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OBJECTIVE: Since little is known about the effects of carbamide peroxide (CP) containing fluoride (F) or calcium (Ca), this study evaluated the effects of experimental and commercially available bleaching agents, with or without F and Ca, on enamel. METHOD AND MATERIALS: Sound enamel slabs were randomly divided into six groups (n = 10): placebo gel (PLA); Whiteness (WHI-10% CP; FGM); Opalescence F (OPA-10% CP+F; Ultradent); Pola Night F (PN-10% CP+F; SDI); and experimental gels: 10% CP + F (CPF) and 10% CP + Ca (CPCa). The samples were submitted to 6-hour gel applications daily for 14 days and stored in remineralizing solution after treatment. Enamel microhardness measurements were performed at baseline and after bleaching. In addition, the analytical concentrations of F and Ca and the pH of the water used to rinse the bleached surface were analyzed by means of ion-selective electrode, atomic absorption spectroscopy, and pH meter, respectively. RESULTS: Enamel surface microhardness significantly decreased after bleaching with nonenhanced 10% CP (WHI). The chemical analyses suggest F uptake promoted by high-concentrate F bleaching gels (CPF, OPA, and PN) and a F loss with nonenhanced 10% CP bleaching gels (PLA, WHI). CP agent enhanced with Ca (CPCa) also caused Ca enamel uptake. CONCLUSION: Enamel was susceptible to mineral changes during bleaching treatment, but mineral loss was minimized by the addition of F and Ca to bleaching agents. [ABSTRACT FROM AUTHOR]

Background: Metal ions perform important functions in the body and their concentrations in cells and tissues are tightly controlled. Alterations in metal homeostasis can occur in certain disease states including infection. In this study urinary excretion of several metals including calcium, cadmium, cobalt, copper, iron, magnesium, nickel, selenium, and zinc in Covid-19 patients (n=35) and control (n=60) individuals, spanning ages and sexes., Methods: Urinary samples were analysed using ICP-MS and the differences in metal concentrations between the Covid-19-infected and control groups were assessed using multivariate data analysis and univariate data analysis employing Student's t-test and Pearson's correlation, with significance set at p<0.05., Results: The urinary concentrations of all metals analysed were significantly higher in the Covid-infected group (compared to controls), with the exception of copper, which was markedly reduced. The increase in calcium excretion was lower and magnesium excretion greater in Covid-19-positive individuals aged 41 or over compared to those aged 40 or lower. Whilst the increase in iron excretion was lower, and cobalt excretion greater in Covid-19-positive males compared to females., Conclusions: The study highlights significant alterations in the handling of a range of metals in the body during Covid-19 infection. It also highlights both age and sex-specific differences in metal homeostasis. The results suggest an important role for copper in the body during Covid-19 infection and suggests that urinary concentrations of copper and other metals may serve as markers to predict progression of the disease., Competing Interests: Declaration of Competing Interest The authors declare that they have no competing interests. The funders had no role in the design of the study, the collection, analyses, or interpretation of data, in the writing of the manuscript, or in the decision to publish the results., (Copyright © 2024 Elsevier GmbH. All rights reserved.)

Sample preparation in an analytical sequence increases the number of errors, is highly time-consuming, and involves the manipulation of hazardous reagents. Therefore, when an improvement in an analytical method is required, the sample preparation step needs to be optimised or redesigned. Moreover, this step can involve significant toxic reagents and a high volume of waste. In that regard, this study proposes a new procedure based on microwave-assisted wet digestion combining two green strategies: a miniaturised system (with a few microlitres of volume) and the only use of hydrogen peroxide. Three biological samples (human serum, urine, and plant in vitro material) were chosen due to their high potential for disease monitoring, toxicological studies, and biotechnology applications. Several trace elements (Ca, Cd, Co, Cu, Fe, Mg, Mn, Mo, Ni, Se, and Zn) were determined by inductively coupled plasma optical emission spectroscopy and inductively coupled plasma mass spectrometry. For human serum and urine, a certified reference material was used to check for accuracy; the recovery ranged from 72% (Cd, ICP-MS) to 105% (Mg, ICP OES) for serum, while for urine, they varied from 82% (Ni, ICP-MS) to 122% (Zn, ICP-MS). For the soybean callus sample (in vitro plant material), a comparison between the proposed method and the acid digestion method was conducted to evaluate the accuracy, and the results agreed. The detection limits were 0.001-60 µg L -1 (lowest for Cd), thus demonstrating a suitable sensitivity. Moreover, the decomposition efficiency was demonstrated by determining the residual carbon, and a low amount was found in the final product digested (below 0.8% w v -1 ). A green metric approach was calculated for the proposed method, and according to AGREEprep software, it was found to be around 0.4. Finally, the method was applied to urine samples collected in patients with COVID-19 and soybean callus cultivated with silver nanoparticles. This sample preparation method is a new acidless and miniaturised alternative for elemental analysis involving biological samples., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

Carbon nanotubes are promising materials for biomedical applications like delivery systems and tissue scaffolds. In this paper, magnetic carbon nanotubes (M-CNTs) covered with bovine serum albumin (M-CNTs-BSA) or functionalized with hydrophilic monomers (M-CNTs-HL) were synthesized, characterized, and evaluated concerning their interaction with Caco-2 cells. There is no comparison between these two types of functionalization, and this study aimed to verify their influence on the material's interaction with the cells. Different concentrations of the nanotubes were applied to investigate cytotoxicity, cell metabolism, oxidative stress, apoptosis, and capability to cross biomimetic barriers. The materials showed cytocompatibility up to 100 μg mL -1 and a hemolysis rate below 2 %. Nanotubes' suspensions were allowed to permeate Caco-2 monolayers for up to 8 h under the effect of the magnetic field. Magnetic nanoparticles associated with the nanotubes allowed estimation of permeation through the monolayers, with values ranging from 0.50 to 7.19 and 0.27 to 9.30 × 10 -3  μg (equivalent to 0.43 to 6.22 and 0.23 to 9.54 × 10 -2  % of the initially estimated mass of magnetic nanoparticles) for cells exposed and non-exposed to the magnets, respectively. Together, these results support that the developed materials are promising for applications in biomedical and biotechnological fields., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Eduardo Costa Figueiredo reports financial support was provided by Federal University of Alfenas. Mariana Azevedo Rosa reports financial support was provided by Coordination of Higher Education Personnel Improvement. Eduardo Costa Figueiredo reports financial support was provided by Minas Gerais State Foundation of Support to the Research. Eduardo Costa Figueiredo reports financial support was provided by National Council for Scientific and Technological Development. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

This study investigated the effect of AgNPs and AgNO 3 , at concentrations equivalent, on the production of primary and secondary metabolites on transgenic soybean plants through an NMR-based metabolomics. The plants were cultivated in a germination chamber following three different treatments: T0 (addition of water), T1 (addition of AgNPs), and T2 (addition of AgNO 3 ). Physiological characteristics, anatomical analyses through microscopic structures, and metabolic profile studies were carried out to establish the effect of abiotic stress on these parameters in soybean plants. Analysis of the 1 H NMR spectra revealed the presence of amino acids, organic acids, sugars, and polyphenols. The metabolic profiles of plants with AgNP and AgNO 3 were qualitatively similar to the metabolic profile of the control group, suggesting that the application of silver does not affect secondary metabolites. From the PCA, it was possible to differentiate the three treatments applied, mainly based on the content of fatty acids, pinitol, choline, and betaine.

The aim of this work is to evaluate two quantitative methods, based on the external calibration applied in laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis, known as (i) analytical curve and (ii) one-point calibration, using the concept of matrix matching to quantify three potentially toxic elements (PTEs) in wood samples. These can biologically register changes in the abiotic environment and be applied to monitoring climate change or environmental toxicity. In this case, standard sample preparation was evaluated to prepare the standard pellets using Pinus taeda species as a matrix-matching concept. Six pellets of P. taeda, with different Pb, Cd, and Ba concentrations, were prepared to build the analytical curve and one-point calibration strategies. The LA-ICP-MS parameters were optimised for 206 Pb, 208 Pb, 112 Cd, 114 Cd, 137 Ba, and 138 Ba isotope analysis in wood samples. The two calibration strategies provided 74-110% analytical recovery from certified reference materials and similar results to those obtained by ICP-MS through the acid digestion of environmental wood samples from São Paulo City (Brazil). This demonstrated the applicability of the one-point calibration strategy in quantifying PTEs in wood samples, which could be used with environmental analyses. Differences observed between the Ba isotope results obtained via LA-ICP-MS and ICP-MS quantification were related to sampling by LA-ICP-MS and the ICP-MS sample introduction, as well as to laser matrix and transport effects because of the difference between the wood species evaluated., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

A better understanding of the relative roles of internal climate variability and external contributions, from both natural (solar, volcanic) and anthropogenic greenhouse gas forcing, is important to better project future hydrologic changes. Changes in the evaporative demand play a central role in this context, particularly in tropical areas characterized by high precipitation seasonality, such as the tropical savannah and semi-desertic biomes. Here we present a set of geochemical proxies in speleothems from a well-ventilated cave located in central-eastern Brazil which shows that the evaporative demand is no longer being met by precipitation, leading to a hydrological deficit. A marked change in the hydrologic balance in central-eastern Brazil, caused by a severe warming trend, can be identified, starting in the 1970s. Our findings show that the current aridity has no analog over the last 720 years. A detection and attribution study indicates that this trend is mostly driven by anthropogenic forcing and cannot be explained by natural factors alone. These results reinforce the premise of a severe long-term drought in the subtropics of eastern South America that will likely be further exacerbated in the future given its apparent connection to increased greenhouse gas emissions., (© 2024. The Author(s).)

Interactions between proteins and metal ions and their complexes are important in many areas of the life sciences, including physiology, medicine, and toxicology. Despite the involvement of essential elements in all major processes necessary for sustaining life, metalloproteomes remain ill-defined. This is not only owing to the complexity of metalloproteomes, but also to the non-covalent character of the complexes that most essential metals form, which complicates analysis. Similar issues may also be encountered for some toxic metals. The review discusses recently developed approaches and current challenges for the study of interactions involving entire (sub-)proteomes with such labile metal ions. In the second part, transition metals from the fourth and fifth periods are examined, most of which are xenobiotic and also tend to form more stable and/or inert complexes. A large research area in this respect concerns metallodrug-protein interactions. Particular attention is paid to separation approaches, as these need to be adapted to the reactivity of the metal under consideration.

The imbalance in metal homeostasis can be associated with several human diseases, and exposure to increasing concentrations of metals promotes cell stress and toxicity. Therefore, understanding the cytotoxic effect of metal imbalance is important to unravel the biochemical mechanism of homeostasis and the action of potential protective proteins against metal toxicity. Several studies, including gene deletion in yeast, provide evidence indicating the possible indirect involvement of cochaperones from the Hsp40/DNAJA family in metal homeostasis, possibly through modulating the activity of Hsp 70.This work first investigated the effect of zinc and copper on the conformation and function of the human Hsp40 cochaperone DNAJA1, a zinc-binding protein. DNAJA1 was capable to complement the phenotype of a yeast strain deleted of the ydj1 gene, which was more sensitive to the presence of zinc and copper than the wild-type strain. To gain further insight about the role of the DNAJA family in metal binding, the recombinant human DNAJA1 protein was studied. Zinc removal from DNAJA1 affected both its stability and ability to act as a chaperone, i.e., to protect other proteins from aggregation. The reintroduction of zinc restored the native properties of DNAJA1 and, surprisingly, the addition of copper partially restored the native properties., Competing Interests: Declaration of competing interest The authors declare no competing interests., (Copyright © 2023 Elsevier B.V. and Société Française de Biochimie et Biologie Moléculaire (SFBBM). All rights reserved.)

A rapid and environmentally friendly synthesis of thermodynamically stable silica nanoparticles (SiO 2 -NPs) from heating via microwave irradiation (MW) compared to conductive heating is presented, as well as their evaluations in a soy plant culture. The parameters of time and microwave power were evaluated for the optimization of the heating program. Characterization of the produced nanomaterials was obtained from the dynamic light scattering (DLS) and zeta potential analyses, and the morphology of the SiO 2 -NPs was obtained by transmission electron microcopy (TEM) images. From the proposed synthesis, stable, monodisperse, and amorphous SiO 2 -NPs were obtained. Average sizes reported by DLS and TEM techniques were equal to 11.6 nm and 13.8 nm, respectively. The water-stable suspension of SiO 2 -NPs shows a zeta potential of -31.80 mV, and the homogeneously spheroidal morphology observed by TEM corroborates with the low polydispersity values (0.300). Additionally, the TEM with fast Fourier transform (FFT), demonstrates the amorphous characteristic of the nanoparticles. The MW-based synthesis is 30 times faster, utilizes 4-fold less reagents, and is ca. 18-fold cheaper than conventional synthesis through conductive heating. After the synthesis, the SiO 2 -NPs were added to the soil used for the cultivation of soybeans, and the homeostasis for Cu, Ni, and Zn was evaluated through the determination of their total contents by inductively coupled plasma mass spectrometry (ICP-MS) in soy leaves and also through bioimages obtained using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Although the results corroborate through both techniques, they also show the influence of these nanoparticles on the elemental distribution of the leaf surface with altered homeostasis of such elements from both transgenic crops compared to the control group., Competing Interests: The authors declare no potential conflict of interest., (This journal is © The Royal Society of Chemistry.)

Background: Nanoparticles (NPs) are currently found in the world in the form of natural colloids and volcanic ash, as well as in anthropogenic sources, such as nanofertilizers; however, in the literature, there is still a lack of toxicological evidence, risk assessment, and regulations about the use and environmental impact of NPs in the agroindustrial system. Therefore, the aim of this work was to evaluate alterations caused by the presence of AgNPs during the development of soybean plants., Methods: The BRS232 non-transgenic (NT) soybean plant and 8473RR (T RR ) and INTACTA RR2 PRO (T Intacta ) transgenic soybean plants were irrigated for 18 days under controlled conditions with deionized water (control), AgNPs, and AgNO 3 . The isotopes 107 Ag + , 55 Mn + , 57 Fe + , 63 Cu + , and 64 Zn + were mapped in leaves, using 13 C + as an internal standard (IS), and carried out using a laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) technique with a Nd:YAG (213 nm) laser source in the imagagin mode using the LA-iMageS software and also Mathlab., Results: Leaf images showed a low Ag translocation, indicated by the basal signal of this ion. Additionally, the presence of Ag in the ionic form and as NPs altered the homeostasis of 112 Cd + , 64 Zn + , 55 Mn + , 63 Cu + , and 57 Fe + in different ways. Quantitative image analysis was performed for Cu., Conclusion: The behavior of T RR and T Intacta plants was different in the presence of ionic silver or AgNPs, confirming that the metabolism of these two plants, despite both being transgenic, are different. Through the images, it was observed that the response of plants was different in the face of the same stress conditions during their development., Competing Interests: Declaration of Competing Interest The authors declare that they have no competing interests. The funders had no role in the design of the study, the collection, analyses, or interpretation of data, in the writing of the manuscript, or in the decision to publish the results., (Copyright © 2023 Elsevier GmbH. All rights reserved.)

Somatic embryogenesis is an essential technology for high productivity in plant culture, and with the advent of nanotechnology, the synergism between these areas could be the answer to developing concepts involving Agriculture 4.0. This perspective permeates both areas, presenting the opportunities and challenges for the consolidation of ideas involving the application of nanoparticles to micropropagation processes (callus induction, preservation, growing, and modification, among others) and also to the production of byproducts (such as biosynthesis of nanoparticles and production of secondary metabolites). Nanotoxicological aspects are also emphasized as well as up-to-date instrumentation involved in these studies.

The heterogeneity properties shown by cells or unicellular organisms have led to the development of analytical methods at the single-cell level. In this sense, considering the importance of trace elements in these biological systems, the inductively coupled plasma mass spectrometer (ICP-MS) configured for analyzing single cell has presented a high potential to assess the evaluation of elements in cells. Moreover, advances in instrumentation, such as coupling laser ablation to the tandem configuration (ICP-MS/MS), or alternative mass analyzers (ICP-SFMS and ICP-TOFMS), brought significant benefits, including sensitivity improvement, high-resolution imaging, and the cell fingerprint. From this perspective, the single-cell ICP-MS has been widely reported in studies involving many fields, from oncology to environmental research. Hence, it has contributed to finding important results, such as elucidating nanoparticle toxicity at the cellular level and vaccine development. Therefore, in this review, the theory of single-cell ICP-MS analysis is explored, and the applications in this field are pointed out. In addition, the instrumentation advances for single-cell ICP-MS are addressed., (Copyright © 2022 Elsevier GmbH. All rights reserved.)

Hydrocarbons may have a natural or anthropogenic origin and serve as a source of carbon and energy for microorganisms in Antarctic soils. Herein, 16S rRNA gene and shotgun sequencing were employed to characterize taxonomic diversity and genetic potential for hydrocarbon degradation of the microbiome from sediments of sites located in two Antarctic islands subjected to different temperatures, geochemical compositions, and levels of presumed anthropogenic impact, named: Crater Lake/Deception Island (pristine area), Whalers Bay and Fumarole Bay/Deception Island (anthropogenic-impacted area), and Hannah Point/Livingston Island (anthropogenic-impacted area). Hydrocarbon concentrations were measured for further correlation analyses with biological data. The majority of the hydrocarbon-degrading genes were affiliated to the most abundant bacterial groups of the microbiome: Proteobacteria and Actinobacteria. KEGG annotation revealed 125 catabolic genes related to aromatic hydrocarbon (styrene, toluene, ethylbenzene, xylene, naphthalene, and polycyclic hydrocarbons) and aliphatic (alkanes and cycloalkanes) pathways. Only aliphatic hydrocarbons, in low concentrations, were detected in all areas, thus not characterizing the areas under study as anthropogenically impacted or nonimpacted. The high richness and abundance of hydrocarbon-degrading genes suggest that the genetic potential of the microbiome from Antarctic sediments for hydrocarbon degradation is driven by natural hydrocarbon occurrence., (© The Author(s) 2022. Published by Oxford University Press on behalf of FEMS.)

The study of chemical speciation and the refinement and expansion of omics-based methods are both consolidated and highly active research fields. Although well established, such fields are extremely dynamic and are driven by the emergence of new strategies and improvements in instrumentation. In the case of omics-based studies, subareas including lipidomics, proteomics, metallomics, metabolomics and foodomics have emerged. Here, speciomics is being proposed as an "umbrella" term, that incorporates all of these subareas, to capture studies where the evaluation of chemical species is carried out using omics approaches. This paper contextualizes both speciomics and the speciome, and reviews omics applications used for species identification through examination of proteins, metalloproteins, metabolites, and nucleic acids. In addition, some implications from such studies and a perspective for future development of this area are provided. SIGNIFICANCE: The synergic effect between chemical speciation and omics is highlighted in this work, demonstrating an emerging area of research with a multitude of possibilities in terms of applications and further developments. This work not only defines and contextualizes speciomics and individual speciomes, but also demonstrates with some examples the great potential of this new interdisciplinary area of research., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Background: Several studies have suggested that COVID-19 is a systemic disease that can affect several organs, including the brain. In the brain, specifically, viral infection can cause dyshomeostasis of some trace elements that promote complex biochemical reactions in specialized neurological functions., Objective: Understand the neurovirulence of SARS-CoV-2 and the relationship between trace elements and neurological disorders after infection, and provide new insights on the drug development for the treatment of SARS-CoV-2 infections., Methods: The main databases were used to search studies published up September 2021, focusing on the role of trace elements during viral infection and on the correct functioning of the brain., Results: The imbalance of important trace elements can accelerate SARS-CoV-2 neurovirulence and increase the neurotoxicity since many neurological processes can be associated with the homeostasis of metal and metalloproteins. Some studies involving animals and humans have suggested the synapse as a vulnerable region of the brain to neurological disorders after viral infection. Considering the combined evidence, some mechanisms have been suggested to understand the relationship between neurological disorders and imbalance of trace elements in the brain after viral infection., Conclusion: Trace elements play important roles in viral infections, such as helping to activate immune cells, produce antibodies, and inhibit virus replication. However, the relationship between trace elements and virus infections is complex since the specific functions of several elements remain largely undefined. Therefore, there is still a lot to be explored to understand the biochemical mechanisms involved between trace elements and viral infections, especially in the brain., (Copyright © 2022 Elsevier GmbH. All rights reserved.)

Background: The distribution of trace elements in tree rings although poorly known may be useful to better understand environmental changes, pollution trends, long-term droughts, forest dieback processes, and biology of trees., Method: Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is used for imaging micronutrients and potentially toxic elements distribution, allowing the investigation of trace elements at high spatial resolution within the tree rings. To ensure a more efficient determination of micronutrients and potentially toxic elements, LA-ICP-MS instrumental conditions were optimized and carbon, a major element in wood, is used as an internal standard during analysis to correct for random fluctuations., Results: Spatial distributions maps of Ba, Cu, Fe, Mn, Ni, and Pb in growth layers of six tropical tree species were built-up using the LA-iMageS software, namely: Amburana cearensis (Fabaceae), Cedrela fissilis (Meliaceae), Hymenaea courbaril (Fabaceae), Maclura tinctoria (Moraceae), Parapiptadenia zehntneri (Fabaceae), Peltogyne paniculata (Fabaceae). A correlation between the trace element composition and different cell types (parenchyma, fiber, and vessel) was distinctly observed. It was observed a general pattern of Ba, Cu, Ni, Mn, and Pb accumulation mainly in the axial parenchyma and vessels. But the elemental composition of xylem cells is strongly species dependent. The multivariate analysis also points to a distinct accumulation of minerals between heartwood and sapwood in the same species., Conclusions: Imaging both essential and deleterious element distributions in the tree rings may improve visualization and can effectively contribute to understanding the lifetime metabolism of trees and evaluating the effects of environmental changes related to climatic seasonality, pollution, and future paleoclimate reconstructions., (Copyright © 2021 Elsevier GmbH. All rights reserved.)

We report a complete set of strategies for characterization and an accurate determination of gold in metallic nanoparticles. For this, gold nanorods (AuNR) were synthesized by using the surfactant hexadecyltrimethylammonium bromide (CTAB) as the stabilizer and shape-directing agent. The surfactant CTAB forms a bilayer structure around the nanoparticles and became a challenge for the development of the microwave-assisted decomposition of the AuNR colloid. The bilayer structure of CTAB prevents the Au 3+ release for the acidic media during the decomposition procedure. To overcome this limitation, a combination of low sample volume consumption (only 200 μL), an acidic mixture of reverse aqua regia (1:3 v/v, HCl:HNO 3 ), and sulfuric acid, and a microwave program was used. The gold quantification by ICP-MS and checked through the ICP OES, demonstrated that the seed-mediated growth method used for the AuNR synthesis has a high yield, presenting ca. 100% of gold content (ca. 100 mg L -1 of gold concentration) in the post-synthesis colloid (AuNR-total) as well as in the colloid after a washing step (AuNR-res). The microwave-assisted decomposition procedure also demonstrated to be efficient in the acidic decomposition of the gold-silver core-shell nanoparticle (Au@AgNR), which presents a high content of polyvinylpyrrolidone (PVP) (Mw ~55000 g mol -1 ) acting as a stabilizer, in addition to the matrix with CTAB. The results demonstrated an accurate recovery of ca. 100% of gold content for the Au@AgNR regarding the gold nanorod before the growth of the silver shell (AuNR&#95;Core). The proposed microwave-assisted decomposition platform demonstrated to be an efficient, reliable, and robust characterization tool for the gold quantification in metallic nanoparticles, presenting no interference of the complex matrix with high organic content., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Understanding the biological process involving metals and biomolecules in the brain is essential for establishing the origin of neurological disorders, such as neurodegenerative and psychiatric diseases. From this perspective, this critical review presents recent advances in this topic, showing possible mechanisms involving the disruption of metal homeostasis and the pathogenesis of neurological disorders. We also discuss the main challenges observed in metallomics studies associated with neurological disorders, including those related to sample preparation and analyte quantification.

Background: An in vitro physiologically relevant test based on the standard Unified Bioaccessibility Method (UBM) combined with inductively coupled plasma mass spectrometry was performed in this study to ascertain the elemental bioaccessibility pools of tape tea as emerging low-cost abuse drug under fasted conditions., Methods: Elemental quantification in tape tea and body fluid extracts was performed by an inductively coupled plasma quadrupole mass spectrometer - ICP-MS, and for sample preparation of the bioaccessibility extracts prior to ICP-MS analysis, a microwave-assisted acid decomposition was applied by using a microwave oven. The Unified Bioaccessibility Method (UBM) was considered for investigation of elemental bioaccessibility in tape tea, required a full set of organic compounds, salts, and enzymes., Results: Considering total element evaluation through ICP-MS, Co, Ni, Mn, and Zn are found at the highest concentrations in the sample, namely 415 ± 36, 202 ± 55, 1389 ± 225 and 2397 ± 197 μg L -1 , respectively. Regarding the oral bioaccessibility test, after both gastric and gastrointestinal extractions Co, Ni, and Mn are fully bioaccessible while for Zn the bioaccessibility is ca. 66 %., Conclusion: According to the first results in the literature proposed for these samples, the bioaccessibility results indicate an increment in day-to-day total element concentration and depending on the concentration of each element that an individual consumes in its usual diet, the total concentration can exceed the TDI. There are several possible toxic effects caused by the excess of Co, Ni and Mn, which might be expected by their high total concentrations., (Copyright © 2020 Elsevier GmbH. All rights reserved.)

This work evaluates different generations of transgenic (cp4-EPSPS gene) and non-transgenic soybean plants through proteomics and metabolomics. For proteomics purpose, 24 differentially abundant protein spots were found through 2-D DIGE, being 4 belonging to transgenic plants. From this total, 19 were successfully identified, storage proteins as predominant class. Some identified proteins are involved in growing and cell division, and stress response, such as LEA and dehydrin. For metabolomics, 17 compounds were putatively annotated, mainly belonging to the secondary metabolism, such as flavonoids. From these analyzes, all generations and varieties of the soybean are prone to be differentiate by PLS-DA. According to our results, transgenic plants appear to be more stable than non-transgenic ones. In addition, the omics-based approaches allowed access some relations between those differential spot proteins and metabolites, mainly those storage proteins and flavonoid., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Rationale: A viable and accurate method based on high-power ultrasound-assisted microextraction and inductively coupled plasma mass spectrometry was developed to determine metals in human serum from patients with bipolar disorder and schizophrenia., Methods: A simple and rapid sample preparation method using a cup-horn sonoreactor was developed. The acid concentration of HNO 3 (10, 20, and 40% v/v) and HCl (1, 5, 15, and 30% v/v) of the extraction solution, the sonication time (1, 3, 6, and 10 min), and the sonication amplitude (20, 40, 60, and 80%) were evaluated. Cd, Cu, Fe, Li, Pb, and Zn were determined in serum samples from patients with bipolar disorder and schizophrenia, and from healthy controls. Quantitative metal recoveries using the proposed method were compared under the same conditions using an ultrasonic bath, magnetic stirring, and microwave-assisted digestion., Results: Optimum extraction conditions were obtained using HNO 3 (40% v/v) + HCl (30% v/v) as the extraction solution with 3 min sonication time and 60% sonication amplitude. Significant differences were observed among the methods compared. On application of the sample preparation method based on high-power ultrasound-assisted microextraction coupled with inductively coupled plasma mass spectrometry, Pb and Cd in all the studied samples were below the limit of detection of our method. Compared with healthy controls, the concentration of Cu, Li, Fe, and Zn was found to be significantly higher for the bipolar disorder group, while these metals and Li were found at a lower level for the group diagnosed with schizophrenia., Conclusions: Principal component analysis showed a significant separation for the groups studied based on their ionomic profiles after the application of high-power ultrasound-assisted microextraction as a sample preparation strategy., (© 2020 John Wiley & Sons, Ltd.)

Rationale: An evaluation of bipolar disorder (BD) and schizophrenia (SCZ) was carried out, from a metallomics point of view, using native conditions, attempting to preserve the interaction between metals and biomolecules., Method: For this task, blood serum samples from healthy individuals and patients were compared. In addition, the profiles of metal ions and metalloids involved in the pathologies were quantified, and a comparison was carried out of the protein profile in serum samples of healthy individuals and diseased patients., Results: After optimization and accuracy evaluation of the method, different concentrations of Li, Mg, Mn and Zn were observed in the samples of BD patients and high levels of copper for SCZ patients, indicating an imbalance in the homeostasis of important micronutrients. The treatment, especially with lithium, may be related to competition between metallic ions. BD-related metallobiomolecules were detected, preserving the binding between metal ions and biomolecules, with four fractions detected in the ultraviolet range (280 nm). Four fractions were collected by high-performance liquid chromatography/inductively coupled plasma mass spectrometry (HPLC/ICP-MS) and the proteins were identified by liquid chromatography/tandem mass spectrometry (LC/MS/MS). The Ig lambda chain V-IV region Hil, immunoglobulin heavy constant gama 1 (IGHG1) and beta-2-glycoprotein 1 (or ApoH) was identified in SCZ samples, suggesting its relationship with mood disorders. Surprisingly, Protein IGKV2D-28 was identified only in BD samples, opening up new possibilities for studies regarding the role of this protein in BD., Conclusions: This approach brings new perspectives to the comprehension of mood disorders, highlighting the importance of metallomics science in disease development. This strategy showed an innovative potential for evaluating mood disorders at the proteomic level, making it possible to identify proteins related to mood disorders and BD., (© 2019 John Wiley & Sons, Ltd.)

The widespread application of nanoparticles (NPs) in recent times has caused concern because of their effects in biological systems. Although NPs can be produced naturally, industrially synthesized NPs affect the metabolism of a given organism because of their high reactivity. The biotransformation of NPs involves different processes, including aggregation/agglomeration, and reactions with biomolecules that will be reflected in their toxicity. Several analytical techniques, including inductively coupled plasma mass spectrometry (ICP-MS), have been used for characterizing and quantifying NPs in biological samples. In fact, in addition to providing information regarding the morphology and concentration of NPs, ICP-MS-based platforms, such as liquid chromatography/ICP-MS, single-particle ICP-MS, field-flow fractionation (asymmetrical flow field-flow fractionation)-ICP-MS, and laser ablation-ICP-MS, yield elemental information about molecules. Furthermore, such information together with speciation analysis enlarges our understanding of the interaction between NPs and biological organisms. This study reports the contribution of ICP-MS-based platforms as a tool for evaluating NPs in distinct biological samples by providing an additional understanding of the behavior of NPs and their toxicity in these organisms., (© 2020 John Wiley & Sons, Ltd.)

Although air pollution decreased in some cities that shifted from an industrial to a service-based economy, and vehicular emission regulation became more restrictive, it is still a major risk factor for mortality worldwide. In central São Paulo, Brazil, air quality monitoring stations and tree-ring analyses revealed a decreasing trend in the concentrations of particulate matter and metals. Such trends, however, may not be observed in industrial districts located in the urban periphery, where the usual mobile sources may be combined with local stationary sources. To evaluate environmental pollution in an industrial district in southeastern São Paulo, we assessed its spatial variability, by measuring magnetic properties and concentrations of Al, Ba, Ca, Cl, Cu, Fe, K, Mg, Mn, P, S, Sr, Zn in the bark of 62 trees, and its temporal trends, by measuring Cd, Cu, Ni, Pb, V, Zn in tree rings of three trees. Source apportionment analysis based on tree barks revealed two clusters with high concentrations of metals, one related to vehicular and industrial emissions (Al, Ba, Cu, Fe, Zn) in the east side of the industrial cluster, and the other related to soil resuspension (Cu, Zn, Mn) in its west side. These patterns are also supported by the magnetic properties of bark associated with iron oxides and titanium-iron alloy concentrations. Dendrochemical analyses revealed that only the concentrations of Pb consistently decreased over the last four decades. The concentrations of Cd, Cu, Ni, V, and Zn did not significantly decrease over time, in contrast with their negative trends previously reported in central São Paulo. This combined biomonitoring approach revealed spatial clusters of metal concentration in the vicinity of this industrial cluster and showed that the local population has not benefited from the decreasing polluting metal concentrations in the last decades., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Background: Imbalances in metal concentrations have been suggested to contribute to the pathophysiology of different brain disorders, such as bipolar disorder (BD) and schizophrenia (SCZ)., Objectives: The aim of this exploratory study is to evaluate the association between the concentrations of macro/trace elements in serum from BD and SCZ patients considering the effects from different treatments., Methods: Eleven subjects with SCZ, seven with BD treated with lithium (BDL) and eight subjects with BD treated with other medications except lithium (BDN) were recruited for the study, as well as eleven healthy controls (HC). Serum concentrations of eleven macro/trace elements (Se, Zn, Fe, K, Ca, Mg, P, Al, Cu, Mn, and Ni) were determined using inductively coupled plasma mass spectrometry (ICP-MS)., Results: Se and Zn concentrations were significantly lower for patients with SCZ and BD in comparison to HC by one-way ANOVA test. Moreover, serum concentrations for Fe were significantly higher (p < 0.05) in BDN (548 ± 92 μg L -1 ) and SCZ (632 ± 279 μg L -1 ) in comparison to HC (421 ± 121 μg L -1 ). A significant negative correlation was reported between Se and Fe in BDL group (r = -0.935, p < 0.05). In addition, a significantly higher Cu/Zn ratio was determined in SCZ group against HC (ratio = 2.4, p = 0.028)., Conclusions: The obtained results suggest that the imbalance in Fe concentrations is an effect of BD treatment. Lithium is supposed to have an antagonist effect for Se in BDL patients. A negative correlation reported between Fe and BMI in SCZ group could be related to antipsychotic treatment and the Cu/Zn ratio reported could be considered as a suggesting parameter to relate oxidative stress to SCZ. Future studies including larger number of patients with SCZ and BD before and after treatment are necessary to confirm the investigative results presented herein., Competing Interests: Declaration of Competing Interest The authors declare that there are no conflicts of interest., (Copyright © 2020 Elsevier GmbH. All rights reserved.)

Although high levels of dissolved arsenic were detected in surface and ground waters of Nhecolândia, a sub-region of the vast Pantanal wetlands in Brazil, the possible sources have not been clearly identified and the potential release from the wetland to the draining rivers has not been investigated. In this study we measured the dissolved As content in all the rivers and small streams that supply the southern Pantanal region, as well as in the two main rivers draining the wetland, i.e., the Cuiaba and Paraguay rivers and tributaries. In addition, Arsenic in surface waters, perched water-table, soils and sediments from 3 experimental sites located in the heart of Nhecolândia were compared. On the one hand, the results show the absence of As contamination in rivers that supply the Pantanal floodplain, as well as a lack of significant release from the floodplain to the main drains. The As contents in the rivers are <2 μg L -1 , with variations that depend on the lithology and on the geomorphology at the collection point (uplands or floodplain). On the other hand, they confirm the regional extension of As contamination in Nhecolândia's alkaline waters with some values above 3 mg L -1 . Arsenic is mainly in the arsenate form, and increases with the evaporation process estimated from sodium ion concentrations. The pH of soil solution and surface water increases rapidly during evapo-concentration up to values above 9 or 10, preventing adsorption processes on oxides and clay minerals and promoting the retention of dissolved arsenic in solution. Solutions from organic soil horizons show higher As contents in relation to Na, attributed to the formation of ternary complex As-(Fe/Al)-OM. In this alkaline pH range, despite high levels of dissolved As, soil horizons and lake sediments in contact with these waters show As values that correspond to uncontaminated environments., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Forensic science is an emerging field driven by a number of factors, and the development of different methods of analyses, instruments, and techniques is of great help to experts in the field. Sampling and sample preparation in forensic cases are of utmost importance, and therefore, the methods for processing (or not) the samples are critical for acquiring accurate results. Some alternatives for attaining the minimalist concept, i.e. little or no sample treatment, are discussed in this review. For elemental analysis, analytical techniques, such as X-ray spectrometry, laser-ablation mass spectrometry, laser-induced breakdown spectrometry, inductively coupled plasma mass spectrometry and optical emission spectrometry, and Mössbauer spectrometry are overviewed. Molecular analysis, such as Raman spectroscopy, and ambient ionization mass spectrometry are discussed. Some representative examples are presented that involve in situ analysis, counterfeit bank notes and documents, post-mortem and bone analyses, and forensic analysis of drugs, glass, fingerprints, biological fluids and explosives., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Ydj1, a class B J-protein (Hsp40) in yeast, has two zinc finger domains in each monomer and belongs to an important co-chaperone family that plays crucial roles in cells, such as recognizing and binding partially folded proteins and assisting the Hsp70 chaperone family in protein folding. Yeast cells with ydj1 deletion were less efficient at coping with zinc stress than wild-type cells, and site-directed mutagenesis studies that impair or delete the zinc finger region have confirmed the importance of this region to the function of Ydj1; however, little is known about whether the presence of zinc is critical for the function of the protein. To gain insights into the effect of zinc on the structure and function of Ydj1 without having to modify its primary structure, a method was developed and optimized to quantify and remove the zinc from the protein. Recombinant Ydj1 was produced and purified, and its zinc content was determined by ICP-MS. The result showed that two zinc atoms were bound per monomer of protein, a good indicator that all sites were saturated. To optimize the removal of the bound zinc, variations on chelating agent (EDTA, EGTA, 1,10-phenanthroline), chelator concentration, reaction time, pH, and temperature were tested. These procedures had no effect on the overall secondary structure of the protein, since no significant changes in the circular dichroism spectrum were observed. The most significant removal (91 ± 2%, n = 3) of zinc was achieved using 1,10-phenanthroline (1 × 10 -3 mol L -1 ) at 37°C with a pH 8.5 for 24 h. Zinc removal affected the stability of the protein, as observed by a thermal-induced unfolding assay showing that the temperature at the middle of the transition (Tm) decreased from 63 ± 1°C to 60 ± 1°C after Zn extraction. In addition, the effect on the ability of Ydj1 to protect a model protein (luciferase) against aggregation was completely abolished after the Zn removal procedure. The main conclusion is that zinc plays an important role in the stability and activity of Ydj1. Additionally, the results highlight the medical importance of chaperones, as altered zinc homeostasis is implicated in many diseases, such as neurodegenerative disorders.

Açaí pulp consumption has increased in Brazil and worldwide. Recently, a high average content of manganese (450 mg/kg) was observed in açaí pulp, raising the hypothesis of toxicological effects associated to its ingestion. However, the total concentration of an element does not reflect the real benefits and risks of consuming a food. In this context, the total, bioaccessible and bioavailable concentrations of Fe and Mn were assessed in 9 açaí pulps. Fe and Mn contents ranged from 27.6 to 73 and from 145 to 1197 mg kg -1 , respectively. Fe and Mn bioaccessibilities represented from 29 to 40 and from 39 to 55% of total amounts. Fe bioavailabilities were lower than LOQ and those of Mn varied from 8 to 17% of total. A daily consumption of 100 g of açaí pulp exceeds by at least 1.5-fold the recommended Mn daily intakes for adults whereas poorly contributes to Fe intakes. Since the lowest Mn bioaccessible and bioavailable fraction corresponded to a Mn intake value higher than the tolerable upper intakes for children and that high amounts of Mn intake may impair Fe absorption, higher açaí consumption may be worrisome. Future nutritional, toxicological and speciation studies must be undertaken., (Copyright © 2019 Elsevier GmbH. All rights reserved.)

A combination between gel electrophoresis and smartphone technology is applied for quantifying proteins in a serum sample. Electrophoresis not only allows one to separate different proteins but also to build-up a calibration curve for those proteins. To expand its applicability, a smartphone allows one to capture a gel image, through its camera. Additionally, the treatment of the data extracted through each protein band is performed using a freely available program (PhotoMetrix), which is downloaded to one's own smartphone. Through this approach, the quantification of proteins such as albumin, immunoglobulin, and carbonic anhydrase is performed in a serum sample by acquiring images using 32 × 32 pixels for each image in the region of the protein bands. An LOQ from 1.9 to 2.4 μg and r 2  > 0.980 may be obtained. Comparing results through the analyses of the gels using Image Master 2D Platinum 6.0 software reflects good agreement (95% confidence level) between the results. SIGNIFICANCE STATEMENT: In many biological studies involving structural analysis or biophysical and biochemical characterization after purification process, or even in assays of protein:protein interaction, the estimation of protein quantity and protein purity is a fundamental step. However, even although many methodologies are proposed in the literature for quantifying proteins, they present some limitations, once are frequently expensive and require solution sample. In addition, they usually do not quantify the specific active concentration, but the total amount. Thus, it is necessary to develop an easy, fast and low-cost method that allows to quantify and to evaluate protein purity of reactional system, for example, a protein:protein interaction. In this way, we presented a simple strategy based on the integration of Smartphone technology and gel electrophoresis, where SDS-PAGE provides multiple information regarding the quality of the protein, such as the presence of degradation products, as well as if there was interaction reaction between proteins. Then, the smartphone detects the proteins in the SDS-PAGE gel, allowing to evaluate purity degree and the quantity, at microgram level, of the protein. We believe that the combination of these features may help to increase the productivity and accuracy of gel electrophoresis analysis, and the results obtained through a smartphone, easily achieved in our pockets., (Copyright © 2018 Elsevier B.V. All rights reserved.)

To evaluate the effects of silver nanoparticles (AgNP) exposition, transgenic (through gene cp4EPSPS) and non-isogenic non-transgenic soybeans were cultivated in the presence or absence of AgNP or silver nitrate (AgNO 3 ) at 50 mg/kg of silver. Physiological aspects of the plants including mass production and development of roots, proteomics such as protein amount and differential proteins, enzymes and lipid peroxidation were determined after exposition. The mass production of non-transgenic plants treated with AgNP or AgNO 3 was decreased by 25 and 19%, respectively, on their mass based, while for transgenic soybean this effect was observed for AgNP cultivation only. Fifty-nine proteins were identified from the differentially abundant spots by two-dimensional difference gel electrophoresis and nano-electrospray ionization liquid chromatography coupled tandem mass spectrometry. Identified species as ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO), ATP synthase, superoxide dismutase (SOD), related to plant metabolism were less abundant for the cultivation with either AgNP and AgNO 3 than the control. Finally, this work demonstrated significant correlation as evidenced by changes in lipid peroxidation content and catalase activity, which were a result of exposure to either AgNP or AgNO 3 cultivations. Further, necrotic areas in the basal part of the stems and damage or chlorotic areas were found in the leaves. SIGNIFICANCE: Once nanoparticles have been employed for several applications in recent years and they can be released in the environmental matrices, this study highlights proteomic and enzymatic alterations in transgenic and non-transgenic soybeans, an important crop, after cultivation with silver nanoparticles. Such strategy employing proteomic and enzymatic approaches to evaluate soybeans exposed to silver nanoparticles has not yet been reported. Therefore, the results obtained in this study can expand the information concerning the effects of silver nanoparticles in soybean plants., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Because of strong impact of omics in many fields, and the complexity of the samples when focusing on areas such as genomics, (metallo)proteomics, metabolomics, among others, it is easy to rationalize the great importance that sample preparation has for achieving reliable results, mainly considering plant science. Then, this chapter points out applications of the sample preparation focusing on such areas, and a diversity of strategies, techniques, and procedures is highlighted and commented.

Antipsychotics are the main line of treatment for schizophrenia, a disorder that affects about 1% of the worldwide population. Considering the poor performance of antipsychotics on patients, this work aimed at detecting alterations in the elemental profile resulting from the use of this type of medication using an elemental fingerprinting strategy. We evaluated 56 plasma samples from schizophrenia patients by inductively coupled plasma mass spectrometry (ICP-MS) before (t0) and after 6 weeks (t6) of treatment. The level of response of the patients (good vs. poor responders) and the medications taken were considered. Zinc, aluminum, phosphorus, and iron levels were found to be increased, whereas sodium, potassium, calcium, and magnesium levels decreased after treatment. Aluminum presented a higher level in poor responders at t0 when compared to good responders. At t6, iron showed an increased level when compared to t0 for good responders; however, its level remained constant in poor responders. The results of this exploratory study provide clues for further investigations on the role of metal ions in the treatment of schizophrenia.

Alongside the Brazil nut's role as an excellent source of vitamins, oil, fatty acids, lipids and nutrients, it is also recognized as a rich source of selenium. The pathway along which selenium and sulfur are metabolized in plants is theorized to be the same as that used for tellurium. Total tellurium content and its bioaccessibility are then evaluated by ICP-MS. Interferences and sample preparation are evaluated for the accurate determination of tellurium, and the accuracy determined through analysis of the certified reference material 1643e. A concentration of 4.02 ± 0.391 ng g -1 is obtained as an average concentration through external and internal calibrations. Through this reliable result, tellurium bioaccessibility in Brazil nuts is obtained via an in vitro validated unified bioaccessibility method. Values of 32% and 30% of total tellurium are available in the gastric and gastrointestinal fractions, respectively., (Copyright © 2018 Elsevier GmbH. All rights reserved.)

An ionomic approach is conducted for evaluating the silver distribution, in different soybean plant compartments, as well as its influence on the homeostasis of some macro (P and S) and micro (Cu, Fe, Mn and Zn) nutrients. Silver is added to transgenic and non-transgenic soybean plants as nanoparticles or silver nitrate for comparative purposes. The transgenic plants translocate a higher amount of silver (100 and 65% for silver nanoparticles and silver nitrate expositions, respectively) than non-transgenic, and considering the treatments, the cultivation with silver nanoparticles results in a higher translocation rate (100 and 21% for transgenic and non-transgenic plants, respectively). In addition, significant differences are found (p < 0.05) considering those macro and micronutrients in all plant compartments, mainly in the roots of those treated plants, indicating not only that both silver forms evaluated interfere in the plant metabolism, but also their toxicities., (Copyright © 2018 Elsevier GmbH. All rights reserved.)

About four decades ago, the relationship between dialysis-dementia and aluminum (Al) began to be established. The restriction of drugs containing Al and improvements on water quality used for dialysis resulted in the clinical disappearance of Al intoxication. However, high prevalence of Al deposition in bone tissue from Brazilian dialysis patients is still being detected. Through the case report of a patient on hemodialysis (HD) for one year, presenting significant Al deposition in bone tissue, we speculated if this problem is not being underestimated. We used extensive investigation to identify potential sources of Al exposure with a careful review of medication history and water quality controls. Al concentration was measured by different methods, including mass spectrometry, in poly-electrolyte concentrate solutions and solution for peritoneal dialysis, in an attempt to elucidate the possible sources of contamination. The objective of this case report is to alert the medical community about a potential high prevalence of Al deposition in bone tissue and to discuss the possible sources of contamination in patients with chronic kidney disease (CKD).

Experiments in saturated soil columns were performed to investigate the transport and retention of 25 nm and 75 nm silver nanoparticles stabilized with polyvinylpyrrolidone (PVP-AgNPs) in two Brazilian soils (sandy and sandy-clay). The normalized concentration of the PVP-AgNPs was obtained through a flow injection analysis method based on the surface plasmon ressonance effect of the metallic nanoparticles. The use of the ultraviolet-visible spectroscopy (UV-Vis) allows a rapid and low-cost analysis. The obtained breakthrough curves (BCs) were modeled with a deterministic model of solute transport in steady conditions of water flow and considering two regions of non-physical equilibrium; this model allowed the determination of the hydrodynamic parameters. It was found that the process occurs in condition of non-equilibrium, with a low mass transfer for larger NP, and that the process is predominantly advective and affected by the pore size of the soil packed in the columns. The BCs for PVP-AgNPs obtained by UV-Vis spectroscopy were compared with the BCs obtained by ICP-MS and with BCs of the bromide anion, confirming that the nanoparticles have a low retention and few modifications when transported through the soil column. These PVP-AgNPs are highly mobile and can be transported through the studied tropical soils, representing a potential environmental problem, due to the possibility of these materials reaching groundwater. On the contrary, the conservative behavior of PVP-AgNPs in the studied tropical soils, indicates its potential use as tracers, substituting the bromide anion which has been demonstrated to be not a good tracer in the same conditions., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

A new ultrafast ultrasonic-based method for shotgun proteomics as well as label-free protein quantification in urine samples is developed. The method first separates the urine proteins using nitrocellulose-based membranes and then proteins are in-membrane digested using trypsin. The enzymatic digestion process is accelerated from overnight to four minutes using a sonoreactor ultrasonic device. Overall, the sample treatment pipeline comprising protein separation, digestion and identification is done in just 3h. The process is assessed using urine of healthy volunteers. The method shows that male can be differentiated from female using the protein content of urine in a fast, easy and straightforward way. 232 and 226 proteins are identified in urine of male and female, respectively. From this, 162 are common to both genders, whilst 70 are unique to male and 64 to female. From the 162 common proteins, 13 are present at levels statistically different (p < 0.05). The method matches the analytical minimalism concept as outlined by Halls, as each stage of this analysis is evaluated to minimize the time, cost, sample requirement, reagent consumption, energy requirements and production of waste products., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Chemical speciation approaches is an inherent part of metallomics, once metals/metalloids and organic structures need to be currently evaluated for attaining metallomics studies. Then, this chapter focuses on the applications of the chemical speciation applied to the human health risk, food and human diet, drugs, forensic, nanoscience, and geological metallomics, also pointing out the advances in such area. Some aspects regarding sample preparation is commented along this chapter, and some strategies for maintaining the integrity of the metallomics information are also emphasized.

The mitigation of Cd-stress through Si addition to Arabidopsis thaliana cultivation is evaluated in terms of total metal content, proteomic and enzymatic approaches. Four different treatment are evaluated: TC (control, without Si or Cd addition), T1 (with Si addition), T2 (with Cd addition), and T3 (with Si and Cd addition). Through the total determination of Cd and Si in Arabidopsis leaves, the Cd concentration decreased by half when T2 is compared with T3 treatment. In terms of proteomic approach, some differential protein species are achieved by comparative proteomics through 2-D DIGE of all treatments evaluated. Fifty six differential abundant proteins spots (abundance factor ≥1.5) are detected, and 32 of them accurately characterized and identified through nESI-LC-MS/MS. These proteins are differentially produced due to Cd and/or Si treatments, which mainly include proteins associated with disease/defense, energy and metabolism. The most difference in the abundance of proteins is found due to the presence or absence of Si in plants treated with Cd. Regarding the enzymatic approaches, a major increase is found on APX, CAT and GR activities (5.0, 3.5, and 1.5-fold, respectively). The same is observed for the MDA concentration because an increase of 3-fold is found when TC are compared to those treated with T2. However, when T3 plants are evaluated, the enzymes activities are similar to TC plants. Differences ranging from 6.5 to 21% are detected considering the activity of SOD in the treatments (T1-T3 x TC). The decreased activities of CAT, APX and GR and lower MDA concentration indicate a lower reactive oxygen species production in plants treated with Cd and Si. Based on a proteomics point of view it is possible to conclude that Si-Cd interactions occur at protein level and allow plants to respond effectively to the Cd toxicity, revealing the active involvement of Si on mechanisms involved in Si-induced Cd tolerance in Arabidopsis plants. Additionally, from an enzymatic point of view, it is possible to conclude that Si positively interferes diminishing the negative effects of Cd in Arabidopsis by decreasing the reactive oxygen species generation and increasing the antioxidative enzyme activity., (Copyright © 2017 Elsevier GmbH. All rights reserved.)

Purpose: An exploratory analysis using proteomic strategies in blood serum of patients with bipolar disorder (BD), and with other psychiatric conditions such as Schizophrenia (SCZ), can provide a better understanding of this disorder, as well as their discrimination based on their proteomic profile., Methods: The proteomic profile of blood serum samples obtained from patients with BD using lithium or other drugs (N=14), healthy controls, including non-family (HCNF; N=3) and family (HCF; N=9), patients with schizophrenia (SCZ; N=23), and patients using lithium for other psychiatric conditions (OD; N=4) were compared. Four methods for simplifying the serum samples proteome were evaluated for both removing the most abundant proteins and for enriching those of lower-abundance: protein depletion with acetonitrile (ACN), dithiothreitol (DTT), sequential depletion using DTT and ACN, and protein equalization using commercial ProteoMiner® kit (PM). For proteomic evaluation, 2-D DIGE and nanoLC-MS/MS analysis were employed., Results: PM method was the best strategy for removing proteins of high abundance. Through 2-D DIGE gel image comparison, 37 protein spots were found differentially abundant (p<0.05, Student's t-test), which exhibited ≥2.0-fold change of the average value of normalized spot intensities in the serum of SCZ, BD and OD patients compared to subject controls (HCF and HCNF). From these spots detected, 13 different proteins were identified: ApoA1, ApoE, ApoC3, ApoA4, Samp, SerpinA1, TTR, IgK, Alb, VTN, TR, C4A and C4B., Conclusions: Proteomic analysis allowed the discrimination of patients with BD from patients with other mental disorders, such as SCZ. The findings in this exploratory study may also contribute for better understanding the pathophysiology of these disorders and finding potential serum biomarkers for these conditions., (Copyright © 2017 The Canadian Society of Clinical Chemists. Published by Elsevier Inc. All rights reserved.)

The efficiency of three different depletion methods to remove the most abundant proteins, enriching those human serum proteins with low abundance is checked to make more efficient the search and discovery of biomarkers. These methods utilize magnetic nanoparticles (MNPs), chemical reagents (sequential application of dithiothreitol and acetonitrile, DTT/ACN), and commercial apparatus based on immunoaffinity (ProteoMiner, PM). The comparison between methods shows significant removal of abundant protein, remaining in the supernatant at concentrations of 4.6±0.2, 3.6±0.1, and 3.3±0.2µgµL -1 (n=3) for MNPs, DTT/ACN and PM respectively, from a total protein content of 54µgµL -1 . Using GeLC-MS/MS analysis, MNPs depletion shows good efficiency in removing high molecular weight proteins (>80kDa). Due to the synergic effect between the reagents DTT and ACN, DTT/ACN-based depletion offers good performance in the depletion of thiol-rich proteins, such as albumin and transferrin (DTT action), as well as of high molecular weight proteins (ACN action). Furthermore, PM equalization confirms its efficiency in concentrating low-abundant proteins, decreasing the dynamic range of protein levels in human serum. Direct comparison between the treatments reveals 72 proteins identified when using MNP depletion (43 of them exclusively by this method), but only 20 proteins using DTT/ACN (seven exclusively by this method). Additionally, after PM treatment 30 proteins were identified, seven exclusively by this method. Thus, MNPs and DTT/ACN depletion can be simple, quick, cheap, and robust alternatives for immunochemistry-based protein depletion, providing a potential strategy in the search for disease biomarkers., (Copyright © 2017 Elsevier B.V. All rights reserved.)

This paper describes for the first time the use of paper-based analytical devices at crime scenes to estimate the post-mortem interval (PMI), based on the colorimetric determination of Fe 2+ in vitreous humour (VH) samples. Experimental parameters such as the paper substrate, the microzone diameter, the sample volume and the 1,10-phenanthroline (o-phen) concentration were optimised in order to ensure the best analytical performance. Grade 1 CHR paper, microzone with diameter of 5 mm, a sample volume of 4 μL and an o-phen concentration of 0.05 mol/L were chosen as the optimum experimental conditions. A good linear response was observed for a concentration range of Fe 2+ between 2 and 10 mg/L and the calculated values for the limit of detection (LOD) and limit of quantification (LOQ) were 0.3 and 0.9 mg/L, respectively. The specificity of the Fe 2+ colorimetric response was tested in the presence of the main interfering agents and no significant differences were found. After selecting the ideal experimental conditions, four HV samples were investigated on paper-based devices. The concentration levels of Fe 2+ achieved for samples #1, #2, #3 and #4 were 0.5 ± 0.1, 0.7 ± 0.1, 1.2 ± 0.1 and 15.1 ± 0.1 mg/L, respectively. These values are in good agreement with those calculated by ICP-MS. It important to note that the concentration levels measured using both techniques are proportional to the PMI. The limitation of the proposed analytical device is that it is restricted to a PMI greater than 1 day. The capability of providing an immediate answer about the PMI on the crime scene without any sophisticated instrumentation is a great achievement in modern instrumentation for forensic chemistry. The strategy proposed in this study could be helpful in many criminal investigations., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The uptake and accumulation of Cd in sunflower seeds represents an important pathway for imputing potentially toxic metals into human and animal food. In this way, bioimaging of Cd and micronutrients (Cu, Fe and Mn) in the seeds of sunflower grown in soil contaminated with Cd are performed. For this task, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is used in quantitative approach, considering four groups: precursor, control, Cd-low (50mg) and Cd-high (700mg). For attaining our proposals, ICP-MS (nebulizer and auxiliary flow rates and radiofrequency power) and LA (laser intensity, frequency and spot size) parameters were optimized, and the analytical signal improved to 197%, 217%, 232%, and 283%, for 57 Fe, 112 Cd, 55 Mn and 63 Cu, respectively. The accuracy of proposed method using LA-ICP-MS is evaluated comparing the CRM results (Tomato leaves, NIST SRM 1573a). No difference is found at 95% confidence level. Regarding Cd accumulation in sunflower seeds, the results indicated that cadmium is translocated to seeds, and the cotyledons showed the highest concentration (Cd-high group), ranging from 10 to 20µgg -1 . Considering both total concentration and the distribution in the seeds, Cd uptake is responsible to the homeostasis misbalance of micronutrients, which play an essential role in the sunflower metabolism. Such results highlight the importance of bioimaging evaluation, in the translocation and accumulation of metals, contributing to expand the information available of this culture., (Copyright © 2017 Elsevier B.V. All rights reserved.)

In-vitro physiologically relevant gastrointestinal extraction based on the validated Unified BARGE Method (UBM) is in this work hyphenated to inductively coupled plasma optical emission spectrometry in a batch-flow configuration for real-time monitoring of oral bioaccessibility assays with high temporal resolution. A fully automated flow analyzer is designed to foster in-line filtration of gastrointestinal extracts at predefined times (≤15 min) followed by on-line multi-elemental analysis of bioaccessible micro-nutrients, viz., Cu, Fe and Mn, in well-defined volumes of extracts (300 μL) of transgenic and non-transgenic soybean seeds taken as model samples. The hyphenated flow setup allows for recording of temporal extraction profiles to gain full knowledge of the kinetics of the gastrointestinal digestion processes, including element leaching and concomitant precipitation and complexation reactions hindering bioavailability. Simplification of the overall standard procedure is also feasible by identification of steady-state extraction conditions. Our findings indicate that reliable measurement of oral bioaccessible pools of Cu, Fe and Mn in soybean might be obtained in less than 180 min rather than 240 min as endorsed by UBM. Using a matrix-matched external calibration, limits of detection according to the 3s criteria were 0.5 μg/g for Mn, 0.6 μg/g for Cu and 2.3 μg/g for Fe. Trueness of the automatic bioaccessibility method was confirmed by mass balance validation with recoveries ranging from 87 to 116% regardless of the target element and sample. Cu was the micronutrient with the highest oral bioaccessibility ranging from 73% to 83% (7.5-7.9 μg/g) for non-transgenic and transgenic soybeans, respectively, followed by Mn and Fe within the ranges of 29-31% (10.8-11.4 μg/g) and 11-15% (8-14 μg/g), respectively, regardless of transgenesis. The proposed kinetic method is proven suitable for fast and expedient estimation of the nutritional value of soybeans and elucidation of the potential effect of transgenesis onto bioaccessible fractions of elements., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Bipolar disorder (BD) is a complex and costly psychiatric disorder, which affects one hundred million people worldwide. Due to its heterogeneity, correct BD diagnosis is still a challenge. In order to overcome this issue, different bioanalytical strategies have been proposed in the literature recently. Among these strategies, proteomic approaches have arisen as some of the most promising in the area. Thus, recent applications suggest protein profiles to further refine the proteome of BD as well as the discovery of novel protein biomarkers to facilitate diagnostics. In this review, the state-of-art of proteomic research in BD is summarized. Furthermore, important aspects of proteomics for understanding of BD, such as sample type and size, sampling, sample preparation, gel-based and gel-free proteomics, proteomic quantitative and protein validation are overviewed.

The presence of calcium, iron, and zinc bound to human milk secretory IgA (sIgA) was investigated. The sIgA components were first separated by two-dimensional polyacrylamide gel electrophoresis and then identified by electrospray ionization-tandem mass spectrometry (ESI MS MS). The metal ions were detected by flame atomic absorption spectrometry after acid mineralization of the spots. The results showed eight protein spots corresponding to the IgA heavy chain constant region. Another spot was identified as the transmembrane secretory component. Calcium was bound to both the transmembrane component and the heavy chain constant region, while zinc was bound to the heavy chain constant region and iron was not bound with the identified proteins. The association of a metal ion with a protein is important for a number of reasons, and therefore, the findings of the present study may lead to a better understanding of the mechanisms of action and of additional roles that sIgA and its components play in human milk., (Copyright © 2014 Elsevier Ltd. All rights reserved.)