susceptibility. Our results constitute the first functional explanation for an association identified by a GWAS and thereby elucidate a mechanism of thyroid cancer susceptibility. They also attest to the efficacy of candidate gene approaches in the GWAS era.

One- and two-dimensional direct chiral liquid chromatographic determination of mixtures of diclofop-Acid and diclofop-methyl herbicides.

Simple one- and two-dimensional high-performance liquid chromatography (HPLC) methods for the simultaneous enantiomeric determination of alkyloxyphenoxypropionic acid herbicides is presented. Compounds studied were ( R, S)-2-[4-(2,4-dichlorophenoxy)phenoxy]propionic acid (diclofop-acid) and ( R, S)-2-[4-(2,4-dichlorophenoxy)]methyl propionate (diclofop-methyl). Mobile phases necessary to separate their enantiomers on an alpha1-acid glycoprotein chiral stationary phase are different; therefore, the simultaneous separation by an isocratic mode is not possible. The chiral separation method proposed involves a one-step gradient allowing for the simultaneous determination of both racemic enantiomers. Detection limits of the method were 0.03 mg/L for both diclofop-acid enantiomers and 0.14 and 0.15 mg/L for diclofop-methyl enantiomers, respectively. The two-dimensional method involves the use of two chromatographs in one achiral-chiral coupling. The LC-LC method is more suitable for complex samples because it involves an online cleanup effect. Detection limits were 1.25 and 1.87 mg/L for diclofop-acid and 2.70 and 3.02 mg/L for diclofop-methyl enantiomers, respectively. Accuracy, repeatability, and reproducibility have been studied in standard samples and a technical product.