Browse Articles

Correction: The relationship between N-terminal pro-brain natriuretic and coronary artery lesions in Kawasaki disease: A meta-analysis

Quantitative metrics to characterize radiologists’ search patterns during multiparametric MRI assessment for prostate cancer

TBC1D9 and TBC1D9B are ARL8 effectors that modulate exosome secretion through a RAB11A–exocyst pathway

Multivesicular endosomes (MVEs) are endolysosomal compartments containing intraluminal vesicles (ILVs) that follow two alternative pathways: fusion with lysosomes, leading to ILV degradation, or fusion with the plasma membrane, resulting in ILV secretion as exosomes. The mechanisms governing this fate decision have only recently begun to be elucidated. Previous work showed that the Biogenesis of lysosome related organelles complex-one-related complex (BORC) and the small guanosine triphosphatase (GTPase) ARL8 promote MVE–lysosome fusion through the ARL8 effector homotypic fusion and protein sorting complex (HOPS), thereby diverting MVEs from exosome secretion. Here, we identify TBC1D9 and TBC1D9B as ARL8 effectors that further suppress exosome release. Acting as GTPase-activating proteins, these proteins drive RAB11A inactivation and dissociation from endolysosomes. This reduces recruitment of the RAB11A effector exocyst complex, preventing MVE fusion with the plasma membrane. These findings thus define a BORC–ARL8–TBC1D9/TBC1D9B axis that further attenuates exosome secretion by blocking MVE–plasma membrane fusion.

Correction: Burnout among anesthesia personnel in Thailand: A national survey of workload, personality traits, and resilience

Cooking and sensory properties of different varieties of rice from various agro-climatic areas of Nigeria

Oncogenic Kras targeting with MRTX1133 or Daraxonrasib specifically synergize with anti-CTLA4 to promote anti-tumor immunity in pancreatic cancer

Macrophage adenylyl cyclase 7 protects against myocardial ischemia/reperfusion injury in male mice

Competitive resource allocation drives asynchronous and rapid nuclear multiplication in the malaria parasite

Abstract The unicellular malaria parasite Plasmodium falciparum proliferates within red blood cells of its human host, where it generates approximately 20 new parasites within a two-day developmental cycle. Before cellularization and release of the daughter cells, the nuclei multiply in a shared cytoplasm. In stark contrast to highly synchronized nuclear division cycles seen in other developing eukaryotes, Plasmodium nuclear cycles desynchronize rapidly. Combining live-cell imaging with biophysical modeling, we elucidate the mechanism of desynchronization and study its impact on parasite proliferation. We find that standard models of autonomous nuclear cycles cannot account for the experimental data, and therefore desynchronization requires nuclear coupling. Competition for a limiting pool of proteins needed for DNA replication explains the data, provided that they are allocated sequentially to individual nuclei. Sequential allocation can be achieved by reversible but stable association of the resources with DNA. Remarkably, the resultant asynchronous nuclear cycles accelerate parasite proliferation by minimizing idling times of the resource. This mechanism may be a general strategy to maximize proliferation in suboptimal growth conditions. Together, our findings identify nuclear cycle asynchrony as a resource-efficient means to achieve rapid proliferation.

Ketazine‐Linked Covalent Organic Framework for Metal‐Free Electrocatalytic Nitrate‐to‐Ammonia Conversion

ABSTRACT The electrocatalytic nitrate reduction reaction (NO 3 RR) enables sustainable nitrate remediation and simultaneous ammonia synthesis as an alternative to the energy‐intensive Haber‐Bosch process. Recently, covalent organic frameworks (COFs) have garnered attention as NO 3 RR platform due to their intrinsic porosity and structural tunability, which enable active‐site engineering. However, current COF‐based systems largely rely on metal active sites, undermining their sustainability and obscuring the catalytic activity of the framework. Here, we introduce a metal‐free COF, that is highly active for NO 3 RR. The electrocatalyst is a fluorinated ketazine‐linked COF (F‐Ketazine COF), which incorporates electron‐withdrawing fluorine atoms that enhance π–π stacking interactions and promote efficient linkage formation. Synthesized via a rapid solvothermal reaction, the F‐Ketazine COF exhibits superior crystallinity and enhanced electrocatalytic activity compared to its non‐fluorinated analog (n‐Ketazine COF). Under neutral pH conditions, the F‐Ketazine COF achieved a Faradaic efficiency of 59.9% for NH 3 and an NH 3 yield rate of 1639.9 µmol h −1 mg COF −1 at −0.9 V versus RHE. To the best of our knowledge, this is the first example of a ketazine‐linked COF applied in electrocatalysis and the first a metal‐free COF for NO 3 RR. This work demonstrates the potential of fluorinated ketazine linkages in developing sustainable and efficient COF‐based electrocatalysts.

Spontaneous Chemical Amine Oxidation in Organic Solvents Paired With Electrochemical Hydrogen Production

ABSTRACT Benzonitrile (BN) is a versatile chemical building block extensively applied across multiple sectors. Electrochemical benzylamine oxidation reaction (BOR) provides a sustainable method for BN synthesis, simultaneously enabling H 2 fuel generation via hydrogen evolution reaction (HER). Alkaline electrolytes are commonly used to reduce the BOR overpotential but promote the hydrolytic decomposition of benzylimine intermediates and BN products, contributing to significant carbon loss. These side reactions become more pronounced under industrially relevant conditions (>50 mM). In this study, redox reservoirs (RRs) were employed to decouple BOR from HER, allowing their independent operation. Utilizing a highly positive formal potential, RRs facilitated spontaneous BOR in hexane, effectively circumventing hydrolysis issues and simplifying the product purification. Furthermore, NiOOH species within RRs functioned as reactive sites with strong affinity toward benzylamine (BA) and negligible self‐reduction, thereby achieving high BN yield and Faradaic efficiency even at BA concentrations exceeding 100 mM. To further demonstrate the versatility, BA derivatives bearing various functional groups were also tested, all of which were successfully converted into their corresponding nitriles. These results highlight the flexibility of RR system to accommodate diverse substrates and meet specific market demands.

Empowering Precision C–H Functionalization: Advances in Peroxygenase Engineering

Abstract Selective C–H functionalization remains a central challenge in modern synthesis as it enables direct diversification of molecular scaffolds without pre‐functionalization. Peroxygenases, including both unspecific peroxygenases and P450 peroxygenases, offer a biocatalytic solution to this challenge, catalyzing oxyfunctionalization reactions in aqueous media under mild conditions with hydrogen peroxide (H 2 O 2 ) as the sole oxidant. In this review, we highlight recent advances in peroxygenase engineering over the past five years, with a particular focus on strategies that enhance heterologous expression, catalytic activity, and control of regio‐ and enantioselectivity. We also discuss protein engineering approaches that mitigate H 2 O 2 ‐induced inactivation and summarize efforts to repurpose NADPH‐dependent P450 enzymes into self‐sufficient peroxygenases, thereby expanding their catalytic repertoire. Furthermore, we examine the integration of peroxygenases with in situ H 2 O 2 generation systems by enzymatic, chemical, photocatalytic, and electrochemical methods to achieve balanced oxidant delivery and sustained turnover. Collectively, these developments have established peroxygenases as versatile and robust catalysts for selective C–H functionalization, opening new opportunities for their application in the synthesis of pharmaceuticals, fine chemicals, and agrochemicals.

A Chiral Saddle‐Shaped Nanographene With Two Heptagon‐Embedded [4]Helicenes

ABSTRACT Chiral non‐benzenoid nanographenes (NGs) remain highly appealing, yet underexplored synthetic targets due to the lack of feasible synthetic strategies to simultaneously construct non‐hexagonal rings and stable chirality. Herein, we demonstrate a novel synthetic strategy to construct a chiral saddle‐shaped nanographene ( cSNG ) via stepwise oxidation of an anthracene‐containing oligophenylene precursor. Scholl‐type oxidation first yields a key intermediate featuring sp 3 ‐defect heptagons, and subsequent oxidative dehydrogenation furnishes target cSNG incorporating two heptagon‐embedded [4]helicenes. The structure of cSNG is unambiguously confirmed by single‐crystal analysis, demonstrating its saddle‐shaped geometry with intrinsic chirality. Remarkably, due to the heptagon‐embedded [4]helicene subunits, cSNG exists as configurationally stable enantiomers which enable chiral resolution, leading to pronounced chiroptical responses and enhanced dissymmetry factors, compared with its sp 3 ‐defect precursor. Moreover, profiting from chiral saddle geometry with shape‐adaptive character, cSNG presents strong host–guest interactions with fullerenes, with association constants up to 2.3 × 10 4  M −1 for C 60 and 8.7 × 10 4  M −1 for C 70 , which are among the highest values reported for negatively curved nanographenes. Crystallographic analysis of cocrystals of cSNG with C 60 further revealed a distinct 1:3 binding mode for supramolecular complexation, featuring two fullerenes accommodated within the saddle cavity and two additional fullerenes externally shared between neighboring saddle units.

Light and Dark Cycles Control the Structural Evolution of Photoresponsive Supramolecular Systems

ABSTRACT As the supply of light on Earth is cyclic and asymmetric, living systems that rely on photochemical energy have adapted to accommodate periods of light and darkness. During the day, light energy is available, while throughout the dark phases, thermal relaxation processes can be used to increase functional and structural organization. While light‐driven supramolecular assembly has been reported, structural adaptation under alternating light/dark input remains largely unexplored in synthetic supramolecular systems. Here, we show how an oscillating light energy supply can facilitate the structural selection of self‐assembling photoswitchable peptides compared to continuous illumination. We demonstrate that polymorphic self‐assembled structures are transiently formed and sustained only under light irradiation, while alternating periods of irradiation and darkness favor the formation of a thermodynamically more stable supramolecular architecture. These findings demonstrate the key role that rest (darkness) periods can have in the self‐assembly pathway selection of molecular and self‐organized supramolecular photosystems.

Structure Engineered Quantum Dots Couple CO ₂ Reduction With Vicinal Diamines Production in a Single Photoredox Cycle

ABSTRACT Photocatalytic CO 2 reduction coupled with organic transformations has attracted significant attention as a promising strategy for efficient solar energy utilization. However, challenges remain, particularly when it comes to achieving high selectivity in CO 2 reduction and further expanding the diversity of oxidative organic transformations. Herein, by subtly engineering the structure of CdSe/CdS quantum dots (QDs), we report the integration of photocatalytic CO 2 reduction with vicinal diamines production via oxidative C–C coupling of amines in a single photoredox cycle under visible light. Dynamic experiments indicate the photogenerated electrons for reducing CO 2 proceed in coordination with photogenerated holes oxidizing amines, thus realizing vicinal diamines with yields up to 97% and CO 2 ‐to‐CO conversion with selectivity as high as 98%. Mechanistic studies indicate that controlled QD structural engineering optimizes exciton dynamics by balancing electron and hole trapping, ensuring efficient charge separation and utilization. The system is applicable to a range of amine substrates and usable for gram‐scale vicinal diamines synthesis, underscoring its potential for synergistic CO 2 valorization and valuable chemicals production.

Natural Sunlight‐Driven Synthesis of Conjugated Microporous Polymers via Electron Donor‐Acceptor Complexes for Highly Efficient Catalytic Upcycling of Real‐World Plastic Waste

ABSTRACT The sustainable upcycling of plastic waste under ambient conditions remains a major challenge due to the lack of efficient, robust, and environmentally benign photocatalysts. Here we report a green and metal‐free strategy for the synthesis of conjugated microporous polymers (CMPs) that directly addresses this challenge. The polymers are prepared using natural sunlight to drive polymerization through in situ–formed electron donor–acceptor (EDA) complexes, eliminating the need for harsh conditions or precious metals. The resulting CMPs, TMPB‐AQ and TTPM‐AQ, function as efficient heterogeneous photocatalysts for the ambient‐temperature upcycling of ten types of real‐world polystyrene‐based plastics into value‐added benzoic acid. The process is readily scalable to gram quantities in both batch and continuous‐flow reactors and maintains high catalytic performance over eleven reuse cycles, highlighting its practical durability. Mechanistic insights from combined experimental and computational studies reveal that the high activity originates from the intrinsic porosity and extended conjugation of the CMPs, which promote spontaneous adsorption of polystyrene chains, efficient mass transport, and effective charge separation at the polymer–plastic interface. Overall, this work demonstrates a sustainable pathway that integrates green materials synthesis with the productive valorization of plastic waste, advancing circular‐economy approaches to polymer recycling.

Variations of Alloying Site Density in Pd ₁ Cu Single‐Atom Alloy Catalysts Lead to Shifted Product Yields in Electrochemical CO Reduction

ABSTRACT Single‐atom alloy (SAA) catalysis research often reports that a SAA catalyst, in the general formulation of a single‐atom metal M1 alloyed on the surface of the host metal M2, facilitates a probe reaction. However, for catalytic reactions that present decoupled rate‐ and selectivity‐limiting steps, the alloying site density may significantly manipulate these independent steps, but it has rarely been explicitly examined for any SAA systems. Herein, using the electrocatalytic CO reduction as a probe reaction, we report that the nominal Pd 1 Cu cube SAA catalysts exhibit distinctive high reactivity toward ethylene or ethanol, respectively, depending on whether the Pd atoms are in dilute or crowded forms. Although the presence of single‐atom Pd embedded on Cu uniformly promotes CHO* formation and C─C coupling, the dilute‐Pd 1 Cu favors ethylene formation by enabling low‐barrier C─O cleavage from a flat CH 2 CH 2 OH* intermediate, whereas the crowded‐Pd 1 Cu promotes ethanol formation by stabilizing an upright hydrogenation transition state of the same intermediate. Furthermore, we present evidence that the catalytic chemistry of crowded Pd 1  species differs from that of the Pd 2 ‐dimer; the latter, albeit unstable, steers reaction selectivity to acetate instead. These results uncovered the underappreciated importance of controlling SAA catalytic chemistry from the perspective of single‐atom site densities.

Unraveling G‐Quadruplex and i‐Motif Coexistence Within a Double‐Stranded DNA

ABSTRACT DNA can transiently fold into variable arrangements, which are expected to exploit regulatory functions. Guanine‐rich sequences can fold into G‐quadruplexes (G4s), while the complementary strand adopts potentially i‐Motif (iM) arrangements. Their concomitant formation at the same genomic site is still under debate. However, recently, single‐molecule analyses have shown the simultaneous G4 and iM presence within a double‐stranded (ds) DNA context, addressing them as synergic blockers of replication fork progression. While these findings point to a functional interplay between G4 and iM, a deeper understanding of the factors enabling their coexistence remains unclear. In this work, we unravel the equilibria governing G4‐ and iM‐folding within dsDNA, adopting an extensive biophysical approach allowing analysis of an optimized modular system, scalable across constructs of increasing molecular complexity. Our findings corroborate the simultaneous formation model and further clarify the thermodynamic determinants driving duplex denaturation and the favorable folding of stable G4 and iM structures.

Controlling Chemical Reactivity Under the Electron Microscope: Single‐Crystal‐to‐Single‐Crystal Splitting of Thymine Dimers Initiated by Electron Beam Ionization and Amplified by Electron Transfer‐Mediated Chain Reactions

ABSTRACT Three crystalline thymine dimers (TDs) obtained by solid‐state topochemical photodimerization were selected to explore radical ion‐initiated solid‐to‐solid splitting reactions when exposed to the high‐energy beam of an electron microscope. While samples of cis ‐ syn ‐thymine dimer ( c,s ‐TD) were available from a previous study, samples of cis ‐ syn ‐N,N‐dimethyl‐thymine dimer ( c , s ‐TD‐Me) and cis ‐ anti ‐N,N‐dimethyl‐thymine dimer ( c , a ‐TD‐Me) were obtained by photoreaction of crystalline N,N‐dimethyl‐thymine (T‐Me). The unexpected formation of c , a ‐TD‐Me was rationalized on a topochemical basis based on a high‐resolution x‐ray structure of T‐Me refined with DFT‐calculated non‐spherical scattering factors. When exposed to the electron beam (30–300 kV), recrystallized dimers underwent the expected splitting reaction back to T and T‐Me as the only products. Electron beam‐induced reactions studied as a function of electron fluence, beam energy, and temperature confirmed an ionization‐induced chain reaction propagated by a single electron transfer (SET) process with a chain length up to 80 000 product molecules per electron. Microcrystal electron diffraction (3D ED) analysis of the photodimers allowed crystal structure determination with approximately 30% of the monomers formed in situ. A long‐lived transient formed in single crystals of c , s ‐TD‐Me was assigned by EPR as the TD‐Me •+ , in support of the suggested reaction mechanism.

An Energy‐Dense Aqueous All‐Polymer Battery Enabled by Unique Cross‐Conjugated Dual‐Active‐Center Design in Organic Redox Chemistry

ABSTRACT The emergence of aqueous all‐organic batteries (AAOBs) has attracted surging attention, yet their progress is hindered by the limited energy density due to the scarcity of large‐capacity and high‐potential positive electrode materials. Herein, we develop a cross‐conjugated dual‐active‐center design strategy to modulate the electron distribution and frontier orbitals of 2D redox polymers (2DRPs) for attaining energy‐dense AAOBs. Theoretical studies reveal that simply embedding more pyrazine units in the polymer skeleton can elevate capacity and potential but at the expense of reduced activity, while introducing quinone units can form a cross‐conjugated donor–acceptor (D–A) structure that improves all above metrics. Accordingly, we synthesized 2DRP with alternating pyrazine‐quinone units (PQ) and its analogues with pure pyrazine units (P1 and P3). All predicted advantages over its analogues are realized by PQ in acidic electrolytes, presenting fast Grotthuss‐type proton transport, a larger capacity (251 mAh g −1 ) and a higher average reduction potential (0.46 V vs. SHE), surpassing most reported polymer electrodes, along with an ultralong low‐temperature lifespan (83.8%@12000 cycles, −20°C). Finally, pairing PQ with a 2DRP negative electrode (PD) in hybrid electrolytes affords a PD//PQ all‐polymer battery with an average output voltage of 1.31 V and a maximum specific energy of 111.7 Wh kg −1 , exceeding most AAOBs.

Organic Intercalation Enables Controllable Single‐Atom Coordination for Efficient H ₂ O ₂ Electrosynthesis

ABSTRACT The electrochemical two‐electron oxygen reduction reaction mediated by single‐atom catalysts provides a sustainable and efficient route for on‐site H 2 O 2 production. Although heteroatom engineering of the first coordination sphere has been shown to effectively tune catalytic performance, existing strategies typically introduce heteroatoms through multistep processes, making it difficult to control the formation of the target coordination environment prior to pyrolysis. Herein, we propose an organic intercalation‐driven precursor modulation strategy that pre‐organizes coordinating atom sources to alter the thermodynamic preference for first‐coordination‐sphere formation during pyrolysis, enabling the preferential formation of the Co‐N 3 O/C coordination environment. This potentially generalizable strategy offers a controllable alternative to conventional multi‐step post‐synthetic modification by enabling in situ coordination engineering. The resulting Co‐N 3 O/C catalyst achieves an H 2 O 2 selectivity of >99.0% and maintains stable operation for 120 h under ambient‐air‐fed conditions at a current density of 100 mA cm −2 , accumulating a 3.2 wt% H 2 O 2 solution. Crucially, the local coordination structure indicates that O incorporation tunes the electronic structure and modulates *OOH adsorption, thereby kinetically favoring *OOH protonation over O─O bond cleavage. This work provides a potentially generalizable strategy for controlling first‐coordination‐sphere formation in single‐atom catalysts and offers deep insights into coordination‐mediated enhancement for industrial‐scale H 2 O 2 electrosynthesis.