Nanoparticles functionalized with dithiocarbamate groups are well known for their high uptake efficiency of Hg(II) from water but where and how Hg coordinates is still an open question.In the present work, Perturbed Angular Correlations spectroscopy was combined with Density Functional Theory modelling to answer that question. Measuring the electric field gradient and comparing it with its calculated counterpart allows to determine the most probable local environment of Hg and its coordination, both for dithiocarbamate functionalized nanoparticles and for silica coated magnetite nanoparticles.The calculated bonding energy also answers why dithiocarbamate functionalized nanoparticles present such a high sorption efficiency.

Polymeric nanocomposite membranes are emerging as promising materials for water treatment. To explore the potential of new materials for the removal of toxic metals from water, novel hydrolyzed polyacrylonitrile (hPAN) membranes coated with graphene oxide (GO) by layer-by-layer (LbL) assembly, using poly(4-vinylpyridinium iodide) (PVPI) as binding agent, were prepared, characterized, and applied to remove toxic metals in multi- component systems. The addition of PVPI and GO to the hPAN membrane modified the surface roughness, hydrophilicity, layers morphology, and introduced oxygenated functions to the pristine polymer. These features enhanced the material's selectivity for Cu2+, Cr3+, and Pb2+, over Ni2+ and Cd2+, with removal efficiencies of 50.4 %, 64.3 %, and 99.9 % in batch assays, at the concentrations of 4.1, 12.2, and 10.2 mg L- 1 , and selectivities relative to Cd2+ of 13.7, 24.2 and 13450, respectively. Governed by the formation of coordination complexes, the increment of nanocomposite layers adhered to the polymer improved the adsorbent/adsorbate interactions. The efficiency of hPAN membrane with three PVPI/GO bilayers in removing metal ions was attested in comparison to other polymer nanocomposite membranes from literature.

The search for new sources of rare earth metals (REM), such as neodymium and dysprosium, has ensued globally due to their strategic value for the sustainability of the energy sector. In this context, this work explored the potential of vermiculite as a sorbent for recovering rare earth cations from the leachate of end-of-life NdFeB magnets by kinetic, equilibrium, and desorption investigations. In which the REM uptake on vermiculite occurred by fast kinetics, and the significant sorbate-sorbate interactions at the equilibrium indicated that the REM sorption was a cooperative process; vermiculite sorbed the metals from the acid leachate in the following order: Fe(III) > Nd(III) > Zn(II) > Pr(III) > Co(II) > Dy(III) > Ni(II) > Al(III) > Mn(II); and the chelating agent ethylenediaminetetraacetic acid desorbed Nd(III) preferably over other metals, indicating the potential for further selective recovery processes. The characterization analyses indicated that the loaded vermiculite preserved the original structure, composition, functional groups, and thermal stability. Also, X-ray photoelectron spectroscopy corroborated the cation exchange mechanism between interlayer magnesium in the REM sorption. Thus, the experimental findings and a cost analysis compared to the literature demonstrated the cost-effectiveness and potential of vermiculite for the valorization of NdFeB magnet leachates.

Measurements of dissolved organic carbon (DOC), nitrogen (DON), and phosphorus (DOP) concentrations are used to characterize the dissolved organic matter (DOM) pool and are important components of biogeochemical cycling in the coastal ocean. Here, we present the first edition of a global database (CoastDOM v1; available at https://doi.org/10.1594/PANGAEA.964012, Lønborg et al., 2023) compiling previously published and unpublished measurements of DOC, DON, and DOP in coastal waters. These data are complemented by hydrographic data such as temperature and salinity and, to the extent possible, other biogeochemical variables (e.g. chlorophyll a, inorganic nutrients) and the inorganic carbon system (e.g. dissolved inorganic carbon and total alkalinity). Overall, CoastDOM v1 includes observations of concentrations from all continents. However, most data were collected in the Northern Hemisphere, with a clear gap in DOM measurements from the Southern Hemisphere. The data included were collected from 1978 to 2022 and consist of 62 338 data points for DOC, 20 356 for DON, and 13 533 for DOP. The number of measurements decreases progressively in the sequence DOC > DON > DOP, reflecting both differences in the maturity of the analytical methods and the greater focus on carbon cycling by the aquatic science community. The global database shows that the average DOC concentration in coastal waters (average ± standard deviation (SD): 182±314 µmol C L−1; median: 103 µmol C L−1) is 13-fold higher than the average coastal DON concentration (13.6±30.4 µmol N L−1; median: 8.0 µmol N L−1), which is itself 39-fold higher than the average coastal DOP concentration (0.34±1.11 µmol P L−1; median: 0.18 µmol P L−1). This dataset will be useful for identifying global spatial and temporal patterns in DOM and will help facilitate the reuse of DOC, DON, and DOP data in studies aimed at better characterizing local biogeochemical processes; closing nutrient budgets; estimating carbon, nitrogen, and phosphorous pools; and establishing a baseline for modelling future changes in coastal waters.

The combination of cyclin-dependent kinase 4/6 inhibitors (CDK4/6i) with endocrine therapy (ET) is the standard-of-care for estrogen receptor (ER)-positive, HER2-negative (ER+/HER2− advanced/metastatic breast cancer (mBC). However, the impact of CDK4/6i on circulating immune cells and circulating tumor cells (CTCs) in patients receiving CDK4/6i and ET (CDK4/6i+ET) remains poorly understood. This was a prospective cohort study including 44 patients with ER+/HER2− mBC treated with CDK4/6i+ET in either first or second line. Peripheral blood samples were collected before (baseline) and 3 months (t2) after therapy. Immune cell’s subsets were quantified by flow cytometry, and microfluidic-captured CTCs were counted and classified according to the expression of cytokeratin and/or vimentin. Patients were categorized according to response as responders (progression-free survival [PFS] ≥ 6.0 months; 79.1%) and non-responders (PFS < 6.0 months; 20.9%). CDK4/6i+ET resulted in significant changes in the hematological parameters, including decreased hemoglobin levels and increased mean corpuscular volume, as well as reductions in neutrophil, eosinophil, and basophil counts. Specific immune cell subsets, such as early-stage myeloid-derived suppressor cells, central memory CD4+ T cells, and Vδ2+ T cells expressing NKG2D, decreased 3 months after CDK4/6i+ET. Additionally, correlations between the presence of CTCs and immune cell populations were observed, highlighting the interplay between immune dysfunction and tumor dissemination. This study provides insights into the immunomodulatory effects of CDK4/6i+ET, underscoring the importance of considering immune dynamics in the management of ER+/HER2− mBC.

Graphene-based materials are attractive adsorbents for water decontamination. In this work, we have produced eco-friendly reduced graphene oxide (rGO)-based sorbents by the hydrothermal reduction of graphene oxide (GO) in presence of caffeic acid (CA) and further modification with chitosan (CA_CS). Scanning electron microscopy observations show porous macrostructures that turn more compact after CA or CA_CS modification. The specific surface area achieves a maximum value of 293 m(2) g(-1) for the pristine rGO foam. The macropores are mainly distributed in a range between 1-170 mu m. The Hg2+ removal efficiency of the rGO-based foams was investigated across several different parameters. The foam modified with caffeic acid exhibited the most promising performance, demonstrating the highest removal efficiency at pH 4-6, with a maximum sorption capacity of 2.79 mg/g as determined by the Sips equation. Kinetic analysis indicates that intraparticle diffusion and the sorption itself are the rate-limiting steps. The notable sorption efficiency, the low desorption rate, and the applicability in real complex water matrices, including tap water, position rGO_CA as a viable material for efficiently capturing Hg(II) from large volumes of water and securely storing it in a small solid volume.

ABSTRACT Some vegetables have the ability to accumulate cadmium (Cd)at levels that are toxic to most other plants. The objective of thisstudy was to evaluate the Cd accumulation and its toxic effects on edible vegetables. Three species were tested: watercress (Barbarea verna); chicory (Cichorium endivia); rocket (Eruca sativa) and four Cd doses (0; 1.5; 3.0; 6.0 mg kg-1), with three replications. We evaluated Cd concentration, fresh and dry mass and SPAD index. We calculated tolerance index (TI), translocation index (TR) and the transfer coefficient (TC). Rocket, chicory and watercress are susceptible to Cd contamination and chicory presented visual symptoms of toxicity (chlorosis and mass loss). The Cd contents above those allowed were 0.6; 0.56 and 1.03 mg kg-1 in rocket, watercress and chicory, respectively, these values were reached by applying doses from 1.5 mg kg-1 for rocket and 3 mg kg-1 for watercress and chicory.

Biosorption successfully remediates saline water contaminated with legacy contaminants, but its effects on the health of marine organisms remain unclear. Therefore, our aim was to address this knowledge gap with data on the accumulation ability, as well as the cytogenetic and biochemical effects in turbot (Scophthalmus maximus). To this end, we exposed turbot for seven days to a mixture of remediated metals (Rem treatments: Cd, Hg, and Pb), with and without the presence of nanoparticles (NP), and compared them with the maximum allowable concentrations (MAC treatment) for effluent discharges. We determined the metal accumulation in the blood and kidney and evaluated haematological changes (red blood cell count, haemoglobin, and mean cell haemoglobin (MCH)) and genotoxicity (erythrocytic nuclear abnormalities assay) in the blood. The results showed that remediation with non-living macroalgae significantly reduced the metallic blood and kidney burdens in the Rem treatments. Furthermore, no genotoxic potential occurred in the Rem and MAC treatments in parallel with the reduction in MCH levels in the Rem treatments, which would reflect hematopoietic disturbances in the MAC. Our results validate biosorption remediation as we achieved a considerable reduction in metal loads while maintaining the health status of fish, highlighting the importance of testing water remediation methods in the biota.

The present study aimed to evaluate the effectiveness of seagrass recolonization as a nature-based solution for the recovery of a coastal area historically contaminated by mercury (Laranjo Bay, Ria de Aveiro, Portugal). A mesocosm approach was employed to assess the resistance of Zostera noltei to transplantation into contaminated sediments collected in-situ (0.5–20 mg kg−1 Hg). At each sampling time (15, 30, 60, 120 and 210 days), the resistance of transplanted Z. noltei was evaluated through growth parameters (biomass and coverage area), photosynthetic performance and elemental composition. Although some significant differences (p ≤ 0.05) were observed between treatments, essentially associated with the elemental composition of plant tissues, the most relevant variations were associated with seasonality. Overall, plants were found to not be affected by sediment contamination, under the tested concentrations, suggesting that recolonization with Z. noltei can be an effective restoration strategy for historically contaminated coastal areas.

In the context of personalized medicine, the analysis of single cells is key in order to understand the origin and evolution of cancer to provide an accurate prognosis. Microfluidics and microdroplets are increasingly used for the handling and understanding of the behavior of single cells, as they offer the perfect isolated environment. However, due to the small volumes handled, it is necessary to couple this technology with an ultrasensitive detection technique. Herein, surface-enhanced Raman scattering (SERS) spectroscopy and droplet microfluidics are combined toward the multiplex phenotypic analysis of single cancer cells. For this, cancer cells are labeled with different SERS tags that recognize membrane proteins and encapsulated individually in microdroplets. Afterward, single cells within microdroplets are imaged by SERS spectroscopy. To the best of the authors' knowledge, this is the first time that a multiplex phenotypic SERS analysis of single cells in microdroplets is shown. This integrated optofluidic platform paves the way toward the multiplex and automated characterization of cell populations in cancer patients.

Water is the most important resource for all kind forms of live. It is a vital resource distributed unequally across different regions of the globe, with populations already living with water scarcity, a situation that is spreading due to the impact of climate change. The reversal of this tendency and the mitigation of its disastrous consequences is a global challenge posed to Humanity, with the scientific community assuming a major obligation for providing solutions based on scientific knowledge. This article reviews literature concerning the development of nanomaterials for water purification technologies, including collaborative scientific research carried out in our laboratory (nanoLAB@UA) framed by the general activities carried out at the CICECO-Aveiro Institute of Materials. Our research carried out in this specific context has been mainly focused on the synthesis and surface chemical modification of nanomaterials, typically of a colloidal nature, as well as on the evaluation of the relevant properties that arise from the envisaged applications of the materials. As such, the research reviewed here has been guided along three thematic lines: 1) magnetic nanosorbents for water treatment technologies, namely by using biocomposites and graphite-like nanoplatelets; 2) nanocomposites for photocatalysis (e.g., TiO2/Fe3O4 and POM supported graphene oxide photocatalysts; photoactive membranes) and 3) nanostructured substrates for contaminant detection using surface enhanced Raman scattering (SERS), namely polymers loaded with Ag/Au colloids and magneto-plasmonic nanostructures. This research is motivated by the firm believe that these nanomaterials have potential for contributing to the solution of environmental problems and, conversely, will not be part of the problem. Therefore, assessment of the impact of nanoengineered materials on eco-systems is important and research in this area has also been developed by collaborative projects involving experts in nanotoxicity. The above topics are reviewed here by presenting a brief conceptual framework together with illustrative case studies, in some cases with original research results, mainly focusing on the chemistry of the nanomaterials investigated for target applications. Finally, near-future developments in this research area are put in perspective, forecasting realistic solutions for the application of colloidal nanoparticles in water cleaning technologies.

[This corrects the article DOI: 10.3389/fchem.2022.1011186.].

Bismuth vanadate (BiVO4) has been investigated as a photocatalyst of great interest due to its ability to harvest photons efficiently in the visible spectral region. In addition, powdered BiVO4 shows high photochemical stability, good dispersibility, and resistance to corrosion in oxidative conditions. Herein, we report the synthesis of monoclinic or tetragonal BiVO4 particles using different methods, as well as the synthesis of hybrids materials through the combination of cobalt ferrite (CoFe2O4) and BiVO4, and their application in the photodegradation of aqueous solutions of sulfamethoxazole (SMX) under simulated solar radiation. We demonstrate that high-crystallinity single-phase monoclinic BiVO4 was synthesized fast and efficiently using a solid-state method and, in combination with magnetic CoFe2O4 particles, gives rise to a hybrid material that can be easily separated from the reaction medium, by applying an external magnetic field, without the need for further downstream treatments.

In recent years, we have seen major advances in the field of liquid biopsy and its implementation in the clinic, mainly driven by breakthrough developments in the area of molecular biology. New developments have seen an integration of microfluidics and also biosensors in liquid biopsy systems, bringing advantages in terms of cost, sensitivity and automation. Without a doubt, the next decade will bring the clinical validation and approval of these combined solutions, which is expected to be crucial for the wide implementation of liquid biopsy systems in clinical routine.

Considering the increasing emergence of new contaminants, such as nanomaterials, mixing with legacy contaminants, including metal(loid)s, it becomes imperative to understand the toxic profile resulting from these interactions. This work aimed at assessing and comparing the individual and combined hepatotoxic and neurotoxic potential of titanium dioxide nanoparticles (TiO2NPs 0.75–75 mg/L), cerium oxide nanoparticles (CeO2NPs 0.075–10 μg/L), arsenic (As 0.01–2.5 mg/L), and mercury (Hg 0.5–100 mg/L) on human hepatoma (HepG2) and neuroblastoma (SH-SY5Y) cells. Viability was assessed through WST-1 (24 h) and clonogenic (7 days) assays and it was affected in a dose-, time- and cell-dependent manner. Higher concentrations caused greater toxicity, while prolonged exposure caused inhibition of cell proliferation, even at low concentrations, for both cell lines. Cell cycle progression, explored by flow cytometry 24 h post-exposure, revealed that TiO2NPs, As and Hg but not CeO2NPs, changed the profiles of SH-SY5Y and HepG2 cells in a dose-dependent manner, and that the cell cycle was, overall, more affected by exposure to mixtures. Exposure to binary mixtures revealed either potentiation or antagonistic effects depending on the composition, cell type and time of exposure. These findings prove that joint toxicity of contaminants cannot be disregarded and must be further explored.

The high demand for greener energy and technological innovation require some crucial elements, such as the rare earths Nd and Dy. Being considered two of the most critical elements (high supply risk), it is vital to recover them from wastes/wastewaters, for later reuse. Here, the influence of operational parameters, such as biosorbent stock density (0.5, 3.0, and 5.5 g L-1), ionic strength (salinity 10 and 30) and contact time (24, 72 and 168 h), in the biosorption/bioaccumulation of Nd and Dy by two living marine macroalgae was evaluated in artificial seawater, seeking the improvement of the process. Results demonstrated that stock density is the most influential parameter, while the ionic strength showed to be a selective parameter, with a major influence only for Dy removal, which can be attributed to the different chemical characteristics observed between light rare earth elements (LREE) and heavy rare earth elements (HREE). For the ranges studied, the greatest removal/recovery for Gracilaria sp. was achieved with a stock density of 3.0 g L-1 at salinity 10, after 72 h for both REEs. For Ulva lactuca optimal conditions were: stock density of 5.5 g L-1 at salinity 10 with a contact time of 72 h for both REEs. Between species, U. lactuca showed to be the most promising, with removal efficiencies up to 98% for Nd and 89% for Dy. Findings substantiate the potential of the proposed process for obtaining Nd and Dy from secondary sources, particularly from low-level contaminated waters. (C) 2021 Elsevier Ltd. All rights reserved.

Increasing emissions of Platinum-Group Elements (PGE) into marine environments may negatively impact ecosystems services and organisms wellbeing. Removing PGE from contaminated systems using efficient and lowcost technologies can therefore provide a sustainable solution to aquatic systems remediation. Previous studies highlight algae's high binding ability to metals in solution. Assessing the viability of various algae species to remove PGE from contaminated solutions, while identifying differences in performance among algae and among elements, was the purpose of this study. For this, six macroalgae species (Ulva lactuca, Ulva intestinalis, Fucus spiralis, Fucus vesiculosus, Osmundea pinnatifida and Gracilaria sp., 3 g L-1) were exposed to PGE (Palladium, Rhodium, Ruthenium, Iridium and Platinum)-spiked seawater (10 and 500 mu g L-1) for 72 h. Removal rates varied with time and among macroalgae and elements. Palladium was easily removed by all species (up to 83 %), while other PGE showed lower affinity to macroalgae. Removal sequence was Pd > Rh > Ru > Ir > Pt. Initial concentration rise induced faster and higher removal. U. lactuca performed best for all elements, while brown macroalgae were the less effective. Macroalgae external area and chemical composition were considered major factors influencing sorption, although each element and macroalgae should be examined individually. Results evidence living macroalgae (particularly U. lactuca) as a promising alternative to remediate PGE contaminated waters.yy

HER2 is a prognostic and predictive biomarker in breast cancer, normally assessed in tumour biopsy and used to guide treatment choices. Circulating tumour cells (CTCs) escape the primary tumour and enter the bloodstream, exhibiting great metastatic potential and representing a real-time snapshot of the tumour burden. Liquid biopsy offers the unique opportunity for low invasive sampling in cancer patients and holds the potential to provide valuable information for the clinical management of cancer patients. This study assesses the performance of the RUBYchip™, a microfluidic system for CTC capture based on cell size and deformability, and compares it with the only FDA-approved technology for CTC enumeration, CellSearch®. After optimising device performance, 30 whole blood samples from metastatic breast cancer patients were processed with both technologies. The expression of HER2 was assessed in isolated CTCs and compared to tissue biopsy. Results show that the RUBYchipTM was able to isolate CTCs with higher efficiency than CellSearch®, up to 10 times more, averaging all samples. An accurate evaluation of different CTC subpopulations, including HER2+ CTCs, was provided. Liquid biopsy through the use of the RUBYchipTM in the clinic can overcome the limitations of histological testing and evaluate HER2 status in patients in real-time, helping to tailor treatment during disease evolution.