Spatial transcriptomics has transformed the understanding of gene regulation by enabling high-resolution mapping of RNA molecules within their native cellular and tissue environments. This is typically accomplished by capturing or imaging RNA in situ, thereby preserving spatial context. Here, an in situ RNA imaging method based on split-probe ligation and rolling circle amplification (RCA) for profiling spatial gene expression is introduced. In this approach, split-probes hybridize to adjacent regions of a target RNA fragment and are then enzymatically ligated to form circular DNA templates, which are subsequently amplified via RCA to boost the signal. It is demonstrated that this method enables robust in situ RNA detection and genotyping in both tissue sections and whole-mount tissue samples. By coupling this technique with in situ sequencing, the spatial expression patterns of 82 genes in the kidneys of healthy and diabetic male and female mice are mapped. This analysis reveals distinct localization of Aqp4 in proximal tubules and principal cells of the collecting ducts, and uncovers sex-specific transcriptomic alterations in diabetic kidneys with spatial resolution.
{"title":"Efficient Spatial Gene Expression Profiling Using Split-Probe Ligation and Rolling Circle Amplification.","authors":"Xueqian Xia, Zhaoxiang Xie, Yu Yang, Yanxiu Liu, Weiyan Ma, Bixuan Zhang, Yueping Huang, Yafang Shi, Hui Lin, Lingyu Zhu, Wenhua Li, Chen Lin, Rongqin Ke","doi":"10.1002/smtd.202501615","DOIUrl":"https://doi.org/10.1002/smtd.202501615","url":null,"abstract":"<p><p>Spatial transcriptomics has transformed the understanding of gene regulation by enabling high-resolution mapping of RNA molecules within their native cellular and tissue environments. This is typically accomplished by capturing or imaging RNA in situ, thereby preserving spatial context. Here, an in situ RNA imaging method based on split-probe ligation and rolling circle amplification (RCA) for profiling spatial gene expression is introduced. In this approach, split-probes hybridize to adjacent regions of a target RNA fragment and are then enzymatically ligated to form circular DNA templates, which are subsequently amplified via RCA to boost the signal. It is demonstrated that this method enables robust in situ RNA detection and genotyping in both tissue sections and whole-mount tissue samples. By coupling this technique with in situ sequencing, the spatial expression patterns of 82 genes in the kidneys of healthy and diabetic male and female mice are mapped. This analysis reveals distinct localization of Aqp4 in proximal tubules and principal cells of the collecting ducts, and uncovers sex-specific transcriptomic alterations in diabetic kidneys with spatial resolution.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01615"},"PeriodicalIF":9.1,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145659815","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}
Shiyu Liu, Xing Lin, Haijin Ji, Kai Huang, Yao Yu, Lin Liu, Yunhui Huang
The formation of lithium dendrites and dead lithium during deposition/stripping process restricts battery performance especially in wide temperature range. However, due to the lack of real-time detection methods, the intrinsic mechanism of how operational temperature affects the dynamic process on lithium metal anodes is still unclear. Here, an in situ investigation of lithium deposition and dead lithium formation during the first charge-discharge cycle in an ether-based electrolyte system is presented. Both the deposition process and stripping process are found to be temperature dependent. Below 293 K, the lithium deposition is less dense plating and the dead lithium is formed, which contributes to the capacity loss. Above 293 K, the lithium deposition becomes denser, and dead lithium formation is significantly reduced. The capacity loss is primarily driven by the formation of solid electrolyte interphase (SEI) resulting from reactions between lithium and ether-based electrolyte. Further study reveals that the ratio of lithium oligoethoxides on the SEI changes abruptly with temperature above 293 K and thus significantly alters the conductivity and reactivity of SEI, which leads to the abrupt change of the deposition/stripping process. These findings highlight the critical role of temperature in lithium deposition/stripping processes in ether-based anode-free lithium metal batteries.
{"title":"Anomalous Temperature Dependence of Lithium Deposition/Stripping Process in Ether-Based Anode-Free Lithium Metal Batteries.","authors":"Shiyu Liu, Xing Lin, Haijin Ji, Kai Huang, Yao Yu, Lin Liu, Yunhui Huang","doi":"10.1002/smtd.202501911","DOIUrl":"https://doi.org/10.1002/smtd.202501911","url":null,"abstract":"<p><p>The formation of lithium dendrites and dead lithium during deposition/stripping process restricts battery performance especially in wide temperature range. However, due to the lack of real-time detection methods, the intrinsic mechanism of how operational temperature affects the dynamic process on lithium metal anodes is still unclear. Here, an in situ investigation of lithium deposition and dead lithium formation during the first charge-discharge cycle in an ether-based electrolyte system is presented. Both the deposition process and stripping process are found to be temperature dependent. Below 293 K, the lithium deposition is less dense plating and the dead lithium is formed, which contributes to the capacity loss. Above 293 K, the lithium deposition becomes denser, and dead lithium formation is significantly reduced. The capacity loss is primarily driven by the formation of solid electrolyte interphase (SEI) resulting from reactions between lithium and ether-based electrolyte. Further study reveals that the ratio of lithium oligoethoxides on the SEI changes abruptly with temperature above 293 K and thus significantly alters the conductivity and reactivity of SEI, which leads to the abrupt change of the deposition/stripping process. These findings highlight the critical role of temperature in lithium deposition/stripping processes in ether-based anode-free lithium metal batteries.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01911"},"PeriodicalIF":9.1,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145646820","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}
Zeao Kang, Jinling Zhong, Carlos M Costa, Senentxu Lanceros-Mendez, Linjuan Zhang, Yao Liu, Jian-Qiang Wang
Solid polymer electrolytes (SPEs) offer flexibility and processability but suffer from low ionic conductivity and inadequate mechanical strength. Here, a facile, solvent-free electron beam (EB) irradiation method is introduced to modify poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (PDADMATFSI)-based SPEs for lithium metal batteries. At an optimal dose, EB irradiation simultaneously generates polar carbonyl groups and induces a crosslinked network. The carbonyl groups facilitate lithium-ion transport and contribute to forming a robust, Li2O-rich solid electrolyte interphase. Concurrently, the crosslinked architecture enhances mechanical integrity and suppresses the growth of lithium dendrites. As a result, Young's modulus increases from 170 to 921 MPa, ionic conductivity rises from 4.7 × 10-4 to 8.2 × 10-4 S cm-1, the lithium-ion transference number (tLi+) improves from 0.29 to 0.48, and the dielectric constant increases from 6.5 to 16.6. Consequently, Li||Li symmetric cells with modified SPE cycle stably for 2000 h (0.05 mA cm-2), 600 h (0.1 mA cm-2), and 180 h (0.2 mA cm-2), with a critical current density of 1.1 mA cm-2. Li||NCM811 (LiNi0.8Co0.1Mn0.1O2) full cells deliver 83.7% capacity retention after 300 cycles at 1C and superior rate performance. This work demonstrates that EB irradiation is a promising and effective strategy for developing high-performance solid-state lithium metal batteries.
固体聚合物电解质(spe)具有灵活性和加工性,但离子电导率低,机械强度不足。本文介绍了一种简单的、无溶剂的电子束(EB)辐照方法,用于改性锂金属电池用聚(二烯基二甲铵)双(三氟甲烷磺酰)亚胺(PDADMATFSI)基spe。在最佳剂量下,EB辐照同时产生极性羰基并诱导交联网络。羰基促进了锂离子的传输,并有助于形成坚固的富含li20的固体电解质界面。同时,交联结构增强了机械完整性,抑制了锂枝晶的生长。杨氏模量从170增加到921 MPa,离子电导率从4.7 × 10-4提高到8.2 × 10-4 S cm-1,锂离子转移数(tLi +)从0.29提高到0.48,介电常数从6.5提高到16.6。因此,在临界电流密度为1.1 mA cm-2的情况下,经过改性SPE的Li||Li对称电池可稳定循环2000 h (0.05 mA cm-2)、600 h (0.1 mA cm-2)和180 h (0.2 mA cm-2)。Li||NCM811 (LiNi0.8Co0.1Mn0.1O2)全电池在1C下循环300次后具有83.7%的容量保持率和优异的倍率性能。研究结果表明,电子束辐照是开发高性能固态锂金属电池的有效方法。
{"title":"Electron Beam Modification of Solid Polymer Electrolytes for Solid-State Lithium Metal Batteries.","authors":"Zeao Kang, Jinling Zhong, Carlos M Costa, Senentxu Lanceros-Mendez, Linjuan Zhang, Yao Liu, Jian-Qiang Wang","doi":"10.1002/smtd.202501980","DOIUrl":"https://doi.org/10.1002/smtd.202501980","url":null,"abstract":"<p><p>Solid polymer electrolytes (SPEs) offer flexibility and processability but suffer from low ionic conductivity and inadequate mechanical strength. Here, a facile, solvent-free electron beam (EB) irradiation method is introduced to modify poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (PDADMATFSI)-based SPEs for lithium metal batteries. At an optimal dose, EB irradiation simultaneously generates polar carbonyl groups and induces a crosslinked network. The carbonyl groups facilitate lithium-ion transport and contribute to forming a robust, Li<sub>2</sub>O-rich solid electrolyte interphase. Concurrently, the crosslinked architecture enhances mechanical integrity and suppresses the growth of lithium dendrites. As a result, Young's modulus increases from 170 to 921 MPa, ionic conductivity rises from 4.7 × 10<sup>-4</sup> to 8.2 × 10<sup>-4</sup> S cm<sup>-1</sup>, the lithium-ion transference number (t<sub>Li</sub> <sup>+</sup>) improves from 0.29 to 0.48, and the dielectric constant increases from 6.5 to 16.6. Consequently, Li||Li symmetric cells with modified SPE cycle stably for 2000 h (0.05 mA cm<sup>-2</sup>), 600 h (0.1 mA cm<sup>-2</sup>), and 180 h (0.2 mA cm<sup>-2</sup>), with a critical current density of 1.1 mA cm<sup>-2</sup>. Li||NCM811 (LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub>) full cells deliver 83.7% capacity retention after 300 cycles at 1C and superior rate performance. This work demonstrates that EB irradiation is a promising and effective strategy for developing high-performance solid-state lithium metal batteries.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01980"},"PeriodicalIF":9.1,"publicationDate":"2025-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145627197","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}
Molybdenum disulfide (MoS2) has attracted a wide range of research attention due to its distinct electronic structures and the great potential for use in emerging microelectronic and photonic devices. However, the development of MoS2-based micro-electronic/photonic devices lags far behind expectations mainly because of the lack of efficient microfabrication technology. Here, a high-resolution precision photoreduction technology is presented for directly printing MoS2 micropatterns that can be decorated into gold nanoparticle (AuNP)/ MoS2 heterostructure for ultrasensitive surface-enhanced Raman spectroscopy (SERS) sensing. Micropatterns of MoSx nanoparticles are initially grown toward a target size in a light-controlled manner and then transformed into a micropatterned pure MoS2 nanofilm through thermal annealing. Thereafter, size and gap-controlled AuNPs are grown selectively on the surface of MoS2 to form a self-aligned AuNP/MoS2 heterostructure with desired optical properties. Thanks to both electromagnetic and chemical enhancements, the directly printed plasmonic AuNP/ MoS2 substrate can greatly enhance Raman signals to detect crystal violet (CV) and 4-mercaptobenzoic acid (4-MBA) at 10-12 m under the excitation of 785-nm laser. This multiscale-engineered plasmonic AuNP/MoS2 substrate is rapidly printed without relying on expensive and time-consuming nanofabrication processes, offering a new technical approach for future development of MoS2-based micro-devices and sensing platforms.
{"title":"Direct Printing of Micropatterned Plasmonic Au Nanoparticle/MoS<sub>2</sub> Heterostructure for Ultrasensitive Surface-Enhanced Raman Spectroscopy Sensing.","authors":"Huimin Xie, Yangxi Zhang, Yu Bai, Hao Li, Dangyuan Lei, Haitao Huang, A Ping Zhang","doi":"10.1002/smtd.202501968","DOIUrl":"https://doi.org/10.1002/smtd.202501968","url":null,"abstract":"<p><p>Molybdenum disulfide (MoS<sub>2</sub>) has attracted a wide range of research attention due to its distinct electronic structures and the great potential for use in emerging microelectronic and photonic devices. However, the development of MoS<sub>2</sub>-based micro-electronic/photonic devices lags far behind expectations mainly because of the lack of efficient microfabrication technology. Here, a high-resolution precision photoreduction technology is presented for directly printing MoS<sub>2</sub> micropatterns that can be decorated into gold nanoparticle (AuNP)/ MoS<sub>2</sub> heterostructure for ultrasensitive surface-enhanced Raman spectroscopy (SERS) sensing. Micropatterns of MoS<sub>x</sub> nanoparticles are initially grown toward a target size in a light-controlled manner and then transformed into a micropatterned pure MoS<sub>2</sub> nanofilm through thermal annealing. Thereafter, size and gap-controlled AuNPs are grown selectively on the surface of MoS<sub>2</sub> to form a self-aligned AuNP/MoS<sub>2</sub> heterostructure with desired optical properties. Thanks to both electromagnetic and chemical enhancements, the directly printed plasmonic AuNP/ MoS<sub>2</sub> substrate can greatly enhance Raman signals to detect crystal violet (CV) and 4-mercaptobenzoic acid (4-MBA) at 10<sup>-12</sup> m under the excitation of 785-nm laser. This multiscale-engineered plasmonic AuNP/MoS<sub>2</sub> substrate is rapidly printed without relying on expensive and time-consuming nanofabrication processes, offering a new technical approach for future development of MoS<sub>2</sub>-based micro-devices and sensing platforms.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01968"},"PeriodicalIF":9.1,"publicationDate":"2025-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145627245","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}
Covalent organic frameworks (COFs) have recently emerged as promising candidates for solar fuel production due to their broad spectral absorption and readily tunable optoelectronic properties. However, their photocatalytic performance is often limited by inefficient charge separation and rapid charge recombination. Herein, novel S-scheme COF heterojunctions is reported by integrating a negatively charged COF host with a positively charged linear conjugated polymer. The electrostatic attraction between them spontaneously generates a robust Coulombic electric field at the heterojunction interface, which shows an identical electric field direction with the intrinsic built-in electric field of S-scheme configuration.The control experiments and spectroscopic characterizations reveal that this dual-field approach significantly enhances directional charge separation and transfer at the interface, effectively suppressing charge recombination. The optimized sample exhibits a highly enhanced photocatalytic hydrogen production rate of 339.4 µmol g-1 h-1 while coupling with a stoichiometric conversion of 5-hydroxymethyl furfural to 2,5-diformylfuran.
{"title":"Coulomb Electric Fields Enhanced Charge Separation in Covalent Organic Framework Heterojunctions for Efficient Photocatalytic Hydrogen Production and Biomass Valorization.","authors":"Yuchen Yan, Jingfan Shao, Zhaoyu Wen, Xiaohan Yu, Yongpan Hu, Yanguang Li, Wei Huang","doi":"10.1002/smtd.202501535","DOIUrl":"https://doi.org/10.1002/smtd.202501535","url":null,"abstract":"<p><p>Covalent organic frameworks (COFs) have recently emerged as promising candidates for solar fuel production due to their broad spectral absorption and readily tunable optoelectronic properties. However, their photocatalytic performance is often limited by inefficient charge separation and rapid charge recombination. Herein, novel S-scheme COF heterojunctions is reported by integrating a negatively charged COF host with a positively charged linear conjugated polymer. The electrostatic attraction between them spontaneously generates a robust Coulombic electric field at the heterojunction interface, which shows an identical electric field direction with the intrinsic built-in electric field of S-scheme configuration.The control experiments and spectroscopic characterizations reveal that this dual-field approach significantly enhances directional charge separation and transfer at the interface, effectively suppressing charge recombination. The optimized sample exhibits a highly enhanced photocatalytic hydrogen production rate of 339.4 µmol g<sup>-1</sup> h<sup>-1</sup> while coupling with a stoichiometric conversion of 5-hydroxymethyl furfural to 2,5-diformylfuran.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01535"},"PeriodicalIF":9.1,"publicationDate":"2025-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145627100","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}
Engineered bacterial therapeutics are gaining attention in tumor therapy, showing significant clinical potential. However, their clinical translation requires stricter regulation of biosafety and targeting specificity. Controlled release systems offer a key strategy to optimize engineered bacteria through precise spatiotemporal gene expression and motility modulation. This review systematically evaluates two core controlled-release platforms in tumor treatment-tumor microenvironment-responsive systems and intelligent controllable systems-summarizes representative therapeutic paradigms and critically analyzes the merits and limitations of each. Therefore, this review aims to provide a theoretical foundation for refining controlled-release strategies in engineered bacteria-mediated antitumor therapy.
{"title":"Engineered Bacterial Therapeutics: Controlled Release Approaches in Oncology.","authors":"Zetao Yu, Ruijie Nie, Wenna Li, Chen Feng, Zhenqi Li, Xiaoyu Gao, Yuting Wang, Rong Liu, Keman Cheng, Xiao Zhao, Xiuping Zhang","doi":"10.1002/smtd.202501593","DOIUrl":"https://doi.org/10.1002/smtd.202501593","url":null,"abstract":"<p><p>Engineered bacterial therapeutics are gaining attention in tumor therapy, showing significant clinical potential. However, their clinical translation requires stricter regulation of biosafety and targeting specificity. Controlled release systems offer a key strategy to optimize engineered bacteria through precise spatiotemporal gene expression and motility modulation. This review systematically evaluates two core controlled-release platforms in tumor treatment-tumor microenvironment-responsive systems and intelligent controllable systems-summarizes representative therapeutic paradigms and critically analyzes the merits and limitations of each. Therefore, this review aims to provide a theoretical foundation for refining controlled-release strategies in engineered bacteria-mediated antitumor therapy.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01593"},"PeriodicalIF":9.1,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145627263","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}
Janghwan Jekal, Jin Tae Park, Eunmi Kim, Yoon Kyeung Lee, Kyung-In Jang
The peripheral nervous system (PNS) has emerged as a versatile and clinically accessible target for neuroengineering, offering unique advantages in modularity, surgical accessibility, and regenerative capacity. These characteristics have led to the development of peripheral nerve interfaces aimed at clinical implementation across therapeutic and prosthetic applications. Peripheral nerve interfaces involve a broad range of technologies designed to record, stimulate, or repair neural pathways. These technologies are increasingly converging toward systems that are not only surgically and functionally integrated, but also capable of adaptive, closed-loop control. Collectively, these developments represent an advancement in peripheral nerve interface design from passive or pre-programmed interventions to interactive, responsive, and personalized platforms for neural repair and modulation. This review highlights recent advances in biotic-abiotic interface engineering for peripheral nerve applications, encompassing wearable and implantable approaches, as well as addressing current challenges and discussing future perspectives.
{"title":"Biotic-Abiotic Interface Engineering for Peripheral Nerve Modulation and Repair.","authors":"Janghwan Jekal, Jin Tae Park, Eunmi Kim, Yoon Kyeung Lee, Kyung-In Jang","doi":"10.1002/smtd.202501620","DOIUrl":"https://doi.org/10.1002/smtd.202501620","url":null,"abstract":"<p><p>The peripheral nervous system (PNS) has emerged as a versatile and clinically accessible target for neuroengineering, offering unique advantages in modularity, surgical accessibility, and regenerative capacity. These characteristics have led to the development of peripheral nerve interfaces aimed at clinical implementation across therapeutic and prosthetic applications. Peripheral nerve interfaces involve a broad range of technologies designed to record, stimulate, or repair neural pathways. These technologies are increasingly converging toward systems that are not only surgically and functionally integrated, but also capable of adaptive, closed-loop control. Collectively, these developments represent an advancement in peripheral nerve interface design from passive or pre-programmed interventions to interactive, responsive, and personalized platforms for neural repair and modulation. This review highlights recent advances in biotic-abiotic interface engineering for peripheral nerve applications, encompassing wearable and implantable approaches, as well as addressing current challenges and discussing future perspectives.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01620"},"PeriodicalIF":9.1,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145627088","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}
Cuprous oxide (Cu2O) has demonstrated great potential in photochemical, electrochemical, and organic catalysis. Developing surfactant-free and scalable synthesis methods is essential for its real application. Conventional batch methods often suffer from inconsistent product quality and limited scalability. In this work, an efficient continuous microflow synthesis system is developed, and the design principles of the flow synthesis system are systematically elucidated. A kinetic control strategy on the millisecond-to-second timescale is proposed to precisely regulate intermediate size and dynamic structural evolution without using surfactants, thereby adjusting particle size and exposed crystal facets, which transformed the conventional thermodynamic control paradigm. Specifically, varying the interval time (0.02→6 s) between precipitant (sodium hydroxide, NaOH) and reductant (ascorbic acid, AA) addition significantly altered nanocube size (75→196 nm), while reversing the feeding sequence (AA before NaOH) led to much smaller nanocubes (76→14 nm) due to changes in the microenvironments for particle formation. Moreover, Cu2O polyhedrons exhibited a greater number of exposed facets at shorter residence times, indicating a non-equilibrium state from the thermodynamic perspective. It is expected that such a continuous microflow synthesis system can be directly integrated with downstream catalytic processes to fully exploit the activity of Cu2O.
{"title":"Surfactant-Free Continuous-Flow Synthesis of Cu<sub>2</sub>O Crystals with Diverse Facets and Sizes.","authors":"Chunli Han, Akira Yoko, Ardiansyah Taufik, Satoshi Ohara, Tadafumi Adschiri","doi":"10.1002/smtd.202501927","DOIUrl":"10.1002/smtd.202501927","url":null,"abstract":"<p><p>Cuprous oxide (Cu<sub>2</sub>O) has demonstrated great potential in photochemical, electrochemical, and organic catalysis. Developing surfactant-free and scalable synthesis methods is essential for its real application. Conventional batch methods often suffer from inconsistent product quality and limited scalability. In this work, an efficient continuous microflow synthesis system is developed, and the design principles of the flow synthesis system are systematically elucidated. A kinetic control strategy on the millisecond-to-second timescale is proposed to precisely regulate intermediate size and dynamic structural evolution without using surfactants, thereby adjusting particle size and exposed crystal facets, which transformed the conventional thermodynamic control paradigm. Specifically, varying the interval time (0.02→6 s) between precipitant (sodium hydroxide, NaOH) and reductant (ascorbic acid, AA) addition significantly altered nanocube size (75→196 nm), while reversing the feeding sequence (AA before NaOH) led to much smaller nanocubes (76→14 nm) due to changes in the microenvironments for particle formation. Moreover, Cu<sub>2</sub>O polyhedrons exhibited a greater number of exposed facets at shorter residence times, indicating a non-equilibrium state from the thermodynamic perspective. It is expected that such a continuous microflow synthesis system can be directly integrated with downstream catalytic processes to fully exploit the activity of Cu<sub>2</sub>O.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01927"},"PeriodicalIF":9.1,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145627233","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}
Graphene nanoribbons (GNRs) with well-defined structures have been prepared via on-surface synthesis through polymerization and dehydrocyclization of on-purpose designed precursor molecules. Although nitrogen-doped (N-doped) GNRs have been achieved using nitrogen-containing precursors, the synthesis of N-doped armchair GNRs with subnanometer width remains challenging due to the difficulties associated with designing appropriately small nitrogen-containing precursor molecules. Here, a confined synthesis approach is employed to synthesize N-doped GNRs with subnanometer width using nitrogen-containing molecules through a decomposition-recombination mechanism. Raman spectroscopy and X-ray photoelectron spectroscopy analyses confirmed the effectiveness of aminoferrocene and cyanoferrocene as precursor molecules for synthesizing N-doped GNRs, achieving nitrogen-to-carbon ratios of ≈9.20 and 5.96 at.%, respectively. Additionally, using a dual precursor mixture of ferrocene and cyanoferrocene allows for the synthesis of N-doped GNRs with tunable doping levels by adjusting the precursor ratio. The thermal conductivity of N-doped GNRs is increased by a factor of 1.4 compared to its undoped counterpart. These findings contribute to the precision synthesis of GNRs with controlled edge structures, widths, and doping levels, paving the way for expanded applications of N-doped GNRs.
{"title":"Confined Synthesis of Subnanometer-Wide Nitrogen-Doped Graphene Nanoribbons.","authors":"Kunpeng Tang, Jiongpeng Huang, Wendi Zhang, Huiju Cao, Yingzhi Chen, Yanghao Feng, Haoyuan Zhang, Weili Cui, Kecheng Cao, Lei Shi, Guowei Yang","doi":"10.1002/smtd.202501886","DOIUrl":"https://doi.org/10.1002/smtd.202501886","url":null,"abstract":"<p><p>Graphene nanoribbons (GNRs) with well-defined structures have been prepared via on-surface synthesis through polymerization and dehydrocyclization of on-purpose designed precursor molecules. Although nitrogen-doped (N-doped) GNRs have been achieved using nitrogen-containing precursors, the synthesis of N-doped armchair GNRs with subnanometer width remains challenging due to the difficulties associated with designing appropriately small nitrogen-containing precursor molecules. Here, a confined synthesis approach is employed to synthesize N-doped GNRs with subnanometer width using nitrogen-containing molecules through a decomposition-recombination mechanism. Raman spectroscopy and X-ray photoelectron spectroscopy analyses confirmed the effectiveness of aminoferrocene and cyanoferrocene as precursor molecules for synthesizing N-doped GNRs, achieving nitrogen-to-carbon ratios of ≈9.20 and 5.96 at.%, respectively. Additionally, using a dual precursor mixture of ferrocene and cyanoferrocene allows for the synthesis of N-doped GNRs with tunable doping levels by adjusting the precursor ratio. The thermal conductivity of N-doped GNRs is increased by a factor of 1.4 compared to its undoped counterpart. These findings contribute to the precision synthesis of GNRs with controlled edge structures, widths, and doping levels, paving the way for expanded applications of N-doped GNRs.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01886"},"PeriodicalIF":9.1,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145627173","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}
Mourad Smari, Tanveer Ul Haq, Mohammad Y Al-Haik, Yousef Haik
Direct seawater electrolysis presents significant challenges due to chloride-induced corrosion and the competitive Cl- oxidation, which undermines the efficiency and durability of anode materials. In this study, the rationally synthesized Ag nanocluster-decorated calcium-manganese borate (AgNCs@Ca-MnB) nanosheets are reported as a highly efficient and corrosionresistant electrocatalyst for oxygen evolution in alkaline seawater. Incorporating boron into the Ca─Mn lattice creates electron-deficient sites that enhance the covalency of Mn─O bonds, promoting favorable adsorption energies for OER intermediates while stabilizing the catalyst structure under oxidative conditions. Ag nanoclusters are strategically introduced to the surface, functioning as selective Cl- traps through Ag─Cl complexation, effectively suppressing the Cl- oxidation pathway. The hybrid design further boosts electrochemical surface area and electronic conductivity, ensuring high current density operation with minimal degradation. The AgNCs@Ca-MnB catalyst achieves an overpotential of ≈310 mV at 10 mA cm-2 in real seawater and demonstrates exceptional operational stability over 100 h, outperforming many reported transition metal-based systems. This study introduces a synergistic strategy combining boron-induced electronic modulation and silver-mediated chloride immobilization, offering a new direction in designing durable and selective seawater oxidation catalysts.
由于氯化物引起的腐蚀和竞争性的Cl-氧化,直接海水电解面临着巨大的挑战,这会破坏阳极材料的效率和耐久性。在本研究中,合理合成了银纳米簇修饰的硼酸钙锰纳米片(AgNCs@Ca-MnB),作为碱性海水中高效耐腐蚀的析氧电催化剂。将硼加入到Ca─Mn晶格中会产生缺电子位点,从而增强Mn─O键的共价,促进OER中间体的有利吸附能,同时稳定氧化条件下的催化剂结构。银纳米团簇被战略性地引入表面,通过银-氯络合作用作为选择性Cl-陷阱,有效地抑制Cl-氧化途径。混合设计进一步提高了电化学表面积和电子导电性,确保在最小退化的情况下实现高电流密度操作。AgNCs@Ca-MnB催化剂在实际海水中,在10 mA cm- 2条件下的过电位约为310 mV,在100小时内表现出优异的运行稳定性,优于许多报道的过渡金属基体系。本研究提出了硼诱导的电子调制与银介导的氯化物固定化相结合的协同策略,为设计耐用和选择性的海水氧化催化剂提供了新的方向。
{"title":"Electron-Deficient Mn Sites Functionalized with Ag Nanoclusters Enable Selective and Durable Seawater Oxidation.","authors":"Mourad Smari, Tanveer Ul Haq, Mohammad Y Al-Haik, Yousef Haik","doi":"10.1002/smtd.202501699","DOIUrl":"https://doi.org/10.1002/smtd.202501699","url":null,"abstract":"<p><p>Direct seawater electrolysis presents significant challenges due to chloride-induced corrosion and the competitive Cl<sup>-</sup> oxidation, which undermines the efficiency and durability of anode materials. In this study, the rationally synthesized Ag nanocluster-decorated calcium-manganese borate (AgNCs@Ca-MnB) nanosheets are reported as a highly efficient and corrosionresistant electrocatalyst for oxygen evolution in alkaline seawater. Incorporating boron into the Ca─Mn lattice creates electron-deficient sites that enhance the covalency of Mn─O bonds, promoting favorable adsorption energies for OER intermediates while stabilizing the catalyst structure under oxidative conditions. Ag nanoclusters are strategically introduced to the surface, functioning as selective Cl<sup>-</sup> traps through Ag─Cl complexation, effectively suppressing the Cl<sup>-</sup> oxidation pathway. The hybrid design further boosts electrochemical surface area and electronic conductivity, ensuring high current density operation with minimal degradation. The AgNCs@Ca-MnB catalyst achieves an overpotential of ≈310 mV at 10 mA cm<sup>-</sup> <sup>2</sup> in real seawater and demonstrates exceptional operational stability over 100 h, outperforming many reported transition metal-based systems. This study introduces a synergistic strategy combining boron-induced electronic modulation and silver-mediated chloride immobilization, offering a new direction in designing durable and selective seawater oxidation catalysts.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01699"},"PeriodicalIF":9.1,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145627267","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}