ConspectusTraditional metal nanoparticles have been widely utilized as heterogeneous catalysts in both fundamental scientific research and industrial applications. Their catalytic performances are commonly statistical and represent averaged results from all of the nanoparticles due to their inherent size polydispersity and structure heterogeneity. Recently, metal clusters (1-2 nm) with precise compositions and well-defined structures have provided opportunities to precisely correlate the catalytic properties with the structure and composition of the clusters at the atomic level. Specifically, the distinct metal core, interface, and surface structures of these clusters render them ideal for exploring the contributions of the surface/interface/core of cluster-based catalysts to catalytic properties.In this Account, we introduce the correlation of the catalytic properties of clusters with their ligand, interface, and metal kernel, ultimately mapping out the key factors that dictate the catalytic activity and selectivity. We first preview atomically precise clusters and the structural characteristics of the surface, interface, and kernel. Then, we emphasize the modulation of catalytic properties of cluster catalysts through the ligand, interface, and core. (i) Surface ligand: An efficient surface modification via ligand exchange is able to not only remarkably enhance the catalytic activity but also effectively modulate the product selectivity. (ii) Metal-ligand interface and cluster-cluster interface: The metal-ligand interface can enable the catalytic sites to directly control the whole catalytic process through the synergy between the metal atom and the ligand. Additionally, the interfaces between the clusters and their surrounding environment can cooperatively tailor the catalytic activity and selectivity. (iii) Metal core: The one-atom variation in the cluster kernel composition can effectively tune the overall electronic structures of clusters, thereby indirectly improving their catalytic activities. Furthermore, the central atom within an open core can also act as the active site to directly participate in and facilitate the catalytic reaction. Ultimately, looking to the future of catalysis science, there are still many challenges, but atomically precise metal clusters deserve more future efforts to unravel fundamental catalysis. Therefore, we offer several perspectives on the future research of precise catalysis using atomically precise cluster catalysts. We anticipate that this Account can provide fundamental insight into the unique contributions of the surface/interface/core of heterogeneous catalysts to their overall catalytic performances. By learning these fundamental principles, we will ultimately be able to design high-performance catalysts for a variety of catalytic processes.
A substantial amount of literature has been published on epileptic seizures. However, adequate evidence is still lacking to demonstrate that utilising explainable artificial intelligence for epileptic seizures can ensure an individual's safety. Furthermore, there is a need to define the fundamental challenges and opportunities present in the current state-of-the-art solutions and guide efforts towards responsible artificial intelligence. To identify fundamental challenges and opportunities in the existing state-of-the-art solutions available for explainable artificial intelligence-based epileptic seizure onset early warning: towards responsible artificial intelligence. The PRISMA checklist was utilised to develop this report. Papers were extracted from original articles and prior conference studies published in reputable databases such as PubMed, IEEE Xplore, ScienceDirect, Scopus and Google Scholar from January 2019 to 17 November 2024. Rayyan's online platform was used to identify duplicates, inclusions and exclusions of papers. This systematic review protocol was registered with the PROSPERO database. The included papers were assessed based on Microsoft's Responsible Artificial Intelligence template. The Responsible AI Impact Assessment Template, Principle 3 (transparency and explainability), determined a high-risk rating. A total of 26 studies are included based on the established inclusion and exclusion criteria. This study investigated 14.29% of responsible artificial intelligence principles applied in at least one paper with a high-risk rate. The results indicate that to transform researched solutions into practical applications, epileptic monitoring applications should be tested within the eight principles set by Microsoft. The black box explanation lacks insight into the deep internal features and operational methods, suggesting that further investigation is necessary. Systematic Review Registration ID: CRD42024544.
High-valence redox-active ions, exemplified by species such as Fe3+, Cr(vi), Mn(vii), and Ag+, pose fundamental challenges for conventional sensing and recognition platforms due to their intrinsic chemical aggressiveness, narrow stability windows, and propensity for uncontrolled redox transformations. In this review, these chemically aggressive high-valence ions are the primary focus, while more moderately oxidizing species such as Cu2+ are referenced only as comparative benchmarks for shifting MXene quantum dot (MQD) responses within a broader redox-activity spectrum. Despite the rapid progress in nanomaterial-based probes, a unified framework that connects ion valence chemistry, redox constraints, and nanoscale material design is still lacking. Here, we present the first comprehensive review that systematically integrates the thermodynamic and kinetic behaviors of high-oxidation-state ions with quantum confinement - driven redox modulation specifically in MXene quantum dot (MQD) systems. This review begins by establishing the valence-driven reactivity windows that govern the accessibility and instability of high-valence ions, independent of specific material classes. Then, it elucidates how quantum confinement fundamentally reshapes redox responsiveness by discretizing energy states, localizing charge carriers, and amplifying surface-dominated interactions. Building on this foundation, MQDs are examined as redox-programmable platforms capable of translating aggressive ion reactivity into controlled optical signals and multifunctional responses, including detection, validation, and chemical intervention. Rather than emphasizing record detection limits, this review highlights design rules that govern when redox activity enhances functionality and when it undermines stability and interpretability. By reframing redox behavior as a programmable design parameter, this work provides a conceptual roadmap for next-generation adaptive sensing and remediation platforms targeting chemically complex, high-valence ion systems.
Investigating the thermodynamics of methane adsorption across varying burial depths is essential for a fundamental understanding of the heat and mass transfer mechanisms within coal seams. This study investigates six coal samples from varying burial depths in the Junggar Basin, Xinjiang, through high-pressure isothermal adsorption experiments conducted at elevated temperatures (313.15, 333.15, 353.15, and 373.15 K). The objectives are to calculate key thermodynamic parameters and to elucidate the mechanistic controls of the burial depth on adsorption thermodynamics. The results indicate that the isosteric heat of adsorption (qst) exhibits a positive correlation with the adsorption amount. Moreover, as the burial depth increases, the variation in qst follows an inverted "U"-shaped pattern. The Gibbs free energy (ΔG) values for samples from different burial depths are all negative. The absolute value of ΔG increases with pressure and falls with temperature. The average ΔG exhibits three distinct trends with burial depths at different temperatures: no significant trend at 313.15 K; an initial rise and a subsequent drop at 333.15 K; and an initial rise that gradually stabilizes at 353.15 and 373.15 K. Under different temperatures, the mean adsorption entropy (ΔS) exhibits an overall decreasing trend with increasing burial depth. Under different temperatures, the maximum adsorption potential (εmax) exhibits distinct trends with increasing burial depth, whereas the mean adsorption potential (εavg) shows little variation with depth. This study further discusses the mechanistic controls of burial depth on adsorption thermodynamics, providing a theoretical foundation for the scientific assessment of coalbed methane (CBM) reserves.
Understanding the glass transition in amorphous polymers and the underlying principles that govern segmental motions remains a key challenge in polymer physics. Here, we investigated random copolymers composed of methyl methacrylate (MMA) and 4-tert-butylstyrene (TBS) monomers across various compositions to elucidate the influence of monomer bulkiness on the glass transition temperature (T g), fragility (m), and segmental dynamics. The calorimetric T g values were observed to strongly deviate from the Fox equation, showcasing a structure-independent behavior at high to medium MMA concentrations, and a 'super-Fox' increase at low MMA content. We correlated this to tacticity as well as frustrated chain packing, as corroborated by changes in the m values. A closer look at the β-relaxation revealed a strong dependence on the molecular composition: below the T g, the activation energy decreased with TBS, indicating a transition toward a side-group reorientation-dominated mechanism, while above the T g, the TBS monomers participate in the process, despite PTBS lacking a β-relaxation. The coexistence of TBS and MMA monomers revealed a fundamental shift in relaxation dynamics manifested by the decoupling of α- and β- relaxations, which we analyzed via the double-percolation mechanism. Our findings offer new insights into polymer relaxation behavior and the relationship between the α- and β- relaxation mechanisms with implications in materials optimization.
Multi-site diffusion MRI studies face scanner-induced variability that can obscure biological signal. Harmonization methods such as ComBat have been developed to address this, but have been evaluated primarily on diffusion scalar metrics. Whether scanner reproducibility differs across fundamentally distinct tract-derived representations has not been systematically compared. Here, we compared the reproducibility of three metric families (diffusion, shape, and connectivity) across 36 association tracts using the MASiVar dataset (5 subjects, 4 scanners, 27 sessions). We assessed intraclass correlation coefficients (ICC) and multivariate subject discrimination at baseline, under dimensionality reduction, and after ComBat harmonization. At baseline, shape metrics showed the highest reproducibility (median ICC 0.69), followed by connectivity (0.49) and diffusion (0.34). Shape and connectivity achieved comparable subject discrimination (both 1.75), significantly exceeding diffusion (1.23). ComBat harmonization improved all families but harmonized diffusion (0.58) remained below unharmonized shape (0.69), indicating that metric family selection remains consequential even after harmonization. Under low-dimensional representation, connectivity showed the largest gains (ICC 0.86, subject discrimination 3.0), exceeding other families at any dimensionality. Analysis of principal component loadings identified a small number of cortical regions per tract (median 6) that capture 95% of the reproducible connectivity signal, providing a per-tract reference for selecting the most informative regions in future multi-site studies. These findings indicate that the choice of which tract-derived metrics to analyze in multi-site studies deserves at least as much consideration as how to harmonize them.
Solid polymer electrolytes (SPEs) offer a promising route toward safe and high-performance electrochemical energy storage, yet a fundamental challenge in SPEs involves improving ionic conductivity while maintaining selective cation transport. The hurdle exists because ion transport is typically coupled closely to polymer segmental dynamics. Herein, a glassy single-ion-conducting polymer, poly-[lithium sulfonyl-(trifluoromethane sulfonyl)-imide methacrylate] (PLiMTFSI), in which the anions were tethered to the polymer, was blended with a flexible polymer, poly-(oligo-oxyethylene methyl ether methacrylate) (POEM), and a series of small-molecule lithium salts, in which the anions were untethered [lithium bis-(trifluoromethanesulfonyl)-imide (LiTFSI), lithium bis-(fluorosulfonyl)-imide (LiFSI), lithium trifluoromethanesulfonate (LiTf), or lithium perchlorate (LiClO4)]. The impact of salt anion volume and tethered-to-untethered anion ratio on the ion conduction behavior and thermal properties of blend electrolytes was investigated. In some cases, conductivity could be enhanced through this ternary blend approach. For example, a POEM-based polymer blend containing a bulky salt anion (TFSI-) and an equimolar mixture of PLiMTFSI and LiTFSI exhibited a Li+ conductivity (4.8 × 10-4 S/cm) an order of magnitude higher than that of a comparable POEM/LiTFSI system (6.3 × 10-5 S/cm) at 100 °C. This enhancement was attributed to a more than 9-fold increase in lithium transference number (0.66 in the ternary blend vs 0.07 in POEM/LiTFSI). Overall, this study highlights the potential for tuning anion composition and mobility to achieve relatively high ionic conductivities and maintain selective cation transport in SPEs, offering a pathway to enable batteries that tolerate elevated temperatures.
Lead-free metal-halide hybrid x-ray detectors are fundamentally limited by strong exciton localization and inefficient carrier transport, preventing their deployment in high-sensitivity flexible imaging systems. Here we establish a chirality-modulated spin-engineering strategy that intrinsically overcomes these limitations by quantitatively linking molecular chirality, Rashba spin splitting, carrier transport, and detector performance in a chiral Bi/Sb metal-halide hybrid series, (S1-rRr-CHEA)4(Bi0.5Sb0.5)2I10 (CHEA = 1-cyclohexylethylamine), where the enantiomeric ratio functions as a continuous structural control parameter. Homochiral assemblies maximize inversion-symmetry breaking, producing a giant Rashba coefficient up to 0.41 eV Å-1 and enabling long-lived (> 1 ns) spin polarization that suppresses excitonic localization. As a result, the exciton binding energy decreases by 42% while the carrier mobility-lifetime product (μτ) increases fourfold, establishing an intrinsic spin-modulated transport mechanism in lead-free metal-halide hybrids. Flexible detectors fabricated from the optimized homochiral composition exhibit deformation-invariant x-ray imaging with a record sensitivity of 8002 µC Gy-1 cm-2, an ultralow detection limit of 75 nGy s-1, and exceptional robust endurance under couples of stresses including thermal, humidity, mechanical, and irradiation. This work identifies molecular chirality as a programmable handle to control spin-orbit interactions and carrier dynamics, providing a general materials-level strategy for high-performance, environmentally benign radiation detectors and spin-enabled optoelectronics.
MXenes have gathered immense scientific attention due to their unique combination of high electronic conductivity, hydrophilicity, and reduced dimensionality. While considerable advances in synthetic methodologies, achieving rapid, high-yield production of dispersible monolayer MXenes with controllable in-plane structure remains a daunting challenge. Herein, we report an ultrafast radical-intensified selective etching (RISE) tactic that enables one-step mild synthesis of monolayer Ti3C2Tx MXene bearing customized in-plane nanoholes with near-quantitative etching efficiency (∼99.9%) within merely 3 h. By fine-tuning the dosage of H2O2, which generates hydroxyl radicals (·OH) in situ, defect-lean monolayer MXene was made in a high yield of 81.6%. Liters of such colloidal dispersion of monolayer MXene were obtained within hours, which could be readily processed into conductive films with improved oxidation resistance. Mechanistic studies reveal that the RISE protocol follows a radical-driven redox pathway fundamentally distinct from traditional proton-mediated etching routes. As a proof of concept, holey MXene-derived conductive films demonstrated an exceptional desalination capacity of 32.71 mg g-1 in capacitive deionization, outperforming most pure MXene-based electrode materials. Our method can potentially revolutionize the prevailing wet chemical etching protocol used for a decade for yielding monolayer MXene and establishes a swift pathway toward customizable MXene architectures for energy and environmental applications.
Single-celled organisms grown in identical conditions have variable life spans. Identifying the factors that drive the inherent variability in life span is crucial for our understanding of aging at a fundamental level. Here, we revisit the role of chromosome XII instability as a source of life span variability in aging populations of the budding yeast, Saccharomyces cerevisiae . We followed populations of mother cells as they aged and quantified changes in karyotype, DNA content, and aberrant DNA structures, including the production of extrachromosomal rDNA circles (ERCs). We found that cells massively amplified their rDNA both as ERCs and as a structural form that could not be resolved on CHEF gels. We propose a model describing how these unresolved structures are generated. Our model, that we call CICR (Catastrophic IntraChromosomal Recombination), describes the consequences of recombination between repeats of different replication status. At the completion of replication, when all other replication forks have successfully terminated, CICR events leave behind a single, unopposed replication fork in a branched form of Chr XII that has profound consequences during mitosis and/or subsequent cycles. This form of instability within the ribosomal DNA can lead to a myriad of toxic recombination products that may contribute to the life span variability in isogenic populations of aging yeast.
Precise regulation of oriented nucleation and growth is critical for optimizing halide perovskite crystal structures and enhancing optoelectronic device performance. This review highlights advances in orientation regulation across various halide perovskite systems, alongside relevant characterization techniques and their applications. First, we introduce the characterization techniques for crystallographic orientation and investigate the impact of preferential orientation on the performance of optoelectronic devices, encompassing scintillators, detectors, solar cells, gas sensors, and transistors. Concurrently, we underscore the orientation modulation mechanisms and strategies in three-dimensional perovskite single crystals, two-dimensional (2D) perovskites, perovskite nanocrystals (NCs), and photovoltaic perovskite films, as well as their impacts on performance. Subsequently, we discuss their impacts on single-junction and tandem solar cells, while elucidating the structure-performance correlations under the preferential orientation of perovskite films. Additionally, we systematically review thin-film fabrication strategies for achieving preferential orientation in large-area perovskite solar cells via solution-based deposition, vapor-based deposition, and printing techniques, particularly emphasizing the significance of composition engineering, additive engineering, and solvent engineering. Finally, the key challenges in the oriented nucleation and growth of perovskites for single crystals, 2D perovskites, NCs, and photovoltaics are outlined. This review aims to provide a fundamental understanding of orientation modulation in halide perovskites and stimulate further innovation.
The formation of M+∙, [M - 2H]+∙, and [M - nH]+ (n = 1, 3, 5) ions has been reported by using atmospheric pressure corona discharge (APCD) of n-heptane. The M+∙ and [M - H]+ ions can be produced by high-electric field tunnel ionization (HEFTI) and hydride abstraction reactions, respectively. It has been proposed that the [M - 2H]+∙, [M - 3H]+, and [M - 5H]+ ions are produced by the loss of hydrogen atoms from the [M - H]+ ion. The geometric and electronic configurations of the M+∙, [M - 2H]+∙, and [M - nH]+ (n = 1, 3, 5) ions were determined by quantum chemical calculations (QCCs). The product ions resulting from higher-energy collisional dissociation (HCD) of the M+∙ ion can be characterized by the loss of alkyl radicals and alkanes, while those of the [M - 2H]+∙ ion can be characterized by the loss of alkyl radicals and alkenes. The HCD product ions of the [M - nH]+ (n = 1, 3, 5) ions can be fundamentally characterized by the loss of alkenes. The product ions present in the HCD spectra can be supported by the geometric and electronic configurations determined by the QCCs. The fragment ions observed in the APCD mass spectrum are likely attributable to the result of collisional interactions between the M+· ion and the air components such as N2, O2, and Ar, or to the result of the HEF-induced cracking reaction leading to the alkyl fragments.
Both splicing and kinase signaling are biochemical processes that fundamentally determine and shape cell physiology. Although there has been some indication that there is an interaction between the two - splicing can alter the availability of exons encoding kinase targets and kinases can phosphorylate splicing factors - it has yet to be established the extent to which altering splicing factor expression impacts kinase signaling networks. In this work, we implemented a data-driven analysis using ENCODE RNA-sequencing data and prior work mapping post-translational modifications onto splice events to identify candidate splice factor perturbations that show extensive alterations to phosphorylation-encoding protein products. We then replicated the ENCODE knockdown experiments and performed global phosphoproteomics for two candidates, U2AF1 and SRSF3, complementing the transcription-level data. Both knockdowns showed extensive changes in phosphorylation and kinase activities, both basally and upon receptor tyrosine kinase stimulation. U2AF1 knockdown drove decreased JNK-associated cell death signaling but elevated chromosome regulation through CSNK2A1, PLK, and EIF2AK4 activity. SRSF3 knockdown, on the other hand, led to decreased cell cycle signaling through CDK and HIPK2 but increased cytoskeletal signaling through various PAKs. In addition, we found a striking enrichment of phosphorylated splicing regulators in both knockdowns that were linked to their splicing activity, such as HNRNPC, suggesting potential feedback and crosstalk between splice factors through signaling pathway activation. Importantly, comparison of differential phosphorylation measurements from this study to mRNA expression and splicing measurements from ENCODE revealed significant knockdown-dependent protein regulation, not captured by transcriptomic measurements alone, underscoring the value of phosphoproteomic profiling after splice factor perturbations. Combined, the transcriptomics and phosphoproteomics reveal deep interconnection between the two processes that are relevant to understanding cell signaling in health and disease.
Scaling wide-band-gap semiconductors to the ultrathin limit offers a transformative pathway for power electronics, with gallium nitride (GaN) representing a cornerstone material in this class. However, the operational resilience and functional tunability of its two-dimensional form (g-GaN) remain underexplored. This work shifts the focus from idealized systems to the complex materials behavior under realistic conditions, investigating how the synergistic effects of point vacancy defects, strain, and external electric fields govern its electronic, magnetic, and sensing landscapes. We demonstrate that these factors are not merely perturbations but are fundamental to modulating the material response. Our first-principles calculations suggest that g-GaN maintains electronic stability under intense electric fields; notably, gallium vacancies are predicted to further extend the theoretical stability limit. While in-plane tension preserves the band gap evolution under an electric field, in-plane compression facilitates low-field metallization. Using nitrogen monoxide (NO) adsorption as a prototype, we find that the interaction is defect-modulated and potentially tunable by electric fields. Analysis of adsorption energetics and diffusion barriers suggests that the gallium vacancy may act as a thermodynamic trap for NO. Targeted hybrid-functional (HSE06) validation confirms the reliability of observed adsorption trends and theoretical metallization thresholds while revealing that precise electronic-exchange treatment is critical for capturing the magnetic ground state of nitrogen vacancies. By systematically examining the geometry, energetics, band structure, density of states, magnetic response, and charge transfer, this study clarifies the interplay between defects and external electric fields, providing insights into theoretical upper bounds for property tuning and semiconductor device engineering.
Traumatic brain injury (TBI) triggers complex and evolving secondary cascades that disrupt mitochondrial homeostasis and contribute to progressive neurodegeneration. Although mitochondrial impairment is a well-recognized driver of post-traumatic pathology, the spatial and temporal progression of mitochondrial dysfunction, particularly in regions distal to the injury site, remains poorly defined, and potential sex-specific responses remain understudied. Here, we performed a comprehensive mitochondrial-focused analysis in a mouse model of controlled cortical impact (CCI), quantifying mtDNA copy number (mtDNA-CN), mitochondrial gene expression, and protein markers regulating biogenesis, transcription, electron transport chain integrity, and mitophagy. Mitochondrial profiles were assessed across four brain regions (cortex at 2, 4, and 6 mm from the injury epicenter, and hippocampus) at four time points (6h, 12h, 24h, and 48h) in both female and male C57BL/6J mice. While mtDNA content exhibited only modest and region-restricted reduction, particularly near the injury core, transcriptional and protein-level changes were far more pronounced and sex-divergent. Females displayed extensive early cortical gene activation followed by widespread hippocampal suppression at 48 h across mitochondrial dynamics, OXPHOS, transcriptional regulation, and biogenesis pathways, accompanied by 48h in PGC-1α, TFAM, and NDUFS1. In contrast, males showed minimal transcriptional disruption but demonstrated delayed compensatory increases in TFAM, NDUFS1, and p62 protein levels, suggesting activation of mitochondrial maintenance and recovery programs. These spatially and temporally distinct responses reveal fundamental sex-specific vulnerabilities in mitochondrial regulation after TBI. Together, our findings provide a direction to an integrated mitochondrial landscape of early post-injury events and identifies critical windows and pathways that may support sex-specific therapeutic targeting to restore mitochondrial function after TBI.
Interoception-the perception and integration of internal bodily signals-is fundamental to emotion regulation, bodily self-awareness, and predictive coding. Emerging evidence suggests that interoceptive disturbances may contribute to core psychopathological features of schizophrenia. Our research group recently conducted a systematic review and meta-analysis demonstrating significant impairments in interoceptive accuracy and sensitivity among individuals with schizophrenia. However, the neural mechanisms underlying these deficits remain unclear. This cross-sectional protocol will recruit 30 individuals with schizophrenia and 30 age- and sex-matched healthy controls. Participants will complete (1) behavioral interoceptive assessment using the heartbeat counting task; (2) subjective interoceptive questionnaires, including the Multidimensional Assessment of Interoceptive Awareness (MAIA) and the Body Perception Questionnaire (BPQ); (3) clinical symptom ratings (PANSS, HAM-A, HAM-D); and (4) cognitive testing (TMT, animal fluency, DSST). All participants will undergo multimodal MRI scanning, including structural T1-weighted imaging, resting-state fMRI, and diffusion tensor imaging. Neuroimaging data will be preprocessed and analyzed using DPABISurf, SPM12, and GRETNA. Expected Results: We anticipate that individuals with schizophrenia will show reduced interoceptive accuracy, altered subjective interoceptive awareness, and abnormal intrinsic neural activity and connectivity within interoception-related circuits, including the anterior insula, anterior cingulate cortex, amygdala, and thalamus. Structural abnormalities within thalamo-cortical pathways are also expected. Interoceptive deficits are hypothesized to correlate with symptom severity and cognitive performance. This study will provide an integrated characterization of interoceptive dysfunction and its neural correlates in schizophrenia. Findings may advance understanding of bodily self-disturbance and emotional dysregulation and support the development of future interoception-focused therapeutic approaches. https://www.chictr.org.cn/, identifier ChiCTR2500110551.
Polyelectrolyte complexation is an entropically driven, associative phase separation that has been leveraged to produce aqueously processed plastics known as polyelectrolyte complexes (PECs). Previously, we showed that their affinity to water and their chain mobility are important aspects to consider when designing PEC materials. To establish a more complete picture of influencing parameters, we examined the effect of polymer chemistry, specifically chain length and the side chain and backbone chemistry, on both the phase behavior and mechanical properties of homopolymer PECs. We combined compositional studies of PEC phase behavior with analyses of PEC dynamics and mechanics to understand how these aspects of polymer chemistry affect material performance. We observed that the identity of the ionizable groups heavily affected ion solvation, where PECs with lower water affinities had higher glass transition humidities and were generally more brittle, compared to PECs with higher water affinities. In contrast, backbone chemistry affected chain mobility, allowing acryloyl chemistries to have lower glass transition humidities compared to methacryloyl. Finally, chain length effects depended on the degree of match/mismatch of the polymer's lengths, with matched PEC systems having higher glass transition humidities than mismatched. Comparisons of the phase behavior and glass transitions revealed that side chain and backbone chemistry effects are universal across different mediums, while length effects are medium specific. These results establish fundamental structure-property relationships for the rational design of functional PEC materials.
Lysine acetylation (LysAc) of proteins plays critical regulatory roles in a wide range of biological processes in both prokaryotes and eukaryotes. However, characteristics of LysAc and related proteins in red algae have not been investigated. In a marine aquaculture species Pyropia yezoensis, thallus cells form and release asexual spores under wound stress, and this process provides an essential source of seedlings in aquaculture. In order to elucidate the underlying regulatory mechanisms during spore formation, we performed a global acetylproteome analysis in both intact and wounded thalli. A total of 4647 LysAc sites were identified on 1398 proteins. Among them, 361 proteins exhibited differential acetylations (DAPs) at the time of sporangia formation and 382 at the time of spore maturation. Functional classification of all the DAPs revealed that they were primarily associated with central metabolic pathways, highlighting the importance of lysine acetylation in asexual spore formation. Particularly, >30 proteins related to photosynthesis and carbon fixation showed coordinated decline, consistent with the repressed photosynthetic efficiency after wounding. Starch was accumulated and the LysAc on the catalytic domain of starch synthase significantly increased during spore formation. Proteins related to cytoskeleton remodeling also had variations in LysAc, aligning with the observed depolymerization of microfilaments in spores. Our study provides not only fundamental information in protein acetylation in Pyropia as a prominent example for red seaweeds but also valuable insights on the post-translational regulation in wound-induced spore formation.
Visual acuity (VA) and stereoacuity (SVA) are fundamental visual functions that decline with increasing retinal eccentricity. Patients with macular degeneration and other central vision disorders often rely on paracentral vision, yet location-specific reference data for VA and SVA across the parafoveal and perifoveal retina remain limited. This study aimed to quantify the distribution of binocular VA and SVA across eccentricity and meridian in young adults, develop prediction equations with 95% prediction intervals, and examine the relationship between these two visual functions in the paracentral retina. Thirty-five healthy young adults (13 males, 22 females; mean age 27.23 ± 2.43 years) were recruited. Binocular VA and SVA were measured at 48 test positions across eight meridians (0°, 45°, 90°, 135°, 180°, 225°, 270°, 315°) and six eccentricities (2.5° to 15° in 2.5° increments) using a polarized 3D display system. A four-alternative forced-choice task was employed with tumbling E optotypes for VA and random-dot stereograms for SVA. Eye tracking ensured fixation stability throughout testing. Generalized estimating equations were used to analyze the effects of eccentricity and meridian. Linear mixed-effects models and Bayesian Tobit models were employed to develop prediction equations. Ten-fold cross-validation assessed model generalizability. Both VA and SVA significantly declined with increasing eccentricity (P < 0.001). VA decreased from a median of 0.40 logMAR at 2.5° to 1.20 logMAR at 15.0°, at a rate of 0.057 logMAR per degree. SVA increased from 2.1 log arcsec at 2.5° to 2.9 log arcsec at 7.5°, declining approximately three times faster than VA (0.154 log arcsec per degree). Both functions showed significant meridional anisotropy (P < 0.001), with the horizontal meridian demonstrating 0.058 logMAR better VA and 0.106 log arcsec better SVA compared to the vertical meridian. Despite parallel declines with eccentricity, no significant correlations were observed between VA and SVA at any test position within 7.5° eccentricity (P > 0.05). VA and SVA deteriorate with increasing eccentricity in the paracentral retina, with stereopsis declining approximately three times faster and demonstrating a more pronounced horizontal-over-vertical advantage. The absence of correlation between VA and SVA suggests distinct neural mechanisms underlying these functions. The prediction equations with 95% prediction intervals provide reference benchmarks for healthy young adults, facilitating clinical interpretation of patient measurements and enabling objective assessment of disease-related changes in paracentral visual function.
Pancreatic adenocarcinoma (PDAC) is an abysmal disease, with a poor clinical outcome, largely due to limited life-extending treatments for patients. Notoriously, PDAC displays a T cell-suppressive tumor microenvironment where underlying molecular mechanisms that lead to this phenotype remain poorly understood. To unravel specific mechanisms, we utilized bioinformatic analyses with functional studies and revealed the cytolinker protein plectin (PLEC) as a novel player in regulating the T cell-suppressive tumor microenvironment of PDAC. Utilizing the TCGA-PAAD dataset, tumor samples were separated by PLEC expression to evaluate patient survival, and pathway analyses associated with increased tumorigenesis. Evaluation of immune infiltration and subsequent immune deconvolution was performed using tidyestimate and CIBERSORTx R packages. Single-cell RNA-seq (scRNA-seq) analysis from 229 PDAC patients was analyzed to investigate signaling dynamics and immune cell infiltration in PLEC High patients. Functional validation was provided using a monoclonal antibody (mAb) against cell surface plectin (CSP) in two murine PDAC models to examine changes in tumor growth and immune cell subset abundance. Our studies revealed that high plectin expression results in an overall worse survival associated with activation of pro-tumorigenic pathways and decreased anti-tumor immune signature in PDAC patients. Analysis via GSEA indicates PLEC High patients display an aggressive phenotype and suppressed pro-inflammatory signaling pathways. Immune ESTIMATE scores were significantly decreased in PLEC High patients, and scRNA-seq analysis revealed that PLEC High tumors display a decrease in anti-tumor CD8 + T cells. In vivo analyses using an anti-CSP mAb revealed a reduction in tumor growth kinetics compared to IgG control corresponding with a significant increase in proliferating and activated cytotoxic CD8 + T cells. Anti-CSP-mediated tumor suppression was inhibited when CD8 + T cells were depleted, indicating that anti-CSP treatment is contingent on cytotoxic T cell functionality. Our findings identify plectin as a biomarker of aggressive disease in PDAC, with high plectin expression associated with decreased T cell infiltration, and that treatment with anti-CSP mAb reinstates anti-tumor immunity and decreases tumor volume in vivo . These findings position plectin as a high-priority therapeutic target, with the potential to fundamentally reshape immune responses in PDAC and improve outcomes for patients with few remaining options.