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Facilitators and barriers to medication adherence in systemic lupus erythematosus: a qualitative study in China
Exploring motor variability in adults with severe athetoid or ataxic cerebral palsy: Impact on error-based and reward-based learning
Individuals with cerebral palsy (CP) are characterized by elevated movement variability. Movement variability has been proposed as a mechanism that facilitates the exploration of diverse movement strategies. However, in the case of CP, this variability is often excessive, potentially impeding effective error correction and motor learning processes. This study aims to investigate motor variability in adults with severe athetoid and ataxic CP profiles, focusing on its impact on error-based and reward-based learning mechanisms. The study included 13 adults with severe CP and a control group of 18 adults without disabilities. The findings revealed that individuals with CP exhibit significantly greater motor variability than the control group, which correlates with higher absolute error rates and a diminished capacity for task-related adjustments. These results suggest that CP negatively affects motor stability and precision, complicating motor learning. Furthermore, it was observed that error-based tasks are more accessible for individuals with CP, as they showed substantial performance improvements following training, in contrast to the reward-based tasks. This study underscores the importance of personalized motor learning interventions for individuals with CP, considering the variability among CP subtypes and the individual characteristics of each person. The research provides essential insights into motor learning adaptation and retention in individuals with severe CP, highlighting the necessity of continuous practice to sustain long-term improvements.
Enhancing Enzyme Activity With Mutation Combinations Guided by Few‐Shot Learning and Causal Inference
ABSTRACT Designing enzyme sequences to enhance product yield represents a fundamental challenge in metabolic engineering. Here, we established a workflow that integrates computational predictions with efficient experimental iteration to obtain outsized gains in product yield. Based on causal inference and examination of published datasets, we realized and ultimately experimentally confirmed that in vivo unit yield (yield/expression) can serve as an attractive surrogate for aqueous k cat / K m when optimizing for activity. In our workflow, we initially predict activity‐enhancing single mutants by calculating the binding affinities of reactive intermediates, followed by experimental investigations of unit yield. Subsequently, we predict activity‐enhancing mutation combinations using a few‐shot learning model we developed called Physics‐Inspired Feature Selection of Protein Language Models (PIFS‐PLM), which requires only 60–100 experimentally examined mutation combinations as input. In a case study of a bicyclogermacrene (BCG) synthase, we achieve a 73‐fold increase in BCG yield or a 15% increase in BCG selectivity based on combinations of 12 individual mutations, and provide extensive crystallographic and biochemical evidence for impacts from specific mutations. Thus, optimizing for unit yield is highly efficient as an alternative to optimizing for thermostability, and our study provides a powerful workflow for the efficient engineering of high‐yield enzyme variants.
Ion‐Precise Electrosynthesis and Memristors of Sequence‐Controlled Conjugated Polymers
ABSTRACT The ion‐precise synthesis of polymer materials remains a challenge because of the counterion exchange during solution‐processed synthesis and processing. Here, we demonstrate ion‐precise electrosynthesis and memristors based on conjugated polymers, in which both backbone cations and counteranions are sequence‐controlled for the first time. Inter‐ and intramolecular counterion exchanges are effectively blocked during surface‐initiated growth of crystalline polymer monolayers, enabling us to distinguish a correlation between a library of sequence‐controlled cationic conjugated polymers and their counteranions, as well as their intrinsic negative differential resistance (NDR). We find that controlled anion migration is a key factor in achieving ultralow NDR bias in redox‐based memristors, dramatically reducing it from 1.75 V to a record low of 0.13 V. The peak‐to‐valley current ratio (PVCR) reaches 117 at 0.55 V, demonstrating a strategy that achieves a giant PVCR while simultaneously maintaining a low NDR bias. Unlike previously reported usual single or rarely double NDR peaks, we observe triple NDR peaks, which are theoretically more advantageous for multivalued logic computing. Our work represents a paradigm shift toward high‐dimensional control of polymer structures within a two‐dimensional molecular system for ion‐precise memristors, while demonstrating advantages in tailoring intrinsic NDR beyond existing methods or materials.
Metal oxides-based catalytic pyrolysis of lignocellulosic biomasses for bio-oil development: a comparative assessment on process optimization and characterization
Water‐Splitting‐Suppressed High‐Capacity Bipolar Electrodes Enabled by Topochemical Electron Buffering for Symmetric Aqueous Batteries
ABSTRACT Symmetric aqueous batteries (SABs) that employ bipolar materials as electrodes have attracted tremendous attention due to their intrinsic safety and satisfactory capacity, while they still suffer from water‐splitting and thus a narrow voltage window. In this work, we propose a novel topochemical design of introducing an electron buffer (EB) to control the electron stream when working, which efficiently attenuates the electron flow toward the water‐splitting reactions at the voltage ends. Careful measurements confirm the sharp reduction of current density applied for water‐splitting due to the EB effect. Theoretical calculations for voltage end verify the lower surface electron density of EB‐involved electrode than that of EB‐excluded electrode, demonstrating the superiority of this EB design in suppressing charge shock for water splitting. Consequently, the charging/discharging plateau of the assembled SABs based on EB increases ∼0.16 V, as well as a high capacity of 80.7 mA h g −1 achieved, which is superior to reported state‐of‐the‐art aqueous bipolar materials. Moreover, the electrolyte loss of EB‐involved SABs reduces to only 24% of that of EB‐excluded SABs, validating suppressed water splitting by confining the electron pathway. This work provides a new thought to guide electron stream through introducing a rational buffer layer, aiming at hindering water splitting while maintaining energy storage performance.
The Role of Li‐Rich Disordered Domain in Li‐Rich Cathodes
ABSTRACT Li‐rich cathodes suffer from electrochemical degradation due to structural incompatibility between the Li‐rich and LiTMO 2 ‐like phases (transition metal [TM] = Mn, Ni). This study identifies and characterizes a previously overlooked transitional phase, the Li‐rich disordered (LRD) domain, which bridges these two primary phases and is the fundamental origin of heterogeneous redox‐driven strain and lattice displacements. Advanced structural analyses reveal that transition metals, particularly Ni, occupy Li sites within this LRD domain. We demonstrate that tailoring the synthesis to constrict the LRD domain effectively mitigates its structural evolution during (de)lithiation. This constricted domain acts as a buffer layer, isolating the anisotropic lattice strain between adjacent domains, thereby suppressing oxygen loss and enhancing structural integrity. In situ high‐temperature XRD further tracks the formation of this domain during synthesis. Consequently, the engineered cathode delivers a 15% (25 mA g −1 , 50 cycles) and 26% (250 mA g −1 , 300 cycles) increase in specific capacity than pristine within 2.0–4.8 V, alongside enhanced long‐term cycling stability. This work elucidates the critical role of the constricted LRD domain in stabilizing anionic redox, offering a fundamental insight for designing advanced Li‐rich cathodes.
Molecular mechanism of p-Coumaric acid in the regulation of AQP2 function through the activation of calcium-sensing receptor signaling
Tailoring Local Superstructure Units to Mitigate Voltage Decay in Na‐Ion Batteries
ABSTRACT The practical application of high‐energy‐density P2‐type cathodes is hindered by severe voltage decay upon high‐potential cycling. This voltage decay primarily originates from irreversible interlayer cation migration and detrimental structural degradation, which can be notably suppressed by regulating the arrangement of superstructure units. Herein, we incorporate LiTiMn 5 superstructure units in P2‐Na 0.7 K 0.04 Li 0.1 Ni 0.22 Mn 0.6 Ti 0.08 O 2 (NaKLNMT) to construct the long‐range in‐plane ordered arrangement within transition metal slabs, creating a stable oxygen coordination environment and high energy barriers along the migration path. Furthermore, the circumscribed P‐type to O‐type stacking evolution and restricted Li/TM migration restrain the formation of vacancy clusters, prohibiting consequential overoxidation of lattice oxygen and inhomogeneous lattice strain accumulation under high‐voltage. Therefore, the target NaKLNMT compound exhibits a negligible voltage decay of 0.15 mV/cycle and 96.3% capacity retention over 100 cycles at 1 C. Our findings demonstrate that regulating cation migration through local superstructure control helps steer strategies to address the issues of voltage decay in sodium‐layered oxide cathodes.
N‐Alkyl Extension in Ionic Molecular Rotors: Facile Tuning of Sensing Modes for Albumin‐Based Host‐Guest Fluorescent Sensors
ABSTRACT Establishing a strategy for fine‐tuning of fluorescent sensing modes (e.g., off ↔ on, ratiometric, fluorocolorimetric) in human serum albumin (HSA)‐dye involved supramolecular systems that can tackle the bottleneck for the development of functional fluorescent sensors and sensor arrays in specific practical applications. Here, we propose a simple strategy by extending the N‐alkyl on the pyridinium of triphenylamine diarylethene (TPA‐Ps), a classic ionic molecular rotor skeleton for protein binding and fluorescent sensing, to fulfill the modulation of sensing modes of TPA‐P@HSA. The structural effects on two factors corresponding to sensing modes, the initial fluorescence (TPA‐Ps dispersions) and the final fluorescence (TPA‐P@HSA), have been comprehensively investigated. The utility of the strategy was examined in the applications of fluorescent analysis of urinary albumin, construction of dye@HSA indicator‐displacement assays for the third analytes, fluorescent imaging, and building sensor arrays for classification. Finally, we demonstrated that this strategy can be generalized to other TPA‐P skeleton‐based dyes, resulting in substantially tunable sensing modes in response to HSA.
Bearing characteristics of modified suction caissons under long-term horizontal cyclic loading
Iron‐Photocatalyzed C(sp <sup>3</sup> )–H Phosphonylation of Alkanes
ABSTRACT Alkyl phosphonate esters are valuable motifs that have broad synthetic utility and are commonly found in bioactive molecules. Therefore, many methods have been developed to enable efficient phosphonylations of organic molecules, typically involving the construction of C(sp 3 )–P bonds by substitutions of common functional groups with phosphorus(III) reagents. However, direct phosphonylations of unactivated C(sp 3 )–H bonds are rare and currently lack the substrate generality required for late‐stage introduction of phosphonate groups into complex molecules. Herein, we report a photoinduced C(sp 3 )–H phosphonylation of unactivated alkanes using a hydrogen atom transfer (HAT) strategy with an iron photocatalyst. Key to the success of the process was the development of a novel mandelonitrile‐derived phosphite radical trap, which is equipped with an oxidizing phenylacetonitrile radical leaving group that enables effective turnover of the photocatalyst. The method displays good functional group tolerance, high selectivity for phosphonylations of sterically unhindered C─H bonds, and was found to be applicable to regioselective late‐stage installation of phosphonate esters into complex molecules.
A lightweight hybrid framework for real-time data refinement in resource-constrained underwater and underground wireless sensor networks
New Water Oxidation Mechanism in Photosystem II Resolves Major Experimental Controversies
ABSTRACT Light‐driven oxygen formation in photosystem II protein is a fundamental process that sustains our biosphere. The research by advanced physical techniques has delivered new insights on the structure and function of the Mn 4 CaO 5 cluster. However, discrepancies in experimental observations and computational models persist, impeding the understanding of O–O bond formation and the role of the protein environment in the process. Here, we show that i) assignment of the OEC unique oxygen O3 ligated by histidine (His337) via dynamic H‐bond as a slow exchanging substrate and ii) its coupling with O6 oxygen generated at Mn1 in the S 2 to S 3 transition—giving an O─O bond formation mechanism most consistent with all currently available experimental data. We propose a mechanism by which the protein environment can steer the O─O bond formation by charge control via H‐bonding and open coordination of Mn1. Obtained O3–O6 peroxide is at lower energy than peroxides in the most studied O5─O6 bond formation pathway. His337 appears to be similar to distal His in globins used for management of the O 2 and H 2 O 2 intermediates. This new mechanism breaks the prior impasse and will undoubtedly invigorate future detailed studies uncovering further details.
A Stable Open‐Shell Polycyclic Hydrocarbon With Schlenk‐Chichibabin Hybrid Conjugation
ABSTRACT Open‐shell polycyclic hydrocarbons (PHs) have emerged as a promising class of molecular materials for organic electronics and spintronics due to their unique electronic structures and properties. However, the design and synthesis of open‐shell π‐systems with intricate internal spin interactions remain a significant challenge in synthetic chemistry. Herein, we report our efforts toward a novel tetraradicaloid system 1 by integrating two distinct conjugation motifs derived from Schlenk and Chichibabin hydrocarbons into a linear PH framework. Its model compounds 2 (Schlenk‐type) and 3 (Chichibabin‐type) were also prepared and compared. Comprehensive experimental and theoretical analyses reveal that 1 exhibits an open‐shell singlet ground state with moderate tetraradical character, effectively bridging the electronic properties of 2 and 3 . All three systems display pronounced open‐shell diradical character, characterized by small singlet‐triplet energy gaps, narrow energy gaps, and amphoteric redox behavior. Notably, the dication and dianion of 1 show significant open‐shell diradical character while its tetracation adopts a closed‐shell configuration. Furthermore, the dianions of 2 and 3 exhibit electronic structures analogous to their respective isoelectronic counterparts, pentacene, and heptaphane. This work will shed new light on the design and synthesis of novel open‐shell PHs with complex internal structural features and adjustable electronic properties.
MXene@Cu@PPy nanocomposites with enhanced electromagnetic response
Breathing Bimetallic MOF Confined Polyoxometalates for Hydration Layer Loosening and Electronic Redistribution Toward Efficient Nitrate Electroreduction and Zn−Nitrate Batteries
ABSTRACT The traditional Haber‐Bosch method suffers from harsh conditions and high energy consumption, while electrocatalytic nitrate reduction to ammonia (ENRA) is a green route for ammonia synthesis and can serve as a cathode reaction for Zn−nitrate batteries. Its development is limited by sluggish intermediate hydrogenation and severe hydrogen evolution reaction (HER). Herein, we develop topology‐engineered isomeric polyoxometalate (POM)‐confined bimetallic metal‐organic framework (MOF) electrocatalysts (NH 2 ‐MIL‐53, ‐88, ‐101). Flexible NH 2 ‐MIL‐88(FeNi) enables tight encapsulation of [PW 12 O 40 ] 3− (PW 12 ) clusters via the “breathing effect”, yielding PW 12 @NH 2 ‐MIL‐88(FeNi) with synergistically modulated electronic distribution and proton transfer. Combined experimental and theoretical studies reveal that confined PW 12 induces electronic redistribution over Fe/Ni centers, concurrently strengthening NO 3 − adsorption on Fe and accelerating *NO 2 hydrogenation on Ni. Beyond electronic effects, PW 12 loosens the rigid hydration layer and forms conjugated acid‐base pairs with MOF amino groups, promoting proton diffusion, boosting *NO 2 hydrogenation, and suppressing HER. Thus, PW 12 @NH 2 ‐MIL‐88(FeNi) achieves an NH 3 yield rate of 20.1 mg h −1 mg cat. −1 with a Faradaic efficiency of 98.6% under neutral electrolytes. When used as a cathode in rechargeable Zn−nitrate batteries, it delivers a peak power density of 13.2 mW cm −2 . This study establishes a generalizable paradigm for engineering interfacial proton transport and electronic properties via POM confinement in MOFs.
Structure‐Encoded Oxidation Enables Nucleotide‐Resolved RNA Editing, Conjugation, and Structural Probing
ABSTRACT RNA oxidation is pervasive in stress and disease biology and has also been harnessed in chemical biology through proximity labeling, ligand‐directed photochemistry, and oxidative RNA targeting. In most settings, the regioselectivity is specified by spatial proximity or a specialized RNA‐binding ligand, and the resulting modification is typically distributed across a local region rather than at a designated nucleotide. Here we show that, with selected oxidants, RNA secondary structure can itself serve as a programmable handle to control RNA oxidation site‐selectively. We define practical structure–reactivity rules that determine which guanosine is oxidized and which lesions predominate, based on loop geometry and oxidant identity. Guided by these rules, we develop LOCAL (Localized Oxidation Constrained at Loops), a DNA‐programmed, postsynthetic method that directs guanosine oxidation to predetermined sites in transcribed RNAs with nucleotide‐resolved selectivity. LOCAL enables oxidative base editing to modulate RNA interactions and stability, provides a plug‐and‐play tool for site‐specific bioconjugation via nucleophile trapping of oxidized guanosines, and serves as a blue‐light‐gated, guanosine‐focused structural readout of RNA single‐strandedness and ligand‐induced structural changes. Together, these results position RNA oxidation as a nucleotide‐resolved, structure‐encoded reaction manifold that complements existing ligand‐encoded oxidative targeting chemistry, and 2´‐OH‐ and enzyme‐based RNA chemistries.
Associations between fat distribution and obstructive sleep apnea severity among individuals with type 2 diabetes: an MRI-based study
Abstract Obstructive Sleep Apnea (OSA) affects 1 billion people globally, with a male-to-female ratio of 2:1. While obesity is a major risk factor, sex differences in fat distribution may influence OSA risk. This study examined the relationship between visceral (VAT), subcutaneous (ASAT), and total abdominal fat (TAAT) and OSA severity in patients with type 2 diabetes (T2DM). We enrolled 164 T2DM patients (97 males, 67 females) from the EPSONIP-Sleep study; 151 had complete MRI and polygraphy data. OSA severity was evaluated by home respiratory polygraphy. Linear regression assessed AHI, logistic regression assessed moderate-to-severe OSA, and the Kruskal–Wallis test compared AHI across VAT-z/ASAT-z strata. In males, VAT, ASAT, and TAAT were associated with AHI in unadjusted analyses (β = 1.3, p = 0.009; β = 1.5, p = 0.010; β = 0.85, p = 0.009, respectively). ASAT (OR = 1.23/L, 95% CI 1.01–1.49, p = 0.049) and TAAT (OR = 1.10/L, 95% CI 1.00–1.22, p = 0.02), but not VAT, were associated with moderate-to-severe OSA. No statistically significant associations were detected in females. Associations were attenuated after BMI adjustment. AHI did not differ across VAT-z/ASAT-z strata ( p = 0.430). Sex differences influenced the relationship between fat and OSA severity. In males, abdominal fat volumes were associated with higher OSA severity in unadjusted analyses, but not after BMI adjustment. No statistically significant associations were detected in females. These findings should be interpreted cautiously given the modest sample size.