Abstract Li 1.875 Na 0.125 FeSiO 4 with polyvinylpyrrolidone (PVP)‐derived carbon was synthesized using wet ball‐milling followed by high‐temperature calcination. The results show that the combined effect of PVP carbon and sodium doping significantly enhances the material's resistance to oxidation and deliquescence. Furthermore, secondary calcination effectively regenerates the stored materials, achieving higher phase purity compared to the initial synthesis. The coin cells with regenerated cathodes exhibit unique continuously increasing capacity with cycling, attributed to the mild agglomeration effect of secondary calcination. Notably, the Li 1.875 Na 0.125 FeSiO 4 /Li cell can maintain a discharge capacity of 166.7 mAh·g −1 after 100 cycles while preserving its crystal characteristics. This work offers novel strategies for enhancing storage protection and optimizing the synthesis of iron‐based silicate electrodes.
ABSTRACT Fluorinated sugars have emerged as powerful tools in glycoscience due to their wide‐ranging biological applications. However, the stereoselective installation of fluorine and subsequent glycosylation remain significant challenges, often complicated by competing rearrangement pathways. This mini review highlights recent advances in the synthesis of fluorinated sugars, encompassing chemical, enzymatic, and automated glycan assembly (AGA) approaches. Furthermore, it discusses the diverse applications of fluorinated carbohydrates in biological systems, including the use of 19 F NMR as a probe to study glycan–protein interactions, as enzyme inhibitors, and in vaccine development. Collectively, these advances underscore the growing importance of fluorinated sugars in expanding the toolkit of modern glycobiology and therapeutic research.
ABSTRACT The partial oxidation of methane (POM) to syngas is a technologically attractive route for H 2 production; however, its practical implementation is hindered by catalyst deactivation, carbon deposition and limited long‐term stability. Herein, we elucidate the promotional role of strontium (Sr) in enhancing the structural and catalytic properties of Ni/ZrO 2 ‐SiO 2 catalysts. Sr incorporation modulates the electronic structure and redox behavior of the catalyst by strengthening metal‐support interactions and promoting oxygen mobility. Notably, Sr induces the formation of oxygen vacancies, thereby increasing the availability of reactive lattice oxygen species (O 2− /O 2 2− ), which facilitates CH 4 activation and suppresses coke formation. Comprehensive characterization using XPS, TPR and XRD demonstrates that Sr enhances Ni reducibility and stabilizes active sites through surface electronic modification. Among the investigated catalysts, Ni3Sr/SZ (3 wt.% Sr) exhibits optimal performance, achieving 54.0% CH 4 conversion and 52.0% H 2 yield with a H 2 /CO ratio of 2.6 at 600°C under CH 4 :O 2 = 2:1 condition, corresponding to an enhancement of > 15% compared to the unpromoted system. Furthermore, the catalyst maintains stable activity over 250 min without noticeable deactivation, attributable to its improved resistance to carbon accumulation. The superior performance is ascribed to the synergistic interplay between enhanced oxygen mobility, increased oxygen vacancy concentration, and strengthened metal‐support interactions. This work provides fundamental mechanistic insights into Sr‐promoted Ni catalysts and offers a scalable strategy for the rational design of robust catalytic systems for hydrogen‐rich syngas production, with potential applications in Fischer‐Tropsch synthesis and fuel cell technologies.
ABSTRACT Using density functional theory (DFT), this work investigates the optical and thermoelectric characteristics of MgLu 2 S 4 and MgLu 2 Se 4 spinel compounds when subjected to pressure. The band gap is reduced by applying pressure up to 20 GPa, particularly in MgLu 2 Se 4 , according to the results. Elastic properties show mechanical stability and increased hardness under applied pressure. Their usage in optoelectronic applications is supported by changes in optical characteristics with pressure, such as a redshift in the absorption edge, higher refractive index, and improved optical conductivity. But the thermoelectric figure of merit (ZT) drops somewhat as a function of pressure, indicating that waste heat recovery is less efficient when compressed. These results show that MgLu 2 X 4 (X = S, Se) spinels have good potential for high‐temperature optoelectronic and thermoelectric applications, but their thermoelectric performance may be limited under high pressure.
Abstract Agrochemicals like 2,4‐dichlorophenoxyacetic acid (2,4‐D) remain one of the widely used herbicides contributing to environmental pollution, especially the aquatic system, which is the lifeblood of nature. Interestingly, to eliminate this hazardous pollutant, the photocatalytic degradation technique as an advanced oxidation process has come to the fore among emerging remediation technologies because of its ability to degrade and mineralize organic pollutants into non‐toxic molecules like CO 2 and H 2 O. Thus, this study aims to critically and extensively review recent advances on the photocatalytic degradation of 2,4‐D in aqueous environments using nano‐architecture materials. Notably, the study revealed key advancements in the area of heterojunction formation, metal‐free photocatalyst, hybrid/assisted system, ternary nanocomposites, oxygen vacancy, biogenic nanomaterials, and the use of natural sunlight. Interestingly, these advancing areas were found to be delivering better photocatalytic degradation efficiency for 2,4‐D. Moreover, various nano‐architecture photocatalysts can degrade 2,4‐D multiple times (3–11 times with >70% efficiency in the last cycle) without seriously trading off their original structural integrity and performance. A few available studies also proved that 2,4‐D degradation byproducts have low ecotoxicity. At the end, challenges and future perspectives were identified in the area of competition with existing remediation technologies, pilot‐scale study, and validation.
ABSTRACT Binuclear copper‐dependent oxidative enzymes (BiNCOs), previously annotated as domain of unknown function 3328 (DUF3328) or UstYa homologs, are involved in the oxidative modification during fungal natural product biosynthesis. Although this family was discovered over a decade ago, the biochemical properties, especially cofactor dependency, remained unsolved until the recent characterization of the C(sp 3 )H halogenase ApnU. Utilizing a protein refolding strategy to obtain soluble and functional enzymes, the unexpected copper‐dependency of ApnU was demonstrated. Subsequent studies with members in this family, including macrocyclase AprY, hydroxylase CctR, and the bifunctional enzyme TruY, showed the diverse types of reactions catalyzed by BiNCOs using molecular oxygen as an oxidant and external ascorbate as reductant. Structurally, this family is defined by conserved dual HXXHC motifs that coordinate the binuclear copper center and an interchain disulfide‐linked homodimer structure. Furthermore, as BiNCOs are frequently associated with a specific family of fungal RiPPs, the study of AprY and TruY have shed light on the fungal RiPP maturation pathway. This review summarizes the current understanding of BiNCOs and provides an updated discussion of reaction mechanisms involved in halogenation, hydroxylation, macrocyclization, and aryl‐coupling reactions.
ABSTRACT Poly(salicylic acid) (PSA) compounds, as representative examples of “carrier‐drug integrated” materials, effectively overcome issues such as low bioavailability, short half‐life, and systemic toxicity associated with the small‐molecule form of salicylic acid (SA) by incorporating this traditional drug molecule into the polymer backbone or side chains. This paper provided a systematic review of PSA synthesis strategies, including self‐polymerization, copolymerization, and grafting onto polymer backbones, with a focus on its extensive applications in the biomedical field. PSA materials demonstrated exceptional performance in antibacterial, anti‐inflammatory, and anticancer applications. Through mechanisms such as smart‐response release, targeted delivery, and synergistic therapy, they enabled precise intervention against diseases including infections, inflammation, and tumors. Furthermore, PSA has demonstrated significant potential in applications such as cardiovascular disease treatment, bone repair, and diabetic wound healing. Despite notable achievements in functional design and clinical application of PSA materials, their clinical translation still faces challenges including in vivo behavior studies, large‐scale synthesis, and multi‐response system design. Future research will focus on developing intelligent PSA materials, advancing their application in areas such as integrated diagnosis and treatment, and immunotherapy.
Abstract A novel colorimetric chemosensor, DCMB (2,4‐dichloro‐N′‐((4‐oxo‐4 H ‐chromen‐3‐yl) methylene) benzohydrazide), was designed to detect Cu 2+ . DCMB exhibited a rapid and highly selective colorimetric response to Cu 2+ , changing from colorless to yellowish green with negligible interference from other metal ions. The limit of detection of DCMB for Cu 2+ was 1.19 μM, and the chemosensor remained effective for Cu 2+ detection across pH 4–10. These features showed the potential of DCMB as a convenient indicator for Cu 2+ monitoring. In environmental water samples such as tap, drinking, stream, and seawater, DCMB reliably recognized Cu 2+ with good recovery. Additionally, DCMB ‐coated test strips enabled on‐site detection of Cu 2+ , and a DCMB ‐based smartphone application offered a portable and practical quantification of Cu 2+ . The detection mechanism of DCMB for Cu 2+ was proposed to be a 1:1 binding reaction by Job plot, ESI‐MS, 1 H NMR titration, and DFT calculations.
Abstract Carbon (C)‐based materials are gaining significant attention as potential alternatives to alkali metal anodes, such as lithium (Li), sodium (Na), and potassium (K). Their advantages lie in relatively lower redox potentials, improved safety, and cost‐effectiveness, rendering them suitable for large‐scale use in metal‐ion batteries (MIBs) and supercapacitors (SCs). Among the available C sources, coal and its derivatives stand out due to their abundance, high C content, and favorable structural features. Despite the moderate electrochemical performance of current coal‐derived C (CDC) materials, developing high‐performance, low‐cost CDC remains essential for reducing the overall cost of energy storage systems. This review focuses on microstructural modification strategies, including heteroatom doping, defect tailoring, and pore architecture optimization, while critically examining their limitations. It also outlines existing challenges and proposes potential research directions toward the advancement of efficient CDC materials.
Abstract Metal‐based nanoparticles (MNPs) are composed of metals, such as gold (Au), silver (Ag), zinc (Zn), iron (Fe), and manganese (Mn), and are utilized across various biomedical applications. The unique physicochemical profile of MNPs, characterized by tunable size, a high surface‐area‐to‐volume ratio, and distinctive optical, magnetic, and catalytic properties, facilitates applications impossible for bulk materials or standard molecular therapeutics. This review examines recent developments and modifications in the functional properties of MNPs, with particular emphasis on potentially groundbreaking applications, including NPs containing Au, Ag, Fe, and other emerging MNPs. Their applications in nanomedicine, specifically in cancer detection and treatment, wound healing, antimicrobial therapy, imaging, as well as liver and fibrosis treatment, are thoroughly discussed. Factors influencing the future clinical utility of these NPs include their interactions within the human body and the relative ease of their production. MNPs hold significant promise for advancing sophisticated diagnostic and therapeutic techniques. The review also delineates prospective future directions in this field.
ABSTRACT The quinoline and its derivatives are a significant group of heterocyclic compounds that have numerous applications in pharmaceuticals, agriculture, materials science, and fine chemicals. There has thus been a lot of interest in developing effective, sustainable, and environmentally safe synthetic methods to quinoline frameworks. In that regard, ethanol‐solvated iron nanoparticles (EtOH‐solvated FeNPs) have come as quite promising heterogeneous catalytic systems due to their low prices, abundance on Earth, magnetic retrieval, and low environmental effects. This review gives an excellent overview of the synthesis, physicochemical properties, and catalytic properties of the EtOH‐solvated FeNPs in quinoline and its derivatives building. The focus is put on their application in catalyzing important quinoline‐containing reactions, such as multi‐component condensations, cyclization reactions, and oxidative coupling reactions, under green and mild reaction conditions. The mechanistic mechanism of FeNPs‐catalyzed pathways, the reusability of the catalyst, and structure–activity correlation are critically reviewed to feature the merit of ethanol solvation in improving the catalytic power and stability. In addition, the review contrasts EtOH‐solvated Fe NP catalysis with traditional homogeneous and heterogeneous systems highlighting its outcome in terms of increased reaction efficiency, selectivity, and sustainability. The limitations, the possibilities, and present difficulties of Fe nanoparticle‐based catalysis to produce quinoline are also discussed. Generally, this review is expected to develop EtOH‐solvated FeNPs into a highly general and environmentally friendly catalytic system to synthesize quinoline derivatives in a sustainable manner.
ABSTRACT The coronavirus nucleocapsid protein (N) is the most abundant viral protein in infected cells and plays a central role in genome packaging, replication, and transcription. Its primary function is to organize an exceptionally large, positive‐sense RNA genome into a helical ribonucleoprotein (RNP) assembly that must be both structurally stable and dynamically accessible. In this review, we summarize our biophysical and structural studies elucidate how the severe acute respiratory syndrome coronavirus (SARS‐CoV) N protein resolves these competing demands. The N protein is shown to be modular, comprising two folded domains embedded within extensive intrinsically disordered regions, resulting in a multivalent, electrostatically driven RNA‐binding architecture. Quantitative binding analyses reveal moderate‐affinity interactions distributed across multiple sites and coupled through positive cooperativity. High‐resolution structures of the C‐terminal dimerization domain obtained by X‐ray crystallography and solution NMR reveal a oligomerization scaffold and delineate an extended helical RNA‐binding surfaces. These findings highlight a simple physical principle, namely that CoV RNP packaging is a symphony of enthalpic contribution from electrostatic interaction and entropic contribution inherent to the intrinsic disordered regions. While the enthalpic energy stabilizes the RNP structure, the entropic effect facilitates the N‐RNA interaction and structural rearrangement. Together, these studies establish a physical framework in which structural order and intrinsic disorder cooperate to enable efficient and reversible ribonucleoprotein assembly.
ABSTRACT The persistent occurrence of hazardous dye pollutants in the environment, especially water bodies, has continued to be a global concern due to their continuous release from various sources, particularly industries. These pollutants are resistant to natural and conventional water self‐cleanup and capable of inducing ecotoxicological effects. Among advanced oxidation processes, photocatalysis has gained considerable attention as an efficient and sustainable method for the degradation and mineralization of dye pollutants. Within this context, zirconium dioxide (ZrO 2 )‐based nanomaterials (ZDBNs) have emerged as promising photocatalysts owing to their excellent chemical stability, tunable surface properties, high thermal resistance, low toxicity, and strong oxidative potential. This study provides a comprehensive and up‐to‐date review of ZrO 2 ‐based nanomaterials for photocatalytic degradation of dyes in an aqueous environment. To establish the foundation of the discussion, the review highlights the crystal structure and unique properties of ZDBNs. Then, the fundamental principle of the dye photocatalytic degradation mechanism by ZDBNs was succinctly underscored. Subsequently, performance trends in the degradation of various dye pollutants under light exposure were critically and comparatively analyzed. Furthermore, photocatalyst stability, regenerability, reusability, and structural durability are evaluated to assess long‐term applicability and economic value. The review also addresses scalability challenges to determine the industrial prospects of ZrO 2 ‐based photocatalytic systems. Finally, future research perspectives are presented to provide a strategic framework for the rational design of highly efficient, visible‐light‐responsive, stable, and environmentally sustainable ZrO 2 ‐based photocatalysts for dye effluent remediation.
ABSTRACT The development of bioconjugates with high payload loading and defined stoichiometry remains a persistent challenge in medicinal chemistry. In this Account, we present a modular multi‐arm linker platform that decouples payload loading from site‐specific antibody conjugation. This platform utilizes a central peptide core with multiple linking arms for attaching effector/targeting molecules and a single coupling arm (e.g., maleimide) for antibody conjugation. To achieve site‐specificity without the need for enzymatic processing, we employ a bioinorganic strategy: a computationally designed zinc‐binding motif (ACPGHA) fused to the antibody C‐terminus. Density functional theory calculations suggest Zn(II) binds and deprotonates the engineered cysteine to a reactive thiolate for rapid, chemoselective Michael addition to the linker's maleimide. We demonstrate how the modular multi‐arm linker platform, paired with Zn 2+ ‐mediated site‐specific conjugation, enables the modular construction of (i) a theranostic antibody‐radionuclide conjugate for pancreatic cancer and (ii) a potent antibody‐drug conjugate for multiple myeloma. This integration of coordination chemistry, computational design/modeling, and protein engineering provides a robust framework for constructing homogeneous bioconjugates with precise stoichiometry. Beyond cytotoxic payload delivery, the same multi‐arm linker architecture enables pharmacokinetic modulation of a peptide agonist via conjugation of two albumin‐targeting fatty acids.
ABSTRACT Proton translocating respiratory chain complexes assemble into supramolecular structures in their native cellular environment, yet the organizational principles and functional consequences of this arrangement remain incompletely understood. In Actinobacteria, the cytochrome bcc ‐ aa 3 supercomplex constitutes an obligatory respiratory unit that integrates menaquinol oxidation with dioxygen reduction and serves as a major driver of aerobic cellular respiration. Central to its architecture is the di‐heme c ‐type cytochrome subunit QcrC, which forms a continuous internal electron transfer conduit linking the Q cycle of the cytochrome bcc complex to catalysis by the cytochrome aa 3 oxidase. This direct electron transfer contrasts with the mitochondrial respiratory chain, where electron transfer between complexes III and IV relies on diffusion of soluble cytochrome c , irrespective of supercomplex formation. In this review, characteristic features of the cytochrome bcc ‐ aa 3 supercomplex are highlighted based on its cryogenic electron microscopic structure from Corynebacterium glutamicum . The latter is an actinobacterial species widely used for the industrial production of l ‐glutamic acid and l ‐lysine, and is a close homolog of pathogenic Actinobacteria which cause diphtheria and tuberculosis. Explicit descriptions of its subunit composition, overall architecture, prosthetic group arrangement, and a comparative analysis with homologous respiratory chain complexes as well as supercomplexes are provided. As Actinobacteria lack the free diffusible cytochrome c , the internal electron transfer pathway in the cytochrome bcc ‐ aa 3 supercomplex is facilitated by tight integration of the di‐heme QcrC subunit. The stable association as an obligate supercomplex is enhanced through supercomplex‐specific peripheral subunits and peripheral domains of catalytic subunits, which are discussed. Additional stabilization is provided by endogenous structural lipids, including acylated phosphatidylinositol mannosides, lipidic post‐translational modifications, and ordered cardiolipin molecules. Together with an analysis of the electrochemical properties of the catalytic subunits, these features elucidate the structural and functional principles that underlie the obligate organization of this respiratory supercomplex.
ABSTRACT The past half‐century has witnessed developments of major structural biology techniques for protein structure and enzymology, from X‐ray crystallography and NMR to cryo‐electron microscopy (cryo‐EM) and free‐electron laser crystallography (XFEL). Having experienced most of these changes directly in my research, I am reviewing my lifetime research work to highlight synergistic developments in structural biology and enzymology, and provide future perspectives for the emerging new frontier of time‐resolved structural biology.
ABSTRACT A great scientific achievement has been the elucidation of the role that the presynaptic protein α‐synuclein (α‐syn) plays in Parkinson's disease (PD). α‐syn has a propensity to aggregate into a myriad of soluble and insoluble states, some of which are cytotoxic and that trigger the degeneration of dopaminergic neurons in the mid‐brain. Although highly expressed in neurons, α‐syn is also expressed in skin, specifically melanocytes, and is robustly expressed in primary and metastatic melanomas. Epidemiological studies have identified a co‐occurrence of melanoma and PD, in that, compared to healthy individuals, melanoma patients have a significantly higher risk of developing PD, and PD patients have a significantly higher risk of developing melanoma. Such a co‐occurrence indicates that shared pathogenic triggers may underlie both diseases. Although there is no definitive evidence that α‐syn is the pathogenic trigger, my interest has been to decipher the function of α‐syn in melanoma. Herein, I give a background on melanoma biology, α‐syn structure and function, pigment production in neurons and melanocytes, and then focus on evidence that α‐syn promotes melanoma proliferation and progression by facilitating the intracellular transport of key proteins, which support invasion and migration, to the plasma membrane.
ABSTRACT In this study, a comprehensive investigation of the alkali‐metal bismuthide compounds XZ 2 Bi 2 (X = K, Rb, Cs; Z = Zn, Cd) using full potential augmented plane wave approach performed. The structural properties confirm a tetragonal ThCr 2 Si 2 ‐type crystal symmetry, with systematic variations in crystal lattice parameters influenced by the choice of cation metals. Compounds reveal ductile nature and mechanically stable. Electronic structure analysis reveals metallic behavior, with prominent Bi‐ p states near the Fermi level. Optical studies indicate high reflectivity and dielectric constants in the visible and UV ranges, making these compounds suitable for photonic applications. Thermodynamic properties such as sound velocity, Debye temperature, and heat capacity were computed, showing moderate values consistent with good thermal stability. Moreover, thermoelectric performance evaluated via the Seebeck coefficient, thermal and electrical conductivities, and figure of merit (ZT) reveals basic characteristics of metallic materials with high conductivity and low ZT.
