Single-atom modification can endow semiconductor photocatalysts with well-defined active sites, but the accompanying impurity states often behave as trapping centers, causing severe carrier loss through multiphonon nonradiative recombination. Here we show that the binding and release of trapped photoelectrons, governed by the impurity-state charge localization, is a key factor controlling charge utilization in single-atom photocatalysts. As a demonstration, by introducing B atoms as hetero p-orbital ligands into the first coordination shell of Cu single atoms on TiO2, we construct O-Cu-B asymmetric coordination that delocalizes Cu-related impurity states through multicenter orbital hybridization. This delocalization lowers the effective barrier for thermally assisted detrapping, converting localized carrier-loss centers into electron-relay states. Photophysical analyses reveal reduced trap-mediated nonradiative loss, while light-field-assisted dynamic computation visualizes the ultrafast redistribution of photogenerated carriers mediated by the delocalized impurity states. Consequently, the engineered (Cu-O/B)TiO2 photocatalyst achieves a near-unity apparent quantum efficiency of 94.7% and delivers a 2.8-fold enhancement in H2 evolution relative to the localized-trap (Cu-O)TiO2 control. This work establishes nanoscale coordination engineering as a route to reprogram impurity states for efficient single-atom photocatalysis.
Chiral N-spiroheterocycles are privileged yet synthetically challenging scaffolds for ligands, functional materials, and drug discovery. Here we show a cobalt-catalyzed asymmetric migratory dearomative annulation of electron-deficient N‑heteroarenes for their construction. The success of this transformation hinges on a dynamic ligand relay catalysis strategy, wherein two distinct ligands work in tandem: one facilitates a 1,4-cobalt/hydride shift, and the other governs the enantioselective dearomative annulation, delivering chiral N-spiroheterocycles with high efficiency and selectivity.
A photocatalyst-free radical SN2'-type alkylation of gem-dichlorocyclobutenones with unactivated alkenes is enabled by visible-light-induced C-Zr bond homolysis. Alkylzirconium intermediates generated in situ from terminal or internal alkenes serve as alkyl radical precursors and undergo radical addition/β-fragmentation with gem-dichlorocyclobutenones to afford ring-retained α-chlorocyclobutenones. This protocol avoids preformed radical donors and external photocatalysts, proceeds under mild conditions, tolerates structurally complex substrates, and furnishes multifunctional α-chlorocyclobutenones suitable for further diversification.
Benzo[a]pyrene (BaP) is highly recalcitrant to efficient biodegradation due to its strong hydrophobicity and low bioavailability, which significantly constrains the efficacy of conventional bioremediation technologies. In this study, a sequential fungal-bacterial consortium comprising Fusarium sp. LF-3 and Stenotrophomonas maltophilia T2-6 was established (with the fungus inoculated 7 days prior to the bacteria). The underlying degradation mechanisms were systematically elucidated through integrated transcriptomics and untargeted metabolomics. Results demonstrated that this sequential system achieved a BaP degradation rate of 51.17% (at 20 mg/L) within 14 days, significantly outperforming both individual strains and the simultaneous co-culture system. A synergistic degradation model was revealed, characterized by fungal-led primary oxidation of BaP, EPS-mediated temporary storage and transfer of metabolic intermediates, and subsequent bacterial uptake and deep mineralization. Mechanistic analysis further clarified that the efficient removal of BaP relies on the integration of the degradation process into a shared fungal-bacterial basal metabolic network, rather than the simple superposition of isolated degradation pathways. This study provides novel mechanistic insights and strategic frameworks for the robust bioremediation of complex polycyclic aromatic hydrocarbons (PAHs) contaminants.
The new racewalking event at the 2024 Paris Olympics was a mixed marathon relay. This poses new physiological challenges, as this competition format has never been attempted before. Therefore, this study will help generate new insights into how metabolism and the endocrine system function and interact in this novel format. This would allow for the identification of limitations and adjustments in the future for this type of protocol. A pilot study was conducted to characterize glycemic and hormonal responses-including glucose (GLUv), insulin (IN), adrenaline (A), noradrenaline (NA), glucagon (GG), and cortisol (C) in plasma during a structured protocol designes mimic the event. The protocol consisted of two high-intensity exercises with an interspersed rest period (40 min of exercise at 90% of HRmax + 40 min of active recovery + 40 min of exercise at 90% of HRmax), conducted under a predefined fluid and carbohydrates (CH) intake strategy. During this protocol, subjects ingested 50 g CH in 500 ml in each phase of the protocol and, in addition, a 45 g CH gel during recovery. No hypoglycemia or dehydration >2% of body mass (BM) was observed throughout protocol. In addition, IN (↑~84%) and GLUv (↑~41%) evolved similarly in both exercise sectors. Despite the carbohydrate and fluid intake strategy, increases in counterregulatory hormones, particularly in NA (161%) and GG (42%), were observed during the second phase of exercise. Within the limitations of this exploratory study, these findings describe the hormonal and metabolic response patterns observed under the conditions tested, without implying causal or functional effects of the intake strategy. The high interindividual variability and small sample size prevent any statistical inferences from being made. In addition, high carbohydrate intake during recovery was accompanied by an increase in IN concentration, with no evidence of hypoglycemia before the second exercise segment.
Efficient removal of recalcitrant aromatic compounds in organic wastewater is hindered by ambiguous reaction pathways in conventional single-process polymerization or ring-opening mineralization. Herein, we report a synergistic relay strategy that integrates phenoxyl-radical-mediated oligomerization and aromatic-ring-opening pathways for the highly efficient treatment of organic wastewater. This approach couples an initial high-valence iron-oxo species (HVIO)-driven oligomerization via formal hydrogen atom transfer at one site with a subsequent singlet oxygen (1O2)-mediated ring-opening reaction at an adjacent site, enabled by a dual-single-atom Fe1Cu1/TiO2 photocatalyst. Under solar-light irradiation, photoinduced electrons are transferred to peroxymonosulfate (PMS) at the Fe1 site, which acts as a critical activator to generate HVIO for oligomerization-based removal. Simultaneously, holes oxidize PMS at the Cu1 site to produce 1O2, leading to efficient aromatic-ring-opening. This sequential strategy achieved nearly 72% chemical oxygen demand removal with 23% carbon recovery into separable polymer products within 10 min for the phenol and ultimately reached complete removal with a rate constant of 1.21 min-1, significantly surpassing most reported values. Moreover, the system exhibited excellent stability and long-term activity in a custom-designed photo-filter reactor, highlighting its practical potential. By coupling oligomerization and mineralization, this work provides a groundbreaking and versatile platform for treating complex organic wastewater.
Proteins in the mitochondrial intermembrane space (IMS) play essential roles in respiratory chain assembly, metabolism, signaling, and organelle dynamics. Their stability and functionality often depend on structural disulfide bonds introduced by the mitochondrial disulfide relay, mediated by MIA40 and ALR. In this system, the sulfhydryl oxidase ALR reoxidizes MIA40, which in turn oxidizes incoming substrate proteins. Although evidence has suggested that ALR can also act independently of MIA40, its endogenous substrates have remained unknown. In this study, we captured proteins directly oxidized by ALR. Among these, we found coproporphyrinogen III oxidase (CPOX), a key enzyme in heme biosynthesis. We show that ALR-mediated disulfide bond formation is crucial for maintaining CPOX stability in the IMS, thereby ensuring effective heme biosynthesis and mitochondrial functionality. Notably, while disulfide-deficient CPOX failed to rescue CPOX loss when localized to the IMS, it retained functionality when redirected to the cytosol. However, this bypass compromised pathway efficiency, leading to the accumulation of protoporphyrinogen IX, a highly hydrophobic and redox-active intermediate that sensitized cells to cell death. Together, our findings reveal that ALR has functions beyond the MIA pathway and highlight that oxidative protein folding in the IMS relies not only on a relay mechanism but also on a broader disulfide-introducing network of enzymes.
Microbial coculture can integrate advantages and overcome the metabolic imbalance of individual species. Programming strain interactions represents a common routine for synthetic microbial communities with distinct species, which causes difficulties and redundant workloads in interaction construction before being available as chassis hosts. This study explores yeast-bacterium consortium without engineered interactions for the co-inducible relayed synthesis of natural products. The Komagataella phaffii-Escherichia coli consortium is explored for co-growth under selected conditions. Low-level glucose- and blue light-responsive transcriptional systems are rebuilt separately for each host, allowing single-signal co-induced activation of compound synthesis in coculture. Pathway redirection, genome mining, and rewiring of key targets for acyl donor degradation result in efficient production of the reporter molecule simvastatin (26.2 mg l-1) through living consortium cultured on simple carbon source. Inducible biosynthesis of another reporter compound (2S)-naringenin (165.6 mg l-1) further validates the extendibility of this community. The described platform represents a breakthrough in engineering microbial consortium for biosynthesis.
To resolve the thermal-mass mismatch bottleneck in solar-driven interfacial evaporation, the study proposes a Janus interface energy-mass relay integrating high-entropy alloy oxide (HEAO) nanoparticles with a double-network hydrogel. The hydrogel acts as an enthalpy modulator, pre-activating bulk water and blocking conductive heat loss. The top HEAO layer serves as an entropy accelerator, leveraging its active sites and oxygen vacancies to rapidly shear the residual hydrogen bonds of pre-activated water. In situ XPS and DFT analyses reveal that photo-induced polarization at HEAO defects injects charge into water anti-bonding orbitals, stretching the O─H bond to 1.209 Å. Consequently, the evaporator achieves an evaporation rate of 4.02 kg m-2 h-1 under one sun illumination. This work reveals the critical role of cascaded hydration editing in breaking the theoretical limits of interfacial phase transitions.
α-Trifluoromethylamines are prevalent in medicinal chemistry, yet synthetic approaches from readily available feedstocks remain limited. Herein, we report a visible-light-induced decarboxylative carboamination of commercially available 2-(trifluoromethyl)acrylic acid with oxime esters, enabling access to α-trifluoromethylimines that can be readily diversified into various α-trifluoromethylamine derivatives. The reaction proceeds under mild conditions and tolerates alkyl-, aryl-, and alkenyl-substituted carboxylic acid oxime esters. Furthermore, mechanistic studies provide detailed insights into the underlying reaction pathway.
Multiple cropping systems are increasingly being adopted worldwide to improve land-use efficiency and promote sustainable agriculture. To optimize the traditional post-tobacco fallow period, we evaluated a novel tobacco-maize-rapeseed (T_M_R) triple-cropping system. Using field experiments and high-throughput amplicon sequencing, we investigated the effects of the preceding tobacco crop and the additional maize season on rapeseed performance and soil microbial ecology. The addition of a maize season enhanced early growth vigor of rapeseed and improved key yield components, resulting in a theoretical yield of 5388.48 kg/ha. Rapeseed nitrogen uptake significantly increased compared with the conventional rotation (P < 0.05), and was positively associated with soil alkali-hydrolyzable nitrogen and major yield components. Different cropping systems significantly reshaped the β-diversity of soil microbial communities in the root-zone soil of rapeseed. Under the maize addition treatment, bacterial co-occurrence networks exhibited greater connectivity and complexity. Chujaibacter, Sporosarcina, and Epicoccum were enriched and identified as discriminative taxa using random forest analysis. In conclusion, the tobacco-maize-rapeseed triple-cropping system enhances nitrogen nutrition and reshapes soil microbial communities, providing a sustainable strategy for improving crop performance and agroecosystem functioning.
This study aimed to (i) compare nucleus-specific thalamic volumes between patients with pediatric-onset multiple sclerosis (POMS) and controls and (ii) examine relationships between lesion burden, thalamic volume, and optical coherence tomography (OCT) measures of retinal neuroaxonal structure. In this single-center retrospective cross-sectional study, we included 119 patients with POMS and 120 clinically referred controls with structurally normal brain MRI. DeepThalamus was used to derive total and nucleus-wise thalamic volumes from volumetric 3D T1-weighted MRI, with additional intracranial volume (ICV) normalization. In patients with POMS, DeepLesionBrain was used to quantify white matter lesion volume, count, and load from 3D T1-weighted and FLAIR images. Available OCT-derived peripapillary retinal nerve fiber layer (pRNFL) and ganglion cell-inner plexiform layer (GC-IPL) thickness were analyzed in relation to thalamic volumes and lesion burden using regression, correlation, and linear mixed-effects models, with FDR correction. Total, right, and left thalamic volumes were smaller in POMS than in controls, with a 0.9 cm3 (~ 7%) lower mean total thalamic volume in the POMS group (all FDR q < 0.05). The pattern of between-group thalamic volume differences was regionally specific, with the largest relative volume differences observed in posterior and visual relay nuclei (particularly pulvinar and LGN), while anterior nuclei were relatively spared. Greater lesion burden showed stronger and more consistent inverse associations with thalamic volume, whereas associations with lower retinal layer thickness (GC-IPL and pRNFL) were statistically significant but generally modest (FDR q < 0.05).  POMS is associated with smaller thalamic volumes, with larger observed relative between-group differences in posterior and visual relay nuclei, particularly the pulvinar and LGN. Smaller thalamic volumes were consistently associated with lesion burden and showed modest but consistent ipsilateral associations with lower retinal thickness. • POMS shows early deep gray matter involvement, and thalamic volume loss can be detected within the first years after diagnosis. • The thalamus is functionally heterogeneous, but nucleus-level vulnerability patterns in POMS and their relationship to lesion burden and OCT measures remain insufficiently characterized. • Larger observed between-group thalamic volume differences were found in the pulvinar and other posterior thalamic nuclei, while greater lesion burden was associated with smaller thalamic volumes. • Lower retinal thickness on OCT showed ipsilateral associations with smaller volumes of posterior and visual relay thalamic nuclei in POMS.
The ventral posterolateral nucleus (VPL) has long been regarded as a linear relay of somatosensory information from the spinal cord to the primary somatosensory cortex (SSp). However, the circuit architecture underlying VPL integration of non-sensory signals, including motor commands and affective states, remains poorly defined; in particular, the relevant circuit mechanisms of canonical excitatory neurons labeled by vesicular glutamate transporter 2 (VGluT2) within this nucleus remain largely unelucidated. By combining monosynaptic rabies tracing with fluorescence micro-optical sectioning tomography (fMOST), we generated a quantitative, single-cell resolution connectome of VPLVGluT2 neurons in mice. We find that these neurons receive substantial convergent inputs from motor, limbic, and basal ganglia circuits, challenging the classical view that VPL is a unimodal sensory relay. Single-neuron reconstructions (n = 149) further reveal four distinct projection subtypes that innervate not only the SSp but also the primary motor cortex (MOp) and higher-order association areas. Notably, projections to MOp preferentially target layer 5, bypassing the canonical sensory hierarchy. These anatomical findings are consistent with the hypothesis that the VPL may serve as a hub for sensorimotor integration, and they provide a critical structural basis for understanding how somatosensation interfaces with action and cognition.
Spinal connectomics is increasingly shifting understanding of the spinal cord from a simple reflex relay toward an active system that contributes to sensorimotor integration and adaptive motor control. This narrative review summarizes recent advances in the study of spinal circuitry and examines how these networks may contribute to flexible, context-dependent motor behavior. We reviewed experimental and computational studies focusing on high-density electrophysiology, advanced imaging, circuit mapping, and computational modeling, with an emphasis on recent and landmark studies. Our review suggests that spinal circuits may implement principles consistent with predictive coding, Bayesian integration, and adaptive gain control, though much of the direct mechanistic evidence for these computations originates in cortical and psychophysics literature; spinal-specific empirical validation remains an active research frontier. High-density recording and imaging techniques permit laminar-specific analysis of spinal activity, while computational models link circuit organization to function and plasticity. These advances are beginning to inform the development of closed-loop neuromodulation, targeted rehabilitation strategies, and brain-machine interface approaches aimed at restoring movement and sensory feedback following spinal cord injury. Together, these findings are consistent with the emerging view of the spinal cord as a dynamic computational system rather than a passive relay. Integrating connectomic data with computational modeling and neuromodulation provides a framework for understanding spinal function and developing more precise therapeutic interventions. Continued progress in neural interface technologies and data-driven modeling has the potential to further advance spinal systems neuroscience and, over the coming years, to improve the treatment of neurological disorders.
This paper presents a wolf-pack-inspired distributed encirclement framework for heterogeneous unmanned aerial vehicle-unmanned surface vehicle (UAV-USV) teams operating with limited communication and intermittent visual sensing. The proposed growth-based visual connectivity encirclement (GB-VCE) method separates high-level role evolution from low-level motion execution. Each agent accumulates local evidence from target observation, visual connectivity contribution, motion stability, and platform characteristics, enabling smooth transitions among leader, relay, searcher, and encircler roles. Visual links and relay relations are treated as coordination resources rather than auxiliary sensing constraints, allowing target-related information to propagate through the team without centralized fusion or persistent all-to-all communication. Simulations with paired random seeds show that GB-VCE improves encirclement accuracy, target-information coverage, convergence consistency, and heterogeneous role complementarity compared with fixed-role, static-leader, UAV-only, and USV-only baselines. The results indicate that biomimetic role growth and visual connectivity preservation provide an interpretable and robust coordination principle for air-sea cooperative encirclement.
In this paper, we consider a coexisting network of cellular transmission and device-to-device (D2D) communication, in which BS wants to communicate with far user, meanwhile, a D2D source desires to transmit information to a D2D destination. However, due to heavy shadowing or severe path loss, their direct links are not available. To cope with this problem, a relay is employed to assist the involved transmission. For such a relay-assisted spectrum sharing network, two transmission schemes are designed, i.e., multiple access broadcast NOMA (M-NOMA) scheme and time division broadcast NOMA (T-NOMA) scheme. For each scheme, we first perform power optimization to minimize the outage probability (OP) of D2D communication under the quality of service (QoS) constraint of cellular transmission. Based on the optimization results, we derive the OPs for both cellular and D2D signals. To gain more insights, the asymptotic OPs and the average throughput for both schemes are provided as well. On this basis, we further propose a more superior hybrid M/T-NOMA cognitive communication scheme, in which the system will adaptively select the one with higher system throughput between M-NOMA and T-NOMA as the final transmission scheme. Simulation results validate the accuracy of our analyses, and reveal the performance gain of our schemes over the benchmark schemes.
Electrochemical glucose sensors and biofuel cells are emerging technologies that rely on the transfer of electrons between an oxidoreductase enzyme and an electrode. In electrochemical glucose sensors, the enzyme glucose oxidase (GOx) generates an electrical signal that corresponds to the amount of glucose in solution. This signal depends on communication between the electrode and the flavin adenine dinucleotide (FAD) active site in the enzyme; however, many redox-active enzymes cannot interact directly with an electrode. Instead, they rely on external relays to mediate electron transfer to/from the electrode. Mediator-functionalized polymers, such as ferrocene-modified linear poly(ethylenimine) (Fc-LPEI), can be cross-linked to immobilize the enzyme of interest in a network of electron relays. Cross-linked films of Fc-LPEI form hydrogel matrices that allow for rapid transport of glucose, while the covalently bound ferrocene groups facilitate rapid electron transfer due to their ability to exchange electrons with one another. For these reasons, Fc-LPEI films have been widely used in the development of high current density bioanode materials. This chapter describes the synthesis of a commonly used dimethylferrocene-modified linear poly(ethylenimine), as well as the subsequent preparation and electrochemical characterization of a GOx bioanode film utilizing the synthesized polymer.
Obstructive sleep apnea (OSA) is increasingly recognized as an independent contributor to atherosclerotic cardiovascular disease, yet the mechanisms linking nocturnal intermittent hypoxia (IH) to plaque progression remain incompletely understood. Beyond oxidative stress and sympathetic activation, emerging evidence suggests that the gut may function as a critical relay organ between OSA and vascular injury. IH reshapes the intestinal ecosystem by altering microbial composition, weakening epithelial and mucus barrier integrity, and remodeling microbial metabolites, thereby increasing systemic exposure to microbial ligands and potentially pro-atherogenic metabolic signals, while reducing protective short-chain fatty acids. Trimethylamine N-oxide(TMAO) and imidazole propionate (ImP) are discussed as representative microbiota-derived metabolites implicated in atherosclerosis, although direct evidence linking OSA-related IH to increased circulating TMAO in human cohorts remains limited. These intestinal inflammatory and metabolic inputs may amplify endothelial dysfunction, macrophage activation, and chronic vascular inflammation. We propose that PANoptosis, an integrated inflammatory cell death program involving pyroptosis, apoptosis, and necroptosis, may represent a plausible downstream inflammatory cell death mechanism through which dysbiosis-associated and plaque-local stressors converge to promote plaque injury. This review summarizes convergent indirect evidence supporting a gut dysbiosis-PANoptosis-vascular injury hypothesis, and discusses potential therapeutic implications for OSA-associated atherosclerosis.
Thoracic endovascular aortic repair (TEVAR) is the preferred intervention for thoracic aortic pathology, offering favorable outcomes compared with open repair. Aortic graft infolding, although rare with an incidence of 0.4% to 3%, can pose significant clinical challenges. We present three patients who developed infolding post-TEVAR using the Terumo Relay Pro endograft, detailing their presentation, management, and outcomes. This case series, along with a review of the literature, provides insight into aortic endograft infolding after TEVAR and helps refine the risk stratification and management protocols.
Neural circuit assembly relies on different neuronal types coming together to form a functional circuit. The question of how the appropriate number of each type is integrated into an emerging circuit remains relatively unknown. To answer this question, we used the mouse retina to uncover the molecular mechanisms responsible for neuron type integration in a developing circuit. In the mammalian retina, bipolar cells (BC) are a class of interneurons that relay visual information from photoreceptors to ganglion cells. Extensive studies have shown there are 15 distinct BC types: 6 types of OFF cone bipolars, 8 types of ON cone bipolars, and 1 type of rod bipolar. During retinal development, BCs are born in excess and through programmed cell death, a precise number of each type remains to give rise to the retinal circuit. Although this process has been well-described, little is known about the key molecules responsible for BC type integration in the developing retina. Our work uncovered a new role for the autism-associated risk gene, Protocadherin 9 (Pcdh9) in BCs of both male and female mice. Deletion of Pcdh9 using a floxed allele leads to loss of OFF and ON cone bipolars; however, disruption in the extracellular binding of Pcdh9 leads to selective loss of ON cone bipolars but not rod bipolars. Moreover, we found this later function of Pcdh9 is mediated by homophilic interactions between ON cone bipolars and their known synaptic partners. Taken together, our work revealed a new role for Pcdh9 in retinal development.Significance statement Neural circuits are comprised of multiple neuronal types where a specific number need to come together to give rise to a functional circuit. Although this is a critical process during neurodevelopment, little is known about the molecular mechanisms that determines the precise number of each type during circuit development. In the present study, we identified the autism risk gene, Protocadherin 9 as a critical molecule in neuronal type integration of bipolar cells within the developing mouse retina. Using newly generated mouse lines, we found distinct requirements of Pcdh9 to promote survival in different BCs during retinal circuit assembly. The significance of this work is that it shed lights into how different neuronal types are integrated in nascent neural circuits.