Search Results (39,754)

Neonicotinoids are synthetic nicotine-like compounds extensively used globally as insecticides for agricultural and urban purposes. Neonicotinoid-contaminated produce is a major public health concern worldwide. Limited epidemiological studies have shown an association of neonicotinoid exposure with abnormal semen analysis. This study aimed to elucidate the potential disruption of the androgen receptor (AR) by eight common neonicotinoids, including imidacloprid (IMI), acetamiprid, clothianidin, thiamethoxam, dinotefuran, thiacloprid (THI), nitenpyram, and nithiazine using docking and molecular dynamics (MD) simulation. The results showed good binding strength of all compounds (except THI) with AR, as indicated by high binding energy, high binding affinity, and number of bonding interactions. The results of MD simulation supported the conformational stability and structural dynamic behavior of the AR-IMI (receptor-neonicotinoid) complex upon binding. This was indicated by root mean square deviation showing stability of the complex; the root mean square fluctuation showing minimized residual fluctuations upon binding; the radius of gyration showing greater compactness of the protein structure; the solvent-accessible surface area showing no changes upon binding; and the Gibbs funnel energy of the landscape showing a stable conformation state with minimum energy and slight change in size and position of the sampled energy basin of the AR, with a stable equilibrium. Taken together, the structural dynamics results showed that neonicotinoids are bound stably in the same ligand-binding domain of the AR as the native ligand testosterone. This may perturb the natural binding of testosterone with the AR and potentially disrupt downstream signaling and biological pathways, leading to male reproductive dysfunction. Full article

Homogeneous Kolbe-Schmitt carboxylation of phenoxides offers a mild and effective alternative to the classical high-temperature solid-phase Kolbe-Schmitt reaction. To develop this into a practical synthetic approach, we investigated several fundamental dependencies, particularly the impact of cations (Na, K, Li, Cs, and Rb), phenoxide concentration, and solvents (DMSO or DMF) on the yield and regioisomeric ratio of hydroxyaromatic carboxylic acids (HACAs). We identified optimal conditions for the effective carboxylation of different phenoxides, including a chiral Ellman’s sulfinamide derived from ortho-vanillin. Both solvents and cations were found to be crucial in the carboxylation of phenoxides. Due to solvation effects, DMSO directs CO₂ attack to the para-position of phenoxide, while DMF, although less selective, generally affords higher HACA yields. The addition of equiv. amounts of mesitolate salt to phenoxide in either DMSO or DMF solution often drives the reaction to completion, resulting in yields of up to 98%. Phenoxides containing several EWG groups, such as halogens or alkyl groups, adjacent to the reaction center show considerably lower reactivity in carboxylation; however, by carefully adjusting parameters, acceptable conversions (>70%) can be achieved. Using the gasometry, we assessed the stability of phenoxide and mesitolate carbonate complexes in DMSO. These experiments revealed distinct stages for the onset of decomposition and carboxylation at atmospheric pressure, indicating a lower energy barrier in the homogeneous process. Further insight into carbonate complex behavior was obtained through DOSY and ¹³C NMR experiments, which support increased molecular association in solution and correlate with enhanced reactivity. Full article

Manipulating the mitochondrial genome remains a significant challenge in genetic engineering, primarily due to the mitochondrial double-membrane structure. While recent advances have expanded the genetic toolkit for nuclear and cytoplasmic targets, precise editing of mitochondrial DNA (mtDNA) has remained elusive. Here we report the first successful mitochondrial import of a catalytically active RNA-guided prokaryotic Argonaute protein from the mesophilic bacterium Alteromonas macleodii (AmAgo). By guiding AmAgo to the single-stranded D- or R-loop region of mtDNA using synthetic RNA guides, we observed a nearly threefold reduction in mtDNA copy number in human cell lines. This proof of concept study demonstrates that a bacterial Argonaute can remain active within the mitochondrial environment and influence mtDNA levels. These findings establish a foundational framework for further development of programmable systems for mitochondrial genome manipulation. Full article

Scaphoideus titanus Ball, 1932 (Hemiptera: Cicadellidae), the main vector of the phytoplasma (FDp) causing Flavescence dorée, is considered a challenging problem in European vineyards. Natural insecticides permitted for S. titanus control in Italian organic viticulture are generally considered of low-to-moderate efficacy. Morever, it should be mentioned that their optimal use requires a careful approach when preparing the insecticide solutions. Synthetic insecticides used in Italian viticulture are included in only two IRAC groups, indicating potential risks for resistance. Therefore, there is a need to identify alternatives or control tools complementary to synthetic insecticides. In this study, we summarize the results obtained in five field experiments (2021–2025) using the main alternatives to synthetic insecticides (i.e., pyrethrins, kaolin, azadirachtin, Beauveria bassiana, and potassium salts of fatty acids). In all seasons, pre-insecticide application populations did not differ significantly among treatments, whereas differences emerged after insecticide applications. The overall results showed that pyrethrin-based insecticides were the most effective in reducing S. titanus nymph densities. Kaolin provided intermediate but comparatively stable levels of control across the years, whereas B. bassiana showed moderate yet highly variable efficacy. The findings obtained here can be considered in designing management strategies for S. titanus in organic viticulture that require an integrated approach combining pyrethrins with complementary, lower-impact tools to achieve effective and sustainable control over time. At the same time, natural insecticides can be incorporated into IPM strategies in conventional vineyards to prevent resistance. Full article

Tissue engineering is a multidisciplinary field that aims to address tissue and organ failure by integrating scientific, engineering, and medial expertise. Gelatin is valued in this field for its biocompatibility; however, it faces thermal and mechanical weaknesses that limit its biomedical utility. This work proposes a strategy for improving gelatin properties by fabricating semi-interpenetrating polymer networks via in situ Diels–Alder crosslinking within gelatin colloidal solutions. Ten systems with variable polymer concentrations (2–4%) and crosslinking degrees (2–5%) were prepared and characterized. Rheological analysis revealed that elastic modulus, zero-shear viscosity, and complex viscosity were substantially enhanced, being especially dependent on the crosslinking degree, while critical strain values mostly depended on gelatin concentration. The incorporation of a synthetic Diels–Alder-crosslinked network also improved the thermal stability of gelatin hydrogels, particularly at physiological temperatures. Additionally, these systems exhibit favorable buoyancy, swelling and biodegradation profiles. Collectively, the resultant hydrogels are cytocompatible, solid-like, and mechanically robust, allowing for further tunability of their properties for specific biomedical uses, such as injectable matrices, load-bearing scaffolds for tissue repair, and 3D bioinks. Full article

Background and Objectives: Toll-like receptors (TLRs) are pattern recognition receptors with an essential role in regulating both the innate and adaptive immune response. Given their pleiotropic effects in mounting an immune response, previous studies have proposed targeting these TLRs might render alternative strategies for cancer therapy. Synthetic immune response modifiers, such as imidazoquinolines, stimulate the immune cells by activating Toll-like receptors, particularly TLR7/8 receptors, consequently mounting an immune response. Agonists of this class activate, via TLR-mediated signaling, dendritic and B cells, as well as myeloid cells and T cells, thus exhibiting good prospects for cancer immunotherapy. In the present study, we sought to evaluate the effect of imiquimod and gardiquimod, two TLR 7 and 7/8 agonists, respectively, on tumor growth and phenotype of NK cells associated with melanoma. Materials and Methods: We generated a syngeneic model of melanoma in C57BL/6J mice by subcutaneously injecting murine melanoma cells and monitoring tumor growth. Starting on day 8 or 14, we applied TLR agonists either intratumorally or topically and followed the tumor dynamics and NK cell-associated pattern. Results: Our results suggest that both TLR agonists displayed an antitumor effect along with a phenotypically activated profile of NK cells. Both imiquimod and gardiquimod treatment inhibited tumor growth, with gardiquimod showing an increased potency compared to imiquimod. Conclusions: This implies that TLR agonists like imiquimod and gardiquimod could serve as neoadjuvant, adjuvant, or complementary immunotherapeutic agents in melanoma therapy. Full article

Synthetic cathinones are cathinone analogues that humans have artificially created. The first compounds appeared on the European market in 2005. They belong to a class of drugs called stimulants, classified as new psychoactive substances. Synthetic cathinones are very popular; people use these drugs because they are cheaper “substitutes” for other stimulants. They produce psychostimulant and hallucinogenic effects similar to cocaine, amphetamine, and MDMA, among others. Despite their presence on the market for several years, the precise toxicological impacts of these compounds on the human body remain unknown. Studies were conducted on the effects of selected cathinones (mephedrone, clephedrone) on blood cells: erythrocytes and platelets. The effect of cathinones was determined by measuring the surface density of biological membranes using microelectrophoresis. The continued popularity of these compounds, coupled with limited knowledge of their precise effects on the human body, makes the problem significant and requires ongoing research. Based on the results obtained for mephedrone and clephedrone, it can be concluded that at the tested concentrations (170 ng/mL and 2700 ng/mL), they alter the surface charge density of the biological membranes of red blood cells and platelets. Full article

The escalating release of synthetic dyes from textile and allied industries has become a pressing global environmental issue due to their toxicity, persistence, and resistance to biodegradation. Among the various treatment strategies, adsorption has emerged as one of the most efficient, economical, and sustainable techniques for dye removal from aqueous environments. This review highlights recent advances in bio-derived adsorbents—particularly raw biomass powders, biochars, and activated carbons—developed from renewable waste sources such as agricultural residues, fruit peels, shells, and plant fibers. It systematically discusses adsorption mechanisms, the influence of process parameters, kinetic and thermodynamic models, and regeneration performance. Furthermore, the review emphasizes the superior adsorption efficiency and cost-effectiveness of biomass-derived carbons compared to conventional adsorbents. The integration of surface modification, magnetization, and nanocomposite formation has further enhanced dye uptake and reusability. Overall, this study underscores the potential of biomass-derived materials as sustainable alternatives for wastewater treatment and environmental remediation. Full article

Nanoparticle-mediated photothermal conversion exploits the unique light-to-heat transduction properties of engineered nanomaterials to address challenges in energy, water, and healthcare. This review first examines fundamental mechanisms—localized surface plasmon resonance (LSPR) in plasmonic metals and broadband interband transitions in semiconductors—demonstrating how tailored nanoparticle compositions can achieve >96% absorption across 250–2500 nm and photothermal efficiencies exceeding 98% under one-sun illumination (1000 W·m⁻², AM 1.5G). Next, we highlight advances in solar steam generation and desalination: floating photothermal receivers on carbonized wood or hydrogels reach >95% efficiency in solar-to-vapor conversion and >2 kg·m⁻²·h⁻¹ evaporation rates; three-dimensional architectures recapture diffuse flux and ambient heat; and full-spectrum nanofluids (LaB₆, Au colloids) extend photothermal harvesting into portable, scalable designs. We then survey photothermal-enhanced thermal energy storage: metal-oxide–paraffin composites, core–shell phase-change material (PCM) nanocapsules, and MXene– polyethylene glycol—PEG—aerogels deliver >85% solar charging efficiencies, reduce supercooling, and improve thermal conductivity. In biomedicine, gold nanoshells, nanorods, and transition-metal dichalcogenide (TMDC) nanosheets enable deep-tissue photothermal therapy (PTT) with imaging guidance, achieving >94% tumor ablation in preclinical and pilot clinical studies. Multifunctional constructs combine PTT with chemotherapy, immunotherapy, or gene regulation, yielding synergistic tumor eradication and durable immune responses. Finally, we explore emerging opto-thermal nanobiosystems—light-triggered gene silencing in microalgae and poly(N-isopropylacrylamide) (PNIPAM)–gold nanoparticle (AuNP) membranes for microfluidic photothermal filtration and control—demonstrating how nanoscale heating enables remote, reversible biological and fluidic functions. We conclude by discussing challenges in scalable nanoparticle synthesis, stability, and integration, and outline future directions: multicomponent high-entropy alloys, modular photothermal–PCM devices, and opto-thermal control in synthetic biology. These interdisciplinary innovations promise sustainable solutions for global energy, water, and healthcare demands. Full article

In this work, different implementation strategies for a Time-Domain (TD) focusing procedure applied to airborne Synthetic Aperture Radar (SAR) raw data are presented, with the key objective of quantitatively assessing their computing time. In particular, two methodological approaches are proposed: a pixel-wise strategy, which processes each image pixel independently, and a matrix-wise strategy, which handles data blocks collectively. Both strategies are further extended to parallel execution frameworks to exploit multi-threading and multi-node capabilities. The presented analysis is conducted within the context of the airborne SAR infrastructure developed at the Institute for Electromagnetic Sensing of the Environment (IREA) of the National Research Council (CNR) in Naples, Italy. This infrastructure integrates an airborne SAR sensor and a high-performance Information Technology (IT) platform well-tailored to the parallel processing of huge amounts of data. Experimental results indicate an advantage of the pixel-wise strategy over the matrix-wise counterpart in terms of computing time. Furthermore, the adoption of parallel processing techniques yields substantial speedups, highlighting its relevance for time-critical SAR applications. These findings are particularly relevant in operational scenarios that demand a rapid data turnaround, such as near-real-time airborne monitoring in emergency response contexts. Full article

To address the scientific gap concerning optimal urban wind turbine morphology, this work presents an experimental performance comparison between two small-scale wind turbine designs: a conventional three-blade horizontal-axis wind turbine (HAWT) and a duct-equipped Ayanz-inspired screw-blade turbine. Both configurations were tested in a controlled wind tunnel under steady and transient wind conditions, including synthetic gusts designed to emulate urban wind patterns. The analysis focuses on power output, aerodynamic efficiency (via the power coefficient C_p), dynamic responsiveness, and integration suitability. A key novelty of this study lies in the full-scale experimental comparison between a non-conventional Ayanz screw-blade turbine and a standard three-blade turbine, since experimental data contrasting these two geometries under both steady and gusty urban wind conditions are extremely scarce in the literature. Results show that while the three-blade turbine achieves a higher C_ppeak and greater efficiency near its optimal operating point, the Ayanz turbine exhibits a broader performance plateau and better self-starting behavior under low and fluctuating wind conditions. The Ayanz model also demonstrated smoother power build-up and higher energy capture under specific gust scenarios, especially when wind speed offsets were low. Furthermore, a methodological contribution is made by comparing the C_p vs. tip speed ratio λ curves at multiple wind speeds, providing a novel framework (plateau width analysis) for realistically assessing turbine adaptability and robustness to off-design conditions. These findings provide practical insights for selecting turbine types in variable or urban wind environments and contribute to the design of robust small wind energy systems for deployments in cities. Full article

Lexicographic preference trees (LP-Trees) provide a compact and expressive representation for modeling complex decision-making scenarios, yet measuring similarity between complete or partial structures remains a challenge. This study introduces PLPSim, a novel metric for quantifying alignment between partial lexicographic preference trees (PLP-Trees) and develops three coalition formation algorithms—HRECS1, HRECS2, and HRECS3—that leverage PLPSim to group agents with similar preferences. We further propose ContractLex and PriceLex protocols (comprising CLF, CFB, CFW, CFA, CFP) for coalition-based contract and pricing strategies, along with a new evaluation metric, F@Lex, which is designed to assess satisfaction under lexicographic preferences. To illustrate the framework, we generate a synthetic dataset (PLPGen) contextualized in a hybrid renewable energy market, where consumers’ PLP-Trees are aggregated and matched with suppliers’ tariff contracts. Experiments across 162 market scenarios, evaluated using Normalized Discounted Cumulative Gain (nDCG), Davies–Bouldin dispersion, and F@Lex, demonstrate that PLPSim-based coalitions outperform baseline approaches. The combination HRECS3 + CFP yields the highest consumer satisfaction, while HRECS3 + CFB achieves balanced satisfaction for both consumers and suppliers. While electricity tariffs and renewable energy contracts—static and dynamic—serve as the motivating example, the proposed framework generalizes to diverse multi-agent systems, offering a foundation for preference-driven coalition formation, adaptive policy design, and sustainable market optimization. Full article

The proliferation of algorithmically generated malicious URLs has overwhelmed traditional threat intelligence systems, necessitating a paradigm shift from reactive, single-instance analysis to proactive, automated campaign discovery. Existing systems excel at finding semantically similar URLs given a known malicious seed but fail to provide a real-time, macroscopic view of emerging and evolving attack campaigns from high-velocity data streams. This paper introduces PhishCluster, a novel framework designed to bridge this critical gap. PhishCluster implements a two-phase, online–offline architecture that synergistically combines large-scale Approximate Nearest Neighbor (ANN) search with advanced density-based clustering. The online phase employs an ANN-accelerated maintenance algorithm to process a stream of URL embeddings at unprecedented throughput, summarizing the data into compact, evolving Campaign Micro-Clusters (CMCs). The offline, on-demand phase then applies a hierarchical density-based algorithm to these CMCs, enabling the discovery of arbitrarily shaped, varying-density campaigns without prior knowledge of their number. Our comprehensive experimental evaluation on a synthetic billion-point dataset, designed to mimic real-world campaign dynamics, demonstrates that PhishCluster’s architecture resolves the fundamental trade-off between speed and quality in streaming data analysis. The results validate that PhishCluster achieves an order-of-magnitude improvement in processing throughput over state-of-the-art streaming clustering baselines while simultaneously attaining a superior clustering quality and campaign detection fidelity. Full article

Photocatalysis driven by the visible light of solar energy has received considerable attention in the field of environmental remediation and clean energy production. In this work, monomeric sulfonated palladium phthalocyanine (PdPcS) was encapsulated in zeolitic imidazolate frameworks-8 (ZIF-8) crystals (denoted PdPcS@ZIF-8) through electrostatic interaction in the ammonia system, while their photocatalytic activity was well-maintained together with the structural regularity of ZIF-8 crystals. For comparison, a PdPcS/ZIF-8 sample was obtained from the traditional impregnation method. The ¹³C NMR and UV-DRS spectra confirmed the difference between PdPcS@ZIF-8 and PdPcS/ZIF-8 in terms of the chemical environment effect for PdPcS. Under visible light, the optimal PdPcS@ZIF-8 catalyst achieved complete degradation of 0.1 mM bisphenol A in 120 min. It also exhibited excellent stability, retaining 81.5% activity after four cycles, far outperforming the impregnated sample (32.5%) due to effective encapsulation preventing PdPcS leaching. This versatile one-step synthetic strategy is expected to be useful for designing novel macromolecules@MOF composite materials. Full article

This work explores a novel and efficient synthetic approach to a new class of boron cluster derivatives via the nucleophilic addition of stabilized phosphorus ylides, Ph₃P=CHR² (R² = COOEt, CN), to a series of nitrilium salts of the closo-decaborate anion, [2-B₁₀H₉NCR¹]⁻ (R¹ = Me, Et, ⁿPr, ⁱPr, Ph). The reaction proceeds regio- and stereospecifically, affording a diverse range of iminoacyl phosphorane derivatives, [2-B₁₀H₉NH=C(R¹)C(PPh₃)R²]⁻, in high isolated yields (up to 95%). The obtained compounds (10 examples) were isolated as tetrabutylammonium or tetraphenylphosphonium salts and thoroughly characterized by multinuclear NMR (¹¹B, ¹H, ¹³C, ³¹P), high-resolution mass spectrometry, and single-crystal X-ray diffraction. The reaction feasibility was found to be strongly influenced by the steric hindrance of the R¹ group. Furthermore, the practical utility of these novel hybrids was demonstrated by employing the [2-B₁₀H₉NH=C(CH₃)C(COOC₂H₅)=PPh₃]⁻ anion as a highly effective membrane-active component in ion-selective electrodes. The developed tetraphenylphosphonium (TPP⁺) sensor exhibited a near-Nernstian response, a low detection limit of 3 × 10⁻⁸ M, and excellent selectivity over a range of common inorganic and organic cations, showcasing the potential of closo-borate-based ionophores in analytical chemistry. Full article