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NanoManufacturing

Michael De Volder, Engineering Department - IfM
 
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Table of Contents for Advanced Materials. List of articles from both the latest and EarlyView issues.
Updated: 1 day 17 hours ago

eg Electron Occupancy as a Descriptor for Designing Iron Single‐Atom Electrocatalysts

Mon, 28/04/2025 - 10:10

An e g electron occupancy descriptor for Fe-N-C is proposed to link the reaction rate of the electrocatalytic reduction reaction. This descriptor provides guidelines for the rational design of single-atom catalysts for the ORR as well as various other processes, showing great promise for advancing metal-air batteries to practical applications.


Abstract

A quantitative electronic structure-performance relationship is highly desired for the design of single-atom catalysts (SACs). The Fe single-atom catalysts supported by ordered mesoporous carbon with the e g electron occupancy from 1.7 to 0.7 are synthesized. A linear relationship has been established between the e g electron occupancy of the Fe site and the catalytic activity/activation entropy of oxygen-related intermediates. Fe SAC with an e g electron occupancy of 0.7 alters the rate determining step from *OH desorption to *OOH formation. The value of the turn-over frequency is ≈28 times that of the Fe SAC site with an e g electron occupancy of 1.7 e, and the mass activity is ≈6.3 times that of commercial Pt/C. When used in a zinc–air battery, the Fe SAC gives a remarkable power density of 196.3 mW cm−2 and a long-term stability exceeding 1500 h. The discovery of e g electron occupancy descriptor provides valuable insights for designing single-atom electrocatalysts.

Efficient Low‐temperature Ammonia Cracking Enabled by Strained Heterostructure Interfaces on Ru‐free Catalyst

Mon, 28/04/2025 - 10:09

Leveraging the strong metal-support interaction effect, heterostructured interfaces in a Co-based catalyst are designed to enable low-temperature ammonia (NH3) decomposition. The induced tensile lattice strain within the core-shell structure modulates d-band center of Co, enhancing NH3 adsorption and facilitating N─H bond dissociation. Furthermore, the dynamic lattice strain release and restoration mechanism promotes NH3 dehydrogenation and by-product desorption, effectively optimizing the reaction pathway and ensuring sustained catalytic activity.


Abstract

Ammonia (NH3) has emerged as a promising liquid carrier for hydrogen (H2) storage. However, its widespread adoption in H2 technology is impeded by the reliance on costly Ru catalysts for low-temperature NH3 cracking reaction. Here, a strained heterostructure Co@BaAl2O4−x core@shell catalyst is reported that demonstrates catalytic performance at low reaction temperatures comparable to most Ru-based catalysts. This catalyst exhibits exceptional activity across a range of space velocity conditions, maintaining high conversion rates at 475 to 575 °C and achieving an impressive H2 production rate of 64.6 mmol H2 gcat −1 min−1. Synchrotron X-ray absorption spectroscopy, synchrotron X-ray diffraction, and kinetic studies are carried out to elucidate the dynamic changes of the strained heterostructure interface of Co-core and BaAl2O4−x-overlayer under catalytic working conditions. The performance enhancement mechanisms are attributed to the tensile strained Co surface encapsulated in the defective BaAl2O4−x, which enhances NH3 adsorption and facilitates the rate-determining N─H dissociation. Furthermore, the strain release and restoration during NH3 dehydrogenation enable efficient nitrogen desorption, preventing active site poisoning. This work highlights the effectiveness of lattice strain engineering and the development of synergistic strong metal-support interfaces between active metal nanoparticles and oxide support to boost low-temperature NH3 cracking.

Electric‐Field‐Driven Reversal of Ferromagnetism in (110)‐Oriented, Single Phase, Multiferroic Co‐Substituted BiFeO3 Thin Films

Mon, 28/04/2025 - 09:39

Electric-field-induced magnetization reversal is a long-sought-after achievement in materials engineering for use in next-generation, ultra-low power consumption memory devices. This work demonstrates fully electric-field-driven switching of the out-of-plane component of magnetization in (110)-oriented Co-substituted BiFeO3 thin films at room temperature, enabled through careful engineering of thin film boundary conditions and crystallography.


Abstract

While multiferroic materials are attractive systems for the promise of ultra-low-power-consumption computational technologies, electric-field-induced magnetization reversal is a key challenge for realizing devices at scale. Though significant research efforts have been working toward the realization of a material which couples ferroelectricity and ferromagnetism, there are few, even composite, systems which are practical for device scale applications at room temperature. Co-substituted multiferroic BiFe0.9Co0.1O3 is a promising candidate system, due to coupled ferroelectricity and weak ferromagnetism at room temperature. Here, it is theoretically indicated that the ferroic orders in this material are statically coupled, where an in-plane 109° ferroelectric switching event can result in the reversal of this out-of-plane component of magnetization, and the electric field-induced magnetization reversal is experimentally observed. Such an in-plane poling configuration is particularly desirable for device applications.

Hybrid Formative‐Additive Manufacturing

Mon, 28/04/2025 - 09:35

Hybrid Formative-Additive Manufacturing (HyFAM) integrates formative processes into additive manufacturing. HyFAM 3D-prints exterior walls and complex geometries, then formatively fills interior material. By tuning rheological properties, the study can achieve both 3D-printable ink and self-leveling, moldable ink of the same material. HyFAM speeds up part production and eliminates internal defects by replacing interior 3D-printed sections with bulk-filled material.


Abstract

Material extrusion additive manufacturing (AM) provides extensive design flexibility and exceptional material versatility, enabling the fabrication of complex, multifunctional objects ranging from embedded electronics to soft robotics and vascularized tissues. The bottom-up creation of these objects typically requires discretization into layers and voxels. However, the voxel size, determined by the nozzle diameter, limits extrusion rate, creating a conflict between resolution and speed. To address these inherent scalability challenges, the study proposes a hybrid formative-additive manufacturing technology that combines the respective strengths of each method—speed and quality with complexity and flexibility. The approach involves 3D-printing complex geometries, multimaterial features, and bounding walls of bulky, lower-resolution volumes, which are rapidly filled via casting or molding. By precisely controlling the materials’ rheological properties—while maintaining similar solidified properties and high interfacial strength—several typical AM flaws, such as bulging and internal voids, are eliminated, achieving exponentially faster production speeds for objects with varying feature sizes.

Modulating Crystal Growth with Sacrificial Coordination for High‐Performance Perovskite Solar Cells via Intense Pulsed Light Annealing

Mon, 28/04/2025 - 09:35

DodecylMSO, a sacrificial Lewis base additive, modulates perovskite crystallization during intense pulsed light annealing by strongly binding PbI₂ and volatilizing at high temperatures. This results in larger grains, lower defect density, and minimum trace residues, achieving the highest efficiency in its class.


Abstract

Intense pulsed light (IPL) annealing has emerged as a transformative technology for the high-throughput, low-cost fabrication of perovskite films, enabling the rapid conversion of precursor wet films into perovskite films within milliseconds. Despite their potential, the efficiencies of IPL-processed devices have yet to match those achieved through conventional thermal annealing (TA), primarily due to the challenges of uncontrolled crystallization and defect formation during the IPL process. In this study, a solid Lewis base additive, dodecyl methyl sulfoxide (DodecylMSO) is introduced, to modulate perovskite crystal growth and improve film morphology and uniformity under IPL conditions. DodecylMSO acts as a sacrificial additive, with X-ray photoelectron spectroscopy (XPS) confirming the majority of it is removed in the final films. Compared to the control films, DodecylMSO-modified films exhibited significantly reduced defect densities and enhanced carrier extraction and transport properties. Leveraging this approach, p-i-n perovskite solar cells (PSCs) is demonstrated with a champion power conversion efficiency of 23.5% fabricated via IPL. This sacrificial coordination strategy not only addresses key challenges in IPL processing but also opens new avenues for advancing the manufacturability and scalability of high-performance PSCs.

Luminescent Liquid Crystalline Elastomer Promoted Self‐Adaptive Smart Active Optical Waveguide with Ultra‐Low Optical Loss

Mon, 28/04/2025 - 09:30

Smart optical waveguides with ultra-low optical loss have been fabricated using luminescent liquid crystalline elastomers. These waveguides exhibit excellent self-adaptive properties, making them promising for integrated photonic systems enabling low-loss, high-speed data transmission.


Abstract

Currently, optical waveguides show extensive application in photonics and optoelectronic devices due to their high information capacity and transmission capabilities. However, developing self-adaptive, smart optical waveguide materials with ultra-low optical loss remains a significant challenge. To address this issue, luminescent liquid crystalline elastomers (LLCEs) with remarkable flexibility and minimal optical loss through one-pot synthetic method is synthesized, marking the first example of such an approach. The resultant organic optical waveguide materials (OOWMs) demonstrate exceptional mechanical performance and low optical loss, even under significant deformation. An optical loss coefficient of 0.0375 dB mm−1 has been achieved in LLCE-based OOWMs through synergistic Förster resonance energy transfer. Additionally, these flexible OOWMs can endure large deformations and be shaped into arbitrary forms within macro-scale dimensions. Notably, LLCE-based OOWMs demonstrate smart, self-adaptive behavior with ultra-low optical loss when exposed to heat or light. Consequently, these OOWMs can be used to fabricate photo switches of various shapes. This work provides a feasible approach to achieving integrated photonic systems with low optical loss for intelligent high-speed data transmission.

Highly Coupled Dynamically Modulated Electrocatalysts on Wafer‐Scale InGaN/GaN Nanowires on Silicon for Successive Acidic Photoelectrochemical Water Oxidation

Mon, 28/04/2025 - 09:25

The sluggish water oxidation kinetics on photoanodes under strongly acidic conditions not only limit the photocurrent but also induce severe photocorrosion. Here, loading a CoRuOX cocatalyst—exhibiting a unique dynamic electron modulation effect—onto wafer-scale InGaN nanowires achieves a dual breakthrough in both oxidation activity and stability for photoelectrochemical (PEC) water oxidation under strongly acidic conditions. This strategy offers a promising pathway for sustained PEC water oxidation in acidic environments.


Abstract

Photoelectrochemical water splitting is considered one of the most promising paths for sustainable hydrogen production. However, the sluggish kinetics of the water oxidation reaction and poor stability of the photoanode significantly limit the overall performance of the photoelectrochemical device, particularly under acidic conditions, which poses great challenges for practical applications. Herein, the coupling of unique CoRuOx nanoclusters with dynamic electronic modulation effects to wafer-scale InGaN nanowires is proposed, demonstrating superior photoelectrochemical activity and stability for acidic water oxidation. Compared with InGaN nanowires loaded with typical RuO₂ cocatalysts, CoRuOx/InGaN photoanodes achieve a remarkable improvement in applied bias photon-to-current efficiency from 0.77% to 2.25%, with stable operation for over 500 min under strongly acidic conditions. Such boosted performance is attributed mainly to Co induced dynamic electronic modulation, which enhances oxygen evolution while maintaining the stable operation of CoRuOx/InGaN photoanodes. Initially, the Co sites increased the oxidation state of Ru, enhancing the activity of oxygen evolution. Moreover, during PEC operation, the Co sites stabilized the Ru sites, preventing dissolution of cocatalyst. This unique self-adaptive process significantly enhances the stability and activity of the photoanode, opening an effective avenue to achieve efficient and durable photoanodes for PEC applications.

Material Selection and Device Design of Scalable Flexible Brain‐Computer Interfaces: A Balance Between Electrical and Mechanical Performance

Mon, 28/04/2025 - 09:15

This review explores the balance between electrical and mechanical performance of flexible BCIs through the careful selection of electronic materials and probe design to achieve long-term stable neural recordings with high signal-to-noise ratios.


Abstract

Brain-computer interfaces (BCIs) hold the potential to revolutionize brain function restoration, enhance human capability, and advance our understanding of cognitive mechanisms by directly linking neural signals with hardware. However, the mechanical mismatch between conventional rigid BCIs and soft brain tissue limits long-term interface stability. Next-generation BCIs must achieve long-term biocompatibility while maintaining high performance, enabling the integration of millions of sensors within tissue-level flexible and soft, stable neural interfaces. Lithographic fabrication techniques provide scalable thin-film flexible electronics, but traditional electronic materials often fail to meet the unique requirements of BCIs. This review examines the selection of materials and device design for flexible BCIs, starting with an analysis of intrinsic material properties—Young's modulus, electrical conductivity and dielectric constant. It then explores the integration of material selection with electrode design to optimize electrical circuits and assess key mechanical factors. Next, the correlation between electrical and mechanical performance is analyzed to guide material selection and device design. Finally, recent advances in neural probes are reviewed, highlighting improvements in signal quality, recording stability, and scalability. This review focuses on scalable, lithography-based BCIs, aiming to identify optimal materials and designs for long-term, reliable neural recordings.

Spectrally Engineered Coatings for Steering the Solar Photons

Sat, 26/04/2025 - 11:21

Spectrum-splitting energy synergy: a spectrally engineered radiative cooling (RC) coating with photoluminescence is integrated with bifacial photovoltaic (biPV) panels to construct a hybrid biPV-RC system. By controlling solar photon conversion pathways and guiding light transport, the system enables synergistic power generation and daytime radiative cooling, offering a scalable solution for carbon-neutral buildings.


Abstract

The spectral properties of radiative cooling (RC) and photovoltaic (PV) govern their capacity to utilize solar photons at distinct energy levels. However, spectral mismatches with the solar spectrum result in significant inefficiencies: non-photovoltaic heat losses in PV panels and wasted energy from reflected solar radiation in RC systems. To address this, a photoluminescent RC coating with spectrally selective reflectivity is developed to be integrated it with bifacial photovoltaic (biPV) panels. The high reflectivity of the RC coating directs photons to the rear side of the PV panels, while its spectral selectivity optimizes the energy distribution of photons reaching the rear side, resulting in a 32% increase in the overall power output of the bifacial PV system. Additionally, the incorporation of photoluminescent materials enables the conversion of absorbed photons into luminescence rather than heat by suppressing non-radiative transitions. This reduces effective solar absorption by 14% and enhances radiative cooling performance. Simulated urban rooftop deployment demonstrates that this dual-harvesting system meet ≈18.1% of Hong Kong's annual electricity demand, offering a scalable pathway toward carbon-neutral cities.

Organic Solar Cell with Efficiency of 20.49% Enabled by Solid Additive and Non‐Halogenated Solvent

Sat, 26/04/2025 - 11:11

This work proposes a feasible solid additive strategy to enhance the performance of organic solar cells. The 4-nitro-benzonitrile (NBN)-treated device owned enhanced molecular crystallinity, more efficient exciton dissociation, suppressed charge recombination, and more favorable morphology. Record efficiency of 20.22% and 20.49% are obtained in binary and ternary devices processed by non-halogenated solvent. NBN is applicable to multiple efficient systems.


Abstract

Recently, benzene-based solid additives (BSAs) have emerged as pivotal components in modulating the morphology of the blend film in organic solar cells (OSCs). However, since almost all substituents on BSAs are weak electron-withdrawing groups and contain halogen atoms, the study of BSAs with non-halogenated strong electron-withdrawing groups has received little attention. Herein, an additive strategy is proposed, involving the incorporation of non-halogenated strong electron-withdrawing groups on the benzene ring. An effective BSA, 4-nitro-benzonitrile (NBN), is selected to boost the efficiency of devices. The results demonstrate that the NBN-treated device exhibits enhanced light absorption, superior charge transport performance, mitigated charge recombination, and more optimal morphology compared to the additive-free OSC. Consequently, the D18:BTP-eC9+NBN-based binary device and D18:L8-BO:BTP-eC9+NBN-based ternary OSC processed by non-halogenated solvent achieved outstanding efficiencies of 20.22% and 20.49%, respectively. Furthermore, the universality of NBN is also confirmed in different active layer systems. In conclusion, this work demonstrates that the introduction of non-halogenated strong electron-absorbing moieties on the benzene ring is a promising approach to design BSAs, which can tune the film morphology and achieve highly efficient devices, and has certain guiding significance for the development of BSAs.

Screening Natural Cholesterol Analogs to Assemble Self‐Adjuvant Lipid Nanoparticles for Antigens Tagging Guided Therapeutic Tumor Vaccine

Sat, 26/04/2025 - 11:07

Cholesterol analogs ginsenosides-Rg3 are screened to assemble lipid nanoparticles, which can deliver nucleic acid antigens to tumors and lymph nodes for antigens tagging tumor cells and dendritic cells activation, thus guiding CTL to accurately recognize and kill tumor cells. Besides, ginsenosides-Rg3 can reshape tumor microenvironment by inhibiting STAT3. Collectively, this work has great clinical value for immune-escaping tumors.


Abstract

The clinical progress of tumor nucleotide vaccines is limited due to insufficient recognition and killing of tumor cells with low antigen expression by cytotoxic T lymphocytes (CTL). Here, natural cholesterol analogs are screened to assemble self-adjuvant lipid nanoparticles (LNPs) for antigens tagging tumor cells and dendritic cells (DC) activation. First, a library of ginsenosides are collected, and then screened according to their anti-tumor immunity. Then, ginsenoside-Rg3 based-LNPs loaded with antigens (Rg3-LNPs) are identified as the optimal formulation by investigating the physicochemical and biological properties. Finally, Rg3-LNPs and granulocyte-macrophage colony-stimulating factor (GM-CSF) are co-loaded into a macroporous hydrogel for long-term immune response. Rg3-LNPs could accumulate into both tumors and LNs. Rg3-LNPs targeted tumor cells with high glucose transporter-1 expression via the targeting ligand Rg3, and anchored antigens on the tumor cell surface, thus promoting the recognition of CTL to tumor cells; Rg3-LNPs can accumulate into the LNs to promote DC activation and antigen presentation, thus stimulating CTL activation. Besides, Rg3, as an adjuvant, cooperated with GM-CSF to remodel the tumor microenvironment, thus promoting the killing of CTL to tumor cells. Collectively, this work highlights the importance of tagging antigens to tumor cells in tumor vaccine and has great clinical value for immune-escaping tumors.

Gold‐Autocatalyzed Synthesis of Multi‐Element Nanoparticles

Sat, 26/04/2025 - 11:04

This work develops a simple and controllable gold-autocatalyzed synthesis method to incorporate multiple metal elements into a single-phase multi-element nanoparticle regardless of its immiscibility at room temperature. This reaction occurs among molecules and can be predicted according to frontier molecular orbital theory.


Abstract

The incorporation of multiple metal elements into a nanoparticle without phase separation holds promise for versatile applications, yet a facile synthetic strategy is lacking. Herein, a simple and facile approach is presented, i.e., gold-autocatalyzed synthesis, in which multiple miscible or immiscible metal elements are incorporated into single-phase nanoparticles at atmospheric pressure and temperature. This study reveals the autocatalytic reduction behavior of gold and the corresponding growth process of multi-element alloy nanoparticles. The mechanism of autocatalytic synthetic reactions is revealed on the basis of molecular orbitals. Furthermore, quinary multi-element nanoparticles were prepared and applied as high-performance electrocatalysts for the hydrogen evolution reaction in alkaline electrolytes (with overpotentials of 24 and 42 mV to deliver 10 and 100 mA cm−2, respectively) to demonstrate the application of this strategy. This strategy enables the synthesis of multi-element materials with high tolerance of synthetic conditions for versatile applications.

Bioxolography Using Diphenyliodonium Chloride and N‐Vinylpyrrolidone Enables Rapid High‐Resolution Volumetric 3D Printing of Spatially Encoded Living Matter

Sat, 26/04/2025 - 11:01

Bioxolography, a novel volumetric 3D-bioprinting technique, enables rapid and high-resolution fabrication of >1 cm3 engineered living materials. A newly developed three-component photoinitiator system significantly enhances the photoreactivity of gelatin methacryloyl-based bioresins, allowing for precise xolographic bioprinting. This platform supports multimaterial printing, concentration-controlled molecular patterning, and grayscale-mediated mechanical modulation to create complex, biomimetic, and spatially controlled architectures.


Abstract

Light-based volumetric bioprinting enables fabrication of cubic centimeter-sized living materials with micrometer resolution in minutes. Xolography is a light sheet-based volumetric printing technology that offers unprecedented volumetric generation rates and print resolutions for hard plastics. However, the limited solubility and reactivity of current dual-color photoinitiators (DCPIs) in aqueous media have hindered their application for high-resolution bioprinting of living matter. Here, we present a novel three-component formulation that drastically improves photoreactivity and thereby enables high-resolution, rapid, and cytocompatible Xolographic biofabrication of intricately architected yet mechanically robust living materials. To achieve this, various relevant additives are systematically explored, which revealed that diphenyliodonium chloride and N-vinylpyrrolidone strongly enhance D-mediated photoreactivity, as confirmed by dual-color photo-rheology. This enables Xolographic bioprinting of gelatin methacryloyl-based bioresins, producing >1 cm3 constructs at ≈20 µm positive and 125 µm negative resolution within minutes. Multimaterial printing, molecular patterning, and grayscale-mediated mechanical patterning are explored to programmably create intricate, biomimetic, and concentration-controlled architectures. We demonstrate the Bioxolographic printing of various cell types, showing excellent cell viability, compatibility with long-term culture, and ability for nascent protein deposition. These results position Bioxolography as a transformative platform for rapid, scalable, high-resolution fabrication of functional living materials with encoded chemical and mechanical properties.

Hybrid Additive Manufacturing of Shear‐Stiffening Elastomer Composites for Enhanced Mechanical Properties and Intelligent Wearable Applications

Sat, 26/04/2025 - 11:01

To achieve anisotropic structural design of shear stiffening materials, a novel hybrid additive manufacturing strategy is proposed to create a lattice-structured soft-hard phase elastomer composite (TPR-SSE composite) with enhanced mechanical properties. Based on this, an intelligent sports shoe is developed, demonstrating the potential application of the TPR-SSE composite material in wearable smart protective equipment.


Abstract

Shear-stiffening materials, renowned for their rate-dependent behavior, hold immense potential for impact-resistant applications but are often constrained by limited load-bearing capacity under extreme conditions. In this study, a novel hybrid additive manufacturing strategy that successfully achieves anisotropic structural design of shear-stiffening materials is proposed. In this strategy, fused deposition modeling (FDM) is synergistically combined with direct ink writing (DIW) to fabricate lattice-structured soft-hard phase elastomer composites (TPR-SSE composites) with enhanced mechanical properties. Through quasistatic characterization and dynamic impact experiments, complemented by noncontact optical measurement and finite element simulation, the mechanical enhancement mechanisms imparted by the lattice architecture are systematically uncovered. The resulting composites exhibit exceptional load-bearing capacity under quasistatic conditions and superior energy dissipation under dynamic impacts, making them ideal for advanced protective systems. Building on this, smart sports shoes featuring a deep-learning-based smart sensing module that integrates structural customizability, buffering capacity, and gait recognition, are developed. This work provides a transformative structure design approach to shear-stiffening materials systems, paving the way for next-generation intelligent wearable protection applications.

Self‐Assembled Multilayered Concentric Supraparticle Architecture

Sat, 26/04/2025 - 11:01

This study introduces Self-Assembled Multilayered Supraparticle (SAMS), the first concentric lamellar spherical structures formed from synergistic interactions between gold nanoparticles, lipidoid, and gelatin. SAMS exhibits unique interlayer spacing, enabling efficient environment responsive delivery of labile payloads like siRNA and mRNA. This work advances complex supraparticle design leveraging self-limiting self-assembly and demonstrates potential applications in nanomedicine.


Abstract

Supraparticles (SPs) with unique properties are emerging as versatile platforms for applications in catalysis, photonics, and medicine. However, the synthesis of novel SPs with complex internal structures remains a challenge. Self-Assembled Multilayered Supraparticles (SAMS) presented here are composed of concentric lamellar spherical structures made from metallic nanoparticles, formed from a synergistic three-way interaction phenomenon between gold nanoparticles, lipidoid, and gelatin, exhibiting interlayer spacing of 3.5  ± 0.2 nm within a self-limited 156.8  ± 56.6 nm diameter. The formation is critically influenced by both physical (including nanoparticle size, lipidoid chain length) and chemical factors (including elemental composition, nanoparticle cap, and organic material), which collectively modulate the surface chemistry and hydrophobicity, affecting interparticle interactions. SAMS can efficiently deliver labile payloads such as siRNA, achieving dose-dependent silencing in vivo, while also showing potential for complex payloads such as mRNA. This work not only advances the field of SP design by introducing a new structure and interaction phenomenon but also demonstrates its potential in nanomedicine.

Rational Ligand Design of Conjugated Coordination Polymers for Efficient and Selective Nitrate Electroreduction to Ammonia

Sat, 26/04/2025 - 10:55

A conjugated coordination polymer (CoN4-pyrr) of single-atom cobalt coordinated with the nitrogen atom of pyrrole ligand can work as an electrocatalyst for efficient and selective nitrate (NO3 −) reduction to ammonia (NH3), where a fast transfer of hydrogen (*H) radicals is induced to accelerate the hydrogenation kinetics of *NO intermediate on the cobalt active site of CoN4-pyrr at the rate-determining step.


Abstract

Electrocatalytic nitrate reduction to ammonia (NRA) offers an attractive route for converting nitrate pollutants to ammonia under mild conditions. Among other catalysts, single-atom catalysts (SACs) with high metal-atom-utilization efficiency and low-coordinated metal sites hold immense potential to be extensively applied, which unfortunately encounter a formidable challenge to obtain simultaneous improvement of NRA activity and selectivity. Here, a novel and general strategy is reported to achieve efficient and selective NRA catalysis on conjugated coordination polymers featuring with high-density and well-defined nitrogen (N)-coordinated single-atom metal sites via precise regulation of N‑heterocyclic ligands toward accelerating the hydrogenation kinetics necessitated in the NRA pathway. Taking cobalt (Co) as an example, two CoN4-centered conjugated coordination polymer electrocatalysts (CoN4-pyrr and CoN4-pyri) are synthesized with pyrrole and pyridine ligands are investigated as a proof-of-concept study. As revealed, the CoN4-pyrr can markedly outperform the CoN4-pyri toward NRA electrocatalysis. Experimental and theoretical results suggest that, relative to the N atoms of pyridine ligand in CoN4-pyri, the N atoms of pyrrole ligand in CoN4-pyrr can enable a faster transfer of hydrogen radicals to the Co active sites for accelerating the hydrogenation kinetics of *NO intermediate at the rate-determining step of NRA pathway.

Microbial Photosynthetic Oxygenation and Radiotherapeutic Sensitization Enables Pyroptosis Induction for Combinatorial Cancer Therapy

Sat, 26/04/2025 - 10:55

This study reports the preparation of lanthanum oxide nanoparticles (La2O3 NPs) via a solid-phase synthesis method, combined with cyanobacteria (Cyan) to effectively alleviate hypoxia. These components are confined within the tumor microenvironment using a thermosensitive hydrogel, enhancing the sensitivity of radiotherapy for colorectal and lung cancers. By alleviating hypoxia through cyanobacteria-mediated photosynthetic oxygenation, La2O3 NPs not only promote reactive oxygen species (ROS) generation, triggering pyroptosis via GSDMD activation, but also amplify radiotherapy-induced pyroptosis mediated by GSDME. This dual mechanism provides a powerful strategy to overcome hypoxia-induced radiotherapy resistance in colorectal and lung cancers.


Abstract

Rectal cancer surgery is challenging due to the complex anatomy, making it difficult to achieve clear surgical margins. Radiotherapy (RT) plays a crucial role, especially in treating locally recurrent rectal cancer and preserving anal function. However, its effectiveness is often limited by tumor hypoxia, particularly prevalent in hypoxic regions near the bowel wall in colorectal cancer. Hypoxia contributes to both radiation resistance and apoptosis resistance, compromising RT outcomes. To overcome hypoxia-driven radiotherapy resistance, this work designs and engineers a radiotherapy-sensitizing bioplatform for efficient cancer RT. It combines lanthanum oxide nanoparticles (La2O3 NPs) with cyanobacteria, which produces oxygen through photosynthesis. This bioplatform uniquely reduces tumor hypoxia, enhances radiation deposition, and improves RT efficacy. La2O3 NPs further enhance reactive oxygen species (ROS) production induced by radiation, triggering pyroptosis via the ROS-NLRP3-GSDMD pathway, while RT amplifies pyroptosis through GSDME, circumventing tumor apoptosis resistance. The further integrated thermosensitive hydrogels ensure precise localization of the bioplatform, reducing systemic toxicity and improving therapeutic specificity. Compared to conventional therapies, this dual-action system addresses hypoxia, RT resistance, and apoptosis resistance more effectively. In vivo and in vitro hypoxia models validate its potent anti-tumor efficacy, offering valuable insights for refining clinical treatment paradigms.

Biomimetic Dynamics of Nanoscale Groove and Ridge Topography for Stem Cell Regulation

Sat, 26/04/2025 - 10:53

Dynamic nanoscale groove-ridge structures are engineered by flexibly conjugating RGD-magnetic nanoparticles to nanogroove templates with variable groove widths at the molecular scale. Magnetic control enables cyclic switching between nanoscale groove and ridge states that modulates ligand accessibility of cellular integrins. The ligands in the ridge state reversibly promote integrin recruitment, adhesion, and differentiation of stem cells in vivo.


Abstract

Native extracellular matrix exhibits multiscale groove and ridge structures that continuously change, such as collagen fibril-based nanogrooves in bone tissue, and regulate cellular responses. However, dynamic switching between groove and ridge nanostructures at the molecular level has not been demonstrated. Herein, materials capable of dynamic groove-ridge switching at tens-of-nanometers scale are developed by flexibly conjugating RGD-magnetically activatable nanoridges (MANs) to non-magnetic nanogrooves with independently tuned widths comparable to the sizes of integrin-presenting filopodia by modulating hydrophobicity in bicontinuous microemulsion, allowing for cyclic modulation of RGD accessibility and cellular adhesion. Nanogrooves with medium width restrict RGD accessibility in the “groove” state in which the RGD-MANs are buried, which is reversed by magnetically raising them to protrude and form the “ridge” state that fully exposes the RGDs. This reversibly stimulates integrin recruitment, focal adhesion complex assembly, mechanotransduction, and differentiation of stem cells in vivo. This is the first demonstration of molecular-level groove and ridge nanostructures that exhibit unprecedented switchability between groove and ridge nanostructures. Versatile tuning of the width, height, pitch, and shape of intricate nanogroove structures with remote manipulability can enlighten the understanding of molecular-scale cell–ligand interactions for stem cell engineering-based treatment of aging, injuries, and stress-related diseases.

Significantly Enhanced Density and Mechanical Strength of Carbon/Graphite Blocks by Waste Gas Pressurized Sintering

Sat, 26/04/2025 - 07:09

The waste gas generated during carbonization in an enclosed space forms a high internal pressure, thereby effectively promoting the polymerization and densification of the carbon block. This self-generated pressure, known as waste gas pressurization (WGP), ensures tighter bonding between carbon particles, lower porosity, and obviously higher mechanical strength without the participation of external gas or mechanical compression.


Abstract

Carbonization under pressure is crucial for enhancing carbon/graphite materials. However, conventional pressure sintering, relying on mechanical or external gas pressure, often results in incomplete densification and structural defects due to uncontrolled volatile gas release. Herein, high-density and high-strength self-sintered carbon block in enclosed-space (SCB-E) are produced using waste gas pressurization (WGP) derived from green petroleum coke (GPC). This method can enhance the formation of C─O─C and C═O bonds by promoting dehydration polymerization reaction, which induces interfacial bonding in the carbonization process. Consequently, a decreased mass loss, increased volume shrinkage, and reduced porosity are observed, thereby endowing the obtained SCB-E with significantly improved density and mechanical strength. Specifically, the compressive and flexural strengths of SCB-E are 6.36 and 5.77 times higher than SCB-O sintered in open-space, respectively, while the corresponding graphite block (SG-E) achieves 7.74 and 4.58 times greater compressive and flexural strengths than SG-O. Notably, WGP not only enhances the yield of crack-free carbon blocks and supports scale-up production but also integrates seamlessly with traditional kneading processes to produce high-density, high-strength carbon blocks (CB-E). The current approach offers an innovative and important platform for enhancing the density and mechanical properties of bulk materials.

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