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Distinct affective and impulsivity-related profiles are associated with facets of state boredom in adults with attention-deficit hyperactivity disorder
Abstract Boredom is an aversive human experience, driving individuals to change their current action in order to acquire new information from their environment and engage in meaningful activity. While boredom under healthy conditions can functionally affect behavior, various mental disorders have been linked with chronically elevated levels of boredom that promote dysfunctional behaviors. In particular, patients with attention deficit hyperactivity disorder (ADHD) often report heightened and persistent boredom experience, driving these individuals to engage in risky and dangerous actions. Despite this relevance, it remains unclear how boredom specifically manifests in ADHD and how aspects of individual psychopathology relate to differences in experiencing boredom and coping with it. In this exploratory study, we address this issue, combining self-reports of adult ADHD patients on experienced boredom with reports on their psychopathology and mind-wandering. We observe that ADHD patients vary substantially in the extent and pattern with which they experience boredom. Moreover, different affective and impulsivity-related symptoms are associated with systematic differences in boredom experience. We apply statistical modeling to quantify this relationship, finding that different components of boredom experience are associated with distinct patterns of psychopathological symptoms. Interestingly, when relating the individual psychopathological patterns to reports of mind-wandering, we observe that mind-wandering is primarily heightened in those ADHD patients who show an association of boredom and affective rather than impulsivity-related symptoms. Taken together, our exploratory study indicates that ADHD patients vary substantially in their experience of boredom, depending on their individual psychopathological constitution. Boredom-related psychopathological patterns may reflect different strategies of individuals to cope with boredom, and thus should be considered when aiming to address boredom in a therapeutic setting.
Exclusive Hydroformylation of Terminal Olefins: A Phosphorus‐Free Ruthenium System for the Selective Functionalization of Complex Mixtures
ABSTRACT We report a paradigm shift in ruthenium‐catalyzed hydroformylation using a remarkably simple, phosphorus‐free system based on ruthenium carbonyl complexes and DBU (1,8‐diazabicyclo[5.4.0]undec‐7‐ene). The optimal catalytic system operates under mild conditions and exhibits an unprecedented “terminal‐only” selectivity. It quantitatively discriminates between terminal and internal or multi‐substituted double bonds, which has been a long‐standing challenge in oxo synthesis. Traditional systems often trigger the isomerization of internal olefins, but our catalyst leaves them untouched, even within complex industrial feedstocks. Comprehensive mechanistic investigations, including in situ IR spectroscopy and high‐pressure VT NMR spectroscopy, identify the tetranuclear ruthenium‐hydride cluster [DBUH] 2 + [H 2 Ru 4 (CO) 12 ] 2− as the pivotal active species. Isolating this cluster and successfully reapplying it confirms its role as the catalytic resting state. Combining low‐cost, air‐stable components with exceptional chemo‐ and regioselectivity provides this system with a robust, economically superior alternative to precious rhodium‐phosphine catalysts for academic synthesis and large‐scale industrial applications .
Cancer survival trends in Shandong Province, China (2016–2024): a population-based study
Directional Second Sphere Effect on CO <sub>2</sub> Activation and Reduction by Iron Porphyrin in Aprotic and Protic Media
ABSTRACT The topological directionality of functional groups in the secondary coordination sphere (SCS) plays a decisive role in enzymatic small‐molecule activation but remains underexplored in synthetic systems. Here, we investigate how symmetry remodeling of a urea‐based SCS modulates electrocatalytic CO 2 ‐to‐CO reduction using two atropisomeric iron porphyrins, αβαβ ‐UrFe and α 2 β 2 ‐UrFe , which differ solely in the spatial arrangement of identical hydrogen‐bond donor groups. Switching from a face‐to‐face to an adjacent urea‐arms configuration enables unprecedented CO 2 ‐to‐CO conversion under strictly aprotic conditions, in the absence of Brønsted or Lewis acids. Combined electrochemical, spectroscopic, kinetic, and DFT studies reveal that the adjacent positioning of the urea arms weakens the stabilization of the initial [Fe─CO 2 ] intermediate but creates a more open and dynamically reorganizable SCS that permits insertion of a second CO 2 molecule as an oxygen‐atom acceptor, to yield CO and CO 3 2 ˉ. Under protic conditions, this improved active‐site accessibility, combined with a dissymmetrization of the activated CO 2 molecule, accelerates proton transfer, with CO 2 ‐to‐CO reduction reaching turnover frequency of up to 2.72 × 10 7 s −1 , among the highest reported for homogeneous catalysis. These results establish directional interactions within the SCS as powerful design strategy for boosting molecular catalysis.
Association between the Eating Assessment Tool-10 and electrokinesiographic study of swallowing in dementia
Buffering the Active State for Proton Exchange Membrane Water Electrolysis
ABSTRACT Proton exchange membrane water electrolysis (PEMWE) is a key technology for renewable hydrogen production. In order to achieve large‐scale commercialization, acidic oxygen evolution reaction (OER) catalysts are required to simultaneously deliver high activity, long durability, and low noble‐metal loading. However, under realistic device operation, catalyst failure is mainly associated with the disruption of the active state, which is driven by coupled processes including active‐species redistribution, oxygen‐framework degradation, oxidative stress accumulation, proton‐transfer imbalance, and mechanistic drift. Accordingly, this review proposes a catalyst‐centered design framework that targets the root factors responsible for active‐species dissolution, buffering and sustaining the active state during PEMWE device operation. Within this framework, the buffering strategies are classified into five categories, including mobility and topology buffering, oxygen‐framework buffering, electron buffering, proton‐water‐ion programming, and the mechanistic dial. Finally, this review outlines how buffered active states can be rationally designed for Ir, Ru, and non‐platinum group metals (PGM) anodes, providing a forward‐looking roadmap for practical PEMWE catalyst development.
Intrinsic capacity patterns and their association with early postoperative functional outcomes in older adults undergoing total knee arthroplasty
Abstract This study aimed to identify latent classes of intrinsic capacity (IC) among older adults undergoing total knee arthroplasty (TKA) and to examine the association between IC patterns and short-term postoperative functional outcomes assessed by the Western Ontario and McMaster Universities Osteoarthritis Index (WOMAC). Following the Integrated Care for Older People framework, IC was assessed across five domains—cognition, psychology, vitality, locomotion, and sensory function—using validated instruments. WOMAC scores were evaluated preoperatively and at 3 months postoperatively. Latent class analysis was performed to identify IC patterns, and multinomial logistic regression was used to examine factors associated with IC pattern classification. Three IC patterns were identified in older adults undergoing TKA: C1 “Low impairment” (59.34%), C2 “Vit + Psy” (10.75%), and C3 “Loc + Sen” (29.91%). Age, manual labour occupations, and use of walking assistive devices were significantly associated with IC pattern classification (all P < 0.05). After adjustment for baseline WOMAC and other covariates, no statistically significant differences were observed among IC pattern groups in WOMAC scores at 3 months postoperatively or ΔWOMAC ( P > 0.05). Identification of IC patterns may enhance the understanding of multidimensional functional heterogeneity among older adults undergoing TKA and provide a potential framework for personalised perioperative assessment and future longitudinal research.
Metal‐Perturbed Through‐Space Charge Transfer Excited State: A Platform for Strongly Emissive Pd(II) Complexes via Thermally Activated Delayed Fluorescence
ABSTRACT The excited states of transition metal complexes generally involve an electron shuttle between the metal center and ligand or between ligands in the first coordination sphere. Herein, a series of pincer‐type C^N^C Pd(II) complexes containing an electron‐accepting but non‐coordinating dibenzo[a,c]‐phenazine (DBPZ) moiety on the ancillary carbazolyl ligand is developed. The face‐to‐face orientation of the C^N^C ligand and DBPZ moiety elicits lowest‐lying singlet metal‐perturbed through‐space charge transfer ( 1 TSCT) excited states. Spectroscopic measurements and theoretical calculations unveiled their lowest triplet excited states possess mixed 3 TSCT, through‐bond charge transfer and locally excited character. The resulting Pd(II) complexes exhibit strong thermally activated delayed fluorescence (TADF) with efficiencies of 68%−93%. The through‐space electronic coupling is found closely associated with the strength of noncovalent interactions between the tridentate C^N^C unit and the lateral acceptor. Orange‐red organic light‐emitting diodes doped with selected Pd(II) complex as an emitter achieve maximum external quantum efficiencies exceeding 30%. Its use as a sensitizer for narrowband multiple‐resonance emitter is also validated by increased device efficiency and reduced roll‐off. This work not only demonstrates the realization of strong TSCT‐TADF emission in Pd(II) complexes but also broadens the molecular design landscape of molecular design for photoactive transition metal complexes toward diverse applications.
Adaptive pathways for multimodal community-based detection of cognitive impairment: the CogScreen I study
Abstract Early detection of cognitive impairment is essential for dementia prevention and timely care. However, implementation in primary care and community settings remains limited. Building dementia-prepared health systems requires scalable and adaptive pathways that integrate subjective, digital and biological indicators, while accounting for heterogeneity in risk, education and age. CogScreen I was a cluster-randomized trial conducted in Munich senior centers from March 2023 to March 2024. Recruitment focused on community-dwelling adults aged ≥ 60 years reporting subjective cognitive concerns. Centers were randomized to: (A) the Subjective Cognitive Decline Questionnaire (SCD-Q) only, (B) SCD-Q plus digital cognitive testing, or (C) SCD-Q plus digital testing plus blood biomarkers (Aβ1-42/1–40, pTau181, GFAP, NfL). The primary endpoints were feasibility and acceptability, assessed through structured questionnaires and follow-up interviews with participants and general practitioners. Secondary endpoints examined latent cognitive structures and biomarker associations. Exploratory factor and clustering analyses revealed multimodal subgroups across subjective, digital, and biological measures, which informed a hypothesis-generating three-tier adaptive detection framework (low, medium, high intensity). Among the 473 participants (mean age 74.1 ± 7.6 years; 66% female; 63% with tertiary education), both feasibility and acceptability were high: Participants described the assessments as personally relevant, clearly communicated, and medically meaningful, and appreciated the added value of digital testing and biomarkers. Digital cognitive testing and biomarkers captured distinct latent dimensions of learning/working memory, psychomotor attention, and glial and amyloid pathology. Exploratory multimodal clustering identified three dementia risk profiles—low concern, intermediate, and at risk—which informed an adaptive, tiered detection model. Notably, subjective cognitive concerns assessed by the SCD-Q were strongly associated with overall subjective symptom burden, supporting the use of brief self-report questionnaires as a pragmatic and scalable first-step stratification approach in community-based dementia detection. Community-based, tiered detection pathways for cognitive decline are feasible, acceptable, and meaningful to older adults. Exploratory multimodal profiling suggests that combining subjective, digital, and biological measures may support individualized assessment strategies. However, limited GP engagement highlights the need for stronger integration with primary care to ensure downstream diagnostics and prevention pathways. The proposed framework remains hypothesis-generating and requires prospective validation. Clinical trials registered CogScreen has been registered at clinical trials (NCT06191952, 2023–12-20).
Unraveling Terminal Cobalt–Antimony Double Bond: Breaking New Ground in Heavy Pnictogen Multiple Bonds
ABSTRACT Terminal pnictinidene complexes featuring heavy group 15 elements (Sb, Bi) doubly bonded to transition metals remain exceptionally elusive compared to their lighter congeners. Herein, we demonstrate that N‐heterocyclic carbenes (NHCs) can effectively cleave the Sb═Sb double bond of distibenes to yield monomeric, zwitterionic stibinide species. Subsequent transfer of the antimony moiety to a cobalt center generates a terminal cobalt–stibinidene complex. Structural analysis reveals a very short Co─Sb bond distance, which is corroborated by Wiberg and Mayer bond indices as well as frontier molecular orbital and natural bond orbital analyses, providing compelling evidence for an unprecedented covalent Co═Sb double bond. In addition, we demonstrate that this compound reacts with an alkyne in a (2π+2π) cycloaddition and with phenyl azide to form a three‐membered ring, providing initial insight into its reactivity and drawing parallels with reactivity patterns established for lighter phosphinidene analogs. This work establishes a rational route to stabilize heavy‐element multiple bonds via a controlled and operationally‐simple distibene cleavage.
Hybrid modeling of electroporation and impedance spectroscopy for label free characterization of stem cells
Abstract Label-free, non-destructive characterization of stem-cell differentiation states remains an important goal in regenerative medicine and cell therapy. Existing computational frameworks commonly treat electroporation either at the tissue scale or for simplified single-cell geometries, and relatively few studies connect time-domain electroporation observables with swept-frequency impedance features measured in a microfluidic platform. This study presents a revised hybrid analytical–numerical and experimental framework for comparing undifferentiated human mesenchymal stem cells (hMSCs) with osteogenic-committed hMSCs. The numerical models are parameterized using the cell-type values : an undifferentiated hMSC model with representative radius $$R_{\textrm{U}}={10}\,\upmu \hbox {m}$$ , cytoplasmic conductivity $$\sigma _{i,\textrm{U}}={0.32}\,\hbox {S m}^{-1}$$ , membrane capacitance $$C_{m,\textrm{U}}=1\times 10^{-2}\,\hbox {F m}^{-2}$$ , and characteristic electroporation voltage $$U_{\textrm{ep,U}}={0.258}\,\text {V}$$ ; and an osteogenic hMSC model with $$R_{\textrm{O}}={13}\,\upmu \hbox {m}$$ , $$\sigma _{i,\textrm{O}}={0.24}\,\hbox {S m}^{-1}$$ , $$C_{m,\textrm{O}}=8\times 10^{-3}\,\hbox {F m}^{-2}$$ , and $$U_{\textrm{ep,O}}={0.32}\,\text {V}$$ . Both models are placed in the same microfluidic electrode environment and excited by electric-field pulses ( $${1}\,\hbox {kV cm}^{-1}$$ to $${5}\,\hbox {kV cm}^{-1}$$ , rise time 1 ns). The passive Schwan RC time constants are $${4.69\times 10^{-7}}\,\text {s}$$ for undifferentiated hMSCs and $${5.96\times 10^{-7}}\,\text {s}$$ for osteogenic hMSCs; the plotted post-threshold rise times are shorter, on the order of $${1\times 10^{-7}}\,\text {s}$$ to $${2\times 10^{-7}}\,\text {s}$$ . The passive polar transmembrane potentials at $${5}\,\hbox {kV cm}^{-1}$$ are approximately $${7.5}\,\text {V}$$ and 9.75 V, respectively. Swept-frequency impedance spectroscopy ( $${1}\,\hbox {kHz}$$ to $${1}\,\hbox {MHz}$$ ) performed on undifferentiated and osteogenic-committed hMSCs provides the matched frequency-domain comparison: low-frequency impedance, series resistance, reactance trough depth, phase angle, and voltage-dependent impedance drop are extracted at applied voltages of 1, 5, 10, 15, 20, and 25 V. The experimental data show that osteogenic hMSCs have higher baseline impedance ( $$|Z|={11029}\,\Omega$$ vs. $${7863}\,\Omega$$ at $${1}\,\text {V}$$ , $${1}\,\hbox {kHz}$$ ), whereas undifferentiated hMSCs exhibit the stronger high-voltage impedance drop at $${25}\,\text {V}$$ approximately (92.4 % compared with 86.9 % for osteogenic hMSCs). Calibrated 10.4 $$\upmu$$ m and 24.9 $$\upmu$$ m polystyrene microbeads are included as cell-free size standards for the impedance workflow. The combined results define a cell-type feature space $${\mathcal {F}}_{\textrm{combined}} = \{\tau _{\textrm{charge}},\; V_m,\; N(t),\; r_p(t),\; \sigma _m(t),\; f_c,\; \Delta |Z|_{f_{c,0}},\; R_{s,1\,\textrm{kHz}},\; |X_{s,\textrm{pk}}|\}$$ for future label-free classification studies. The present work should be interpreted as a matched modelling and impedance-analysis framework; definitive biological classification, direct pore imaging, viability validation, and trained classifier performance remain outside the scope of this study.
Repression of Virulence in <i>Staphylococcus aureus</i> by 2‐Aminothiol‐Mediated Quorum Quenching
ABSTRACT We present a novel strategy for the inhibition of quorum sensing in Staphylococcus bacteria. Previous work has focused on the development of peptides that can compete with native autoinducing peptides (AIPs), to antagonize the receptor histidine kinase responsible for activation of quorum sensing and thereby repress the expression of virulence genes. Here we report simple analogues of cysteine that can eliminate the native AIPs extracellularly, before they activate their receptor, and validate that this alternative strategy can also be applied to turn off quorum sensing in different Staphylococcus aureus reporter strain assays. Further, we show that two selected compounds can reduce skin infection caused by MRSA in a murine model. This work provides impetus for the development of simple small molecules for the topical treatment of staphylococcal skin infections. We anticipate that further studies, including delivery strategies, will help illuminate this potential.
Association between magnesium sulfate use and acute kidney injury in patients undergoing cardiac surgery: a retrospective cohort study
Borylcyclopropanes: Synthetic Strategies and Applications
ABSTRACT The carbon–boron bond is among the most versatile functional groups in organic synthesis, and its installation within the strained cyclopropane framework generates borylcyclopropanes with a rich reactivity profile. The presence of a boron moiety on the cyclopropane ring unlocks a broad spectrum of transformations inaccessible to unfunctionalized cyclopropanes, including Suzuki–Miyaura cross‐coupling, oxidation, amination, Matteson homologation, and stereospecific ring‐opening via 1,2‐metalate rearrangement to enantioenriched acyclic organoboron arrays. Meanwhile, the distinctive reactivity of boron‐stabilized intermediates such as α‐boryl radicals, α‐boryl carbanions, and α‐boryl cations enables cyclopropanation strategies with no classical counterpart. This review provides an exhaustive survey of borylcyclopropane chemistry, organized by mechanistic class: metal–carbene cyclopropanations under palladium, copper, rhodium, and enzyme catalysis; non‐diazo carbene and carbenoid approaches; transition‐metal‐catalyzed and metal‐free intramolecular nucleophilic cyclizations; photocatalytic radical pathways; iridium‐ and palladium‐catalyzed C─H borylation; hydroboration of cyclopropenes and alkylidenecyclopropanes; and miscellaneous strategies including bicyclo[1.1.0]butane (BCB) ring‐opening and 1,2‐metalate rearrangements. Applications in medicinal chemistry, natural product synthesis, and the preparation of stereodefined acyclic building blocks are also discussed.
Establishment of a non-invasive age estimation method based on fecal DNA methylation levels in brown bears
Regulating Hydrogen Bond Competition to Break Ultrawide‐Temperature (−70°C to 100°C) Limits for All‐Climate Zinc Batteries
ABSTRACT Hydrogel electrolytes endow aqueous zinc‐metal batteries with inherent safety and mechanical flexibility, rendering them compelling for wearable energy storage. However, their narrow operating temperature range and poor rate capability remain critical bottlenecks. In this study, a hydrogen‐bond (HB) regulation strategy based on a multifunctional hydrogel electrolyte (PAM‐NAEL, composed of Zn(ClO 4 ) 2 , polyacrylamide (PAM), and N‐acetyl‐L‐glutamine (NAEL)) is proposed to exploit the physicochemical nature of HBs, thereby improving both the operational temperature window and rate performance. Specifically, the NAEL component dynamically reshapes the internal HB network by competing for HB sites. This reconfiguration suppresses ice nucleation at low temperatures and maintains structural integrity at high temperatures, enabling an ultrawide temperature tolerance. Furthermore, the dynamic network lowers the ion migration barrier and accelerates deposition kinetics, endowing the advanced Zn||Zn symmetric cells with an ultrawide temperature adaptability (−70°C to 100°C) and outstanding rate capability (1 to 40 mA cm −2 ). Notably, even at an extremely low temperature of −40°C, the cells maintain exceptional cyclability exceeding 7500 h. Additionally, the Zn||I 2 full‐cell can operate stably over 10000 cycles at −20°C. Remarkably, the practical Zn||I 2 pouch cell with high mass‐loading I 2 cathode (10.60 mg cm −2 ) and limited N/P ratio (2.8) retains 95.12% capacity after 400 cycles.
Peripheral blood mitochondrial DNA copy number as a non‑invasive biomarker for the duration of mechanical ventilation in children with pneumonia‑associated respiratory failure
Catalyst-free, microdroplet-mediated waste plastic conversion to diacids
Abstract Plastic waste accumulation poses a global threat to both the environment and public health 1–3 . Although catalytic upcycling to value-added chemicals holds promise, its industrial adoption is hindered by additive-induced catalyst deactivation, feedstock heterogeneity, process inflexibility and limited economic viability 4 . Here we report a catalyst-free upcycling strategy that makes use of in situ generation of hydroxyl radicals at microdroplet interfaces 5–8 to enable oxidative cleavage of diverse waste plastics—from polyolefins to rubbers—into carboxylic acids under mild conditions. By eliminating catalyst-dependent pathways, this approach circumvents key challenges of catalyst design and poisoning, while substantially lowering technical barriers and costs 9,10 . Our method achieves complete conversion of polyethylene (PE) with selectivity to short-chain diacids approaching 69% under relatively mild conditions and demonstrated broad applicability to mixed commercial plastics, with scalability demonstrated up to the 300-g scale. Radical intermediate analysis reveals the crucial role of H 2 O in mediating a unique oxidative degradation mechanism: sequential hydroxyl radical addition to alkyl radicals, distinct from classical liquid-phase aerobic oxidation of alkane 11 . This interfacial radical-mediated strategy enables sustainable polymer upcycling with minimal infrastructure. More broadly, this work provides a scalable blueprint for the first, to our knowledge, industrial implementation of microdroplet chemistry, with transformative implications for oxidation processes in organic acid synthesis and beyond.
Induction and Stabilization of Peptide Alpha‐Helices on Silica Nanoparticles
ABSTRACT Stabilizing secondary structure elements is critical to controlling peptide and protein bioactivity, stability, and function. The α‐helix, central to molecular recognition and structural integrity, is a particularly valuable target for stabilization in biotechnological and nanomaterial applications. However, non‐covalent peptide–nanomaterial interactions often lack robustness and reproducibility. We report a covalent immobilization strategy to induce and stabilize α‐helical conformations on amino‐functionalized silica nanoparticles (SNPs). This approach leverages dynamic covalent peptide–surface coupling to enable thermodynamic selection of α‐helical conformations. Alanine‐rich peptides incorporating periodic lysine residues were designed to enable covalent anchoring while promoting helix formation. Immobilization markedly enhances thermal stability compared to free peptides. Systematic variation of lysine positioning shows that terminal attachment induces helicity, whereas incorporation every second helical turn provides optimal conformational and thermal stability. Crucially, the helical face oriented away from the nanoparticle surface remains accessible for molecular recognition. Streptavidin‐binding peptides immobilized via this method retain their specific binding activity while exhibiting superior thermal robustness. This sequence‐guided approach establishes a robust framework for covalent peptide–nanoparticle conjugation, enabling precise secondary structure stabilization and functional biointerfaces for thermally stable protein–protein interaction platforms.
Entanglement enables coherence transfer and feedforward corrects the state in quantum teleportation on superconducting dynamic circuits
Abstract Quantum teleportation transfers an unknown qubit state from a sender to a receiver using a shared entangled pair and a classically conditioned correction without moving the physical carrier. On the dynamic-circuit hardware, the complete protocol (which includes mid-circuit measurement and conditional feedforward) now runs on a single circuit. We use this to benchmark three-qubit teleportation on a 156-qubit IBM Heron r2 processor (ibm_fez). A single-qubit RY(θ) input was teleported at six angles along a meridian of the Bloch sphere and reconstructed by state tomography alongside two ablation controls; one without entanglement and the other without feedforward. The full protocol returns a mean fidelity of about 0.945, nearly constant across the angles and above the 2/3 full-Bloch-sphere reference at all six sampled angles. Removing feedforward lowered the fidelity to about 0.51, close to a maximally mixed state. On the other hand, removing entanglement yields (1 + cos²θ)/2 with a mean near 0.75, transferring the population but losing the coherence. Together, these results establish that entanglement and feedforward are both necessary. The calibration-limited fidelity serves as a reference for this class of hardware. A separate run returned a Bell-state fidelity value of 0.957. A branch-resolved analysis confirmed that the four measurement branches are Pauli rotations of the target realigned by feedforward. The reported fidelity depends only on the rotation angle and the device noise.