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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: 33 min 10 sec ago

Biomimetic rhCOL17‐P334 Conjugate for Enhanced Wound Healing

Mon, 24/02/2025 - 06:11

This study presents a novel bioscaffold combining recombinant human collagen XVII (rhCOL17) with porphyra-334 (P334) to create a transparent, injectable hydrogel (GCP) for enhanced wound healing. GCP integrates extracellular matrix-like cues with UVA shielding properties, preventing fibroblast senescence and improving repair outcomes. This platform offers significant potential for advanced, protective wound management.


Abstract

Wound healing remains a significant global health challenge, affecting millions annually and imposing substantial economic burdens. Most commercially available biomaterials for wound management primarily address external symptoms, including hemostasis, exudation, scarring, and infection. Advanced biomaterials derived from endogenous molecules aim to better replicate the native wound microenvironment, promoting enhanced repair. Since wounds frequently occur on exposed skin, which is vulnerable to UVA radiation and requires protective yet invisible materials, traditional wound care products often lack these essential features. Inspired by natural UV protection mechanisms, a novel bioscaffold is developed using recombinant human collagen XVII (rhCOL17) crosslinked with porphyra-334 (P334) to improve wound healing under UVA exposure. The resulting rhCOL17-P334 conjugate integrates extracellular matrix (ECM)-like cues with UVA-shielding properties provided by P334. This conjugate is used to construct a transparent, injectable hydrogel combining gelatin methacryloyl (GelMA) and rhCOL17-P334 (GCP). GCP significantly inhibits UVA-induced fibroblast senescence and improves wound healing outcomes by targeting integrin α6β4 through rhCOL17. Its transparency facilitates convenient wound monitoring while also addressing the aesthetic requirement for invisibility. By combining UVA shielding with wound repair capabilities, GCP presents a promising platform for advanced wound management.

Nonlocal Conduction in a Metawire

Fri, 21/02/2025 - 12:44

A 1D metawire composed of twisted copper wires is designed and realized. This metamaterial exhibits pronounced effects of nonlocal electric conduction according to Ohm's law. The current at one location not only depends on the electric field at that location but also on other locations. As a result, the resistance of the metawire oscillates as a function of its length.


Abstract

Ohm's law of electric conduction is local in the sense that the current density at one position only depends on the electric field at that same position. For a nonlocal medium, the current density at one position depends on the electric field at other positions within the medium as well. As a result of Ohm's law, doubling the length of a wire doubles its resistance. Here, electrically conducting nonlocal architectures are discussed theoretically and experimentally for which changing the length of the metawire rather leads to a complex oscillatory behavior versus wire length. This oscillatory behavior is connected to local currents inside of the metawire flowing in the opposite direction than the externally applied field. The theoretical and experimental results for electric conduction can directly be transferred to thermal conduction or particle diffusion and may enable remote sensing applications.

Mechanosensitive and pH‐Gated Butterfly‐Shaped Artificial Ion Channel for High‐Selective K+ Transport and Cancer Cell Apoptosis

Fri, 21/02/2025 - 12:40

To advance the exploration of mechanisms underlying natural ion channels, this research presents a novel butterfly-shaped bionic K+ transmembrane channel GnC7 (n = 3, 4) with record-breaking K+/Na+ selectivity. The unique mobile channels constructed from poly (propylene imine) dendritic polymers and benzo-21-crown-7-ethers exhibit dual mechanical and pH responsiveness in liposomes/cells. Drastic G4C7-induced intracellular K+ efflux effectively activates mitochondrial- and ER-associated apoptosis.


Abstract

To advance the exploration of mechanisms underlying natural multi-gated ion channels, a novel butterfly-shaped biomimetic K+ channel GnC7 (n = 3, 4) is developed with dual mechanical and pH responsiveness, exhibiting unprecedented K+/Na+ selectivity (G3C7: 34.4; G4C7: 41.3). These channels constructed from poly(propylene imine) dendrimer and benzo-21-crown-7-ethers achieve high K+ transport activity (EC50: 0.72 µm for G3C7; 0.9 µm for G4C7) due to their arc-like mechanical rotation. The dynamic mode relies on butterfly-shaped topology derived from the highly symmetrical core and multiple intramolecular hydrogen bonds. GnC7 can sense mechanical stimulus applied to liposomes/cells and then adapt the K+ transport rate accordingly. Furthermore, reversible ON/OFF switching of K+ transport is realized through the pH-controllable host-guest complexation. G4C7-induced ultrafast cellular K+ efflux (70% within only 9 min) efficiently triggers mitochondrial-dependent apoptosis of cancer cells by provoking endoplasmic reticulum stress accompanied by drastic Ca2+ sparks. This work embodies a multi-dimensional regulation of channel functions; it will provide insights into the dynamic behaviors of biological analogs and promote the innovative design of artificial ion channels and therapeutic agents.

Generating Self‐Adjuvated Nanofiber Vaccines by Coating Bacterial Flagella with Antigens

Fri, 21/02/2025 - 12:39

Coating bacterial flagella with antigens is used as a versatile platform for developing self-adjuvated nanofiber vaccines. The resulting flagellum-based subunit vaccines with appealing features in prolonging tumor retention, recruiting adequate immune cells, and promoting cellular uptake of antigens and subsequent activation of antigen-presenting cells provide a unique paradigm for effective vaccination.


Abstract

Bacteria-based vaccines have received increasing attention given the ability to induce strong systemic immune responses. However, the application of bacteria as therapeutic agents inevitably suffers from infection-associated side effects due to the living characteristics. Here, the use of bacteria-derived flagella is described to construct self-adjuvated nanofiber vaccines. With the help of charge-reversal mediated by decoration with cationic polymers, the flagella can be coated with negatively charged antigens through electrostatic interaction. By virtue of the large aspect ratio, the resulting nanofiber vaccines show prolonged retention at the injection site and increased uptake by dendritic cells and macrophages. Thanks to the innate immunogenicity, self-adjuvated flagella robustly promote dendritic cell maturation and macrophage polarization, resulting in the elicitation of antigen-specific T-cell and B-cell immune responses. In ovalbumin-overexpressing melanoma-bearing mice, immunization with ovalbumin-carried vaccines not only exhibits a favorable tolerance, but also displays superior inhibition efficacies on tumor growth and metastasis separately under the therapeutic and prophylactic settings. The flexibility of this approach is further demonstrated for vaccine fabrication by coating with the SARS-CoV-2 Spike protein S1 subunit. Bacterial flagella-based self-adjuvated nanofiber platform proposes a versatile strategy to develop various vaccines for disease prevention and treatment.

Industrial‐current Ammonia Synthesis by Polarized Cuprous Cyanamide Coupled to Valorization of Glycerol at 4,000 mA cm−2

Fri, 21/02/2025 - 12:27

This work presents a membrane electrode assembly (MEA) system featuring Cu2NCN as an efficient nitrate reduction (NO3RR) electrocatalyst, coupled with glycerol oxidation for low-voltage, industrial-level NH3 production. Achieving 4000 mA cm−2 at 2.52 V with sustained stability at 1000 mA cm−2 over 100 h, the system offers 83% Faradaic efficiency, with theoretical insights on NO₃* adsorption and O–N bond cleavage.


Abstract

The electrocatalytic nitrate reduction (NO3RR) holds significance in both NH3 synthesis and nitrate contamination remediation. However, achieving industrial-scale current and high stability in membrane electrode assembly (MEA) electrolyzer remains challenging due to inherent high full-cell voltage for sluggish NO3RR and water oxidation. Here, Cu2NCN with positive surface electrostatic potential V S(r) is applied as highly efficient NO3RR electrocatalysts to achieve industrial-current and low-voltage stable NH3 production in MEA electrolyzer with coupled anodic glycerol oxidation. This paired electro-refinery (PER) system reaches 4000 mA cm−2 at 2.52 V and remains stable at industrial-level 1000 mA cm−2 for 100 h with the NH3 production rate of 97000 µgNH3 h−1 cm−2 and a Faradaic efficiency of 83%. Theoretical calculations elucidate that the asymmetric and electron-withdrawing [N−C≡N] units enhance polarization and V S (r), promoting robust and asymmetric adsorption of NO3 * on Cu2NCN to facilitate O−N bond dissociation. A comprehensive techno-economic analysis demonstrates the profitability and commercial viability of this coupled system. Our work opens a new avenue and marks a significant advancement in MEA systems for industrial NH3 synthesis.

Giant and Anisotropic Enhancement of Spin‐Charge Conversion in Graphene‐Based Quantum System

Fri, 21/02/2025 - 12:26

New magnetic Fe/Graphene/Pt double Rashba interface displays record spin-charge current interconversion efficiency at room temperature. The effect, which is anisotropic along the Γ-K and Γ-M directions, arises from the Direct and Inverse Edelstein mechanism in this new quantum epitaxial heterostructure.


Abstract

The ever-increasing demand for efficient data storage and processing has fueled the search for novel memory devices. By exploiting the spin-to-charge conversion phenomena, spintronics promises faster and low power solutions alternative to conventional electronics. In this work, a remarkable 34-fold increase in spin-to-charge current conversion is demonstrated when incorporating a 2D epitaxial graphene monolayer between iron and platinum layers by exploring spin-pumping on-chip devices. Furthermore, it is found that the spin conversion is also anisotropic. This enhancement and anisotropy is attributed to the asymmetric Rashba contributions driven by an unbalanced spin accumulation at the differently hybridized top and bottom graphene interfaces, as highlighted by ad-hoc first-principles theory. The improvement in spin-to-charge conversion as well as its anisotropy reveals the importance of interfaces in hybrid 2D-thin film systems, opening up new possibilities for engineering spin conversion in 2D materials, leading to potential advances in memory, logic applications, or unconventional computing.

Engineered Living Memory Microspheroid‐Based Archival File System for Random Accessible In Vivo DNA Storage

Fri, 21/02/2025 - 12:25

Efficient storage and retrieval of DNA (Deoxyribonucleic Acid) data while maintaining scalability and stability remain challenges in the field of molecular data storage. This study introduces Engineered Living Memory Microspheroids (ELMMs), which combine genetically modified microorganisms (GMMs) with matrix materials for DNA storage. The ELMM system improves random access and reduces data encapsulation time, offering scalable, closed-loop storage and reuse.


Abstract

Given its exceptional durability and high information density, deoxyribonucleic acid (DNA) has the potential to meet the escalating global demand for data storage if it can be stored efficiently and accessed randomly in exabyte-to-yottabyte-scale databases. Here, this work introduces the Engineered Living Memory Microspheroid (ELMM) as a novel material for DNA data storage, retrieval, and management. This work engineers a plasmid library and devises a random access strategy pairing plasmid function with DNA data in a key-value format. Each DNA segment is integrated with its corresponding plasmid, introduced into bacteria, and encapsulated within matrix material via droplet microfluidics within 5 min. ELMMs can be stored at room temperature following lyophilization and, upon rehydration, each type of ELMM exhibits specific functions expressed by the plasmids, allowing for physical differentiation based on these characteristics. This work demonstrates fluorescent expression as the plasmid function and employs fluorescence-based sorting access image files in a prototype database. By utilizing N optical channels, to retrieve 2 N file types, each with a minimum of 10 copies. ELMM offers a digital-to-biological information solution, ensuring the preservation, access, replication, and management of files within large-scale DNA databases.

Arylamine‐Linked Porous Organic Polymers with Abundant Redox‐Active Sites as High‐Capacity and High‐Rate Organic Cathodes for Lithium‐Ion Batteries

Fri, 21/02/2025 - 12:14

A series of novel arylamine-linked and bipolar porous organic polymers (POPs) are designed and prepared as organic cathode materials for lithium-ion batteries (LIBs). Benefiting from their high-density redox-active sites, bipolar feature, and arylamine linkage, these POPs exhibited high-capacity, high-rate, and excellent long-term cycling stability as organic cathode materials for LIBs.


Abstract

Redox-active porous organic polymers (POPs) have emerged as promising and sustainable organic cathode materials (OCMs) for lithium-ion batteries (LIBs). However, their performance is significantly limited by insufficient redox-active sites and low intrinsic conductivity. Herein, a series of novel arylamine-linked and bipolar POPs (denoted as HATN-AQ, HATN-BQ, HATN-CBD, and HATN-PTO) are designed and prepared as OCMs for LIBs. Benefiting from their high density of redox-active sites, bipolar feature, and arylamine linkage, these POPs exhibited high capacity, high rate, and excellent long-term cycling stability. Among them, HATN-PTO displayed an ultrahigh reversible capacity of 329.6 mAh g−1 at 0.2 A g−1 with a high energy density of 716.7 Wh kg−1, outstanding rate performance (208.7 mAh g−1 at 20 A g−1), and superior cycling stability (188.9 mAh g−1 capacity retained after 500 cycles at 1 A g−1). Furthermore, the HATN-PTO//graphite full battery exhibited a high specific capacity of 227.3 mAh g−1 at 0.2 A g−1 and maintained a high capacity of 99.1 mAh g−1 after 200 cycles at 0.5 A g−1. Ex situ FT-IR and XPS spectra combined with theoretical calculations are employed to elucidate the dual-ion storage mechanism. This work provides an effective strategy for designing POPs with high-capacity and high-rate for OCMs.

CuPt Alloy Enabling the Tandem Catalysis for Reduction of HCOOH and NO3− to Urea at High Current Density

Fri, 21/02/2025 - 12:09

Electrocatalytic liquid HCOOH and NO3 − synthesis of urea with high Faraday efficiency at high current density is successfully achieved by synthesizing the Cu4Pt tandem catalyst loaded on copper foam. The doped Pt sites can enrich liquid HCOOH reactants, promote HCOOH intermolecular dehydration, and form a large number of *CO key intermediates to lay the foundation for subsequent C─N coupling.


Abstract

The formation of urea by electrocatalytic reduction of C1-reactants and NO3 − is an attractive way to store renewable electricity, close the carbon cycle, and eliminate nitrate contaminants from wastewater. Involving insufficient supply of C1 reactants and multiple electron transfers makes the reaction difficult to achieve high Faraday efficiency and high yield at high current density. Here, a urea synthesis approach is presented via electrocatalytic reductive coupling between liquid HCOOH and NO3 − on copper foam (CF) loaded Cu4Pt catalyst with optimized ratios. A urea yield of 40.08 mg h−1 cm−2 is achieved with FE up to 58.1% at a current density of −502.3 mA cm−2, superior to the productivity of previously reported catalysts. No degradation is observed over 120-h continuous operation at such a high yield rate. The highly efficient activity of Cu4Pt/CF can be attributed to the synergetic effect between Pt and Cu sites via tandem catalysis, in which the doped Pt sites enrich liquid HCOOH reactants, promote HCOOH intermolecular dehydration, and form and adsorb large amounts of *CO key intermediates. The Cu sites can generate large quantities of the key intermediate *NH2. The Cu4Pt/CF adsorbed intermediates *CO and *NH2 are the basis for subsequent thermodynamic spontaneous C─N coupling.

High‐Entropy 1T‐Phase Quantum Sheets of Transition‐Metal Disulfides

Fri, 21/02/2025 - 12:08

An efficient high-entropy strategy is developed to produce 1T-phase quantum sheets of transition-metal disulfides based on controllable introduction of multiple metal atoms with large size differences to retard the sliding of basal plane. The key is the topological conversion of in-plane ordered carbide laminates (i-MAX) compatible with multiple atoms to high-strained high-entropy transition-metal disulfides with 1T phase, which facilely triggers the fracture into 1T-phase quantum sheets during the exfoliation process. The resultant 1T-phase disulfide quantum sheets show high electrocatalytic activities for lithium polysulfides, achieving good electrochemical properties in lithium-sulfur batteries.


Abstract

Quantum sheets of transition-metal dichalcogenides (TMDs) are promising nanomaterials owing to the combination of both 2D nanosheets and quantum dots with distinctive properties. However, the quantum sheets usually possess semiconducting behavior associated with 2H phase, it remains challenging to produce 1T-phase quantum sheets due to the easy sliding of the basal plane susceptible to the small lateral sizes. Here, an efficient high-entropy strategy is developed to produce 1T-phase quantum sheets of transition-metal disulfides based on controllable introduction of multiple metal atoms with large size differences to retard the sliding of basal plane. The key is the topological conversion of in-plane ordered carbide laminates (i-MAX) compatible with multiple atoms to high-entropy transition-metal disulfides with high strains and 1T phase, which facilely triggers the fracture into 1T-phase quantum sheets with average size of 4.5 nm and thickness of 0.7 nm during the exfoliation process. Thus, the 1T-phase disulfide quantum sheets show high electrocatalytic activities for lithium polysulfides, achieving a good rate performance of 744 mAh g−1 at 5 C and a long cycle stability in lithium-sulfur batteries.

Cooling‐induced Strains in 2D Materials and Their Modulation via Interface Engineering

Fri, 21/02/2025 - 12:05

This study investigates the internal and external cooling-induced strains in monolayer MoSe2 at cryogenic temperatures, focusing on strain effects arising from thermal expansion coefficient mismatch at 2D-bulk interfaces. Interface engineering demonstrates that compressive strain induces direct-to-indirect bandgap transitions. Notably, hexagonal boron nitride encapsulation effectively mitigates external strain via 2D–2D interfaces, yielding performance comparable to suspended samples.


Abstract

2D materials exhibit unique properties for next-generation electronics and quantum devices. However, their sensitivity to temperature variations, particularly concerning cooling-induced strain, remains underexplored systematically. This study investigates the effects of cooling-induced strain on monolayer MoSe2 at cryogenic temperatures. It is emphasized that the mismatch in thermal expansion coefficients between the material and bulk substrate leads to significant external strain, which superimposes the internal strain of the material. By engineering the material-substrate 2D-bulk interface, the resulting strain conditions are characterized and reveal that substantial compressive strain induces new emission features linked to direct-to-indirect bandgap transition, as confirmed by photoluminescence and transient absorption spectroscopy studies. Finally, it is demonstrated that encapsulation with hexagonal boron nitride can mitigate the external strain by 2D–2D interfaces, achieving results similar to those of suspended samples. The findings address key challenges in quantifying and characterizing strain types across different 2D-bulk interfaces, distinguishing cooling-induced strain effects from other temperature-dependent phenomena, and designing strain-sensitive 2D material devices for extreme temperature conditions.

Epitaxial Ferroelectric Hexagonal Boron Nitride Grown on Graphene

Fri, 21/02/2025 - 12:03

The epitaxial growth of hexagonal boron nitride (h-BN) multilayer films on graphene, synthesized on a miscut SiC (0001) substrate, is demonstrated using nitrogen plasma-assisted molecular-beam epitaxy. Robust ferroelectricity with switchable out-of-plane polarization via interlayer sliding is supported by theoretical and experimental insights, providing a scalable pathway for integrating ferroelectric vdW materials into advanced 2D devices with diverse functionalities.


Abstract

Ferroelectricity realized in van der Waals (vdW) materials with non-centrosymmetric stacking configurations holds promise for future 2D devices with nonvolatile and reconfigurable functionalities. However, the epitaxial growth of ferroelectric vdW materials often struggles to achieve an energetically unfavorable stacking configuration that enables electric polarization. This challenge is particularly evident when performing heteroepitaxy on another vdW substrate to create versatile and scalable ferroelectric building blocks designed for large-area, atomic-scale thicknesses. Here, epitaxial hexagonal boron nitride (h-BN) multilayer films are successfully grew on single-crystal graphene synthesized on a miscut SiC (0001) substrate. Theoretical calculations illustrate that the moiré-patterned h-BN/graphene hetero-interface intrinsically exhibits polarization, leading to a polarized AB stacking in multilayer h-BN films to minimize the total formation energy, which is validated experimentally by the layer-dependent band dispersions. The as-grown multilayer h-BN layers demonstrated robust, homogeneous ferroelectricity with switchable out-of-plane polarization via interlayer sliding. This study establishes an effective route for stacking-controlled heteroepitaxy, enabling the large-scale integration of vdW materials with ferroelectricity and versatile functionalities, offering a promising platform for next-generation 2D ferroelectric devices.

Toward Intrinsically Stretchable OLEDs with High Efficiency

Fri, 21/02/2025 - 12:00

This perspective provides a systematic discussion on the challenges and solutions in designing materials for intrinsically stretchable organic light-emitting diodes (ISOLEDs). It also highlights prospective challenges and offers insights into the development of highly efficient and stable ISOLEDs for practical applications.


Abstract

Wearable electronics require stretchable displays that can withstand large and repeated mechanical deformation without failure. Intrinsically stretchable organic light-emitting diodes (ISOLEDs) that operate under DC voltage provide promising candidates for wearable display applications. However, the lack of sophisticated stretchable materials and processing techniques suitable for ISOLEDs results in a significant deficit in the efficiency of state-of-the-art ISOLEDs compared to industrial standards. The design of stretchable conducting and semiconducting materials poses a significant challenge because of trade-off relationships between stretchability and properties such as conductivity and charge carrier mobility. To increase the efficiency of ISOLEDs to meet industrial standards, strategies to overcome these trade-offs must be developed. This perspective discusses recent progress and challenges in designing stretchable electrodes, light-emitting materials, transport materials, and potential applications of ISOLEDs. It provides a useful guide in this field to develop efficient ISOLEDs for system-level integration.

Red Phosphorescence at Elevated Temperatures Enabled by Dexter Energy Transfer in Polyaromatic Hydrocarbon‐Xanthone Systems

Fri, 21/02/2025 - 11:59

Pure Organic red persistent phosphorescent materials, possessing high-temperature resistance and superior tissue penetration, can be efficiently fabricated using a host–guest doping strategy. The triplet-to-triplet Dexter energy transfer process plays a crucial role in modulating the luminescent properties of both the host and the guest. These materials hold promise for applications in advanced information encryption and bioimaging.


Abstract

Organic materials with red persistent phosphorescence hold immense promise for biotechnology due to their excellent tissue permeability and high signal-to-background ratios. However, inefficient spin-orbit coupling, high triplet susceptibility, and narrow energy gapspromoted nonradiative deactivations, pose a formidable obstacle to achieving efficient red phosphorescence. This study addresses these challenges by introducing xanthone (Xan)-based host–guest systems. Utilizing polyaromatic hydrocarbons (PAHs) as guests, efficient red to near-infrared (NIR) phosphorescent materials with ultralong lifetimes and high quantum yields of up to 821 ms and 2.32%, respectively, are successfully developed. Ultrafast spectroscopy and theoretical studies reveal that Dexter energy transfer (DET) is the dominant mechanism responsible for red phosphorescence. This DET process between Xan and PAHs not only effectively utilizes the dark triplet state of the Xan host but also significantly enhances the triplet generation of the PAH guests, transforming them into potent phosphorescent luminophores. Furthermore, the inherent rigidity of Xan and PAHs endows the resulting materials with excellent phosphorescence performance, even at elevated temperatures (e.g., 423 K). This strategy, proven to be general, paves the way for designing efficient red/NIR phosphorescent materials through the DET mechanism, enabling their applications in molecular imaging and advanced high-temperature encryption.

The Influence of Ionizing Radiation on Quantification for In Situ and Operando Liquid‐Phase Electron Microscopy

Fri, 21/02/2025 - 11:43

Liquid-phase transmission electron microscopy enables visualization of nanoscale processes involving liquid media. Yet, it suffers from beam effects, such as radiolysis of the liquid, sample heating, and membrane charging. This review summarizes beam effect fundamentals, describes modeling and assessment, and illustrates handling strategies. The findings are transferable to other ionizing radiation techniques using, for example, γ- or X-rays.


Abstract

The ionizing radiation harnessed in electron microscopes or synchrotrons enables unique insights into nanoscale dynamics. In liquid-phase transmission electron microscopy (LP-TEM), irradiating a liquid sample with electrons offers access to real space information at an unmatched combination of temporal and spatial resolution. However, employing ionizing radiation for imaging can alter the Gibbs free energy landscape during the experiment. This is mainly due to radiolysis and the corresponding shift in chemical potential; however, experiments can also be affected by irradiation-induced charging and heating. In this review, the state of the art in describing beam effects is summarized, theoretical and experimental assessment guidelines are provided, and strategies to obtain quantitative information under such conditions are discussed. While this review showcases these effects on LP-TEM, the concepts that are discussed here can also be applied to other types of ionizing radiation used to probe liquid samples, such as synchrotron X-rays.

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