Endemism, a hallmark of island biodiversity, reaches its lowest levels among bryophytes compared with other land plants. Whether this pattern reflects low diversification rates, and why, or whether it is a result of loss of endemicity due to extinctions or subsequent continental (back-)colonization, is examined here through a review of available evidence in the Macaronesian flora. Significant genetic differentiation (GST, based on allele frequencies) was consistently found between Macaronesian and continental populations, ruling out the hypothesis that intense migrations necessarily hamper differentiation. A significant phylogeographical signal in the data (NST > GST; where NST is a GST analog incorporating phylogenetic relationships among alleles), involving higher mutation rates than dispersal rates and evidencing incipient speciation, was further found in more than 1/3 of the species investigated. The significantly higher average NST between extra-European regions and Macaronesia compared to Europe and Macaronesia suggests, however, that incipient speciation is more likely to occur between distant (Macaronesian versus extra-European) than closer (Macaronesian versus European) populations. In line with this, ancestral area estimations in Macaronesian endemic bryophyte species revealed that at least 50% of them have an extra-European origin, in contrast with the almost exclusively (>90%) European/Mediterranean origin of Macaronesian endemic spermatophytes. Allopatric speciation via long-distance dispersal and subsequent divergence of a single endemic species prevails in island bryophytes, wherein sympatric radiations virtually never occur. Such a speciation mode does not trigger high rates of endemism, in contrast to radiations in Macaronesian spermatophytes, which contribute to 56% of the total number of endemics. Several mechanisms may explain the failure of island bryophytes to diversify in situ, including the fact that oceanic islands are too small or insufficiently isolated from each other or from continents to promote sympatric speciation, the lack of key innovations, and phylogenetic niche conservatism for stable habitats not prone to trigger radiations. In comparison with spermatophytes, continental (back-)colonization further largely prevails in bryophytes and, unlike in many instances in angiosperms, is not followed by in situ speciation on the mainland. The consequent loss of the endemic status of species that did speciate on islands but subsequently enlarged their range further accounts for the low rates of endemism among island bryophyte floras and invalidates the use of endemism rates as a proxy of speciation rates in this group.

A practical and efficient regio- and stereoselective hydrophosphorylation of propiolates, as well as a multicomponent reaction incorporating an aldehyde component, is reported. Both processes proceed with atom economy in very straightforward experimental procedures. The reactions are catalyzed by DABCO (1,4-diazabicyclo[2.2.2]octane) and use readily available H-phosphonates as the phosphorylating agent.

Reactive oxygen species (ROS) are context-dependent mediators that function as second messengers at low, localized flux and as drivers of damage when production overruns buffering capacity. Outcomes are dictated by source identity, subcellular compartment and pulse kinetics—the “where–when–how much” rule. We synthesize advances (2015–2025) across principal generators—mitochondrial electron transport, NADPH oxidases, xanthine oxidoreductase and ER/peroxisomal oxidoreductases—to show how compartmental H2O2 microgradients encode reversible cysteine signaling, while iron-rich niches pivot chemistry toward peroxynitrite, Fenton-derived ·OH, lipid peroxidation and regulated cell death (apoptosis, ferroptosis, parthanatos). We integrate these mechanisms with endothelial dysfunction, innate immune priming, ECM remodeling and barrier failure across cardiovascular, metabolic, neurodegenerative, oncologic, pulmonary, renal and critical-illness contexts, emphasizing crosstalk with RNS/RSS and iron metabolism as key modulators. Methodologically, we advocate species-resolved, compartment-aware assessment—e.g., DHE → 2-OH-E⁺ HPLC for O2·−, targeted HyPer/roGFP-Orp for H2O2 and peroxiredoxin redox state—embedded in composite panels that pair flux with damage footprints and iron/ferroptosis metrics for attribution and trial guidance. Therapeutically, we argue against indiscriminate antioxidant loading in favor of node-specific, compartment-targeted modulation (NOX/NOS tuning, mitochondrial QC/RET tempering, ER redox control, iron/ferroptosis management, calibrated sulfur-axis support), implemented as time-staged sequences and titrated to biomarkers. Clarifying which species arise, where and when, reframes ROS from generic toxicity to precision redox modulation with translational impact.

Key Biodiversity Areas (KBAs) are sites that contribute significantly to the global persistence of biodiversity. Distinct genetic diversity has been introduced as one of the metrics to estimate whether a site holds a threshold proportion of a species' global genetic diversity during the KBA identification process. However, genetic data has so far not been applied in KBA identification due to the lack of thoroughly tested methods and guidance. We tested the suitability of six analytical methods for identification of KBAs based upon genetic data: allelic overlap, Analyses of Molecular Variance (AMOVA), average taxonomic distinctness (AvTD, Δ+), effective population size (Ne), the genetic differentiation index (Dest), and the diversity index Simpson's λ. We conclude that Δ+, a measure that was developed to measure taxonomic distinctness of biotic communities, performs best in the context of KBA identification as it reflects the unique nature of a species' genetic diversity, is based on simple allele frequencies, and can be easily applied and calculated. AMOVA, Ne, allelic overlap, and our modified version of λ were difficult to apply, interpret, or both. Dest is easily applied for measuring genetic distinctiveness but not genetic diversity. For this reason, it may not be suitable for prioritising areas for the long-term protection of the species.

Dedicated to the memory of Dra. Celina García, whose mentorship was essential to the development of this project. The authors express their deep gratitude to Prof. Víctor S. Martín, recently retired, for his generous contribution and financial support in the design of the synthesized products. Leishmaniasis and Chagas disease are parasitic infections with limited treatment options due to drug toxicity and rising resistance. Leishmaniasis, caused by Leishmania spp., often manifests in a cutaneous form and is treated with drugs like amphotericin B and miltefosine, which can cause severe side effects. Chagas disease, caused by Trypanosoma cruzi, is endemic in the Americas and classified by the WHO as a neglected tropical disease. Existing treatments are effective mainly in the acute phase but have significant limitations. In search of new therapies, this study explored diversity-oriented synthesis to generate a library of β,γ-unsaturated carboxylic acid derivatives. From 23 synthesized compounds −12 reported for the first time– several showed promising antiparasitic activity. Four compounds were effective against Leishmania amazonensis, with three also targeting the amastigote form. Two compounds showed activity against Trypanosoma cruzi, outperforming reference drugs in selectivity. Signs of parasite apoptosis, including mitochondrial damage and ROS accumulation, suggest strong therapeutic potential for these derivatives.

The earliest documentation of hundreds of ancient settlements in South Asia, including some of the most famous and significant sites, lies in largely unacknowledged subaltern hands. Operating during the British colonial period, teams employed by the Survey of India systematically mapped the colonial dominions and produced high-quality maps that depicted topography and land use across vast areas. Systematic analysis of these map sheets combined with ground-truthing is demonstrating that these teams documented thousands of mound features, and a significant number of these are (or sadly in many cases were) archaeological sites. Members of the original survey teams were for the most part not in a position to contribute their thoughts to the historical narrative, but the legacy of what they documented has long been hidden in plain sight. The collaborative Mapping Archaeological Heritage in South Asia (MAHSA) project is systematically documenting this archaeological heritage. Its work is demonstrating that the teams carrying out the Survey of India topographic surveys incidentally conducted the first systematic survey of archaeological sites in South Asia. This was potentially the world’s most extensive (albeit incidental) archaeological survey.

Rotaxanation is an efficient method to control the tetrazine-mediated inverse electron demand Diels–Alder (IEDDA) reaction. Tetrazine rotaxanes were synthesized in high yield by crown ether active template applied to the nucleophilic aromatic substitution of tetrazines. Kinetics of the bioorthogonal reaction with tetrazine rotaxanes were much slower than those with the corresponding threads. Interestingly, disassembly of the mechanical bond upon the application of the right stimulus activates IEDDA. Control of IEDDA in live cells was proved by means of a β-galactosidase sensitive tetrazine rotaxane: Enzymatic digestion allowed the Diels–Alder reaction, which resulted in a fluorescent compound.

This work proposes a graphical analysis based on a new chiral picolinate of the (S)-BINOL derivative, designated as the reference ligand L1. The models establish the influence of temperature on L1 and identify a new coordination polymer (CP) [Cu₂(pic)₂(OTf)₂(H₂O)₂(Py)]n_₂n(Py) 1.2(Py), where [Hpic = pyridine 2-carboxylic acid and pic = picolinate], as the predominant structure through the pathway in dioxane at room temperature or the known complex [Cu(pic)2.2H₂O] 2.(H₂O)₂ at reflux in dioxane. This work provides a detailed description of the preparation method, the structural characteristics of the new CP containing the zinc complex [Zn₂(pic-Hpic)3]n.n(OTf) 3.(OTf), and density functional theory (DFT) calculations. Coordination polymer 1 2(Py) exhibits unusual magnetic properties at low temperature and high magnetic fields. This behavior may be associated with the presence of superparamagnetic particles or the influence of crystal field effects. In contrast, its origin is unlikely to be associated with common ferromagnetic impurities such as Fe, Co, or Ni, given its characteristic high Curie temperature.

Climate change is reducing agricultural productivity through altered weather patterns and extreme events, potentially decreasing yields by 10–25%. Biostimulants like pyroglutamic acid can enhance plant tolerance to water stress, but their rapid degradation in the soil limits effectiveness. Encapsulation in alginate matrices promises to be a good solution, protecting the compound and enabling controlled release. This study reports, for the first time, that encapsulated pyroglutamic acid markedly enhances drought tolerance in tomato and maize plants. The encapsulation strategy reduces effective concentration by an order of magnitude while significantly improving water use efficiency, photo-synthetic performance, and overall stress resilience. These findings demonstrate that alginate-based encapsulation substantially increases biostimulant uptake and efficacy, providing a novel and efficient strategy to mitigate water stress in crops, with important implications for climate-resilient agriculture. Two encapsulation methods for generating the alginate microcapsules are compared: ionic gelation with Nisco® system and the electrospray technique.

Metabolic enzymes and cancer-driving transcriptions factors are often overexpressed in neoplastic cells, and their exposed cysteine residues are amenable to chemical modification. This review explores cysteine alkylation as a cancer treatment strategy, focusing on Michael acceptors like curcumin and helenalin, which interact with transcription factors NF-κB, STAT3 and HIF-1α. Molecular docking studies using AutoDockFR revealed distinct binding affinities: curcumin showed strong interactions with STAT3 and NF-κB, while helenalin exhibited high affinity for STAT3 and HIF-1α. Synthetic compounds like STAT3-IN-1 and CDDO-Me demonstrated superior binding in most targets, except for CDDO-Me with HIF-1α, suggesting unique structural incompatibilities. Natural products such as zerumbone and umbelliferone displayed moderate activity, while palbociclib highlighted synthetic-drug advantages. These results underscore the importance of ligand−receptor structural complementarity, particularly for HIF-1α’s confined binding site, where helenalin’s terminal Michael acceptor system proved optimal. The findings advocate for integrating computational and experimental approaches to develop cysteine-targeted therapies, balancing synthetic precision with natural product versatility for context-dependent cancer treatment strategies.