Search Results (2,300)

Alkenylidenecyclopropanes (ACPs) have emerged as versatile and highly reactive building blocks in transition-metal-catalyzed transformations. Their strained cyclopropane framework, combined with an exocyclic alkene, enables diverse bond-activation pathways and promotes efficient cycloaddition reactions. In recent years, ACPs have been widely developed as three-carbon synthons in a variety of higher-order cycloadditions. This review provides a systematic overview of transition-metal-catalyzed ACP transformations, focusing on their applications in [3+2], [3+2+2], [3+2+1], [4+3], and [4+3+2] cycloaddition reactions with reaction partners such as alkenes, alkynes, carbonyl compounds, imines, dienes, and carbon monoxide. Particular attention is given to mechanistic aspects, including cyclopropane ring-opening processes and the formation of key metal–carbene and π-allyl intermediates that govern reactivity and selectivity. Factors influencing regioselectivity, stereoselectivity, and catalyst design are also discussed. The synthetic potential of ACP chemistry is illustrated through representative applications in the total synthesis of complex natural products, such as pyrovellerolactone and (+)-zizaene. Overall, this review highlights recent advances in ACP-based cycloaddition strategies and emphasizes their growing significance in modern synthetic chemistry. Full article

Crop fungal and viral diseases cause annual economic losses exceeding USD 150 billion globally, demanding rapid, sensitive, and field-deployable diagnostic technologies. This review critically evaluates recent advances in electrochemical biosensing platforms for early crop pathogen detection, focusing on immunosensors, genosensors, aptasensors, and VOC-based systems. Reported analytical performances demonstrate ultralow detection capabilities, including 0.3 fg mL⁻¹ for viral coat proteins, 15 DNA copies for bacterial pathogens, 0.5 fg µL⁻¹ RNA detection for viroids, and nanomolar-level VOC sensing (35–62 nM), with response times ranging from 2 to 60 min. Comparative analysis reveals that genosensors and aptasensors generally achieve the lowest LODs due to nucleic acid amplification or high-affinity recognition, while immunosensors provide robust protein-level specificity validated against ELISA. Volatile organic compound (VOC) sensors enable non-invasive, pre-symptomatic monitoring but face specificity challenges. Despite strong laboratory performance, practical adoption is limited by matrix-derived electrochemical interference, environmental instability of biorecognition elements, workflow complexity, and insufficient standardization across studies. Emerging innovations, including magnetic bead enrichment, nanoporous and graphene-based electrodes, microfluidic integration, AI-assisted impedance interpretation, and biodegradable substrates, are progressively addressing these bottlenecks. This review emphasizes that successful field translation requires holistic workflow engineering, matrix-matched validation, and harmonized performance metrics rather than incremental sensitivity improvements alone. By integrating analytical chemistry, nanomaterials engineering, and agricultural decision-support frameworks, electrochemical biosensing platforms hold significant potential to enable decentralized, rapid, and sustainable crop disease management. Full article

Unsaturated carbon–carbon bonds are fundamental building blocks in organic compounds. The difunctionalization of olefins allows for the rapid construction of drugs and complex molecular architectures. This transformation, which simultaneously installs two distinct functional groups across a carbon–carbon double bond, has therefore emerged as prominent research frontier in organic chemistry. In recent years, the synergy between photoredox and transition metal catalysis has emerged as a powerful and sustainable platform for constructing C-X bonds. This review covers advances since 2018 in the asymmetric difunctionalization of olefins enabled by synergistic visible light photoredox and transition metal catalysis, encompassing the construction of both carbon–carbon and carbon–heteroatom bonds. It systematically summarizes the reaction conditions, substrate scope, mechanisms, and merits and limitations of these catalytic systems, aiming to provide a useful reference for researchers in this field. Full article

Understanding and developing habits in complex systems thinking using STEM-integrated perspectives is essential in addressing education and workforce needs in society. In this study, we investigated a learning intervention that incorporated multiple models designed to improve engineering students’ understanding of complex systems through investigating the mechanobiology of the Venus flytrap. Mechanobiology is a transdisciplinary field that integrates biology, engineering, chemistry, and physics to explore how cells and tissues sense and respond to forces in their environment. We used an exploratory, mixed-methods approach to examine the impact of this new curriculum on investigating flytrap closure and prey digestion. We then evaluated students’ understanding of complex systems characteristics (i.e., many interacting parts, decentralization, non-linear interactions, emergence, and adaptation) and in their ability to transfer these principles to other systems. Qualitative analyses demonstrate that students articulated key systems principles in relation to their understanding of flytrap mechanobiology, while descriptive summaries of pre- and post-surveys suggest broader conceptual gains. Furthermore, students demonstrated the transfer of systems thinking to other contexts and reported an enhanced understanding of real-world STEM research. Full article

How does the complex, adaptive, and autonomous organization of life emerge from the laws of physics and information? This review argues that the answer lies in a convergent set of universal organizational principles that constitute a physical and informational grammar of the living. Living systems are dissipative structures that achieve organizational closure—materially and energetically open, yet causally closed—thereby attaining genuine autonomy and agency. Their architecture exhibits fractal and modular scaling laws that maximize energy flow, robustness, and evolvability under universal physical constraints. Critically, organisms operate at critical transitions—zones of controlled instability where fluctuations amplify information processing, transforming noise into adaptive signal. This self-organized criticality enables functional degeneracy, relational redundancy, and evolutionary antifragility. Cognition emerges as a distributed process of active inference, operating through a predictive–corrective cycle that integrates perception, action, and learning under the Free Energy Principle. From molecular networks to ecosystems, the same physico-informational grammars unfold recursively, revealing a deep organizational holography: the principles of organization are replicated across scales. Evolution under the Law of Increasing Functional Information is not random drift, but a directional expansion of functional complexity—a thermodynamic gradient towards greater agency. This synthesis challenges biological exceptionalism: the trajectory from thermodynamics to cognition is continuous, physically constrained, and potentially inevitable. Life does not violate physical laws—it fulfills them in regimes of high informational complexity, instantiating fundamental principles in self-organized architectures capable of prediction, memory, and purpose. The objective of this work is to articulate how the synthesis of these principles not only unifies physics and biology, but also illuminates the profound continuity between thermodynamics, chemistry, informational constraints, organization, and the mind. Full article

Azo dyes represent the largest and most extensively used class of synthetic dyes in industries such as textiles, leather, paper, food, cosmetics, and pharmaceuticals. Due to their complex aromatic structures and the presence of azo (–N=N–) bonds, these dyes exhibit high chemical stability and resistance to degradation, leading to their persistent discharge into the environment through industrial wastewater. This review provides a comprehensive overview of the chemistry, sources, environmental fate, and toxicological impacts of azo dyes, with a particular focus on microbial remediation strategies. The roles of bacteria, fungi, algae, and microbial consortia, along with their enzymatic mechanisms and influencing factors, are critically discussed. The presence of azo dyes in aquatic and terrestrial ecosystems causes severe environmental problems, including reduced light penetration, disruption of photosynthetic activity, and deterioration of water quality. Moreover, the reductive cleavage of azo dyes can result in the formation of toxic, mutagenic, and carcinogenic aromatic amines, posing significant risks to ecological and human health. Conventional physicochemical treatment methods, although effective in decolorization, suffer from limitations such as high cost, energy demand, sludge generation, and incomplete mineralization. This review identifies key strategies for achieving scalable and eco-friendly solutions for industrial wastewater management. Full article

Marine invertebrates produce a remarkable diversity of polyhydroxylated steroids and secosteroids whose structural features—particularly vicinal (1,2-)diols, 1,3-diols, and clustered hydroxyl arrays—make them well suited for coordination with boron species. In the marine environment, where boron is abundant, chemically stable, and predominantly present as borate under mildly alkaline conditions, such interactions are not only plausible but may be widespread. This review examines the chemistry of boron–steroid complexation in marine systems, emphasizing how rigid steroidal frameworks preorganize diol motifs to form reversible yet stable borate esters under environmentally relevant conditions. We discuss how polyhydroxy steroids may exist in dynamic equilibria between free and boron-bound forms, with speciation governed by pH, boron concentration, and local microenvironmental factors rather than enzymatic control. Boron complexation can modulate key physicochemical properties, including solubility, conformation, and membrane affinity, thereby influencing the biological activity of marine steroids without covalent modification of the carbon framework. By integrating examples from sponges, echinoderms, and corals together with well-characterized model polyols, this review highlights boron complexation as an underrecognized but potentially important factor influencing the structure, function, and bioactivity of marine steroid metabolites. Full article

Background: The control of fleas and ticks in companion animals is a persistent challenge with animal welfare and public health implications. The increasing resistance to antiparasitic treatments, coupled with concerns over the environmental impact and non-target effects of synthetic acaricides, has driven interest in sustainable alternatives. Essential oils (EOs) have emerged as potential candidates due to their complex chemistry and modes of action. Methods: This review critically analyzes the scientific literature on essential oils for ectoparasite control in companion animals. Specifically, it examines their chemical composition, multi-target mechanisms of action, laboratory and field efficacy, role in resistance mitigation, and integration into IPM strategies. Results: Several EOs, particularly those rich in phenolic compounds (thymol, carvacrol, eugenol, and cinnamaldehyde), demonstrate promising in vitro insecticidal and acaricidal activity. Their multi-target mechanisms, affecting neuronal, respiratory, and cuticular functions, not only provide efficacy but also represent a significant barrier to rapid resistance development. However, their translation to reliable field performance is hampered by high volatility, formulation instability, and innate variability. Conclusions: EOs represent a valuable source of bioactive compounds for reducing reliance on conventional acaricides and can play a key role within IPM strategies. To realize their full potential in mitigating resistance, focused advancements are needed in standardized testing, formulation science to enhance stability and residual activity, and rigorous field studies to confirm safety and efficacy. Full article

Boron is a chemically distinctive bioelement whose electron-deficient structure enables reversible coordination with oxygen-rich functional groups such as diols and hydroxyls. This property allows boron to modulate molecular stability, conformation, and biological reactivity, giving rise to both beneficial pharmacological effects and toxicological outcomes. This review examines the dual biological role of boron through the framework of bioactive boron-containing natural products and natural compounds capable of forming reversible boron complexes. Particular attention is given to naturally occurring boron-containing antibiotics, including the polyketide macrodiolides boromycin, aplasmomycin, tartrolons, and hyaboron, where boron plays a direct structural and functional role in antimicrobial activity. These compounds demonstrate how boron coordination can influence ion transport, membrane interactions, and molecular assembly, contributing to potent antibacterial properties. Beyond intrinsically boron-containing metabolites, many natural antibiotics and toxins possess oxygen-rich architectures capable of forming transient borate complexes through vicinal 1,2-diol motifs. Examples include polyene macrolide antibiotics such as amphotericin B, fungichromin, and nystatin, as well as tetracyclines, rifamycins, and macrolides such as sorangicin A, where boron coordination may affect solubility, aggregation, ionophoric behavior, and biological selectivity. Similar chemistry is observed in marine neurotoxins and polyether toxins—including tetrodotoxin, saxitoxin derivatives, azaspiracids, pectenotoxins, ciguatoxins, and gambierones—whose hydroxyl-rich frameworks enable reversible interactions with boron species present in seawater. Such complexation may enhance aqueous stability and contribute to trophic transfer and bioaccumulation within marine ecosystems. By framing boron as a molecular “double edge,” this review integrates chemical, biological, and environmental perspectives to highlight how boron coordination can simultaneously enhance antimicrobial activity while influencing toxicity and ecological persistence. Recognizing the role of boron in shaping the activity of natural products provides new insight into antibiotic function, toxin behavior, and the broader impact of boron chemistry in biological systems. Full article

The origin of life is, to the best of our knowledge, impossible to imagine without the formation of complex prebiotic biomolecules such as RNA, DNA, proteins and lipids. Lipids play a crucial role in the spontaneous formation of cell membranes, which are responsible for cell integrity, compartmentalization, selective permeability, and providing a microenvironment for biochemical reactions. The goal of the current work is to summarize the current state of the art regarding the abiotic formation of membrane building blocks, such as glycerol, fatty acids, and their phosphorylated version as phospholipid precursors. We describe the necessity of a systems chemistry approach for the complexification and expansion of the prebiotic network, enabling the formation of several membranogenic precursors. We also discuss prebiotic pathways for phosphorylation and acylation that could lead to phospholipid availability in hydrothermal environments and on the early Earth surface. We conclude with the possible spontaneous vesiculation of these molecules as a primitive version of the cell membrane. Thus, we present a comprehensive perspective on prebiotic vesicle formation, starting from simple molecules and developing until the self-assembly of vesicles. Full article

Accurate and interpretable air quality prediction remains a critical challenge for environmental health management due to complex, nonlinear interactions among emissions, meteorology, and atmospheric chemistry. This study presents a hybrid physics informed and multimodal deep learning framework for city-scale air quality and health risk prediction. The framework combines a Gaussian plume dispersion model with a residual CNN-LSTM network that learns data driven corrections while preserving physical consistency. Multimodal open datasets, including ground based pollutant sensors, meteorological records, and satellite derived aerosol and temperature features, are jointly fused to improve spatiotemporal fidelity. An Exposure Health Index module further links predicted pollutant fields with respiratory morbidity indicators, providing a quantitative bridge between atmospheric variability and health outcomes. Using open source datasets from Riyadh, Jeddah, and Dammam, the proposed approach achieves up to 25% lower mean absolute error and $R^2$ values above 0.85 compared with physics only and purely data driven baselines. Explainability analyses using SHAP and spatial attention highlight physically plausible drivers and confirm feature relevance. The results demonstrate that physics guided residual learning can unify deterministic dispersion modeling and multimodal inference, providing a transparent, scalable, and reproducible foundation for air quality forecasting and health risk assessment. Full article

Metal packaging materials remain fundamental across food, beverage, pharmaceutical, cosmetic, and technical sectors owing to their combination of mechanical robustness, total light and gas barrier performance, thermal resistance, and established recyclability. Aluminum alloys, tinplate, tin-free steel (TFS/ECCS), stainless steels, metal–matrix composites (MMCs), and metal–polymer or metal–paper laminates define distinct metal-based packaging architectures whose metallurgical and interfacial design governs forming behaviour, corrosion and migration pathways, coating integrity, and mechanical reliability. In this review, these architectures are examined from a materials- and systems-oriented perspective, linking composition, microstructure, processing routes, and surface engineering to functional performance across rigid, semi-rigid, and flexible formats. The analysis also considers the ongoing transition from bisphenol A (BPA)-based epoxy linings to BPA-free and hybrid coating chemistries, the use of nano-structured metallic and metal-oxide surfaces, and the role of composite laminates in which thin metallic foils are combined with polymeric or paper-based structural layers. These material and architectural aspects are discussed together with safety, regulatory, and circularity considerations that increasingly influence the design and selection of metal-based packaging. Ion migration, coating degradation, and corrosion under realistic storage environments are considered in relation to EU, FDA, ISO, and sector-specific requirements, while attention is also paid to the contrast between well-established closed-loop recycling infrastructures for aluminum and steel and the more complex end-of-life management of coated metals and multilayer laminates. The review provides a unified framework connecting materials selection, metallurgical design, processing, performance, regulatory compliance, and sustainability in metal-based packaging systems. Applications spanning consumer goods, pharmaceuticals, cosmetics, and advanced electronics are integrated to support an overall understanding of how metallic and hybrid metal-based architectures underpin functional reliability and life-cycle sustainability. Full article

While many [FeFe]-hydrogenase biomimetics are effective proton-reduction catalysts, few are active for H₂ oxidation, and examples containing both a pendant amine group, able to act as a proton relay, and a second redox center, both essential features of the enzymes, are rare. Here we report the preparation and oxidation chemistry of two ferrocene-functionalized amino-diphosphines (PCNCP), (CH₂PR₂)₂NCH₂Fc (R = Ph (1), Cy (2)), and their ethylenedithiolate (edt) diiron complexes, [Fe₂(CO)₄(μ-edt){κ²-(R₂PCH₂)₂NCH₂Fc}] (R = Ph (3), Cy (4)). Their crystallographic characterization shows that PCNCP occupies an apical–basal position. CV responses are slightly R-dependent, showing for 3 and 4 in three separate oxidative processes assigned to successive one-electron oxidation of the diiron core (quasireversible), appended Fc (reversible), and the amine–diiron moiety (irreversible), as confirmed by IR and UV–Vis spectroelectrochemical studies supported by Density Functional Theory (DFT) and Time-dependent Density Functional Theory (TDDFT) calculations. The first oxidation results in a structural rearrangement of the Fe(PNP)(CO) unit and the formation of a semi-bridging carbonyl. Slow protonation of 3 with HBF₄∙Et₂O affords the corresponding N-protonated cation in acetone, whilst μ-hydride products dominate for both 3 and 4 in CD₂Cl₂. A preliminary H₂ oxidation study was carried out with 3, and while there was some evidence of activity, it was much lower than reported for alkyl-functionalized PCNPC diiron derivatives. Full article

The photocycloaddition (PCA) of chalcones represents an important reaction pathway for accessing substituted cyclobutanes, which is a molecular framework with utility in synthetic chemistry, materials science, and medicine. In the past, our group has demonstrated the utility of the large cavity of γ-CD as a container for encapsulating two photo reactants for directing the PCA of several classes of aryl alkenes with high stereo- and regioselectivity: the cavitand-mediated photodimerization (CMP) approach. The CMP of chalcones reported in this work further demonstrates the effectiveness of this approach as high yields of dimers were observed in the photoreactions, while they were non-reactive in the solid state and yielded only the isomerization product in homogeneous media. The γ-CD CMP of chalcones yielded predominantly dimerized products in very good to high yields (>70%), composed of a mixture of three dimers in different proportions with syn HH as the major product. Computational analysis of the ground state complex structures revealed a strong correlation between the stability of the complex and predominance of the stereoisomer in the mixture. Further insights were deduced from temperature-dependence studies, which showed a shift in dimer selectivity tending towards a single stereoisomer. Full article

Real-time PCR (qPCR) is today’s definitive quantitative technology in molecular biology and diagnostics. Until 30 years ago, PCR product analyses were generally performed after amplification using gel-based methods. Quantification typically relied on visual inspection or densitometry of end-point products and was therefore relatively unreliable and poorly suited to high-throughput automation. To celebrate real-time PCR’s 30-year anniversary of commercial availability, Professor Stephen Bustin, Guest Editor for the special edition, “Advancing Molecular Science Through Reproducible qPCR: MIQE Guidelines and Beyond,” asked Russell Higuchi to give a historical account on how his idea of real-time PCR was conceived and brought to fruition. Dr. Higuchi then asked his collaborator, Lincoln McBride, who drove the development of the ABI 7700—the high-throughput real-time PCR instrument that gave researchers access to this technology—to co-author this dual memoir. This story is told from the perspectives of the two scientists most directly responsible for making real-time PCR practical and widely accessible. Taking turns, Russell Higuchi describes the conceptual and experimental steps at Cetus and then Roche that led from homogeneous PCR detection to continuous fluorescence monitoring, whilst Lincoln McBride details ABI’s parallel efforts to commercialize Russ’s invention. Together, they trace how experimental insight, engineering constraints, product development, and commercial decision-making shaped the Applied Biosystems 7700 Sequence Detection System and established real-time PCR as a practical and reliable quantitative technology. Their team’s efforts persevered through technological uncertainty and within a complex corporate collaboration. They share key historical documents in their original form. Their accounts show how the 7700 system emerged as the convergence of chemistry, optics, software, and product development. The eventual global reliance on real-time PCR during the COVID-19 pandemic demonstrated, at unprecedented scale, the profound and enduring impact of these early technical and organizational choices. Full article