Microplastics ingestion and endocrine disrupting chemicals (EDCs) by breeding seabirds in the east tropical Atlantic: Associations with trophic and foraging proxies (δ15N and δ13C).

In this study we found that endocrine disrupting chemicals (EDCs) were omnipresent in a tropical seabird community comprising diverse ecological guilds and distinct foraging and trophic preferences. Because EDCs tend to bioaccumulate within the food web and microplastics can absorb and release harmful chemical compounds, our findings draw attention to the potential threats to wildlife. Thus, the goal of this study was to investigate the role of plastic ingestion, trophic and foraging patterns (δ15N and δ13C) of five tropical seabird species breeding in sympatry, on the exposure to EDCs, namely Polybrominated diphenyl ethers (PBDEs), methoxylated polybrominated diphenyl ethers (MeO-PBDEs) and personal care products (PCPs, e.g., musk fragrances and UV-filters). Results indicated that microplastics occurrence and EDCs detection frequency varied among species. Microplastics occurrence was higher in species with dual and coastal foraging strategies. Preen oil had higher levels of MeO-PBDEs and PCPs, while serum had higher levels of PBDEs. In brown boobies, the correlation between microplastics and ∑PBDEs levels was significant, suggesting that microplastics ingestion is a key PBDEs route. Trophic position (δ15N) plays a key role in PBDEs accumulation, particularly in Bulwer's petrel, which occupies a high trophic position and had more specialized feeding ecology than the other species. MeO-PBDEs were linked to foraging habitat (δ13C), although the link to foraging locations deserves further investigation. Overall, our findings not only fill key gaps in our understanding of seabirds' exposure to microplastics and EDCs, but also provide an essential baseline for future research and monitoring efforts. These findings have broader implications for the marine wildlife conservation and pollution management in sensitive environments, such as the tropical regions off West Africa.

Effectiveness of the third wave cognitive behavior therapy for peripartum depression treatment-A systematic review.

INTRODUCTION: To investigate the effectiveness of third-wave cognitive behavior therapies in the treatment of peripartum depression. METHOD: A systematic review of the effectiveness of psychological interventions in treating peripartum depression focus on the Third Wave has been conducted. The electronic databases MEDLINE, PsycINFO, Web of Science and Clinical Trials were searched, using a combination of different search terms. Data were independently extracted by two authors and a synthesis of the results was offered. Methodological quality was assessed by three authors, using ROBE-2 and MINORS. Search date was conducted in February 2022 and the search was re-run in November 2022 for new entries. FINDINGS: Six papers were included and reported, focused on, the effectiveness of Third Wave approach interventions in reducing depressive symptoms. Papers included the following intervention approaches: Behavioral intervention (n = 2), Mindfulness (n = 2), Dialectical Behavior Therapy (n = 1) and Acceptance and Commitment Therapy (n = 1). All six papers were consistent in that interventions lead to a decrease in depression symptoms. However, risk of bias evaluation showed that all were critical low, but one paper was high quality. CONCLUSION AND IMPLICATIONS FOR PRACTICE AND RESEARCH: Systematic review showed that third-wave approaches are promising in effectiveness to reduce depression symptoms in peripartum women. However, more high-quality studies with follow-up are needed.

Cellular dynamics as a marker of normal-to-cancer transition in human cells.

Normal-to-cancer (NTC) transition is known to be closely associated to cell´s biomechanical properties which are dependent on the dynamics of the intracellular medium. This study probes different human cancer cells (breast, prostate and lung), concomitantly to their healthy counterparts, aiming at characterising the dynamical profile of water in distinct cellular locations, for each type of cell, and how it changes between normal and cancer states. An increased plasticity of the cytomatrix is observed upon normal-to-malignant transformation, the lung carcinoma cells displaying the highest flexibility followed by prostate and breast cancers. Also, lung cells show a distinct behaviour relative to breast and prostate, with a higher influence from hydration water motions and localised fast rotations upon NTC transformation. Quasielastic neutron scattering techniques allowed to accurately distinguish the different dynamical processes taking place within these highly heterogeneous cellular systems. The results thus obtained suggest that intracellular water dynamics may be regarded as a specific reporter of the cellular conditions-either healthy or malignant.

Half a century of systematic research on heat-induced colour changes in bone - A review.

Skeletal human remains presenting heat-induced changes have been a focus of study for a long time. However, there is still a long way to go for the anthropologists to be able to fully interpret and understand these changes. Heat-induced colour modifications are one of the least understood phenomena in bone, displaying a variety of exceptions (e.g., tints of yellow, orange, blue, green, pink, and red) to the expected colour variations that bone can produce when exposed to high temperatures (i.e., ivory, brown, black, various shades of grey, and white). In addition to these, there is a lack of uniformization in the literature regarding the methods to determine the exact colourations observed and the nomenclature used, giving way to subjective descriptions. However, commitment to more objective and reliable methods is visible in more recent research. In this review, we compiled data published in the literature throughout the years to portray the state of the art regarding the potential of heat-induced colour changes for inferring the circumstances of death and the applicability of these methods in the legal framework.

Physical and chemical characterization of drill cuttings: A review.

Drill cuttings comprise a mixture of rocks generated during drilling activities of exploration and production of oil and gas. These residues' properties are variable, depending on several drilling parameters and drilled rock composition. Many scientific studies have been published regarding the characterization of these residues. Articles summarizing these residues' characteristics and toxicity data are poorly explored in the literature. This work reviews the principal methods used to characterize drill cuttings and data about these residues' properties. Some authors have reported the large content of Zn in drill cuttings. These cuttings can be associated with base fluids (as olefins, varying from C11 to C18), and some time crude oil (high range of TPH, unresolved complex mixtures, and PAH compounds). Acute and chronic toxicity tests have shown negative impacts of different types of fluids, the components of these fluids, and cuttings on other marine organisms.

Development of Films from Spent Coffee Grounds' Polysaccharides Crosslinked with Calcium Ions and 1,4-Phenylenediboronic Acid: A Comparative Analysis of Film Properties and Biodegradability.

Most polymeric materials are synthetic and derived from petroleum, hence they accumulate in landfills or the ocean, and recent studies have focused on alternatives to replace them with biodegradable materials from renewable sources. Biodegradable wastes from food and agroindustry, such as spent coffee grounds (SCGs), are annually discarded on a large scale and are rich in organic compounds, such as polysaccharides, that could be used as precursors to produce films. Around 6.5 million tons of SCGs are discarded every year, generating an environmental problem around the world. Therefore, it was the aim of this work to develop films from the SCGs polysaccharide fraction, which is comprised of cellulose, galactomannans and arabinogalactans. Two types of crosslinking were performed: the first forming coordination bonds of calcium ions with polysaccharides; and the second through covalent bonds with 1,4-phenylenediboronic acid (PDBA). The films with Ca2+ ions exhibited a greater barrier to water vapor with a reduction of 44% of water permeability vapor and 26% greater tensile strength than the control film (without crosslinkers). Films crosslinked with PDBA presented 55-81% higher moisture contents, 85-125% greater permeability to water vapor and 67-150% larger elongations at break than the films with Ca2+ ions. Film biodegradability was demonstrated to be affected by the crosslinking density, with the higher the crosslinking density, the longer the time for the film to fully biodegrade. The results are promising and suggest that future research should focus on enhancing the properties of these films to expand the range of possible applications.

Anthropogenic debris ingestion in a tropical seabird community: Insights from taxonomy and foraging distribution.

Oceans have been considered as an unlimited supply of goods and services, but resource extraction and waste disposal became ubiquitous and have been damaging the health of marine ecosystems. Finding suitable sentinel species of the human impacts on the oceans is thus imperative, since they may work as early warnings of disruptive situations. In this study, we investigated how taxonomy and foraging distribution influenced the occurrence of anthropogenic debris among five seabird species inhabiting the tropical Atlantic region. Occurrence of anthropogenic debris was assessed using faeces of breeding individuals as a proxy of ingestion. A total of 268 particles were extracted from all samples. The categories "fragments" and "fibres", as well as the colour "blue", were the most prevalent characteristics across species. There was a high diversity of polymers from cellulosic particles to synthetic plastics (Anthropogenic Cellulosic 26.9 %; Polyester 7.7 %; Varnish 5.8 %; Polypropylene 1.9 %). Species with a more coastal foraging strategy exhibited higher occurrence and number of anthropogenic debris when compared to species foraging comparably more in pelagic areas. This suggests that anthropogenic debris are more prevalent in coastal foraging areas, where human activities occur in higher number and frequency (e.g., fisheries) and sources of freshwater input from inland are at close distance. These results provide more evidence to the growing perception on the ubiquity and diversity of anthropogenic debris in the marine environment, and further support the usefulness of using seabirds as bio-indicators of anthropogenic pollution in both neritic and oceanic regions.

Pd(II) and Pt(II) Trinuclear Chelates with Spermidine: Selective Anticancer Activity towards TNBC-Sensitive and -Resistant to Cisplatin.

Triple-negative breast cancer (TNBC) is one of the most aggressive forms of breast cancer and constitutes 10-20% of all breast cancer cases. Even though platinum-based drugs such as cisplatin and carboplatin are effective in TNBC patients, their toxicity and development of cancer drug resistance often hamper their clinical use. Hence, novel drug entities with improved tolerability and selectivity profiles, as well as the ability to surpass resistance, are needed. The current study focuses on Pd(II) and Pt(II) trinuclear chelates with spermidine (Pd3Spd2 and Pt3Spd2) for evaluating their antineoplastic activity having been assessed towards (i) cisplatin-resistant TNBC cells (MDA-MB-231/R), (ii) cisplatin-sensitive TNBC cells (MDA-MB-231) and (iii) non-cancerous human breast cells (MCF-12A, to assess the cancer selectivity/selectivity index). Additionally, the complexes' ability to overcome acquired resistance (resistance index) was determined. This study revealed that Pd3Spd2 activity greatly exceeds that displayed by its Pt analog. In addition, Pd3Spd2 evidenced a similar antiproliferative activity in both sensitive and resistant TNBC cells (IC50 values 4.65-8.99 µM and 9.24-13.34 µM, respectively), with a resistance index lower than 2.3. Moreover, this Pd compound showed a promising selectivity index ratio: >6.28 for MDA-MB-231 cells and >4.59 for MDA-MB-231/R cells. Altogether, the data presently gathered reveal Pd3Spd2 as a new, promising metal-based anticancer agent, which should be further explored for the treatment of TNBC and its cisplatin-resistant forms.

Differentiating present-day from ancient bones by vibrational spectroscopy upon acetic acid treatment.

Acetic acid treatment for an accurate differentiation between ancient and recent human bones was assessed using Raman and FTIR-ATR spectroscopies. Each set of skeletal samples was analysed by these techniques, prior and after chemical washing, in order to determine the variations in bone´s chemical composition and crystallinity. Bone samples were collected from several independent sources: recent bones burned under controlled experimental conditions or cremated, and archaeological (XVII century and Iron Age). The effect of acetic acid, expected to impact mostly on carbonates, was clearly evidenced in the spectra of all samples, particularly in FTIR-ATR, mainly through the bands typical of A- and B-carbonates. Furthermore, as seen for crematoria and archaeological samples, acetic acid was found to remove contaminants such as calcium hydroxide. Overall, acetic acid treatment can be an effective method for removing carbonates (exogenous but possibly also endogenous) and external contaminants from bone. However, these effects are dependent on the skeletal conditions (e.g. post-mortem interval and burning settings). In addition, this chemical washing was shown to be insufficient for an unequivocal discrimination between recent and archaeological skeletal remains. Based on the measured IR indexes, only cremated bones could be clearly distinguished.

Temperature-induced formation of Pd nanoparticles in heterogeneous nanobiohybrids: application in C-H activation catalysis.

The effect of the temperature in the synthesis of Pd nanoparticles in the metal-enzyme biohybrids is evaluated. The effect on the formation, size, and morphology of nanoparticles was evaluated using C. antarctica B lipase as the protein scaffold. XRD analyses confirmed the formation of crystalline Pd(0) as the metal species in all cases. TEM analyses revealed spherical crystalline nanoparticles with average diameter size from 2 nm at 4 °C synthesis to 10 nm obtained at 50 °C synthesis. The thermal phenomenon was also critical in the final hybrid formation using more complex enzymes, where the relation of the protein structure and temperature and the influence of the latter has been demonstrated to be critical in the reducing efficiency of the enzyme in the final Pd nanoparticle formation, in the metal species, or even in the final size of the nanoparticles. Different Pd biohybrids were evaluated as catalysts in the C-H activation of protected l-tryptophan under mild conditions. Pd@CALB4 showed the best results, with >99% conversion for C-2 arylation in methanol at room temperature with a TOF value of 64 min-1, being 2 or 4 times higher than that of the other synthesized hybrids. This catalyst showed a very high stability and recyclability, maintaining >95% activity after three cycles of use.

Evaluation of the Cytotoxic Effect of Pd2Spm against Prostate Cancer through Vibrational Microspectroscopies.

Regarding the development of new antineoplastic agents, with a view to assess the selective antitumoral potential which aims at causing irreversible damage to cancer cells while preserving the integrity of their healthy counterparts, it is essential to evaluate the cytotoxic effects in both healthy and malignant human cell lines. In this study, a complex with two Pd(II) centers linked by the biogenic polyamine spermine (Pd2Spm) was tested on healthy (PNT-2) and cancer (LNCaP and PC-3) prostate human cell lines, using cisplatin as a reference. To understand the mechanisms of action of both cisplatin and Pd2Spm at a molecular level, Fourier Transform Infrared (FTIR) and Raman microspectroscopies were used. Principal component analysis was applied to the vibrational data, revealing the major metabolic changes caused by each drug, which were found to rely on DNA, lipids, and proteins, acting as biomarkers of drug impact. The main changes were observed between the B-DNA native conformation and either Z-DNA or A-DNA, with a higher effect on lipids having been detected in the presence of cisplatin as compared to Pd2Spm. In turn, the Pd-agent showed a more significant impact on proteins.

Practical synthesis and biological screening of sulfonyl hydrazides.

A methodology for the synthesis of sulfonyl hydrazides mediated by hypervalent iodine is described. Taking advantage of the umpolung properties of hypervalent iodine reagents, the polarity of sodium sulfinate salts is reversed, and a key intermediate is generated and reacted with mono- and disubstituted hydrazines. To highlight the practical utility of this protocol, a diverse range of sulfonyl hydrazides were synthesized in yields up to 62%. Furthermore, a gram-scale reaction was performed, showing the robustness of the procedure. Mechanistic studies, including DFT calculations, were performed and the bioactivity of the generated compounds was evaluated.

Synthesis of Bis(3-indolyl)methanes Mediated by Potassium tert-Butoxide.

The indole moiety is an important N-heterocycle found in natural products, and a key structural component of many value-added chemicals including pharmaceuticals. In particular, bis(3-indolyl)methanes (BIMs) are an important subgroup of indoles, composed of two indole units. Herein, we report the development of a simple method to access BIMs derivatives in yields of up to 77 % by exploiting a tBuOK-mediated coupling reaction of indoles and benzyl alcohols.

Plastisphere assemblages differ from the surrounding bacterial communities in transitional coastal environments.

Marine plastic contamination is currently considered ubiquitous in aquatic environments. These particles present a resistant and hydrophobic substrate known to promote microbial colonisation and biofilm formation in aquatic ecosystems, the so-called "Plastisphere", raising concerns about its potential ecological risks. The novelty of this topic translates into a relatively low number of studies, including for transitional coastal ecosystems, such as sandy beaches or estuarine habitats. Therefore, a sampling campaign was conducted in two transitional coastal ecosystems - the Mondego estuary (Portugal) - and adjacent sandy beaches (winter 2020). After visual sorting and filtering of suspected particles under sterile conditions DNA extraction and 16S rRNA amplicon high throughput sequencing was used to profile the bacterial communities on the surface of plastic particles and from those found on the water and sediments from the sampled transitional coastal ecosystems. All particles were characterised according to type, colour and size, and the chemical nature of the particles was determined by FTIR-ATR or µ-FTIR spectroscopy after DNA extraction. All samples contained plastics in several sizes (micro and mesoplastics), shapes (higher abundances of fragments on beaches and fibres in the estuarine waters), colours and polymers. Although no significant differences were detected in the α-diversity indexes of the bacterial communities between plastics and their surrounding environments, data showed the occurrence of unique key bacterial groups on plastics from both environments, such as pathogens (e.g., Lactococcus, Staphylococcus and Streptococcus) and groups commonly associated with wastewater treatment plants (e.g., members of the phylum Firmicutes). This highlights the concerns for plastics to act as vectors of transmission and spread of these bacterial groups in transitional coastal ecosystems. Furthermore, it raises the possibility that (micro)plastics entering the estuary from the sea play a substantial contribution to overall dynamics of (micro)plastics and their microbial assemblages in the estuarine system.

Influence of natural seawater variables on the corrosion behaviour of aluminium-magnesium alloy.

Corrosion is an important issue for alloys in natural seawater, where microorganisms can accelerate or mitigate corrosion. Al-Mg alloys are used for marine activities and various associated technologies. Here, the behaviour of AA5083 alloy was investigated in natural seawater with marine exposure lasting up to 50 days and detailing the first 8 days in two experimental series. Experimental work was carried out, including semi-field tests in natural seawater (biotic conditions) compared with abiotic conditions. The open circuit potential (OCP) measurements, during the immersion time, exhibited significantly different behaviours: an OCP downward displacement occurred under abiotic conditions, while, in biotic conditions OCP remained generally stable since the beginning of the immersion, revealing an inhibiting effect of the biological activity on the Al-Mg corrosion. This was accompanied by different surface modifications under biotic conditions: surface and cross-section characterization, performed by scanning electron microscopy with energy dispersive X-ray spectroscopy, showed less corrosion developed on the surface after 8-day immersion and formation of a protective layer during 50-day immersion. The present study shows that marine biological activity positively influences the Al alloy corrosion process, with surface modifications resulting in a protective effect counteracting the aggressiveness of chloride ions.

The mechanisms underlying montelukast's neuropsychiatric effects - new insights from a combined metabolic and multiomics approach.

AIMS: Montelukast (MTK) is an antagonist of the cysteinyl leukotrienes receptor 1 widely used to manage asthma symptoms among adults and children. However, it has been associated with an increasing number of neuropsychiatric adverse drug reactions (ADRs), particularly among children, including depression, sleep disturbance, and suicidal ideation. The aims of this work were to characterize MTK metabolism in vitro and in vivo and to identify its effects at the metabolome and proteome levels in order to explain its toxicity. MAIN METHODS: An extensive study of montelukast metabolism was carried out using in vitro systems, an embryonic neuron-enriched cell model, and a mouse model. Metabolites were identified by high-resolution mass spectrometry, and a combined mass spectrometry-based metabolomics and proteomics approach was employed to assess the effect of MTK on mice and isolated chicken neurons. KEY FINDINGS: Eighteen new MTK metabolites were identified. MTK's ability to react with glutathione was confirmed. The multi-omics approach employed confirmed that montelukast interferes with the glutathione detoxification system in the brain. Moreover, montelukast is also able to dysregulate various neurotransmitter and neurosteroid pathways, particularly those involved in regulation of the hypothalamic-pituitary-adrenal axis, also interfering with mitochondrial function in neuronal cells. SIGNIFICANCE: Results clearly indicate that montelukast therapeutic effects are accompanied by a strong modulation of specific processes in the central nervous system that may explain the observed neuropsychiatric reactions. Moreover, the results also suggest that adverse drug reactions are more likely to occur in children, due to the early maturation stage of their brains.