Abstract Organometallic reagents and catalysts have now assumed an integral role in contemporary organic synthesis. However, the intellectual progression from early stoichiometric reagents to advanced catalytic systems is rarely presented in a manner accessible to newcomers in the field. While standard textbooks and specialized reviews offer comprehensive descriptions of organometallic bonding and individual transformations, they often either assume significant prior knowledge or examine each development in isolation, without elucidating the mechanistic connections that span over a century of advancements. This review aims to provide a brief historical overview of this progression, beginning with the discovery of Zeise's salt and the development of organometallic reagents of the 19th century and extending through the rise of homogeneous catalysis, asymmetric hydrogenation, cross‐coupling, and olefin metathesis, and ending with the emergence of C–H bond activation in the 20th century. Throughout, the focus remains on the underlying mechanistic principles that propelled each breakthrough and the new synthetic opportunities they facilitated.
Abstract Type 2 diabetes (T2D) occurs due to a lack of insulin secretion by glucose stimulation, so high blood glucose levels predominate that associated with metabolic dysregulation. The exploration of bioactive compounds from natural sources has attracted considerable attention because these molecules provide chemically diverse scaffolds with broad pharmacological potential and have historically contributed to the successful development of numerous clinically approved drugs. In this study, we examined the effect of compounds isolated from Dregea volubilis (L.f.) Benth. ex Hook. f. (Apocynaceae) on glucose‐stimulated insulin secretion (GSIS) from the pancreatic β ‐cells. 17 β ‐Marsdenin ( 1 ), drevoluoside N ( 2 ), and dreageoside A11 ( 3 ) were screened for their ability to increase GSIS using a rat insulin ELISA kit. Western blotting was used to investigate the levels of pancreatic and duodenal homeobox‐1 (PDX‐1), phosphorylation of insulin receptor substrate‐2 (P‐IRS‐2), phosphorylation of phosphatidylinositol 3‐kinase (P‐PI3K), and phosphorylation of Akt (P‐Akt), which are related to β ‐cell function and insulin secretion in INS‐1 cells. Compounds 1 – 3 stimulated insulin secretion in INS‐1 cells without inducing cytotoxicity. A further experiment showed that compound 3 enhanced the expressions of PDX‐1, P‐IRS‐2, P‐PI3K, and P‐Akt in INS‐1 cells. The data suggest that compounds 1 – 3 from D. volubilis have the potential to improve insulin secretion in β ‐cells, representing the first step toward the development of potent antidiabetic drugs.
Abstract Double‐stranded DNA molecules are sharply bent into arcs with radii on the order of 10 nanometers in the formation of nucleosomes in biology and when they are looped into minicircles for nanoscale applications. In this Personal Account, we describe our computational efforts over the past several years to understand the structure and dynamics of sharply bent DNA using molecular dynamics simulations. First, using coarse‐grained models of DNA and cationic nanoparticles, we discuss how a small difference in sequence‐dependent DNA flexibility, on the order of 10 nm in persistence length, substantially influences the structure and thermodynamics of DNA–nanoparticle complex formation. Potential of mean force calculations quantify the thermodynamic preference for nanoparticle binding to more flexible DNA, with the free energy difference arising primarily from the sequence‐dependent elastic energy of DNA bending. We then turn to all‐atom simulations of DNA minicircles with approximately 90 base pairs. Sequence‐dependent coupling between DNA bending and its helical twist is identified for specific dinucleotide steps, and the internal dynamics of poloidal rotation and in‐plane circular vibration are characterized on time scales of tens and several nanoseconds, respectively. Finally, we present our recent investigations of mechanically interlocked DNA nanostructures: rotaxanes, in which a DNA minicircle is threaded onto a linear DNA axle, and catenanes, composed of two mutually interlocked DNA minicircles. The effects of torsional stress‐induced shape distortion on the structure and dynamics of these topologically constrained architectures are discussed. Together, these studies illustrate how the interplay of DNA sequence, flexibility, and topology governs the behavior of sharply bent DNA, providing molecular‐level insights for the design of DNA‐based nanoscale devices.
Abstract We report probe 1 , a novel melatonin–naphthalimide‐based fluorescent probe for the rapid and sensitive detection of hydrogen sulfide (H 2 S). The probe exhibits a distinct “turn‐on” fluorescence response through the specific reduction of an azide group to an amine, a mechanism rigorously validated by spectroscopic analysis, LC/MS, and TD‐DFT calculations. Probe 1 displays high sensitivity with a detection limit of 0.19 μM and excellent selectivity over other relevant analytes. Furthermore, bio‐imaging in A549 cells confirmed its low cytotoxicity and efficient membrane permeability, enabling real‐time monitoring of intracellular H 2 S fluctuations. These results demonstrate the potential of 1 as a robust and biocompatible tool for H 2 S detection in both environmental and biological contexts.
Abstract All‐inorganic perovskites are promising absorber materials for next‐generation perovskite solar cells (PSCs) owing to their potentially superior thermal and environmental stability compared with organic–inorganic counterparts. However, the instability of the black perovskite phase poses coupled challenges for device efficiency and durability. While noticeable progress has been made using solution process routes, its compatibility with mass production is questionable. Vapor‐phase routes, especially thermal evaporation, offer a solvent‐free pathway to highly uniform thin films with precise control over thickness, composition, and interfaces, and can be integrated into existing semiconductor toolsets. This review discusses recent progress in all‐dry‐processed inorganic PSCs, covering thermally evaporated inorganic absorbers and vacuum‐grown inorganic transport layers. First, phase behavior of Cs‐based inorganic perovskites under vacuum processing is discussed where composition, crystallite size, and surface chemistry govern access to and retention of the photoactive black framework. We then summarized various vapor deposition routes to form inorganic perovskites with desirable phase purity, morphology, and optoelectronic quality. The vacuum‐compatible additive engineering and passivation strategies are also discussed. Finally, inorganic hole and electron transport layers based on dry processes are reviewed. Collectively, this review provides insights into research directions toward efficient, scalable, and intrinsically more robust all‐dry inorganic PSCs.
Abstract Microwave‐assisted organic synthesis provides a rapid and sustainable platform for synthesizing various heterocycles. Microwave‐assisted transition‐metal‐catalyzed C–H activation enables selective bond formation under mild, efficient, and environmentally benign conditions, particularly when using green solvents such as water and biomass‐derived media. This review highlights recent advances in microwave‐promoted methods for N ‐ and O ‐heterocycle synthesis, demonstrating how transition‐metal catalysts accelerate cyclization, annulation, oxidative coupling, and C–H functionalization. In addition, this review also discusses microwave‐assisted transformations employing pre‐activated C–X bonds, which further broaden synthetic access to diverse heterocycles. Overall, microwave‐assisted transition‐metal catalysis offers a versatile and eco‐friendly approach with increasing relevance to medicinal chemistry, materials science, and sustainable synthesis.
Abstract Dried blood spot (DBS) analysis is a sample collection strategy that requires minimal volume of blood while providing practical advantages such as a simple collection procedure, enhanced sample stability, and efficient transport and storage. Due to these benefits, DBS has been applied in newborn screening, therapeutic drug monitoring, and pharmacokinetic studies for clinical and life sciences. Recently, the potential of DBS has gained attention for antidoping; therefore, the World Anti‐Doping Agency (WADA) has advanced the introduction and application of DBS‐based analytical approaches as a complementary strategy to conventional urine and venous blood samples. Consequently, various studies have been conducted for the development of high‐sensitivity analytical methods for prohibited substances, evaluation of DBS sampling devices, and the advancement of sample preparation focused on overcoming matrix‐related challenges. The development of DBS analysis and its clinical applications are overviewed, followed by a discussion of the rationale for its adoption in antidoping analysis and WADA's strategy. The challenges in DBS sampling and instrumental analysis were also investigated comprehensively, and recent advances in addressing limitations were also investigated. The analysis of steroid esters and other methods for substances in WADA technical documents was mainly focused on, and emerging approaches for erythropoietin and its markers in blood doping. Perspectives for the DBS analysis in antidoping operation in the large sports events were discussed.
Abstract Mixed Sn–Pb perovskites provide the 1.2–1.3 eV narrow‐bandgap absorber needed for high efficiency of all perovskite tandems, but their deployment is limited by operational instability under light. This review synthesizes mechanistic origins and recent mitigation strategies for mixed Sn–Pb perovskite solar cells. The oxidation of Sn 2+ to Sn 4+ , often driven by iodine formation under light and bias, is the primary failure pathway; it creates Sn vacancies, self‐doping, and nonradiative loss. Surface/grain‐boundary defects, halide migration, reactive oxygen species, and interfacial redox at charge‐transport layers, along with hole accumulation from poor band alignment, further accelerate Sn–Pb perovskite degradation. Here we survey recent stability advances across additive chemistry, surface and grain‐boundary passivation, buried‐interface redesign with modified or alternative hole transport layers, and solvent systems that preserve Sn 2+ and correct Sn–Pb speciation for scalable coating. Together, these recent advances have enabled devices to retain 80%–90% output for hundreds to over a thousand hours. Lastly, we provide our perspectives on further improving the operational stability of Sn–Pb perovskite and solar cells.
Abstract Precise genome engineering is fundamental to understanding biological functions, unveiling regulatory networks, and developing therapeutic strategies for genetic diseases. While conventional gene regulation and editing approaches are widely used, they often lack the spatiotemporal resolution required to study dynamic processes within living cells. The emergence of light‐controlled Clustered Regularly Interspaced Short Palindromic Repeats (CRISPR) systems has revolutionized this field, providing non‐invasive, high‐resolution control over genomic and transcriptomic activities. By integrating the programmable DNA/RNA binding specificity of CRISPR systems with diverse optogenetic strategies, researchers can now regulate gene activity with unprecedented precision. This review provides a comprehensive overview of the molecular principles underlying CRISPR‐based light‐controlled genome engineering techniques, evaluates their strengths and limitations, and discusses the future directions for the field.
Abstract Metal‐halide perovskites have emerged as promising semiconductors for wide‐spectrum photodetection owing to their exceptional optoelectronic properties, tunable band gaps, and facile synthesis. Their strong light–matter interactions and long carrier diffusion lengths have enabled devices capable of detecting radiation across an extraordinary spectral range, from γ‐rays and x‐rays to ultraviolet (UV), visible, and near‐infrared (NIR) light. This review highlights key advancements in perovskite‐based photodetectors (PPDs) and phototransistors, with an emphasis on high responsivity, detectivity, and ultrafast response times. We categorize device architectures by dimensionality (0D–3D) and detection regime, covering recent innovations such as flexible, lead‐free, and self‐powered PPDs. Special attention is given to novel chiral perovskites and polarization‐sensitive photodetectors enabling circularly polarized light (CPL) discrimination. Furthermore, this work discusses the extension of perovskite detection to the single‐photon level and evaluates underlying mechanisms for optical, ionizing, and near‐infrared regimes. The review concludes with perspectives on challenges and future trends, emphasizing interface engineering, stability enhancement, and scalable fabrication toward next‐generation optoelectronic imaging and communication systems.
Abstract N ‐heterocyclic carbene (NHC)‐based tetradentate Pt(II) complexes have attracted significant attention as promising phosphorescent dopants for blue organic light‐emitting diodes (OLEDs), because their rigid coordination frameworks enable narrow emission bandwidths and high color purity. However, square‐planar Pt(II) complexes suffer from intrinsic limitations, including limited triplet metal‐to‐ligand charge transfer ( 3 MLCT), long excited‐state lifetimes, and susceptibility to intermolecular interactions in the solid state, which collectively lead to reduced efficiency and operational stability. From a structure‐oriented perspective, this review systematically summarizes recent efforts aimed at overcoming these challenges, focusing on Pt(II) phosphorescent emitters based on the NHC‐phenyl‐O‐carbazole‐pyridine (NHCPhOCzPy) tetradentate ligand framework as a reference scaffold. The photophysical, electrochemical, and thermal properties are compiled together with key OLED device metrics, including emission wavelength, full width at half maximum (FWHM), Commission Internationale de L'Éclairage (CIE) coordinates, external quantum efficiency (EQE), efficiency roll‐off, and operational lifetime. Furthermore, diverse molecular design strategies are discussed, such as suppression of dopant‐dopant and host‐dopant interactions through steric engineering, fused‐ring extension, and enhanced molecular rigidity; modulation of charge injection and emitting dipole orientation by controlling the substituent and electronic‐structure control; and mitigation of intrinsic 3 MLCT limitations through incorporating nitrogen into the NHC framework to shorten decay lifetimes and enhance spin‐orbit coupling. This comprehensive review also critically assesses the trade‐offs among deep‐blue color coordinates, high efficiency, and long device lifetime, and it proposes design guidelines for next‐generation blue Pt(II) phosphorescent dopants.
Abstract Genetic code expansion (GCE) enables site‐specific incorporation of noncanonical amino acids (ncAAs) that introduce chemical functionalities beyond the canonical amino acid set and provide programmable control over protein state and function. This review focuses on chemically triggered strategies that regulate protein activity through engineered ncAA reactivity. We summarize core mechanistic principles, including reaction‐driven control, reversible coordination and molecular binding, and spectroscopic readout strategies. We organize system architectures for chemosensing into direct and indirect interaction modes and discuss how ncAA‐encoded protein state transitions are converted into measurable signals. Chemical actuation strategies extend protein‐level control to higher‐order biological outcomes, including enzymatic activation, regulated proteolysis, gene editing, signaling network modulation, and cell fate control, thereby positioning GCE‐enabled chemical sensing and actuation as a general molecular approach that links defined chemical inputs to precise biological actions.
Abstract Serotonin 7 receptor (5‐HT 7 R) has emerged as a multifunctional G protein‐coupled receptor that regulates neuronal excitability, structural plasticity, and circuit function across the central nervous system. Beyond canonical Gs‐dependent signaling, accumulating evidence indicates that 5‐HT 7 R also engages G12‐associated Rho GTPase pathways and β ‐arrestin/SRC family kinase‐mediated signaling, thereby enabling diverse and context‐dependent regulation of intracellular effectors involved in cytoskeletal remodeling, translational control, and sustained kinase activation. In this review, we summarize three representative 5‐HT 7 R signaling axes and discuss how these pathways may differentially contribute to the pathophysiology of major neuropsychiatric disorders, with a particular focus on autism spectrum disorder, depression, and schizophrenia. Across these disorders, 5‐HT 7 R‐linked signaling is associated with developmental wiring, synaptic maturation, stress‐responsive plasticity, glutamatergic dysfunction, and cognitive circuit regulation. Importantly, the functional consequences of 5‐HT 7 R activation appear to depend on developmental stage, brain region, cell type, ligand condition, and subcellular signaling context, indicating that similar downstream readouts may carry distinct mechanistic meanings. By adopting a pathway–disease mapping perspective, this review highlights 5‐HT 7 R as a versatile molecular interface connecting serotonergic signaling to disease‐relevant neural plasticity and suggests that future therapeutic strategies may benefit from pathway‐informed modulation rather than a simple agonist–antagonist framework.
Abstract Tandem solar cells have emerged as a promising next‐generation photovoltaic technology capable of surpassing the Shockley–Queisser limit of single‐junction devices. In particular, perovskite/Si tandem architectures employing wide‐bandgap perovskites as top absorbers have demonstrated certified power conversion efficiencies approaching 35%, owing to their exceptional bandgap tunability and high achievable open‐circuit voltages. These remarkable advances have been enabled by passivation of various defects in wide‐bandgap perovskites, thereby reducing non‐radiative recombination losses and halide segregation‐related stability issues. This review focuses on recent progress in defect passivation strategies for wide‐bandgap perovskites, as well as earlier studies that established key milestones for state‐of‐the‐art tandem devices. Defect passivation strategies are systematically discussed according to defect location: (i) bulk passivation using additives that enlarge grain sizes, coordinate with detrimental point defects via functional groups, and passivate grain boundaries; (ii) surface passivation by inorganic insulators (e.g., LiF) and molecular passivators; (iii) buried interface passivation via functional self‐assembled monolayers and modulated inorganic interlayers. Particular emphasis is placed on elucidating the relationships between defect‐induced recombination losses, ion migration, and device performance and stability. By critically summarizing recent advances in defect engineering approaches, this review highlights current research trends and key considerations for realizing highly efficient and stable perovskite/Si tandem solar cells.
Abstract The growth and characterization of two‐dimensional (2D) crystalline boron‐carbon‐nitride (BCN) have received tremendous attention in the past decade, offering potential applications in optoelectronic and semiconductor technologies. Borazine derivatives have emerged as versatile molecular precursors for the bottom‐up synthesis of 2D BCN materials, enabling atomic‐level control over heteroatom doping and, consequently, precise tuning of the electronic band structure. This review provides a comprehensive overview of the synthetic strategies developed for organoborazines and their use as single‐source precursors for on‐surface synthesis and subsequent scanning tunneling microscopy (STM) characterization of BN‐doped carbon architectures. Particular emphasis is placed on the relationship between molecular design and resulting on‐surface supramolecular architectures. This review highlights current challenges and outlines future perspectives toward the rational design of borazine precursors for controlled BCN structures.
Abstract Perovskite solar cells (PSCs) have achieved power conversion efficiencies comparable to crystalline silicon, yet their commercial deployment is hindered by inherent susceptibility to environmental stressors. To overcome this, the integration of two‐dimensional (2D) layered perovskites with three‐dimensional (3D) absorbers to form 2D/3D heterojunctions has emerged as a definitive strategy for enhancing device longevity. However, current research has predominantly focused on defect passivation, often leaving the broader structural and electronic interactions between 2D and 3D lattices less explored. This review moves beyond the traditional perspective of 2D layers as passive encapsulants and establishes a design‐oriented framework for their strategic integration into 2D/3D heterojunctions. We classify 2D structures from macroscopic inorganic slab thickness to microscopic interlayer connectivity defined by spacer cation chemistry. Centering on the 2D/3D heterojunction architecture, we elucidate the multifaceted roles of 2D perovskites ranging from thermodynamic stabilization and defect passivation to active electronic functions such as built‐in potential modulation and structural templating. Furthermore, we discuss practical strategies for forming 2D/3D heterojunctions, categorizing them into surface post‐treatments for top‐junction engineering and emerging techniques for buried‐interface control to minimize non‐radiative recombination. This review confirms that the 2D layer functions as an active semiconductor component that fundamentally dictates the device physics of high‐performance PSCs.
Abstract Perovskite solar cells (PSCs) have achieved power conversion efficiencies exceeding 26%, yet their commercialization remains limited, mainly due to instability caused by defect‐mediated nonradiative recombination, ion migration, and environmental degradation of the three‐dimensional (3D) perovskite. Introducing two‐dimensional (2D) perovskite layers at the top, bottom, or both interfaces of the 3D perovskite has emerged as an effective strategy to passivate defects, optimize band alignment, suppress ion migration, and enhance moisture and thermal stability. This mini‐review summarizes recent progress in mixed‐dimensional 2D–3D perovskite heterostructures, highlighting different approaches, including ligand design, phase‐pure 2D growth, and solvent engineering, that lead to high‐efficiency and stable PSCs. Finally, the review outlines remaining challenges and future directions, pointing toward mixed‐dimensional perovskite architectures as a promising route to commercialize PSC technology.
Abstract The activation of CO 2 represents one of the most enduring challenges in catalysis, energy conversion, and carbon utilization. Recent studies reveal that excess electron density, whether localized on metallic clusters, delocalized within π‐conjugated organic frameworks, or transiently formed as radical anions, plays the decisive role in breaking the thermodynamic inertness of CO 2 . This review integrates experimental and theoretical advances, tracing the evolution of anionic activation of CO 2 from Pt hydride cluster anions to nitrogen‐doped polyaromatic catalysts. By connecting in vacuo spectroscopy, density functional theory (DFT), and ab initio molecular dynamics (AIMD), we delineate a unified electronic framework linking associative and dissociative activation, static and dynamic electron donation, and metal versus metal‐free paradigms. The role of the CO 2 radical anion in photocatalysis is discussed alongside the emerging design principles for next‐generation catalysts that exploit charge accumulation rather than expensive metallic centers.
Abstract Poly(triarylamine)s (PTAAs) are widely employed as hole‐transporting materials in organic electronic and optoelectronic devices, including organic field‐effect transistors, organic light‐emitting diodes, and perovskite solar cells. However, their synthesis has historically been limited by the modest yields and narrow substrate scope associated with copper‐mediated Ullmann condensation. Although palladium‐catalyzed Suzuki–Miyaura coupling offers a versatile alternative to overcome these limitations, the multistep preparation of monomers remains a significant drawback. In contrast, Buchwald–Hartwig amination has emerged as a powerful synthetic platform for the construction of PTAAs from readily accessible building blocks. In this review, we systematically examine various Buchwald–Hartwig amination‐based synthetic approaches for producing structurally diverse PTAA materials and discuss how each strategy governs the structural precision and molecular architecture of the resulting materials.
Protein misfolding and aggregation are critical in amyloidogenic diseases such as Alzheimer's disease, diabetes, and prion disorders. While aggregation has been widely studied in terms of extrinsic factors, the influence of intrinsic molecular features, particularly histidine tautomerism, remains poorly understood. In this mini‐review, we summarize recent computational studies elucidating how histidine tautomeric states regulate the structural changes, aggregation propensity, and intermolecular interactions of major amyloidogenic proteins, including amyloid‐β (Aβ40/42), Tau, amylin, prion protein, and profilin‐1, as well as their disease‐associated variants. We discuss tautomer‐dependent effects on monomer conformations, early oligomerization, fibril formation, and cross‐seeding behavior, and highlight the integration of molecular dynamics simulations and computational two‐dimensional infrared spectroscopy for resolving tautomer‐specific signatures. These findings emphasize histidine tautomerism as a critical but underestimated factor in amyloid aggregation mechanisms.
