All-carbon quaternary centers represent a fundamental structural unit found in a wide range of functional molecules. Within the versatile synthetic toolbox, the semipinacol rearrangement (SPR) stands as one of the most powerful tools for assembling this sterically congested motif. In this context, ‌radical-mediated SPR pathways‌, especially those entailing alkyl migrations, remain underexplored from a strategic standpoint. Herein, we report a visible light-promoted formal SPR of tertiary allyl alcohols using in situ-generated triplet nitrene species as the initiator under redox-neutral conditions. This method demonstrates broad substrate scope, enabling efficient construction of all-carbon quaternary centers across various steric environments, including rigid cyclic/spiro frameworks and flexible acyclic systems. Mechanistic investigations reveal substrate-dependent pathways: alkenyl cyclobutanols undergo triplet nitrene addition followed by concurrent ring-expansion and hydrogen atom transfer (HAT) to form cyclic ketones, while nonactivated allyl alcohols proceed through aziridination/ring-opening/SPR sequences to produce linear β-amino ketones. Preliminary biological assessments of these α-quaternary β-aminoketone derivatives revealed that compound 4a exhibited potent anti-DENV-2 activity, with an EC50 value of 0.95 ± 0.02 µM against viral replication.

Phototheranostic agents operating in the second near-infrared (NIR-II) window hold great potential for precision cancer therapy, yet the rational regulation of excited-state processes to simultaneously optimize fluorescence and phototherapeutic performances remains a fundamental challenge. Herein, we report a topology-driven excited-state engineering strategy for constructing conjugated oligomers with tailored excited-state manifolds and multi-channel excitation dynamics. By precisely manipulating molecular topology, conjugated topological oligomers achieve enhanced light-harvesting capability and optimized exciton utilization, thereby enabling synergistic regulation of excitation dynamics. Under 808 nm laser irradiation, nanoparticles (NPs) derived from TBT-3 exhibit 2.8-fold enhanced NIR-II fluorescence brightness, 2.7-fold improved photothermal performance, and 7.5-fold increased total reactive oxygen species (ROS) generation compared with TBT-1. In vivo studies demonstrate that TBT-3 NPs enable high-resolution NIR-II fluorescence imaging and efficient tumor elimination. Moreover, TBT-3-mediated phototherapy induces immunogenic cell death and enhances antitumor immunity, leading to improved therapeutic efficacy when combined with anti-PD-1 immune checkpoint blockade. This work provides a molecular topology-based strategy for manipulating excited-state landscapes and establishes conjugated oligomers as versatile candidates for NIR-II phototheranostics and cancer immunotherapy.

Bioorthogonality-activatable optical imaging activates caged or quenched probes via bioorthogonal reactions for disease diagnosis. Although chemiluminescence enables low-background detection, it has rarely been applied to bioorthogonality-activatable imaging. Here, we synthesize chemiluminescent tetrazine probes (CLTZs) by coupling a tetrazine acceptor to a phenoxy-1,2-dioxetane donor through π-conjugated vinylene linkers, enabling biomarker and bioorthogonality dual-locked activation for cancer urine testing. Unlike conventional chemiluminophores, tetrazine in CLTZs mediates an internal-conversion-to-a-dark-state quenching mechanism, suppressing chemiluminescence even after phenolate formation. Strong chemiluminescence is restored only when the phenolate form undergoes bioorthogonal reaction with bicyclononyne (BCN), generating pyridazine-containing donor-π-acceptor chemiluminophores. This unique dark state enables development of an H2O2 and bioorthogonality dual-locked probe ([H]BCP), emitting only when both H2O2 and BCN are present. By engineering BCN into a cancer-activatable bioorthogonal urinary reporter ([C]BUR) that releases renal-clearable BCN in tumors, a chemiluminescent bioorthogonal pair ([H]BCP & [C]BUR) is created. This pair achieves in vivo tumor imaging with a signal-to-background ratio of 438 and detects lung metastasis in early urinary assays with up to 23.9-fold signal enhancement over healthy mice. This work provides a molecular design for bioorthogonality-activatable chemiluminescence toward noninvasive, sensitive disease diagnosis.

Electrocatalytic nitric oxide reduction to ammonia (NORR) offers a dual opportunity for NO remediation and decentralized NH3 production, yet its efficiency is often limited by competing pathways and unclear structure-function relationships. Here we introduce a reactant-shunting strategy that installs a guiding electrocatalytic step via isolated Ru atoms to supply surface-bound [*]H species and enforce a Langmuir-Hinshelwood (LH) hydrogenation pathway. Using Ru1/Co3O4 as a model catalyst, we show that single Ru sites promote water adsorption and dissociation, forming stable Ru-H intermediates that thermodynamically and kinetically accelerate the coupling-hydrogenation steps in NORR. The optimized catalyst delivers an NH3 yield of 533.49 µmol cm[-2] h[-1] with a 97.19% faradaic efficiency, surpassing state-of-the-art systems. The reactant-shunting principle further generalizes across multiple oxide hosts, enhancing NH3 productivity by up to threefold. These findings establish pathway steering through controlled hydrogen delivery as a powerful strategy for high-efficiency electrocatalytic ammonia synthesis.

Body-focused repetitive behaviour disorders (BFRBDs), including trichotillomania (TTM) and skin-picking disorder (SPD), typically emerge during adolescence. These disorders have been conceptualized within emotion regulation models, in which body-focused repetitive behaviours (BFRBs) may function as attempts to regulate aversive emotional states. Although anxiety frequently co-occurs with BFRBDs, its association with BFRB severity is generally modest, highlighting the need to examine affective and regulatory processes. This cross-sectional study examined the associations among social anxiety, shame-proneness, emotion regulation difficulties and BFRB severity using a serial mediation model. Participants were 107 adolescents aged 12-18 years (80.4% female) who met DSM-5 criteria for TTM or SPD and were recruited from a tertiary child and adolescent psychiatry clinic. Diagnoses were established using semi-structured clinical interviews. The analysis controlled for age and sex. Social anxiety was positively correlated with shame, emotion regulation difficulties and BFRB severity (r = 0.28-0.31, all p < 0.01). In the serial model, social anxiety was associated with greater shame, which was associated with greater emotion regulation difficulties; in turn, emotion regulation difficulties were associated with greater BFRB severity. The total indirect effect (B = 0.162, 95% CI [0.038, 0.337]) and the serial indirect effect through both mediators (B = 0.117, 95% CI [0.040, 0.257]) were significant, whereas neither single-mediator indirect effect was significant. The direct association remained significant (B = 0.302, p = 0.022), consistent with partial statistical mediation. These findings support the proposed theory-based model but do not establish temporal or causal ordering.

Functional nucleic acids (FNAs), including aptamers and DNAzymes, offer programmable recognition and catalysis for biosensing, but their performance in real samples is often compromised by nuclease degradation, matrix effects, and interface-associated losses. For diagnostic translation, stability must, therefore, be defined not only as strand persistence, but as retained folding, binding, catalysis, and signal generation under assay-relevant conditions. This review examines strategies for stabilizing FNAs in complex biological matrices and organizes the field around four design levers: Chemical, topological, architectural, and microenvironment/interface engineering. Chemical modification of sugars, backbones, and bases can reduce nuclease susceptibility, but requires functional validation. Topological approaches, including terminus shielding, circularization, covalent locking, and mechanically interlocked structures, limit strand accessibility, and reinforce functional conformations. Architectural strategies use multivalency, scaffolded presentation, DNA nanostructures, and rolling circle amplification-derived concatemers to improve robustness and signal retention. Microenvironment engineering further stabilizes FNAs through controlled immobilization, antifouling interfaces, nanomaterial-assisted protection, hydrogel or microgel confinement, and sample processing. Case studies in saliva, serum, urine, and stool illustrate how these levers can be combined to enable reliable FNA-based real-sample diagnostics.

Mn-based materials are widely used for syngas conversion, where MnO is generally regarded as the catalytically active phase under reducing conditions. Yet catalysts derived from different Mn oxide precursors often exhibit markedly different performances despite evolving into the same MnO bulk structure during reaction. Here we show that trace Mn[3+] sites stabilized on oxygen-deficient MnO surfaces serve as the decisive active sites. Time-resolved energy-dispersive x-ray absorption spectroscopy combined with iterative target transformation factor analysis and depth-resolved synchrotron photoemission spectroscopy reveals a persistent minor Mn3O4-like spectral contribution and its enrichment near the surface of Mn2O3-derived MnO. These stabilized sites strongly enhance CO adsorption and activation, thereby promoting C─O bond cleavage and markedly improving activity and selectivity for syngas-to-light-olefin conversion. More broadly, this work reveals how minority surface sites can govern catalytic function despite identical bulk phases and establishes an operando strategy for quantitatively resolving low-coverage active sites in reducible oxide catalysts.

A major bottleneck for the practical application of lithium-oxygen (Li-O2) batteries is the high overpotential resulting from sluggish kinetics of oxygen redox chemistry. This kinetic limitation can rise in part from the spin-state transition barriers in converting triplet oxygen ([3]O2) into peroxide species, alongside the parasitic generation of singlet oxygen ([1]O2). Here, we demonstrate that metal-support magnetic interactions can effectively overcome this spin barrier. Using palladium (Pd) nanoparticles anchored on ferrimagnetic CoFe2O4 (CFO) substrates as a model catalyst, we reveal that interfacial magnetic coupling restructures the spin and electronic states of Pd sites, generating spin-polarized active ensembles with optimized adsorption toward oxygen intermediates. This interfacial spin-electronic effect promotes the conversion of [3]O2 into peroxide species while suppressing parasitic [1]O2 evolution during charging, thereby improving the reversibility of oxygen redox chemistry. As a result, the Pd/CFO catalyst achieves a low charging overpotential of 0.05 V and remarkable energy efficiency (91.2%) under spin alignment. This finding establishes metal-support magnetic interaction as a powerful strategy for controlling spin-dependent oxygen electrocatalysis, providing a general design principle for catalysts involving multi-site interactions.

Time perception is a fundamental aspect of human cognition, influencing motor coordination, decision-making, and planning. Unlike sensory modalities such as vision or hearing, which rely on dedicated sensory organs, the perception of time lacks a specific neural substrate, making it highly dependent on internal physiological and psychological states. Research suggests that physiological arousal plays a crucial role in temporal distortions, with pacemaker-accumulator models proposing that heightened arousal accelerates the internal clock, leading to an overestimation of time. We provide a systematic review of the available literature on the complex relationship between physiological indices of arousal and time distortion. Overall while a relatively consistent association emerged between baseline cardiac autonomic activity and temporal accuracy. When physiological arousal was experimentally manipulated, its relationship with temporal distortion was substantially less consistent. These differences were observed across pain, stress, emotional, and physical-activity paradigms and appeared to vary according to the characteristics of the eliciting stimulus. This pattern highlights the need to distinguish physiological arousal from the other cognitive processes involved and provides a basis for future research investigating also the other potential explanatory factors in the relationship between arousal and time perception.

Caring for patients receiving ECMO in the ICU is a complex process that requires advanced knowledge, technical skills, and confident clinical decision-making from nurses. Despite the increasing use of ECMO in Türkiye, no comprehensive, validated tool exists to measure ICU nurses' self-efficacy in ECMO care. This methodological study aimed to develop the ECMO Nursing Self-Efficacy Perception Scale (ECMO-SEPS) and evaluate its psychometric properties. The scale was developed in two stages. In the first stage, an item pool was generated through an extensive literature review and qualitative interviews with seven ICU nurses experienced in ECMO care. In the second stage, the scale's content and construct validity were assessed using confirmatory factor analysis, including convergent and discriminant validity evaluations. Reliability analyses included internal consistency, evaluated by Cronbach's alpha coefficients, and test-retest reliability, assessed with intraclass correlation coefficients. The final scale consists of 37 items across three subscales: cognitive, affective, and psychomotor, collectively explaining 70.5% of the total variance. Confirmatory factor analysis supported the three-factor structure with acceptable to good model fit indices. The overall Cronbach's alpha was 0.97, with 0.97, 0.81, and 0.96 for the cognitive, affective, and psychomotor subscales, respectively, indicating high internal consistency. Test-retest results demonstrated excellent stability over time. In conclusion, the ECMO-SEPS is a valid and reliable instrument for objectively assessing ICU nurses' self-efficacy in ECMO care. Its use may facilitate standardized evaluations and inform evidence-based education, workforce planning, and clinical practice in ECMO programs.

Diverticulitis is a common emergency general surgical condition that affects patients worldwide. Research remains heterogeneous, meaning the provision of high-quality, evidence-based care for these patients remains a challenge. We aimed therefore to complete a core outcome and core descriptor set for acute left-sided diverticulitis.

Wiskott-Aldrich syndrome (WAS) is an X-linked primary immunodeficiency caused by pathogenic variants in the WAS gene, resulting in absent or dysfunctional WAS protein (WASp) and a clinical triad of eczema, recurrent infections, and micro-thrombocytopenia. Allogeneic hematopoietic stem cell transplantation has historically represented the only curative option, but outcomes are constrained by donor availability, graft-versus-host disease, and transplant-related toxicity. Autologous gene therapy emerged as a compelling alternative. Early gammaretroviral vector trials confirmed that ex vivo correction of hematopoietic stem and progenitor cells could restore WASp expression and produce meaningful clinical benefit. However, insertional oncogenesis exposed an unacceptable genotoxic liability and drove the field toward self-inactivating lentiviral vectors. Clinical trials employing lentiviral platforms demonstrated durable, multi-lineage engraftment, sustained WASp expression, and robust immune reconstitution, with no reported cases of vector-related leukemia. These outcomes culminated in the FDA approval of WASKYRA (etuvetidigene autotemcel) in December 2025, establishing autologous gene therapy as a licensed standard of care for WAS patients lacking a suitable HLA-matched related donor. Next-generation precision gene-editing strategies and in vivo delivery platforms offer a path toward safer and more accessible correction. This review traces the full arc of WAS gene therapy, from early preclinical proof of concept through regulatory approval.