Thermodynamic analysis of POPs interaction with biosubstrates

Persistent organic pollutants (POPs) as polycyclic aromatic hydrocarbons (PAH), pesticides and herbicides are nowadays ubiquitous [1]. These species are highly lipophilic and all at least suspected of carcinogenic effects [2,3]. However, information on their toxic activity is often related to in vitro/in vivo studies, whereas a detailed analysis of the mechanistic/chemical aspects of the binding to biosubstrates is sometimes missing. To contribute to this field and in the frame of our participation to PNRA (National Antarctic Research Program) we have done some tests on the binding of model targets (two PAHs, two pesticides and two herbicides, Fig. 1) to biosubstrates (natural DNA and bovine serum albumin - BSA). The interaction with micelles and liposomes was also tested, both as to scale the lipophilicity and to get information on the possible accumulation on membranes. The results collected show that the high hydrophobicity of these species turns into very high affinity for DNA. Absorbance and fluorescence titrations suggest complex binding modes that are discussed in relation with the different pollutant/DNA ratio. BSA binding is also found to occur. Ultrafiltration coupled with absorbance spectroscopy enables the percentage of retention (R%) on the micelle/liposome be measured. R% dependence on the molecule and on the type of system (sodium dodecyl sulphate anionic micelles, TritonX-100 neutral micelles, dodecyl trimethyl ammonium chloride positive micelles and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine liposomes) is discussed. References: [1] A. Lo Giudice, P. Casella, V. Bruni, L. Michaud, Ecotoxicology 2013, 22, 240-250. [2] H. Yu, Journal of Enviromental Science and Health 2002, 20, 149-183. [3] M.C.R. Alavanja, M.R. Bonner, Journal of Toxicology and Environmental Health B 2012, 15, 238-263

Laboratory tests for the phytoextraction of heavy metals from polluted harbor sediments using aquatic plants

The aim of this study was to investigate the concentrations and pollution levels of heavy metals, organochlorine pesticides, and polycyclic aromatic hydrocarbons in marine sediments from the Leghorn Harbor (Italy) on the Mediterranean Sea. The phytoextraction capacity of three aquatic plants Salvinia natans, Vallisneria spiralis, and Cabomba aquatica was also tested in the removal of lead and copper, present in high concentration in these sediments. The average detectable concentrations of metals accumulated by the plants in the studied area were as follows: >3.328±0.032mg/kg dry weight (DW) of Pb and 2.641±0.014mg/kg DW of Cu for S. natans, >3.107±0.034g/kg DW for V. spiralis, and >2.400±0.029mg/kg DW for C. aquatica. The occurrence of pesticides was also analyzed in the sediment sample by gas chromatography coupled with mass spectrometry (GC/MS). Due to its metal and organic compound accumulation patterns, S. natans is a potential candidate in phytoextraction strategies

Occurence of legacy and emerging persistent organic pollutants at the Ross Sea and circumpolar deep water convergence (Antarctica)

Persistent organic pollutants (POPs) have attracted the attention of scientists and policy makers in recent decades due to their extreme persistence, semi-volatility, capacity to bio-accumulate in the food chain, and toxic properties. Despite its geographical isolation, extreme meteorological conditions and an almost total absence of local point sources, the Antarctic continent is vulnerable to contamination by POPs, due to the ability of these chemicals to undergo long range atmospheric transport (LRAT) and deposition in the open sea. In a few cases and for limited areas, POPs may be also introduced into the Antarctic ecosystem by human activities (scientific stations, fishing, tourism, accidental oil pills, waste incineration and sewage). Even if various studiesi.e.1,2,3,4,5 have revealed the presence of POPs in air, seawater, sediments and biota in Antarctica, more investigations are needed to implement the number of observations, integrate the data series and meet the indications of the Stockholm Convention and the UNECE protocol in terms of improving knowledge of the temporal and spatial trends of POPs in biotic and abiotic environmental compartments. In this study we present POP concentrations in water samples collected along vertical water columns from seven oceanographic stations located in the Ross Sea and close to the Circumpolar Convergence (see Figure 1). Moreover, the occurrence of emerging and legacy POPs, including polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated naphthalenes (PCNs), organochlorine pesticides (OCPs) and polybrominated diphenylethers (PBDEs) were investigated in order to evaluate their possible sources and relationship with physical and biological processes taking place in the water column. The Ross sea is the formation site of two shelf waters which constitute an important part of the Antarctic Bottom Water (AABWs): the High Salinity Shelf Water (HSSW), which is relatively cold and generated inside the Ross Sea basin and the Ice Shelf Water (ISW). The Ross sea is influenced by only one water mass of external origin, the Circumpolar Deep Water (CDW), which is the largest circulation feature of the Southern Ocean, manly responsible for possible exchange processes between the Antarctic seas and the outer oceans, and thus a possible source of persistent organic pollutants (POPs)2 . The CDW is a relatively warm, salty and nutrient rich water mass carried around Antarctica by the Antarctic Circumpolar Current (ACC)6. Associated with the ACC is the Antarctic Convergence where the cold Antarctic waters meet the warmer waters of the subantarctic creating a zone of upwelling nutrients. Moreover, the Drygalski Glacie Tongue plays an important role in the Polynya development in the Terra Nova Bay, in the Ross sea. An important environmental concern is the accelerated glacier and snow melting that represent a massive release of both naturally occurring chemical substances and organic/inorganic pollutants of anthropogenic origin, which are stored in the deeper layers of the ice and may be delivered to surrounding ecosystems

Synthesis, electrochemical and spectroscopic characterization of selected quinolinecarbaldehydes and their Schiff base derivatives

A new approach to the synthesis of selected quinolinecarbaldehydes with carbonyl groups located at C5 and/or in C7 positions is presented in this paper in conjunction with spectroscopic characterization of the products. The classical Reimer-Tiemann, Vilsmeier-Haack and Duff aldehyde synthesis methods were compared due to their importance. Computational studies were carried out to explain the preferred selectivity of the presented formylation transformations. A carbene insertion reaction based on Reimer-Tiemann methodology is presented for making 7-bromo-8-hydroxyquinoline-5-carbaldehyde. Additionally, Duff and Vilsmeier-Haack reactions were used in the double formylation of quinoline derivatives and their analogues benzo[h]quinolin-10-ol, 8-hydroxy-2-methylquinoline-5,7-dicarbaldehyde, 8-(dimethylamino) quinoline-5,7-dicarbaldehyde and 10-hydroxybenzo[h]quinoline-7,9-dicarbaldehyde. Four Schiff base derivatives of 2,6-diisopropylbenzenamine were prepared from selected quinoline-5-carbaldehydes and quinoline-7-carbaldehyde by an efficient synthesis protocol. Their properties have been characterized by a combination of several techniques: MS, HRMS, GC-MS, FTIR, electronic absorption spectroscopy and multinuclear NMR. The electrochemical properties of 8-hydroxy-quinoline-5-carbaldehyde, 6-(dimethylamino)quinoline-5-carbaldehyde and its methylated derivative were investigated, and a strong correlation between the chemical structure and obtained reduction and oxidation potentials was found. The presence of a methyl group facilitates oxidation. In contrast, the reduction potential of methylated compounds was more negative comparing to non-methylated structure. Calculations of frontier molecular orbitals supported the finding. The structures of 8-hydroxy-2-methylquinoline-5,7-dicarbaldehyde and four Schiff bases were determined by single-crystal X-ray diffraction measurements

Polymer Identification and Specific Analysis (PISA) of Microplastic Total Mass in Sediments of the Protected Marine Area of the Meloria Shoals

Microplastics (MPs) quantification in benthic marine sediments is typically performed by time-consuming and moderately accurate mechanical separation and microscopy detection. In this paper, we describe the results of our innovative Polymer Identification and Specific Analysis (PISA) of microplastic total mass, previously tested on either less complex sandy beach sediment or less demanding (because of the high MPs content) wastewater treatment plant sludges, applied to the analysis of benthic sediments from a sublittoral area north-west of Leghorn (Tuscany, Italy). Samples were collected from two shallow sites characterized by coarse debris in a mixed seabed of Posidonia oceanica, and by a very fine silty-organogenic sediment, respectively. After sieving at <2 mm the sediment was sequentially extracted with selective organic solvents and the two polymer classes polystyrene (PS) and polyolefins (PE and PP) were quantified by pyrolysis-gas chromatography-mass spectrometry (Pyr-GC/MS). A contamination in the 8–65 ppm range by PS could be accurately detected. Acid hydrolysis on the extracted residue to achieve total depolymerization of all natural and synthetic polyamides, tagging of all aminated species in the hydrolysate with a fluorophore, and reversed-phase high performance liquid chromatography (HPLC) (RP-HPLC) analysis, allowed the quantification within the 137–1523 ppm range of the individual mass of contaminating nylon 6 and nylon 6,6, based on the detected amounts of the respective monomeric amines 6-aminohexanoic acid (AHA) and hexamethylenediamine (HMDA). Finally, alkaline hydrolysis of the residue from acid hydrolysis followed by RP-HPLC analysis of the purified hydrolysate showed contamination by polyethylene terephthalate (PET) in the 12.1–2.7 ppm range, based on the content of its comonomer, terephthalic acid

Enrichment, isolation and biodegradation potential of psychrotolerant polychlorinated-​biphenyl degrading bacteria from the Kongsfjorden (Svalbard Islands, High Arctic Norway)

Persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs), have been detected in abiotic Arctic matrices: surface sediments and seawater from coastal areas in the Kongsfjorden were collected and analyzed. Levels of PCBs varied depending on the sampling site. Total PCB concentrations were between 11.63 (site C2W) and 27.69 pg l− 1 (site AW). These levels were comparable to those reported previously in lake sediments from the northern Svalbard. The occurrence and biodegradation potential of cold-adapted PCB-oxidizing bacteria in seawater and sediment along the fjord was also evaluated. After enrichment with biphenyl, 246 isolates were obtained with 45 of them that were able to grow in the presence of the PCB mixture Aroclor 1242, as the sole carbon source. The catabolic gene bphA was harbored by 17 isolates with affiliates to the genera Algoriphagus, Devosia and Salinibacterium that have been never reported as able to utilize PCBs, thus deserving further investigation. The total removal of Aroclor 1242 and selected PCB congeners was evaluated at 4 and 15 °C for eight bphA-harboring isolates and Gelidibacter sp. DS-10. With few exceptions, tested strains showed greater efficiency at 15 than at 4 °C. Isolates were able to reduce most chromatographic peaks by > 50%, with some di- and trichlorobiphenyls that were quite totally removed (> 90%)

Benthic Microbial Communities in a Seasonally Ice-Covered Sub-Arctic River (Pasvik River, Norway) Are Shaped by Site-Specific Environmental Conditions

The Pasvik River experiences chemical, physical, and biological stressors due to the direct discharges of domestic sewage from settlements located within the catchment and runoff from smelter and mine wastes. Sediments, as a natural repository of organic matter and associated contaminants, are of global concern for the possible release of pollutants in the water column, with detrimental effects on aquatic organisms. The present study was aimed at characterizing the riverine benthic microbial community and evaluating its ecological role in relation to the contamination level. Sediments were sampled along the river during two contrasting environmental periods (i.e., beginning and ongoing phases of ice melting). Microbial enzymatic activities, cell abundance, and morphological traits were evaluated, along with the phylogenetic community composition. Amplified 16S rRNA genes from bacteria were sequenced using a next-generation approach. Sediments were also analyzed for a variety of chemical features, namely particulate material characteristics and concentration of polychlorobiphenyls, polycyclic aromatic hydrocarbons, and pesticides. Riverine and brackish sites did not affect the microbial community in terms of main phylogenetic diversity (at phylum level), morphometry, enzymatic activities, and abundance. Instead, bacterial diversity in the river sediments appeared to be influenced by the micro-niche conditions, with differences in the relative abundance of selected taxa. In particular, our results highlighted the occurrence of bacterial taxa directly involved in the C, Fe, and N cycles, as well as in the degradation of organic pollutants and toxic compounds.Benthic Microbial Communities in a Seasonally Ice-Covered Sub-Arctic River (Pasvik River, Norway) Are Shaped by Site-Specific Environmental ConditionspublishedVersio

A 17-Gene Expression Signature for Early Identification of Poor Prognosis in Clear Cell Renal Cell Carcinoma

: The Identification of reliable Biomarkers able to predict the outcome after nephrectomy of patients with clear cell renal cell carcinoma (ccRCC) is an unmet need. The gene expression analysis in tumor tissues represents a promising tool for better stratification of ccRCC subtypes and patients' evaluation. Methods: In our study we retrospectively analyzed using Next-Generation expression analysis (NanoString), the expression of a gene panel in tumor tissue from 46 consecutive patients treated with nephrectomy for non-metastatic ccRCC at two Italian Oncological Centres. Significant differences in expression levels of selected genes was sought. Additionally, we performed a univariate and a multivariate analysis on overall survival according to Cox regression model. Results: A 17-gene expression signature of patients with a recurrence-free survival (RFS) < 1 year (unfavorable genomic signature (UGS)) and of patients with a RFS > 5 years (favorable genomic signature (FGS)) was identified and resulted in being significantly correlated with overall survival of the patients included in this analysis (HR 51.37, p < 0.0001). Conclusions: The identified Genomic Signatures may serve as potential biomarkers for prognosis prediction of non-metastatic RCC and could drive both follow-up and treatment personalization in RCC management

Response to metal stress of Nicotiana langsdorffii plants wild-type and transgenic for the rat glucocorticoid receptor gene

Recently our findings have shown that the integration of the gene coding for the rat gluco-corticoid receptor (GR receptor) in Nicotiana langsdorffii plants induced morphophysiological effects in transgenic plants through the modification of their hormonal pattern. Phytohormones play a key role in plant responses to many different biotic and abiotic stresses since a modified hormonal profile up-regulates the activation of secondary metabolites involved in the response to stress. In this work transgenic GR plants and isogenic wild type genotypes were exposed to metal stress by treating them with 30 ppm cadmium(II) or 50 ppm chromium(VI). Hormonal patterns along with changes in key response related metabolites were then monitored and compared. Heavy metal up-take was found to be lower in the GR plants. The transgenic plants exhibited higher values of S-abscisic acid (S-ABA) and 3-indole acetic acid (IAA), salicylic acid and total polyphenols, chlorogenic acid and antiradical activity, compared to the untransformed wild type plants. Both Cd and Cr treatments led to an increase in hormone concentrations and secondary metabolites only in wild type plants. Analysis of the results suggests that the stress responses due to changes in the plant's hormonal system may derive from the interaction between the GR receptor and phytosteroids, which are known to play a key role in plant physiology and development. (C) 2013 Elsevier GmbH. All rights reserved

Neutralizing antibodies to Omicron after the fourth SARS-CoV-2 mRNA vaccine dose in immunocompromised patients highlight the need of additional boosters

IntroductionImmunocompromised patients have been shown to have an impaired immune response to COVID-19 vaccines.MethodsHere we compared the B-cell, T-cell and neutralizing antibody response to WT and Omicron BA.2 SARS-CoV-2 virus after the fourth dose of mRNA COVID-19 vaccines in patients with hematological malignancies (HM, n=71), solid tumors (ST, n=39) and immune-rheumatological (IR, n=25) diseases. The humoral and T-cell responses to SARS-CoV-2 vaccination were analyzed by quantifying the anti-RBD antibodies, their neutralization activity and the IFN-γ released after spike specific stimulation.ResultsWe show that the T-cell response is similarly boosted by the fourth dose across the different subgroups, while the antibody response is improved only in patients not receiving B-cell targeted therapies, independent on the pathology. However, 9% of patients with anti-RBD antibodies did not have neutralizing antibodies to either virus variants, while an additional 5.7% did not have neutralizing antibodies to Omicron BA.2, making these patients particularly vulnerable to SARS-CoV-2 infection. The increment of neutralizing antibodies was very similar towards Omicron BA.2 and WT virus after the third or fourth dose of vaccine, suggesting that there is no preferential skewing towards either virus variant with the booster dose. The only limited step is the amount of antibodies that are elicited after vaccination, thus increasing the probability of developing neutralizing antibodies to both variants of virus.DiscussionThese data support the recommendation of additional booster doses in frail patients to enhance the development of a B-cell response directed against Omicron and/or to enhance the T-cell response in patients treated with anti-CD20