While lab-scale spin-coating in inert environments has delivered record efficiencies for perovskite solar cells (PSCs) employing self-assembled monolayers (SAMs), their fabrication via fully ambient-air printing-a prerequisite for low-cost industrialization-remains unreported. Here, we report the first PSCs exceeding 26% efficiency based on fully ambient-air printed SAMs and perovskite films and elucidate the governing role of SAM physicochemical properties through fluid-crystallization synergy. SAMs with higher surface energy (γ) flatten the perovskite ink meniscus, attenuating the temperature gradient and Marangoni stress along the gas-liquid interface, thereby enabling more uniform perovskite deposition and smoother films. Simultaneously, γ systematically modulates perovskite crystallization by delaying nucleation onset and shifting the growth mode from continuous to instantaneous on higher-γ SAMs. The fluid-crystallization synergy yields a record power conversion efficiency (PCE) of 26.31% (certified 25.85%), a benchmark for all reported ambient-air printed devices, including non-SAM-based counterparts. The approach further enables scalable fabrication, achieving a champion PCE of 22.3% in 13.04 cm2 mini-modules with over 90% performance retention after 1200 h operation under the ISOS-L-1 protocol. This work establishes a quantitative link between SAM physicochemical properties and perovskite fluid dynamics and crystallization thermodynamics in ambient-air printing, providing guidance for perovskite photovoltaics toward scalable ambient manufacturing.
Semiflexible fibrous networks are extensively found in biological tissues and engineered materials, exhibiting distinct mechanical properties situated between purely flexible and rigid networks. Understanding the underlying mechanisms governing their nonlinear strain-stiffening behavior remains challenging due to limitations in current theoretical frameworks, which predominantly focus on fiber stiffness, crosslinking density, and fiber interactions, without fully addressing changes in the network topology during deformation. Here, we propose a percolation-based theoretical model to elucidate the mechanical response and strain-stiffening behavior of semiflexible fibrous networks under tensile loading. By explicitly defining percolation parameters such as node connectivity, fiber connection probability, percolation threshold, and the rigidity percolation giant component (RPGC), we quantitatively correlate the microscopic fiber rigidity transitions with macroscopic network mechanics. Our molecular dynamics simulations combined with graph theory analysis demonstrate the central role of RPGC formation in the transition from non-affine to affine deformation regimes. Numerical results confirm that our percolation model captures the nonlinear stress-strain trend observed in simulation, particularly the onset of strain-stiffening. Additionally, we identify a three-stage deformation behavior: initially non-affine, transitioning to entropy-driven affine deformation, and ultimately dominated by enthalpic affine deformation, which provides detailed insights into the microstructural evolution of fibrous networks under strain. This percolation-based framework offers a comprehensive mechanistic understanding of semiflexible fiber networks, which may inform the rational design and optimization of biomimetic materials and engineered network structures.
Given limited meniscus self-repair capacity, an ideal implant fulfilling biomechanical and biological needs remains unmet. Inspired by natural meniscus microstructure, we developed a biomimetic scaffold using three-dimensional (3D)-printed polycaprolactone (PCL) reinforced with continuous silk fibers via in situ impregnation. The continuous-silk-reinforced composites (CSRC) scaffold replicates meniscus anisotropy and viscoelasticity, outperforming PCL in mechanical reinforcement. Preliminary tests confirmed cytocompatibility and in vivo biocompatibility, highlighting silk’s regenerative potential. Mechanistically, the CSRC scaffold synergizes rapid stress relaxation with silk bioactivity to activate the phosphatidylinositol 3-kinase (PI3K)-protein kinase B (Akt) pathway in synovial mesenchymal stem cells (SMSCs) under mechanical stimulation. This activation enhances SMSC survival/differentiation and accelerates tissue remodeling. Our strategy offers a promising meniscus tissue engineering solution and broadens applications of fiber composites in biomedical engineering.
3D printing has emerged as a transformative technology for fabricating patient-specific scaffolds with macroscopic precision for maxillofacial bone reconstruction. Yet, current designs fail to replicate the microscale topological cues of the native bone extracellular matrix (ECM), which are critical for orchestrating the sequential cellular events that drive effective bone regeneration. Here, digital light processing (DLP) 3D printing is integrated with polymerization-induced phase separation (PIPS) to fabricate gelatin methacrylate (GelMA) hydrogel scaffolds that recapitulate ECM-mimetic topographies within anatomically accurate constructs. PIPS affords robust, precise control over pore morphology while maintaining DLP's high-resolution fidelity for patient-specific mandibular repair. The resulting microporous architecture acts as a potent mechanotransductive cue, amplifying phosphorylated-focal adhesion kinase (pFAK) activation, cytoskeletal remodeling, and Yes-associated protein (YAP) nuclear localization. This cascade enhances bone marrow mesenchymal stem cells (BMSCs) adhesion, osteogenic differentiation, and pro-angiogenic paracrine signaling, leading to rapid and functional bone regeneration in vivo. By integrating microscale phase-separation thermodynamics with macroscale additive manufacturing, this study presents a proof-of-concept approach for mechano-instructive scaffold design, validated in a rabbit mandibular defect model and offering potential relevance to future clinical applications in regenerative medicine.
Background: Despite the clinical significance of circumcision, traditional suturing is frequently compromised by intraoperative bleeding and lengthy recovery periods. While high-frequency electric welding (HFEW) presents a compelling alternative, its utility in foreskin removal procedures remains unexplored. Methods: Employing freshly excised human foreskin tissues, this study simulated the circumcision procedure to benchmark HFEW against standard suturing techniques. Critical performance metrics, encompassing tensile integrity, thermal injury scope, and operative efficiency, were rigorously quantified. Results: HFEW demonstrated exceptional time efficiency, averaging 2.01 ± 0.9 min—a 77.02% reduction relative to conventional suturing (p < 0.001). However, mechanical testing revealed disparities in tissue adhesion; the HFEW cohort recorded lower forces for initial tearing (4.42 ± 1.02 N) and complete rupture (6.15 ± 1.65 N) compared to the superior tensile resistance of the suturing group (7.91 ± 3.26 N and 14.22 ± 6.91 N, respectively). Conclusions: Although HFEW yields comparatively lower tensile strength, its remarkable operational efficiency positions it as a viable technical innovation for circumcision. These preliminary findings support the pursuit of further in vivo investigations to confirm its clinical applicability.
The repair of critical-sized bone defects remains a significant challenge in regenerative medicine. Using guided bone regeneration (GBR) membranes has emerged as a promising treatment strategy. In this study, we fabricate a novel multilayer density-gradient electrospun nanofiber membrane comprising bone morphogenetic protein-2 (BMP-2) combined with nano-hydroxyapatite (nHA) and vascular endothelial growth factor (VEGF) embedded in a polylactic acid (PLA) and type I collagen (COL) nanofiber matrix, denoted as BMP-2@nHA/VEGF@(PLA/COL). The gradient density structure of membranes is engineered to mimic the periosteum tissue, thereby creating an optimal microenvironment for bone regeneration while preventing soft tissue invasion. The membrane exhibits commendable mechanical properties and favorable degradation characteristics. Drug release experiments reveal that the membrane enables an early-phase release of VEGF, coupled with a prolonged release of BMP-2, advantageous for fostering early vascularization and long-term osteogenesis. In vitro studies confirm that the membrane effectively maintains barrier function while enhancing the coordinated advancement of both vascularization and osteogenesis. Furthermore, experiments with a rat cranial bone defect model demonstrate that the membrane substantially accelerates bone regeneration. Consequently, the bionic membrane developed in this research shows considerable potential for clinical applications in GBR therapies.
Ferrate(VI) (Fe(VI)) is an environmentally benign oxidant for water treatment, yet its inherently sluggish kinetics under neutral-to-alkaline conditions critically limit its practical application and necessitate effective activation strategies. While carbon nanotubes (CNTs) have shown promise in activating Fe(VI), the specific active sites and the underlying mechanism remain poorly defined, frustrating the rational design of high-performance carbon-based activators. This study demonstrates that CNTs-mediated Fe(VI) activation proceeds through a nonradical pathway governed by in situ generated high-valent Fe(IV)/Fe(V) intermediates, delivering near-complete 6-methylquinoline removal with a rate constant 3.8-fold higher than Fe(VI) oxidation alone. The activation initiates through the formation of metastable CNTs−Fe(VI)* surface complexes via interfacial interaction. A key mechanistic advance lies in deconvoluting the antagonistic roles of carbon surface chemistry and lattice architecture. Carbonyl, carboxyl, and hydroxyl functionalities serve as critical active sites responsible for anchoring Fe(VI) and triggering the formation of CNTs−Fe(VI)*, from which electron transfer from the intact sp2 framework generates Fe(IV)/Fe(V) species. In contrast, excessive structural defects disrupt π-electron delocalization and suppress interfacial electron transfer, thereby inhibiting the generation of Fe(IV)/Fe(V). The Fe(VI)/CNTs process achieves over 95% removal of structurally diverse micropollutants, sustains its performance in real water matrices and in the presence of co-existing anions, and yields transformation products with substantially reduced ecotoxicity. This work resolves the previously obscured structure-function relationship in carbon-mediated Fe(VI) activation, and establishes a clear design paradigm, i.e., enriching active oxygen functionalities while preserving graphitic sp2 carbon integrity, for advancing metal-free catalytic Fe(VI) activation toward water decontamination.
The inability to achieve uniform hole transport with solution-processed self-assembled monolayers (SAMs) constitutes a fundamental bottleneck for scaling perovskite photovoltaics. Herein, we demonstrate that thermal-evaporated SAMs (eSAMs) overcome this limitation by enabling precise thickness control. Crucially, a thickened eSAM spontaneously forms a vertical-to-horizontal gradient in molecular orientation, which creates a descending energy barrier that directionally facilitates hole transport. This tailored interface also ensures excellent surface coverage and directs the growth of high-quality perovskite films. Consequently, the resultant photovoltaic devices set new benchmarks, delivering impressive power conversion efficiencies (PCEs) of 21.46% (small-area, 0.108 cm2) and 19.38% (large-area module, 15.52 cm2) for fully vacuum-evaporated devices, while also setting an impressive PCE of 23.67% for eSAM-based devices with solution-processed perovskites. This new strategy effectively addresses the critical challenge of scalable SAM deposition, positioning eSAM as a key enabler for the industrial advancement of perovskite photovoltaics.
Multifunctional membranes integrating pollutant separation, treatment, and detection are highly desirable but challenging to create. Here, we report a coordination-adsorption-reduction strategy to fabricate ultrathin, flexible, self-supporting silk fibroin-Ag (SAFE) membranes at the air-water interface. Mechanistic studies reveal that silver(Ι) center coordination guides silk fibroin aggregation, which templates uniform AgNP growth. The resulting membranes achieve exceptional electrical conductivity (up to 1.9 × 107 S m-1) and mechanical robustness. Functionally, they provide high-flux separation and superior pollutant adsorption, while the embedded AgNPs offer multifaceted treatment via antimicrobial, catalytic, and electrochemical activities and enable sensitive SERS detection of trace contaminants. This integrated "separation-treatment-detection" approach establishes SAFE membranes as a promising platform for intelligent and sustainable water purification.
Tin oxide (SnO2) is a preferred electron transport layer for n-i-p perovskite solar cells (PSCs), yet its inherent oxygen vacancy and large energy-level offset hinder the pursuit of ultra-high efficiency. To address these issues, we engineered a hybrid electron-selective layer by sandwiching the SnO2 layer with a newly designed self-assembled monolayer (SAM) featuring cyano and pyrazine units. The SAM-cladded SnO2 sandwich configuration promotes superior charge transport by establishing an ohmic-like contact at the interface, while the cyano and pyrazine groups synergistically act on both interfaces. This dual-interfacial modification ensures optimized energy-level alignment and culminates in the effective passivation of interfacial defects. The optimized perovskite photovoltaic devices achieve a power conversion efficiency (PCE) of 26.00%, with markedly enhanced operational stability. The developed strategy establishes a generalized framework for defect-tolerant, energy-level-matched electron-selective interfaces in emerging perovskite photovoltaics.
In the fabrication of n-i-p structured perovskite solar cells (PSCs), the perovskite layer is usually annealed in a humid environment to obtain large-sized grains. However, the uncontrollable crystallization of complex solution components and moisture-induced degradation result in poor crystalline quality of the perovskite layer. In this work, a novel hydrolysis-triggered intelligent passivation of inert precursor (HTIPIP) strategy is proposed. Specifically, the inert precursor 3-(trifluoromethyl)phenylboronic acid pinacol ester (3-CF3-PhBpin) in the perovskite solution is in situ hydrolyzed to 3-(trifluoromethyl) phenylboronic acid (3-CF3-PhB(OH)2), which acts as a strong Lewis acid to precisely and on-demand passivate the defects generated during the crystallization process, while the -CF3 group simultaneously provides hydrophobic protection. This strategy converts the notorious water-induced crystallization damage of perovskite films into a chemical reaction driving force for improving the crystallization quality. Therefore, the rigid and flexible n-i-p perovskite solar cells fabricated based on this strategy achieved power conversion efficiencies (PCE) of 26.25% and 24.80%, respectively, and also realized significant improvements in operational stability. This work elucidates a new molecular design paradigm of actively adapting to and intelligently utilizing the processing environment, which provides critical support for the ambient-compatible manufacturing of large-scale perovskite photovoltaics.
The remarkable mechanical properties of silk fibroin originate from its hierarchical fibrous architecture spanning multiple length scales; however, how these intricate networks precisely govern macroscopic mechanical behavior remains incompletely understood. Here, experimental characterization with computational modeling is integrated to elucidate the structural and molecular mechanisms underpinning silk fibril network formation and mechanical function. High-resolution imaging coupled with deep-learning-based morphological extraction enables precise quantification of critical architectural features within the networks. Coarse-grained molecular dynamics simulations reveal that network mechanical properties and stability are predominantly governed by interfibrillar interaction strengths, with hydrophobic forces identified as the primary molecular drivers of fibril bundling. Specifically, weak interfibrillar cohesive interactions result in flexible and deformable networks under applied stresses, whereas strong interactions induce excessive fibril aggregation, reducing structural adaptability and leading to premature mechanical failure. Simulations under spatially confined conditions, mimicking natural spinning processes, further clarify mechanisms essential for fibril alignment. This study significantly advances the fundamental understanding of silk's structure-property relationships, providing valuable guidelines for designing and precisely controlling silk-based materials for biomedical and structural engineering applications.
Bacterial biofilms shield embedded cells behind extracellular polymeric substance (EPS) barriers, frustrate antibiotic penetration, and protect persisters, demanding materials that show broad antimicrobial activity coupled with efficient biofilm clearance. We establish a design framework for host defense peptide (HDP) mimics using poly(alpha-amino acid) copolymers with a cationic lysine backbone (degree of polymerization approximate to 20) and tunable hydrophobic modules-valine (Val), norvaline (Nva), phenylalanine (Phe), and N-epsilon-carbobenzoxy-lysine (CBL). Random ring-opening copolymerization of alpha-amino acid N-carboxyanhydride (NCA) (0-60% hydrophobic feed) yields amphiphilic libraries whose composition programs the secondary structure: Val biases beta-sheet formation, high Nva favors alpha-helices, Phe promotes ordered states via pi-pi stacking, and CBL side-chain amides build stabilizing hydrogen-bond networks. Across MIC/MBC testing, S. aureus and P. aeruginosa exhibit distinct requirements: the cationic charge density is the primary determinant for penetrating EPS and clearing mature Gram-positive biofilms, whereas moderate hydrophobicity-notably Nva and CBL-optimizes activity against Gram-negative pathogens by balancing the solubility, membrane affinity, and EPS interactions. Self-assembly refines performance further; nanoscale aggregates with elevated surface potential (e.g., Lys60CBL40) deepen penetration and accelerate persister eradication. Critically, the antibacterial potency against planktonic cells does not predict the antibiofilm efficacy, revealing mechanistic decoupling that necessitates independent tuning. These results deliver a quantitative structure-function map and actionable rules for engineering amphiphilic polymers that recapitulate the functional hallmarks of HDPs, enabling simultaneous planktonic killing and robust clearance of mature biofilms and offering promising candidates for multidrug-resistant, biofilm-associated infections.
ABSTRACT The chemical imperative of surface passivation for perovskite solar cells (PSCs) is hindered by the non‐complementary mechanisms employed by current aliphatic and aromatic ammonium halides. Even the widely used aromatic passivator 2‑(4‑fluorophenyl)ethylammonium iodide (FPEAI) faces efficiency limitations due to residual lead defects and interfacial charge‑transport barriers. Through mechanistic analysis of the functional moieties in FPEAI, we designed and synthesized novel passivation molecules, elucidating the respective roles of lead‑chelation, π‑conjugation, and steric hindrance in defect suppression. The optimized molecule 2‐(methylthio)ethoxy‐p‐phenylene ethylammonium iodide (OSPEAI) forms a coordinative cage‑like architecture around Pb 2 + sites via synergistic aliphatic‑chain and benzene‑ring interactions, effectively passivating lead‑related defects and inhibiting non‑radiative recombination. As a result, OSPEAI‑modified PSCs achieved a power conversion efficiency of 26.35% with enhanced operational stability, offering innovative molecular‑design insights for chemical passivation in perovskite photovoltaics.
The instability of metal halide perovskites (PVKs) is a major obstacle to the commercialization of perovskite solar cells (PSCs). While (111)-faceted PVKs exhibit inherent stability, the commonly observed coexisting (100) facets are prone to degradation. Here, we introduce tris(4-formylphenyl)amine (TFPA) into the FAPbI3 PVK. Calculations predict TFPA can preferentially bind onto the (100) facets, increasing the energy barrier for phase transition from alpha-FAPbI3 to delta-phase, and thus stabilizing the PVK structure. In situ grazing-incidence wide-angle X-ray scattering data show that TFPA alters crystal growth to favor (111) facets with face-on orientation. Electron microscopy characterizations reveal that TFPA predominantly localizes at grain boundaries, aligning PVK crystals and suppressing phase transition. Time-resolved terahertz (THz) emission spectroscopy identifies an additional polaron mode that enhances charge carrier transport. TFPA-doped devices achieve a record efficiency of 26.4% (certified 26.1%) for (111) facet-dominated PSCs and retain 96.5% of their initial efficiency after 1,100 h of continuous operation under 1 sun illumination at 65 degrees C.
Flexible perovskite solar cells (FPSCs) exhibit significant potential for applications in wearable and portable electronics, yet they are inherently constrained by insufficient mechanical deformation tolerance and suboptimal charge transport properties. Despite diverse strategies pursued to address these challenges, fundamental solutions have remained elusive. In this study, these limitations are overcome through a ligand-assisted heterointerface growth equilibration (HGE) strategy that synchronizes nucleation and extends the growth window across heterointerfaces, leading to synergistic perovskite crystallization. This approach contributes to high-quality films characterized by reduced buried voids, enhanced fracture energy, significantly lowered residual stress, and improved elastic compliance, thereby intrinsically toughening the perovskite material and substantially boosting mechanical durability. The resulting FPSCs achieve an impressive power conversion efficiency (PCE) of 25.76%, alongside exceptional flexibility, retaining over 90% of their initial PCE after 30 000 bending cycles at a 4 mm radius. Notably, this represents the best bending performance reported to date for >= 25.5% perovskite-based flexible photovoltaics. The application of the ISOS-LM-1 standard is also pioneered under light-mechanical coupling conditions to evaluate operational stability in FPSCs. This work highlights the critical importance of intrinsic crystallinity and mechanical modulations in perovskites, providing a viable pathway toward highly efficient and mechanically robust flexible photovoltaics.
Carbapenem-resistant Klebsiella pneumoniae (CRKP) has emerged as a critical global health threat, often causing life-threatening infections with limited therapeutic options. Polymyxins are often used as the last-line agent, but its efficacy is limited by heteroresistance-where resistant subpopulations emerge during treatment. To combat this, we evaluated the synergistic activity of colistin combined with nitroxoline against polymyxin heteroresistant (PHR) CRKP subpopulations. The prevalence of PHR was 90.9
Corneal neovascularization (CoNV) is a primary contributor to corneal scarring and vision impairment. During its initiation and progression, inflammatory reactions and oxidative stress synergistically trigger a pathological vicious cycle of oxidative stress, inflammation, and angiogenesis, posing a severe therapeutic challenge. In this study, a noninvasive transepithelial therapeutic strategy using ultrasmall polydopamine nanoparticles (UPDA NPs) with triple effects is developed. Their unique small size, approximately 3 nm, greatly enhances their radical-scavenging capability and facilitates superior transepithelial delivery. Extensive research demonstrated that the obtained UPDA NPs possess excellent anti-inflammatory, antioxidant, and anti-angiogenic properties. By scavenging reactive oxygen species (ROS), activating the nuclear factor erythroid 2-related factor 2 (NRF2) antioxidant pathway, and suppressing multiple proangiogenic signaling cascades, they can disrupt the pathological cycle of inflammation, oxidative stress, and neovascularization at molecular, cellular, and animal levels. In an alkali-burned mouse model, UPDA NPs notably reduce CoNV area and length, accelerate corneal repair, and exhibit no local or systemic toxicity, providing a new nanomedicine with translational potential for precise treatment of CoNV.
Compositional segregation resulting from non-uniform crystallization remains a critical bottleneck limiting the performance of wide-bandgap (WBG) mixed-halide perovskite photovoltaics. Herein, we report a halide-specific coordination strategy by employing a eutectic molecule to stop the phase segregation in WBG perovskites. Owing to the differential affinity of stronger for bromine-based octahedra than iodine-based ones, the urea phosphate molecule acts as a molecular pacemaker synchronizing the crystallization of disparate perovskite phases. This strategy successfully eliminates vertical and lateral phase segregation within the films, leading to a substantial reduction in non-radiative recombination and charge transport losses. Consequently, the champion perovskite photovoltaic devices present a power conversion efficiency (PCE) of 22.27% under AM 1.5G illumination and a promising indoor PCE of 42.64% under 1000 lux. The finding offers a robust paradigm to fabricate high-quality WBG photovoltaic perovskites for indoor energy harvesting in the Internet of Things.
Over 400,000 anterior cruciate ligament (ACL) reconstructions are performed worldwide annually. The ability of patients to return to their pre-injury or adapted level remains limited. Although autografts and allografts are recognized as good choices for ACL reconstruction, postoperative complications are frequently reported. The emergence of artificial ligaments offers a promising strategy to solve these challenging medical conditions. However, artificial grafts composed of different materials have been associated with complications such as chronic effusions, synovitis, and graft failure to varying degrees. Although great progress has been made in modifying artificial grafts, the optimal strategy remains to be explored. Magnesium and recombinant spidroin have been proven to be promising implantable materials that can facilitate osteogenesis both in vitro and in vivo, thus exhibiting good potential for orthopaedic implants or grafts. In this study, a novel nano-to-macroscale dual core-shell structured bioartificial ligament integrating magnesium and recombinant spidroin has been developed using conjugate coaxial electrospinning. This innovative graft promoted graft-bone integration by facilitating early expression of osteogenic, neurogenic, and cell adhesion markers (e.g., BMP2, RUNX2, CGRP, and ITGA5) at the interface and accelerating new bone mineralization around the bone tunnel. These effects resulted in improved healing outcomes after ACL reconstruction in a rat model, suggesting significant clinical potential for future ACL applications.