Brian George Barbery, Nicole Rose Lukesh, Eric M. Bachelder, Kristy M. Ainslie
The field of immunotherapeutics is rapidly evolving with the advent of cell therapies, complex biologics, and a host of other compounds. Polymeric carriers are often used to tune the safety and efficacy profiles of these novel drugs. Despite their prevalence in pre-clinical and clinical applications, non-degradable materials present delivery challenges including diffusion-limited release, frustrated phagocytosis, and limited clearance. In contrast, biodegradable polymeric systems provide a safer alternative in addition to displaying advantageous properties for the delivery of immunotherapies. In this review, discussion of polymers including poly(lactic-co-glycolic acid) (PLGA), poly(beta-amino esters) (PBAEs), acetalated dextran (Ace-DEX), chitosan, alginate, and hyaluronic acid (HA) as immunomodulatory biomaterial carriers suggest that a variety of systems can be used to generate tailored formulations for different therapeutic payloads and disease indications. These carrier systems can enhance the delivery of immunotherapies via tunable degradation rates, enhanced antigen-presentation, and inherent immunomodulatory properties of the biomaterials, among other mechanisms. Polymers formulated for immunomodulatory applications can be synthetic, semi-synthetic, or naturally derived. Therefore, it is crucial to consider the environmental impact of polymer sources, particle fabrication methods, and solvent usage to sustainably develop effective immunomodulatory therapies in this evolving field.
{"title":"Biodegradable Polymers for Application as Robust Immunomodulatory Biomaterial Carrier Systems","authors":"Brian George Barbery, Nicole Rose Lukesh, Eric M. Bachelder, Kristy M. Ainslie","doi":"10.1002/smll.202409422","DOIUrl":"https://doi.org/10.1002/smll.202409422","url":null,"abstract":"The field of immunotherapeutics is rapidly evolving with the advent of cell therapies, complex biologics, and a host of other compounds. Polymeric carriers are often used to tune the safety and efficacy profiles of these novel drugs. Despite their prevalence in pre-clinical and clinical applications, non-degradable materials present delivery challenges including diffusion-limited release, frustrated phagocytosis, and limited clearance. In contrast, biodegradable polymeric systems provide a safer alternative in addition to displaying advantageous properties for the delivery of immunotherapies. In this review, discussion of polymers including poly(lactic-co-glycolic acid) (PLGA), poly(beta-amino esters) (PBAEs), acetalated dextran (Ace-DEX), chitosan, alginate, and hyaluronic acid (HA) as immunomodulatory biomaterial carriers suggest that a variety of systems can be used to generate tailored formulations for different therapeutic payloads and disease indications. These carrier systems can enhance the delivery of immunotherapies via tunable degradation rates, enhanced antigen-presentation, and inherent immunomodulatory properties of the biomaterials, among other mechanisms. Polymers formulated for immunomodulatory applications can be synthetic, semi-synthetic, or naturally derived. Therefore, it is crucial to consider the environmental impact of polymer sources, particle fabrication methods, and solvent usage to sustainably develop effective immunomodulatory therapies in this evolving field.","PeriodicalId":228,"journal":{"name":"Small","volume":"48 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418111","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yi Ding, Chenyu Xu, Wenyou Zhang, Yuhang Di, Junyu Yue, Kun Yu, Wei Wang, Dichen Li, Jiankang He
Hydroprinting has emerged as a cost-effective solution to transfer planar flexible electronics onto diverse curved surfaces for the fabrication of conformal transparent electrodes (CTEs) in the fields of microelectronics and healthcare monitoring. However, current hydroprinting strategies commonly rely on intricate multiple-step microfabrication processes or inkjet/direct/screen printing, largely limiting accessibility or resolution for microscale CTEs. Here, an integration strategy is proposed by combining electrohydrodynamic printing and hydroprinting, simplifying the fabrication of microscale CTEs with remarkable electrical/thermal/sensing capabilities and robust mechanical stability. Stable electrohydrodynamic printing of microscale silver mesh electrodes on non-conductive water-soluble polyvinyl alcohol films achieves excellent compatibility with diverse curved surfaces and distinct substrate materials. The smallest feature size of the CTEs is 48.5 ± 3.7 µm, showing a figure of merit of 1304. Interestingly, the CTEs hydroprinted on rough surfaces demonstrate better adhesion and scratching resistances than those hydroprinted on smooth counterparts, maintaining a negligible sheet resistance increase after 100 cyclic mechanical tests. The CTEs on a cylindrical glass bottle exhibit excellent transparency and electrothermal properties. The CTEs onto human skin for electrocardiogram sensing and monitoring realize a notable 30.24% signal enhancement, improved motion artifact resistance and negligible skin irritation compared to the commercialized Ag/AgCl electrodes.
{"title":"Integration of Electrohydrodynamic Printing and Hydroprinting for the Cost-Effective Fabrication of Microscale Conformal Transparent Electrodes on Diverse Curved Surfaces","authors":"Yi Ding, Chenyu Xu, Wenyou Zhang, Yuhang Di, Junyu Yue, Kun Yu, Wei Wang, Dichen Li, Jiankang He","doi":"10.1002/smll.202410919","DOIUrl":"https://doi.org/10.1002/smll.202410919","url":null,"abstract":"Hydroprinting has emerged as a cost-effective solution to transfer planar flexible electronics onto diverse curved surfaces for the fabrication of conformal transparent electrodes (CTEs) in the fields of microelectronics and healthcare monitoring. However, current hydroprinting strategies commonly rely on intricate multiple-step microfabrication processes or inkjet/direct/screen printing, largely limiting accessibility or resolution for microscale CTEs. Here, an integration strategy is proposed by combining electrohydrodynamic printing and hydroprinting, simplifying the fabrication of microscale CTEs with remarkable electrical/thermal/sensing capabilities and robust mechanical stability. Stable electrohydrodynamic printing of microscale silver mesh electrodes on non-conductive water-soluble polyvinyl alcohol films achieves excellent compatibility with diverse curved surfaces and distinct substrate materials. The smallest feature size of the CTEs is 48.5 ± 3.7 µm, showing a figure of merit of 1304. Interestingly, the CTEs hydroprinted on rough surfaces demonstrate better adhesion and scratching resistances than those hydroprinted on smooth counterparts, maintaining a negligible sheet resistance increase after 100 cyclic mechanical tests. The CTEs on a cylindrical glass bottle exhibit excellent transparency and electrothermal properties. The CTEs onto human skin for electrocardiogram sensing and monitoring realize a notable 30.24% signal enhancement, improved motion artifact resistance and negligible skin irritation compared to the commercialized Ag/AgCl electrodes.","PeriodicalId":228,"journal":{"name":"Small","volume":"80 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418068","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Second near-infrared (NIR-II) responsive hydrogels have shown significant potential in biomedical applications due to their excellent remote actuation property and the high tissue penetrations of the NIR-II light. Nevertheless, hydrogels with a single NIR-II light response may not meet the diverse requirements and complex conditions of clinical applications. Here, a novel multi-responsive nanocomposite hydrogel with enhanced suitability for controlled drug release is developed. This nanocomposite hydrogel is constructed by combining alginate dialdehyde (ADA), polyethyleneimine (PEI), poly(N-isopropylacrylamide) (PNIPAM), and phenylboronic acid-modified polyethyleneimine (PBA-PEI) functionalized multi-walled carbon nanotubes (PP-CNT) through the formation of dynamic covalent bonds (i.e., imine bonds and boronate ester bonds), forming ADA/PEI/PNIPAM/PP-CNT (APN/PP-CNT) hydrogel. PNIPAM is incorporated into the hydrogel network to facilitate drug release triggered by its aggregation when subjected to the high temperatures produced by NIR-II light irradiation. The dynamic covalent bonds and CNT in the network provide the APN/PP-CNT nanocomposite hydrogels with responsiveness to multiple stimuli, including pH, hydrogen peroxide, temperature, and NIR-II light. The APN/PP-CNT nanocomposite hydrogel performs effective NIR-II light responsiveness in both in vitro and in vivo drug release, highlighting its potential as a promising drug delivery platform.
{"title":"Engineering Multiresponsive Alginate/PNIPAM/Carbon Nanotube Nanocomposite Hydrogels as On-Demand Drug Delivery Platforms","authors":"Bo-Yan Li, Tung-Yi Lin, Yi-Jhen Lai, Ting-Hsiang Chiu, Yi-Cheun Yeh","doi":"10.1002/smll.202407420","DOIUrl":"https://doi.org/10.1002/smll.202407420","url":null,"abstract":"Second near-infrared (NIR-II) responsive hydrogels have shown significant potential in biomedical applications due to their excellent remote actuation property and the high tissue penetrations of the NIR-II light. Nevertheless, hydrogels with a single NIR-II light response may not meet the diverse requirements and complex conditions of clinical applications. Here, a novel multi-responsive nanocomposite hydrogel with enhanced suitability for controlled drug release is developed. This nanocomposite hydrogel is constructed by combining alginate dialdehyde (ADA), polyethyleneimine (PEI), poly(N-isopropylacrylamide) (PNIPAM), and phenylboronic acid-modified polyethyleneimine (PBA-PEI) functionalized multi-walled carbon nanotubes (PP-CNT) through the formation of dynamic covalent bonds (i.e., imine bonds and boronate ester bonds), forming ADA/PEI/PNIPAM/PP-CNT (APN/PP-CNT) hydrogel. PNIPAM is incorporated into the hydrogel network to facilitate drug release triggered by its aggregation when subjected to the high temperatures produced by NIR-II light irradiation. The dynamic covalent bonds and CNT in the network provide the APN/PP-CNT nanocomposite hydrogels with responsiveness to multiple stimuli, including pH, hydrogen peroxide, temperature, and NIR-II light. The APN/PP-CNT nanocomposite hydrogel performs effective NIR-II light responsiveness in both in vitro and in vivo drug release, highlighting its potential as a promising drug delivery platform.","PeriodicalId":228,"journal":{"name":"Small","volume":"32 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418106","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A novel all-carbon visible light detector is fabricated on a nitrogen-doped (N-doped) single-crystalline diamond (SCD) with interdigitated nanocarbon ohmic contacts. It has been posited that the formation of nitrogen-vacancy (NV) centers within the photoabsorption layer serves as an effective strategy to augment the device's detection capabilities. To illustrate the significance of this enhancement, NV density is manipulated and augmented by electron beam irradiation in a moderately N-doped diamond. Despite the incompetent nitrogen doping, the enhancement of NV density in the diamond active layer has resulted in a substantial enhancement of nearly 1.5 orders of magnitude for several critical detection parameters. The NV-enabled all-carbon detector demonstrates a high degree of tolerance toward thermal and corrosive environments. The dark current is maintained at a level below 0.01 pA even when the device is operated at a temperature of 250 °C. The robust interfacial bonding between the diamond and the nanocarbon-interdigitated electrodes ensures that the device exhibits no physical or performance deterioration when subjected to highly corrosive environments. The results of this study may provide insights that can inform the development of high-sensitivity, harsh environment immune diamond visible light detectors benefiting from the multiple photon excitation of NV quantum centers.
{"title":"Harsh Environment-Immune All-Carbon Visible Light Photodetector: Sensitivity Improvement by Nitrogen-Vacancy Center Density Enhancement Through Electron Irradiation","authors":"Sreenath Mylo Valappil, Taisuke Kageura, Shinya Ohmagari, Shinobu Onoda, Phongsaphak Sittimart, Hiroshi Naragino, Tsuyoshi Yoshitake","doi":"10.1002/smll.202409876","DOIUrl":"https://doi.org/10.1002/smll.202409876","url":null,"abstract":"A novel all-carbon visible light detector is fabricated on a nitrogen-doped (N-doped) single-crystalline diamond (SCD) with interdigitated nanocarbon ohmic contacts. It has been posited that the formation of nitrogen-vacancy (NV) centers within the photoabsorption layer serves as an effective strategy to augment the device's detection capabilities. To illustrate the significance of this enhancement, NV density is manipulated and augmented by electron beam irradiation in a moderately N-doped diamond. Despite the incompetent nitrogen doping, the enhancement of NV density in the diamond active layer has resulted in a substantial enhancement of nearly 1.5 orders of magnitude for several critical detection parameters. The NV-enabled all-carbon detector demonstrates a high degree of tolerance toward thermal and corrosive environments. The dark current is maintained at a level below 0.01 pA even when the device is operated at a temperature of 250 °C. The robust interfacial bonding between the diamond and the nanocarbon-interdigitated electrodes ensures that the device exhibits no physical or performance deterioration when subjected to highly corrosive environments. The results of this study may provide insights that can inform the development of high-sensitivity, harsh environment immune diamond visible light detectors benefiting from the multiple photon excitation of NV quantum centers.","PeriodicalId":228,"journal":{"name":"Small","volume":"85 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418113","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Memristors with high computing capabilities hold significant potential as processing devices in the era of information explosion, but their applications are largely hindered by the trade-off between memristive performance and operation uniformity. Extensive efforts are devoted to designing or regulating memristive layers of memristors to improve device performance, while few studies focused on the interface structure at cross points of memristors. Herein, inspired by the tip effect, a nanofiber memristor with highly-curved interwoven interface is designed by assembling nanofiber electrodes using dielectrophoretic method. The nanofiber memristor shows high operation uniformity with an ultralow set voltage standard deviation of 0.014 V, which is even superior to that of state-of-the-art oxide-based planar memristors. Experimental and simulation analysis reveals that the highly-curved interface can efficiently concentrate electric field distribution and confine the switching region, thus facilitating the migration of silver ions and suppressing the formation of random conductive filaments. Nanofiber memristor arrays with good device reproducibility are further integrated for fundamental logic gate circuits like NOT, AND, and OR. This work offers a new insight for constructing high-performing nanoelectronics.
{"title":"High-Performing Nanofiber Memristor via Field-Induced Ion Migration Concentration at Highly-Curved Interwoven Interface","authors":"Yue Liu, Yuanhang Zhang, Xufeng Zhou, Zhuming Wang, Zhe Yang, Jialin Meng, Chen Wang, Xuemei Sun, Lin Chen, Peining Chen, Huisheng Peng","doi":"10.1002/smll.202409951","DOIUrl":"https://doi.org/10.1002/smll.202409951","url":null,"abstract":"Memristors with high computing capabilities hold significant potential as processing devices in the era of information explosion, but their applications are largely hindered by the trade-off between memristive performance and operation uniformity. Extensive efforts are devoted to designing or regulating memristive layers of memristors to improve device performance, while few studies focused on the interface structure at cross points of memristors. Herein, inspired by the tip effect, a nanofiber memristor with highly-curved interwoven interface is designed by assembling nanofiber electrodes using dielectrophoretic method. The nanofiber memristor shows high operation uniformity with an ultralow set voltage standard deviation of 0.014 V, which is even superior to that of state-of-the-art oxide-based planar memristors. Experimental and simulation analysis reveals that the highly-curved interface can efficiently concentrate electric field distribution and confine the switching region, thus facilitating the migration of silver ions and suppressing the formation of random conductive filaments. Nanofiber memristor arrays with good device reproducibility are further integrated for fundamental logic gate circuits like NOT, AND, and OR. This work offers a new insight for constructing high-performing nanoelectronics.","PeriodicalId":228,"journal":{"name":"Small","volume":"2 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418148","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Irfan Ayoub, Umer Mushtaq, Govind B. Nair, Gaurav Sundaram, Hendrik C Swart, Vijay Kumar
A series of Sr2-xGa2GeO7: x Tb3+ (0 mol% ≤ x ≤ 10 mol%) phosphors exhibiting persistent luminescence is synthesized via a high-temperature solid-state reaction. Structural analysis and phase identification are conducted using X-ray powder diffraction and Rietveld refinement. The reflectance spectra revealed that the synthesized phosphor exhibited a direct bandgap with a value of 4.99 eV. The photoluminescence excitation spectra displayed broad absorption bands corresponding to the 4f8 → 4f75d1 transition of the Tb3+ ion, along with narrow-band absorption peaks attributed to the 4f-4f transitions. The emission spectra featured peaks resulting from transitions from the excited energy-state (5D3/5D4) to the ground-state levels (7FJ). Among these transitions, the 5D4 → 7F5 transition is dominant, producing the green emission of the synthesized phosphor. Concentration quenching is observed, attributed to the radiative reabsorption process. Additionally, the synthesized phosphor demonstrated thermal stability up to 675 K. The kinetic scan and afterglow measurements showed that the persistent luminescence lifetime is ≈7000 s, and the afterglow persistence is up to 100 s. Thermoluminescence measurements revealed that besides the intrinsic defect, doping introduced the interstitial and vacancy defects that contributed to improving the persistent luminescence of the synthesized phosphor. The synthesized phosphor demonstrated a practical application for latent fingerprint detection and anticounterfeiting applications.
通过高温固态反应合成了一系列 Sr2-xGa2GeO7: x Tb3+ (0 mol% ≤ x ≤ 10 mol%)荧光粉，这些荧光粉具有持久的发光特性。利用 X 射线粉末衍射和里特维尔德精炼进行了结构分析和相鉴定。反射光谱显示，合成的荧光粉具有 4.99 eV 的直接带隙。光致发光激发光谱显示了与 Tb3+ 离子的 4f8 → 4f75d1 转变相对应的宽吸收带，以及归因于 4f-4f 转变的窄带吸收峰。发射光谱中的峰值来自从激发能态（5D3/5D4）到基态水平（7FJ）的跃迁。在这些跃迁中，5D4 → 7F5 跃迁占主导地位，产生了合成荧光粉的绿色发射。观察到的浓度淬灭现象归因于辐射再吸收过程。热释光测量结果表明，除了本征缺陷外，掺杂引入的间隙和空位缺陷也有助于改善合成荧光粉的持续发光性能。合成的荧光粉在潜指纹检测和防伪应用中得到了实际应用。
{"title":"Exploring the Sr2Ga2GeO7:Tb3+ Long Persistent Luminescence Phosphor for Cutting-Edge Forensic Solutions in Latent Fingerprint Detection and Anticounterfeiting Applications","authors":"Irfan Ayoub, Umer Mushtaq, Govind B. Nair, Gaurav Sundaram, Hendrik C Swart, Vijay Kumar","doi":"10.1002/smll.202500285","DOIUrl":"https://doi.org/10.1002/smll.202500285","url":null,"abstract":"A series of Sr<sub>2-x</sub>Ga<sub>2</sub>GeO<sub>7</sub>: <i>x</i> Tb<sup>3+</sup> (0 mol% ≤ <i>x</i> ≤ 10 mol%) phosphors exhibiting persistent luminescence is synthesized via a high-temperature solid-state reaction. Structural analysis and phase identification are conducted using X-ray powder diffraction and Rietveld refinement. The reflectance spectra revealed that the synthesized phosphor exhibited a direct bandgap with a value of 4.99 eV. The photoluminescence excitation spectra displayed broad absorption bands corresponding to the 4f<sub>8</sub> → 4f<sub>7</sub>5d<sub>1</sub> transition of the Tb<sup>3+</sup> ion, along with narrow-band absorption peaks attributed to the 4f-4f transitions. The emission spectra featured peaks resulting from transitions from the excited energy-state (<sup>5</sup>D<sub>3</sub>/<sup>5</sup>D<sub>4</sub>) to the ground-state levels (<sup>7</sup>F<sub>J</sub>). Among these transitions, the <sup>5</sup>D<sub>4</sub> → <sup>7</sup>F<sub>5</sub> transition is dominant, producing the green emission of the synthesized phosphor. Concentration quenching is observed, attributed to the radiative reabsorption process. Additionally, the synthesized phosphor demonstrated thermal stability up to 675 K. The kinetic scan and afterglow measurements showed that the persistent luminescence lifetime is ≈7000 s, and the afterglow persistence is up to 100 s. Thermoluminescence measurements revealed that besides the intrinsic defect, doping introduced the interstitial and vacancy defects that contributed to improving the persistent luminescence of the synthesized phosphor. The synthesized phosphor demonstrated a practical application for latent fingerprint detection and anticounterfeiting applications.","PeriodicalId":228,"journal":{"name":"Small","volume":"110 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418062","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Soft robots have demonstrated exceptional potential in various applications, particularly in biomedicine, which is attributed to their motional agility and machinability. However, their potential applications in water remediation have not been fully explored. The main challenge is to achieve both precise motion and efficient pollutant degradation. Herein, a modular design is reported for fabricating soft robots. These robots are designed with spatially separated components. One is superparamagnetic iron oxide nanoparticles for magnetic actuation and the other is photocatalysts for targeted pollutant degradation (i.e., methyl orange, congo red, rhodamine B, tetracycline, and soybean oil). The helical structure enables diverse programmable motional modes, including high-speed propulsion up to 3.54 mm s−1. At the same time, the photocatalytic module enables efficient degradation of multiple pollutants with excellent reusability. The modular design combines structural stability with multifunctionality and opens new opportunities for soft robots in environmental remediation.
{"title":"Helical Soft Robots with Magnetic and Photocatalytic Components for Water Remediation","authors":"Pengyang Xuan, Jiaming Gong, Tongfang Fu, Yazhou Zhou, Jingjing Qin, Haoxiang Chen, Tianlu Wang, Guohao Xue, Xiaoyuan Peng, Yun Qian, Silvio Osella, Radek Zbořil, Johan Hofkens, Klaus Müllen, Feili Lai, Tianxi Liu","doi":"10.1002/smll.202412516","DOIUrl":"https://doi.org/10.1002/smll.202412516","url":null,"abstract":"Soft robots have demonstrated exceptional potential in various applications, particularly in biomedicine, which is attributed to their motional agility and machinability. However, their potential applications in water remediation have not been fully explored. The main challenge is to achieve both precise motion and efficient pollutant degradation. Herein, a modular design is reported for fabricating soft robots. These robots are designed with spatially separated components. One is superparamagnetic iron oxide nanoparticles for magnetic actuation and the other is photocatalysts for targeted pollutant degradation (i.e., methyl orange, congo red, rhodamine B, tetracycline, and soybean oil). The helical structure enables diverse programmable motional modes, including high-speed propulsion up to 3.54 mm s<sup>−1</sup>. At the same time, the photocatalytic module enables efficient degradation of multiple pollutants with excellent reusability. The modular design combines structural stability with multifunctionality and opens new opportunities for soft robots in environmental remediation.","PeriodicalId":228,"journal":{"name":"Small","volume":"80 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418338","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The electrocatalytic methanol oxidation reaction (MOR) is considered as an effective method to replace oxygen evolution reaction (OER) for efficient hydrogen production. However, the sluggish kinetics and the difficulty of breaking C─H bond of the Ni-based catalysts limit further application. Herein, three high-entropy layered double hydroxides (HELHs), namely ZnNiFeCoV-HELH, ZnNiFeCoCr-HELH, and ZnNiFeCoAl-HELH (denoted as V-HELH, Cr-HELH, and Al-HELH, respectively), are successfully synthesized. Among them, the V-HELH displays the lowest potential of 1.39 V at 100 mA cm−2 compared to Cr-HELH (1.41 V) and Al-HELH (1.44 V). After five cycles, the formate yield of V-HELH maintains over 95% of the first cycle with excellent stability. Such outstanding performance surpasses that of most state-of-the-art MOR catalysts reported so far. A series of experiments reveal that the V-HELH exhibits the fastest reaction kinetics and the largest number of active Ni3+ species. Further investigations and theoretical calculations prove that the V-HELH shows the strongest methanol adsorption with the lowest energy of −3.31 eV. The introduction of vanadium (V) with relatively larger tensile strain optimizes the d─band center of V-HELH (−0.54 eV) and lowers the energy barrier (−1.62 eV) from *CH3O to *CH2O. This work provides new insights for rational design of efficient MOR electrocatalysts.
{"title":"High-Entropy Layered Double Hydroxides for Efficient Methanol Electrooxidation","authors":"Yuying Wang, Yihang Hu, Zhaohui Wu, Ziheng Song, Xiang Chen, Yu-Fei Song","doi":"10.1002/smll.202411550","DOIUrl":"https://doi.org/10.1002/smll.202411550","url":null,"abstract":"The electrocatalytic methanol oxidation reaction (MOR) is considered as an effective method to replace oxygen evolution reaction (OER) for efficient hydrogen production. However, the sluggish kinetics and the difficulty of breaking C─H bond of the Ni-based catalysts limit further application. Herein, three high-entropy layered double hydroxides (HELHs), namely ZnNiFeCoV-HELH, ZnNiFeCoCr-HELH, and ZnNiFeCoAl-HELH (denoted as V-HELH, Cr-HELH, and Al-HELH, respectively), are successfully synthesized. Among them, the V-HELH displays the lowest potential of 1.39 V at 100 mA cm<sup>−2</sup> compared to Cr-HELH (1.41 V) and Al-HELH (1.44 V). After five cycles, the formate yield of V-HELH maintains over 95% of the first cycle with excellent stability. Such outstanding performance surpasses that of most state-of-the-art MOR catalysts reported so far. A series of experiments reveal that the V-HELH exhibits the fastest reaction kinetics and the largest number of active Ni<sup>3+</sup> species. Further investigations and theoretical calculations prove that the V-HELH shows the strongest methanol adsorption with the lowest energy of −3.31 eV. The introduction of vanadium (V) with relatively larger tensile strain optimizes the d─band center of V-HELH (−0.54 eV) and lowers the energy barrier (−1.62 eV) from <sup>*</sup>CH<sub>3</sub>O to <sup>*</sup>CH<sub>2</sub>O. This work provides new insights for rational design of efficient MOR electrocatalysts.","PeriodicalId":228,"journal":{"name":"Small","volume":"15 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418067","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Taegyu Jang, Seon Yeong Cho, Jaegeol Kim, Eunjin Choi, Simone L. Holzmann, Ulrike Krewer, Hyeyoung Shin, Hye Ryung Byon
Lithium bis(fluorosulfonyl)imide (LiFSI) is widely used in lithium-metal batteries to form a stable lithium fluoride (LiF)-based solid electrolyte interphase (SEI). However, the FSI⁻ itself fails to create a protective passivation layer on aluminum (Al) current collectors, leading to Al3⁺ dissolution and severe corrosion. While fluorinated ether solvents have shown promise in mitigating Al corrosion, the mechanisms remain unclear. Here, the role of cation solvations and ion pairing structures is shown in corrosion mitigation. 2,2,3,3-tetrafluoro-1,4-dimethoxybutane (FDMB), a 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE)/1,2-dimethoxyethane (DME) mixture, and non-fluorinated ethers are evaluated in 1 m LiFSI. FDMB promoted the formation of AlF₃ while preventing corrosion under extreme conditions (e.g., 4.5 V vs Li/Li⁺, 60 °C). Electrochemical and DFT analyses showed that FDMB underwent favorable defluorination in coordination with both Li⁺ and Al3⁺ that arose from the oxidizing Al surface. Meanwhile, the formation of aggregated ion pairs between Li+ and FSI⁻ inhibited the generation of soluble Al3+ species coordinated with FSI−. Modifying FDMB with alkyl chains further enhanced the anti-corrosive effects by reducing the solubility of Al3+ species. In contrast, DME/TTE exhibited more Al corrosion, similar to tetraethylene glycol dimethyl ether (TEGDME), due to less favorable defluorination by the limited solvation of Li+ and Al3+ on TTE.
{"title":"Effects of Li+ Solvation Structures on Aluminum Corrosion in Ether-Based Electrolyte Solutions with Lithium Bis(Fluorosulfonyl)imide (LiFSI)","authors":"Taegyu Jang, Seon Yeong Cho, Jaegeol Kim, Eunjin Choi, Simone L. Holzmann, Ulrike Krewer, Hyeyoung Shin, Hye Ryung Byon","doi":"10.1002/smll.202500166","DOIUrl":"https://doi.org/10.1002/smll.202500166","url":null,"abstract":"Lithium bis(fluorosulfonyl)imide (LiFSI) is widely used in lithium-metal batteries to form a stable lithium fluoride (LiF)-based solid electrolyte interphase (SEI). However, the FSI⁻ itself fails to create a protective passivation layer on aluminum (Al) current collectors, leading to Al<sup>3</sup>⁺ dissolution and severe corrosion. While fluorinated ether solvents have shown promise in mitigating Al corrosion, the mechanisms remain unclear. Here, the role of cation solvations and ion pairing structures is shown in corrosion mitigation. 2,2,3,3-tetrafluoro-1,4-dimethoxybutane (FDMB), a 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE)/1,2-dimethoxyethane (DME) mixture, and non-fluorinated ethers are evaluated in 1 <span>m</span> LiFSI. FDMB promoted the formation of AlF₃ while preventing corrosion under extreme conditions (e.g., 4.5 V vs Li/Li⁺, 60 °C). Electrochemical and DFT analyses showed that FDMB underwent favorable defluorination in coordination with both Li⁺ and Al<sup>3</sup>⁺ that arose from the oxidizing Al surface. Meanwhile, the formation of aggregated ion pairs between Li<sup>+</sup> and FSI⁻ inhibited the generation of soluble Al<sup>3+</sup> species coordinated with FSI<sup>−</sup>. Modifying FDMB with alkyl chains further enhanced the anti-corrosive effects by reducing the solubility of Al<sup>3+</sup> species. In contrast, DME/TTE exhibited more Al corrosion, similar to tetraethylene glycol dimethyl ether (TEGDME), due to less favorable defluorination by the limited solvation of Li<sup>+</sup> and Al<sup>3+</sup> on TTE.","PeriodicalId":228,"journal":{"name":"Small","volume":"3 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418107","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ruthenium has emerged as a promising alternative to iridium in water-splitting anodes. However, it becomes overoxidized and dissolves at industry-relevant working conditions. To enhance the activity and stability of electrocatalysts for oxygen evolution reaction, an isostructural rutile MnRu oxide with low Ru concentration (Mn0.75Ru0.25O2) is synthesized and an asymmetric Mn-O-Ru dual-site active center is developed. It exhibits 154 mV overpotential at 10 mA cm−2 and can operate stably at 200 mA cm−2 for 670 h with a degradation rate of 29 uV/h−1. A proton exchange membrane water electrolyzer achieves stable operation at 1 A cm−2 for 700 h with a degradation rate of 53 uV h−1. Structural analysis and isotopic labeling correlate the asymmetric nature of the Mn-O-Ru dual-site active center, which facilitates the oxygen evolution reaction along the radical coupling pathway, with the stabilization of the cations and the lattice oxygen in isostructural rutile Mn0.75Ru0.25O2.
{"title":"Mn0.75Ru0.25O2 with Low Ru Concentration for Active and Durable Acidic Oxygen Evolution","authors":"Daojin Zhou, Yuxin Chang, Jialun Tang, Pengfei Ou","doi":"10.1002/smll.202412265","DOIUrl":"https://doi.org/10.1002/smll.202412265","url":null,"abstract":"Ruthenium has emerged as a promising alternative to iridium in water-splitting anodes. However, it becomes overoxidized and dissolves at industry-relevant working conditions. To enhance the activity and stability of electrocatalysts for oxygen evolution reaction, an isostructural rutile MnRu oxide with low Ru concentration (Mn<sub>0.75</sub>Ru<sub>0.25</sub>O<sub>2</sub>) is synthesized and an asymmetric Mn-O-Ru dual-site active center is developed. It exhibits 154 mV overpotential at 10 mA cm<sup>−2</sup> and can operate stably at 200 mA cm<sup>−2</sup> for 670 h with a degradation rate of 29 uV/h<sup>−1</sup>. A proton exchange membrane water electrolyzer achieves stable operation at 1 A cm<sup>−2</sup> for 700 h with a degradation rate of 53 uV h<sup>−1</sup>. Structural analysis and isotopic labeling correlate the asymmetric nature of the Mn-O-Ru dual-site active center, which facilitates the oxygen evolution reaction along the radical coupling pathway, with the stabilization of the cations and the lattice oxygen in isostructural rutile Mn<sub>0.75</sub>Ru<sub>0.25</sub>O<sub>2</sub>.","PeriodicalId":228,"journal":{"name":"Small","volume":"22 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418108","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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