Anthropogenic debris pollution in yellow-legged gull (Larus michahellis atlantis) nests in biosphere reserves of the Canary Islands.

Anthropogenic debris, particularly plastic pollution, has emerged as a significant environmental threat to biodiversity. Given that seabirds interact with artificial debris through ingestion, entanglement, and nest incorporation, it is particularly important to quantify the quantity, origins, and chemical composition of these debris items. In this work, it was evaluated for the first time the occurrence of anthropogenic debris in nests of yellow-legged gull (Larus michahellis atlantis) in biosphere reserves of the Canary Islands (Spain). A total of 48 abandoned nests were collected from five remote and hardly accessible sampling areas, revealing that 81.3 % contained anthropogenic waste, with plastic accounting for 34.7 % of the debris, followed by metal (33.6 %) and paper (19.6 %). On average, 32.8 ± 40.9 items were found per nest. Regarding the origin, food packagings (47.8 %), personal hygiene products (21.7 %), and textiles (15.8 %) were identified as the predominant sources. Furthermore, the polymer composition of the plastics was characterised by means of Fourier-transform infrared spectroscopy analysis, being polyester the most abundant (38.2 %), followed by polyethylene (25.6 %) and rayon (10.3 %). The incorporation of anthropogenic debris into nest construction may result from outdoor human activities carried out far from nesting areas.

Tracking anthropogenic microparticles in wildlife of an alpine insular environment.

Despite the isolation of remote natural regions, it has been discovered that they are experiencing the accumulation of anthropogenic microparticles (i.e., microplastics or natural or semisynthetic cellulosic particles). Teide National Park (Canary Islands, Spain) is a high-mountain protected area known for its rich biodiversity. This study aims to assess the occurrence of coloured anthropogenic particles in the faecal matter of wild mammals, specifically rabbits and mouflons, residing in the park. With this purpose, faeces were collected from 68 systematically distributed sampling points. A stereomicroscopy-guided grinding process allowed a chemical-free and quick visual inspection of 616 individual excreta, revealing that 96% were particle-free. However, 37 anthropogenic particles were found, which correspond to 0.79 ± 0.20 items per gram of dry faecal matter. The archetypical particle was a cellulosic blue microfibre of 2721 ± 407 µm, though poly(ethylene-vinyl acetate) and polypropylene were also identified via micro Fourier-transform infrared spectroscopic analysis. Atmospheric deposition and touristic pressure may be the sources of the anthropogenic particles, as they were randomly found in 36% of the sampling points. These findings represent the first evidence of anthropogenic particle ingestion by wild rabbits and mouflons, signifying the introduction of microplastics into terrestrial food chains in a remote high-mountain environment.

Nanoplastics in the soil environment: Analytical methods, occurrence, fate and ecological implications.

Soils play a very important role in ecosystems sustainability, either natural or agricultural ones, serving as an essential support for living organisms of different kinds. However, in the current context of extremely high plastic pollution, soils are highly threatened. Plastics can change the chemical and physical properties of the soils and may also affect the biota. Of particular importance is the fact that plastics can be fragmented into microplastics and, to a final extent into nanoplastics. Due to their extremely low size and high surface area, nanoplastics may even have a higher impact in soil ecosystems. Their transport through the edaphic environment is regulated by the physicochemical properties of the soil and plastic particles themselves, anthropic activities and biota interactions. Their degradation in soils is associated with a series of mechanical, photo-, thermo-, and bio-mediated transformations eventually conducive to their mineralisation. Their tiny size is precisely the main setback when it comes to sampling soils and subsequent processes for their identification and quantification, albeit pyrolysis coupled with gas chromatography-mass spectrometry and other spectroscopic techniques have proven to be useful for their analysis. Another issue as a consequence of their minuscule size lies in their uptake by plants roots and their ingestion by soil dwelling fauna, producing morphological deformations, damage to organs and physiological malfunctions, as well as the risks associated to their entrance in the food chain, although current conclusions are not always consistent and show the same pattern of effects. Thus, given the omnipresence and seriousness of the plastic menace, this review article pretends to provide a general overview of the most recent data available regarding nanoplastics determination, occurrence, fate and effects in soils, with special emphasis on their ecological implications.

Synthetic efforts on the road to marine natural products bearing 4-O-2,3,4,6-tetrasubstituted THPs: an update.

Scientific literature is inundated with secondary metabolites from marine sources. In this ocean of natural products, the presence of recurring patterns has traditionally led scientists to unravel the biosynthetic mechanisms that naturally yield these products, as well as to imitate Nature to prepare them in the laboratory, especially when promising bioactivities and stimulating molecular architectures are involucrate. For instance, natural products containing multisubstituted oxygenated rings and macrocyclic lactones are recurrently selected as targets for developing total syntheses. Thus, in the last decades a noteworthy number of synthetic works regarding miyakolide, madeirolide A and representative compounds of polycavernosides, lasonolides and clavosolides have come to fruition. Up to now, these families of macrolides are the only marine natural products bearing a tetrasubstituted tetrahydropyran ring with carbon substituents at positions 2, 3 and 6, as well as an oxygen at position 4. Their splendid structures have received the attention of the synthetic community, up to the point of starring in dozens of articles, and even some reviews. This work covers all the synthetic studies towards miyakolide and madeirolide A, as well as the synthetic efforts performed after the previous specialised reviews about lasonolide A, polycavernoside A and clavosolides, published in 2006, 2007 and 2016, respectively. In total, this review summarises 22 articles in which these marine natural products with 4-O-2,3,4,6-tetrasubstituted tetrahydropyrans have the leading role.

The 9H-Fluoren Vinyl Ether Derivative SAM461 Inhibits Bacterial Luciferase Activity and Protects Artemia franciscana From Luminescent Vibriosis.

Vibrio campbellii is a major pathogen in aquaculture. It is a causative agent of the so-called "luminescent vibriosis," a life-threatening condition caused by bioluminescent Vibrio spp. that often involves mass mortality of farmed shrimps. The emergence of multidrug resistant Vibrio strains raises a concern and poses a challenge for the treatment of this infection in the coming years. Inhibition of bacterial cell-to-cell communication or quorum sensing (QS) has been proposed as an alternative to antibiotic therapies. Aiming to identify novel QS disruptors, the 9H-fluroen-9yl vinyl ether derivative SAM461 was found to thwart V. campbellii bioluminescence, a QS-regulated phenotype. Phenotypic and gene expression analyses revealed, however, that the mode of action of SAM461 was unrelated to QS inhibition. Further evaluation with purified Vibrio fischeri and NanoLuc luciferases revealed enzymatic inhibition at micromolar concentrations. In silico analysis by molecular docking suggested binding of SAM461 in the active site cavities of both luciferase enzymes. Subsequent in vivo testing of SAM461 with gnotobiotic Artemia franciscana nauplii demonstrated naupliar protection against V. campbellii infection at low micromolar concentrations. Taken together, these findings suggest that suppression of luciferase activity could constitute a novel paradigm in the development of alternative anti-infective chemotherapies against luminescent vibriosis, and pave the ground for the chemical synthesis and biological characterization of derivatives with promising antimicrobial prospects.

Stereoselective Synthesis of Highly Substituted Tetrahydropyrans through an Evans Aldol-Prins Strategy.

A direct and general method for the synthesis of naturally occurring 2,3,4,5,6-pentasubstituted tetrahydropyrans has been developed, employing ß,γ-unsaturated N-acyl oxazolidin-2-ones as key starting materials. The combination of the Evans aldol addition and the Prins cyclization allowed the diastereoselective and efficient generation of the desired oxacycles in two fashions: a one-pot Evans aldol-Prins protocol, in which five new σ bonds and five contiguous stereocenters were straightforwardly generated, and a two-step version, which additionally permitted the isolation of ß,γ-unsaturated alcohol precursors bearing an N-acyl oxazolidin-2-one in the α position. From these alcohols were also obtained halogenated pentasubstituted tetrahydropyrans as well as 2,3,4,5-tetrasubstituted tetrahydrofurans, shedding light on the mechanism of the process. Computational studies were consistent with the experimental findings, and this innovative Evans aldol-Prins strategy was performed for the preparation of a battery of more than 30 densely substituted tetrahydropyrans, unprecedentedly fused to a 1,3-oxazinane-2,4-dione ring, both in a racemic fashion and in an enantiomeric fashion. These novel molecules were successfully submitted to several transformations to permit simple access to a variety of differently functionalized tetrahydropyrans. Most of these unique molecules were evaluated for their antimicrobial activity against Gram-positive and Gram-negative bacteria and the yeast Candida albicans, and some structure-activity relationships were established.

One-pot synthesis of enantiomerically pure N-protected allylic amines from N-protected α-amino esters.

An improved protocol for the synthesis of enantiomerically pure allylic amines is reported. N-Protected α-amino esters derived from natural amino acids were submitted to a one-pot tandem reduction-olefination process. The sequential reduction with DIBAL-H at -78 °C and subsequent in situ addition of organophosphorus reagents yielded the corresponding allylic amines without the need to isolate the intermediate aldehyde. This circumvents the problem of instability of the aldehydes. The method tolerates well both Wittig and Horner-Wadsworth-Emmons organophosphorus reagents. A better Z-(dia)stereoselectivity was observed when compared to the previous one-pot method. The (dia)stereoselectivity of the process was affected neither by the reaction solvent nor by the amount of DIBAL-H employed. The method is compatible with the presence of free hydroxy groups as shown with serine and threonine derivatives.

The Evans Aldol-Prins cyclization: a general and stereoselective method for the synthesis of 2,3,4,5,6-pentasubstituted tetrahydropyrans.

A general and stereoselective method to synthesize 2,3,4,5,6-pentasubstituted tetrahydropyrans in three steps starting from three different aldehydes is described. Key substrates ß,γ-unsaturated N-acyloxazolidin-2-ones were subjected to an "Evans Aldol-Prins" protocol to generate five σ-bonds and five stereocenters in only a one-pot process with yields up to 60% and excellent stereoselectivities.

Oxasqualenoids from Laurencia viridis: Combined Spectroscopic-Computational Analysis and Antifouling Potential.

The chemical study of the red alga Laurencia viridis has led to the isolation of four new polyether triterpenoids: 28-hydroxysaiyacenol B (2), saiyacenol C (3), 15,16-epoxythyrsiferol A (4), and 15,16-epoxythyrsiferol B (5). The structures of 2 and 3 were established mainly by NMR data analysis and comparison with the well-known metabolite dehydrothyrsiferol (1). However, due to the existence of a nonprotonated carbon within the epoxide functionality, stereochemical assignments in 4 and 5 required an in-depth structural study that included NOESY data, J-based configuration analysis, comparison with synthetic models, and DFT calculations. The biological activities of the new metabolites and other related oxasqualenoids were evaluated for the first time against a panel of relevant biofouling marine organisms, and structure-activity conclusions were obtained.