Ana Barragán, Maxence Urbani, Aurelio Gallardo, Elena Pérez-Elvira, Óscar Jover, Koen Lauwaet, José M Gallego, Rodolfo Miranda, Marco Di Giovannantonio, David Écija, Tomás Torres, José I Urgel
The synthesis of porphyrinoid-based low-dimensional polymers has recently attracted considerable interest in view of their intriguing electronic, optical, and catalytic properties. Here, this is introduced by the surface-assisted synthesis of two carbaporphyrinoid-based polymers of increasing dimensionality under ultrahigh-vacuum conditions. The structural and electronic characterization of the resulting polymers has been performed by scanning tunneling and non-contact atomic force microscopies, complemented by theoretical modeling. First, a carbon-carbon coupling between dicarbahemiporphyrazine precursors is achieved by thermal activation of their isopropyl substituents via a [3+3] cycloaromatization, giving rise to one-dimensional (1D) polymers. Second, the same precursor is functionalized with chlorine atoms to complement the [3+3] cycloaromatization with orthogonal dehalogenation and homocoupling, affording two-dimensional (2D) molecular nanostructures. In addition, both low-dimensional free-base porphyrinoid-based polymers are exposed to an atomic flux of cobalt atoms, giving rise to cobalt-metalated macrocycles, with the metal atoms coordinated only to the two pyrrolic nitrogens, in contrast to the typical four-fold coordination that occurs inside tetrapyrroles. This on-surface protocol renders atomically precise covalently-linked porphyrinoid polymers and provides promising model systems toward the exploration of low-coordinated metals with utility in diverse technological areas.
{"title":"On-Surface Synthesis of Covalently-Linked Carbaporphyrinoid-Based Low-Dimensional Polymers.","authors":"Ana Barragán, Maxence Urbani, Aurelio Gallardo, Elena Pérez-Elvira, Óscar Jover, Koen Lauwaet, José M Gallego, Rodolfo Miranda, Marco Di Giovannantonio, David Écija, Tomás Torres, José I Urgel","doi":"10.1002/smll.202408085","DOIUrl":"https://doi.org/10.1002/smll.202408085","url":null,"abstract":"<p><p>The synthesis of porphyrinoid-based low-dimensional polymers has recently attracted considerable interest in view of their intriguing electronic, optical, and catalytic properties. Here, this is introduced by the surface-assisted synthesis of two carbaporphyrinoid-based polymers of increasing dimensionality under ultrahigh-vacuum conditions. The structural and electronic characterization of the resulting polymers has been performed by scanning tunneling and non-contact atomic force microscopies, complemented by theoretical modeling. First, a carbon-carbon coupling between dicarbahemiporphyrazine precursors is achieved by thermal activation of their isopropyl substituents via a [3+3] cycloaromatization, giving rise to one-dimensional (1D) polymers. Second, the same precursor is functionalized with chlorine atoms to complement the [3+3] cycloaromatization with orthogonal dehalogenation and homocoupling, affording two-dimensional (2D) molecular nanostructures. In addition, both low-dimensional free-base porphyrinoid-based polymers are exposed to an atomic flux of cobalt atoms, giving rise to cobalt-metalated macrocycles, with the metal atoms coordinated only to the two pyrrolic nitrogens, in contrast to the typical four-fold coordination that occurs inside tetrapyrroles. This on-surface protocol renders atomically precise covalently-linked porphyrinoid polymers and provides promising model systems toward the exploration of low-coordinated metals with utility in diverse technological areas.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":" ","pages":"e2408085"},"PeriodicalIF":13.0,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646472","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}
Liquid metals (LMs) illustrate a fantastic future. Thus, great endeavors are made to earn a comprehensive understanding of this fluid and carve it into a niche. Herein, by revisiting the combination of Ga-based LMs and aluminum (Al), a new phenomenon, namely the disintegration of LM films on encountering water, is identified. Deviating from previous investigations where the LM generally took the form of bulk puddles, the LM-Al slurry is spread as thin films here. In this case, Al debris embedded in the LM matrix hydrolyzes and therefore can exert disjoining pressure strong enough to split the thin film into countless tiny LM droplets. Based on this mechanism, transient circuits independent of substrate decomposition are realized. Furthermore, taking advantage of the portfolio strategy of pure LM and the LM-Al slurry, novel concepts of flood warning and information storage and encryption are demonstrated. Integrating these functions all in one demonstrates the versatility of the disintegration of thin LM films engendered by Al corrosion, which provides a scientific insight into ephemeral art and makes the Ga─Al combination more illuminating.
{"title":"Disintegration of Thin Liquid Metal Films Engendered by Aluminum Corrosion.","authors":"Wangyan Wu, Guangyu Chai, Wei Luo","doi":"10.1002/smll.202406363","DOIUrl":"https://doi.org/10.1002/smll.202406363","url":null,"abstract":"<p><p>Liquid metals (LMs) illustrate a fantastic future. Thus, great endeavors are made to earn a comprehensive understanding of this fluid and carve it into a niche. Herein, by revisiting the combination of Ga-based LMs and aluminum (Al), a new phenomenon, namely the disintegration of LM films on encountering water, is identified. Deviating from previous investigations where the LM generally took the form of bulk puddles, the LM-Al slurry is spread as thin films here. In this case, Al debris embedded in the LM matrix hydrolyzes and therefore can exert disjoining pressure strong enough to split the thin film into countless tiny LM droplets. Based on this mechanism, transient circuits independent of substrate decomposition are realized. Furthermore, taking advantage of the portfolio strategy of pure LM and the LM-Al slurry, novel concepts of flood warning and information storage and encryption are demonstrated. Integrating these functions all in one demonstrates the versatility of the disintegration of thin LM films engendered by Al corrosion, which provides a scientific insight into ephemeral art and makes the Ga─Al combination more illuminating.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":" ","pages":"e2406363"},"PeriodicalIF":13.0,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646462","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}
Yang Shang, Bo Ren, Ruixue Wu, Jie Lin, Xiaoxia Li, Jixue Shen, Dong Yan, Hui Ying Yang
Manganese Hexacyanoferrate (Mn─HCF) is a preferred cathode material for sodium-ion batteries used in large-scale energy storage. However, the inherent vacancies and the presence of H2O within the imperfect crystal structure of Mn─HCF lead to material failure and interface failure when used as a cathode. Addressing the challenge of constructing a stable cathode is an urgent scientific problem that needs to be solved to enhance the performance and lifespan of these batteries. In this review, the crystal structure of Mn─HCF is first introduced, explaining the formation mechanism of vacancies and exploring the various ways in which H2O molecules can be present within the crystal structure. Then comprehensively summarize the mechanisms of material and interfacial failure in Mn─HCF, highlighting the key factors contributing to these issues. Additionally, eight modification strategies designed to address these failure mechanisms are encapsulated, including vacancy regulation, transition metal substitution, high entropy, the pillar effect, interstitial H2O removal, surface coating, surface vacancy repair, and cathode electrolyte interphase reinforcement. This comprehensive review of the current research advances on Mn─HCF aims to provide valuable guidance and direction for addressing the existing challenges in their application within SIBs.
{"title":"Building Robust Manganese Hexacyanoferrate Cathode for Long-Cycle-Life Sodium-Ion Batteries","authors":"Yang Shang, Bo Ren, Ruixue Wu, Jie Lin, Xiaoxia Li, Jixue Shen, Dong Yan, Hui Ying Yang","doi":"10.1002/smll.202408018","DOIUrl":"https://doi.org/10.1002/smll.202408018","url":null,"abstract":"Manganese Hexacyanoferrate (Mn─HCF) is a preferred cathode material for sodium-ion batteries used in large-scale energy storage. However, the inherent vacancies and the presence of H<sub>2</sub>O within the imperfect crystal structure of Mn─HCF lead to material failure and interface failure when used as a cathode. Addressing the challenge of constructing a stable cathode is an urgent scientific problem that needs to be solved to enhance the performance and lifespan of these batteries. In this review, the crystal structure of Mn─HCF is first introduced, explaining the formation mechanism of vacancies and exploring the various ways in which H<sub>2</sub>O molecules can be present within the crystal structure. Then comprehensively summarize the mechanisms of material and interfacial failure in Mn─HCF, highlighting the key factors contributing to these issues. Additionally, eight modification strategies designed to address these failure mechanisms are encapsulated, including vacancy regulation, transition metal substitution, high entropy, the pillar effect, interstitial H<sub>2</sub>O removal, surface coating, surface vacancy repair, and cathode electrolyte interphase reinforcement. This comprehensive review of the current research advances on Mn─HCF aims to provide valuable guidance and direction for addressing the existing challenges in their application within SIBs.","PeriodicalId":228,"journal":{"name":"Small","volume":"48 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642738","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}
Hien A. Tran, Anton Maraldo, Trinh Thi‐Phuong Ho, Mai Thanh Thai, Quinn van Hilst, Habib Joukhdar, Marija Kordanovski, Jugal Kishore Sahoo, Onur Hartsuk, Miguel Santos, Steven G. Wise, David L. Kaplan, Thanh Nho Do, Kristopher A. Kilian, Khoon S. Lim, Jelena Rnjak‐Kovacina
Covalent crosslinking of silk fibroin via native tyrosine residues has been extensively explored; however, while these materials are very promising for biomedical, optical, soft robotics, and sensor applications, their structure and mechanical properties are unstable over time. This instability results in spontaneous silk self‐assembly and stiffening over time, a process that is poorly understood. This study investigates the interplay between self‐assembly and di‐tyrosine bond formation in silk hydrogels photo‐crosslinked using ruthenium (Ru) and sodium persulfate (SPS) with visible light. The effects of silk concentration, molecular weight, Ru/SPS concentration, and solvent conditions are examined. The Ru/SPS system enables rapid crosslinking, achieving gelation within seconds and incorporating over 90% of silk into the network, even at very low protein concentrations (≥0.75% wt/v). A model emerges where silk self‐assembly both before and after crosslinking affects protein phase separation, mesoscale structure, and dynamic changes in the hydrogel network over time. Silk concentration has the greatest impact on hydrogel properties, with higher silk concentration hydrogels experiencing two orders of magnitude increase in stiffness within 1 week. This new understanding and ability to tune hydrogel properties and dynamic stiffening aids in developing advanced materials for 4D biofabrication, sensing, 3D cancer models, drug delivery, and soft robotics.
{"title":"Probing the Interplay of Protein Self‐Assembly and Covalent Bond Formation in Photo‐Crosslinked Silk Fibroin Hydrogels","authors":"Hien A. Tran, Anton Maraldo, Trinh Thi‐Phuong Ho, Mai Thanh Thai, Quinn van Hilst, Habib Joukhdar, Marija Kordanovski, Jugal Kishore Sahoo, Onur Hartsuk, Miguel Santos, Steven G. Wise, David L. Kaplan, Thanh Nho Do, Kristopher A. Kilian, Khoon S. Lim, Jelena Rnjak‐Kovacina","doi":"10.1002/smll.202407923","DOIUrl":"https://doi.org/10.1002/smll.202407923","url":null,"abstract":"Covalent crosslinking of silk fibroin via native tyrosine residues has been extensively explored; however, while these materials are very promising for biomedical, optical, soft robotics, and sensor applications, their structure and mechanical properties are unstable over time. This instability results in spontaneous silk self‐assembly and stiffening over time, a process that is poorly understood. This study investigates the interplay between self‐assembly and di‐tyrosine bond formation in silk hydrogels photo‐crosslinked using ruthenium (Ru) and sodium persulfate (SPS) with visible light. The effects of silk concentration, molecular weight, Ru/SPS concentration, and solvent conditions are examined. The Ru/SPS system enables rapid crosslinking, achieving gelation within seconds and incorporating over 90% of silk into the network, even at very low protein concentrations (≥0.75% wt/v). A model emerges where silk self‐assembly both before and after crosslinking affects protein phase separation, mesoscale structure, and dynamic changes in the hydrogel network over time. Silk concentration has the greatest impact on hydrogel properties, with higher silk concentration hydrogels experiencing two orders of magnitude increase in stiffness within 1 week. This new understanding and ability to tune hydrogel properties and dynamic stiffening aids in developing advanced materials for 4D biofabrication, sensing, 3D cancer models, drug delivery, and soft robotics.","PeriodicalId":228,"journal":{"name":"Small","volume":"75 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642785","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}
Maida Aysla Costa de Oliveira, Marc Brunet Cabré, Christian Schröder, Hugo Nolan, Filippo Pota, James A. Behan, Frédéric Barrière, Kim McKelvey, Paula E. Colavita
N-doped graphene oxides (GO) are nanomaterials of interest as building blocks for 3D electrode architectures for vanadium redox flow battery applications. N- and O-functionalities have been reported to increase charge transfer rates for vanadium redox couples. However, GO synthesis typically yields heterogeneous nanomaterials, making it challenging to understand whether the electrochemical activity of conventional GO electrodes results from a sub-population of GO entities or sub-domains. Herein, single-entity voltammetry studies of vanadyl oxidation at N-doped GO using scanning electrochemical cell microscopy (SECCM) are reported. The electrochemical response is mapped at sub-domains within isolated flakes and found to display significant heterogeneity: small active sites are interspersed between relatively large inert sub-domains. Correlative Raman-SECCM analysis suggests that defect densities are not useful predictors of activity, while the specific chemical nature of defects might be a more important factor for understanding oxidation rates. Finite element simulations of the electrochemical response suggest that active sub-domains/sites are smaller than the mean inter-defect distance estimated from Raman spectra but can display very fast heterogeneous rate constants >1 cm s−1. These results indicate that N-doped GO electrodes can deliver on intrinsic activity requirements set out for the viable performance of vanadium redox flow battery devices.
掺杂 N 的石墨烯氧化物（GO）是一种纳米材料，是钒氧化还原液流电池应用中三维电极结构的构件。据报道，N-和 O-官能团可提高钒氧化还原偶的电荷传输速率。然而，GO 的合成通常会产生异质纳米材料，这使得了解传统 GO 电极的电化学活性是否来自于 GO 实体的子群或子域变得十分困难。本文报告了利用扫描电化学电池显微镜（SECCM）对掺杂 N 的 GO 上的香草醛氧化进行的单实体伏安研究。研究人员对孤立薄片中的子域绘制了电化学响应图，发现其显示出显著的异质性：小的活性位点穿插在相对较大的惰性子域之间。拉曼-SECCM 关联分析表明，缺陷密度并不能有效预测活性，而缺陷的特定化学性质可能是了解氧化率的更重要因素。电化学响应的有限元模拟表明，活性子域/位点小于拉曼光谱估计的平均缺陷间距，但可以显示出非常快的异质速率常数 >1 cm s-1。这些结果表明，掺杂了 N 的 GO 电极可以满足钒氧化还原液流电池装置可行性能所需的内在活性要求。
{"title":"Single-Entity Electrochemistry of N-Doped Graphene Oxide Nanostructures for Improved Kinetics of Vanadyl Oxidation","authors":"Maida Aysla Costa de Oliveira, Marc Brunet Cabré, Christian Schröder, Hugo Nolan, Filippo Pota, James A. Behan, Frédéric Barrière, Kim McKelvey, Paula E. Colavita","doi":"10.1002/smll.202405220","DOIUrl":"https://doi.org/10.1002/smll.202405220","url":null,"abstract":"N-doped graphene oxides (GO) are nanomaterials of interest as building blocks for 3D electrode architectures for vanadium redox flow battery applications. N- and O-functionalities have been reported to increase charge transfer rates for vanadium redox couples. However, GO synthesis typically yields heterogeneous nanomaterials, making it challenging to understand whether the electrochemical activity of conventional GO electrodes results from a sub-population of GO entities or sub-domains. Herein, single-entity voltammetry studies of vanadyl oxidation at N-doped GO using scanning electrochemical cell microscopy (SECCM) are reported. The electrochemical response is mapped at sub-domains within isolated flakes and found to display significant heterogeneity: small active sites are interspersed between relatively large inert sub-domains. Correlative Raman-SECCM analysis suggests that defect densities are not useful predictors of activity, while the specific chemical nature of defects might be a more important factor for understanding oxidation rates. Finite element simulations of the electrochemical response suggest that active sub-domains/sites are smaller than the mean inter-defect distance estimated from Raman spectra but can display very fast heterogeneous rate constants >1 cm s<sup>−1</sup>. These results indicate that N-doped GO electrodes can deliver on intrinsic activity requirements set out for the viable performance of vanadium redox flow battery devices.","PeriodicalId":228,"journal":{"name":"Small","volume":"12 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642737","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}
Huijuan Wu, Shanshui Lian, Jinqiu Zhang, Bingkun Wang, Wenjun Bai, Guqiao Ding, Siwei Yang, Zhiduo Liu, Li Zheng, Caichao Ye, Gang Wang
To expand the detection capabilities of silicon (Si)-based photodetector and address key scientific challenges such as low light absorption efficiency and short carrier lifetime in Si-based graphene photodetector. This work introduces a novel Si-based Schottky coupled structure by in situ growth of 3D-graphene and molybdenum disulfide quantum dots (MoS2 QDs) on Si substrates using chemical vapor deposition (CVD) and plasma-enhanced chemical vapor deposition (PECVD) techniques. The findings validate the “dual-enhanced absorption” effect, enhancing the understanding of the mechanisms that improve optoelectronic performance. The synergistic effect of 3D-graphene's natural nano-resonant cavity and MoS2 QDs enhances light absorption efficiency and extends carrier lifetime. Introducing MoS2 QDs broadens and intensifies the built-in electric field, promoting the separation of photogenerated electrons and holes. The photodetector exhibits a wideband light response in the wavelength range of 380–2200 nm. It stably outputs photocurrent under high-frequency (1 kHz) modulated laser (2200 nm), with a responsivity (R) of 40 mA W−1 and detectivity (D*) of 1.15 × 109 Jones. Photodetectors show the ability to process and encrypt complex binary signals and achieve versatility in “AND” gate and “OR” gate logic operations, as well as image sensing (240 × 200 pixels).
{"title":"Construction and Multifunctional Photonic Applications of Light Absorption-Enhanced Silicon-Based Schottky Coupled Structures","authors":"Huijuan Wu, Shanshui Lian, Jinqiu Zhang, Bingkun Wang, Wenjun Bai, Guqiao Ding, Siwei Yang, Zhiduo Liu, Li Zheng, Caichao Ye, Gang Wang","doi":"10.1002/smll.202406164","DOIUrl":"https://doi.org/10.1002/smll.202406164","url":null,"abstract":"To expand the detection capabilities of silicon (Si)-based photodetector and address key scientific challenges such as low light absorption efficiency and short carrier lifetime in Si-based graphene photodetector. This work introduces a novel Si-based Schottky coupled structure by in situ growth of 3D-graphene and molybdenum disulfide quantum dots (MoS<sub>2</sub> QDs) on Si substrates using chemical vapor deposition (CVD) and plasma-enhanced chemical vapor deposition (PECVD) techniques. The findings validate the “dual-enhanced absorption” effect, enhancing the understanding of the mechanisms that improve optoelectronic performance. The synergistic effect of 3D-graphene's natural nano-resonant cavity and MoS<sub>2</sub> QDs enhances light absorption efficiency and extends carrier lifetime. Introducing MoS<sub>2</sub> QDs broadens and intensifies the built-in electric field, promoting the separation of photogenerated electrons and holes. The photodetector exhibits a wideband light response in the wavelength range of 380–2200 nm. It stably outputs photocurrent under high-frequency (1 kHz) modulated laser (2200 nm), with a responsivity (R) of 40 mA W<sup>−1</sup> and detectivity (D<sup>*</sup>) of 1.15 × 10<sup>9</sup> Jones. Photodetectors show the ability to process and encrypt complex binary signals and achieve versatility in “AND” gate and “OR” gate logic operations, as well as image sensing (240 × 200 pixels).","PeriodicalId":228,"journal":{"name":"Small","volume":"5 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642969","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}
Current limitations in 3D printing pose significant challenges for the fabrication of hierarchical 3D scaffolds with nanofibrous structures that simulate the natural bone extracellular matrix (ECM) for enhanced bone regeneration. This study presents an innovative approach to 3D printing customized hierarchical porous scaffolds with nanofiber structures using biodegradable nanofibrous microspheres as the bio‐ink. In vitro investigations demonstrate that the hierarchical porous architecture substantially enhances cell infiltration and proliferation rates, while the nanofiber topology provides physical cues to guide osteogenic differentiation and ECM deposition. When serving as a cell carrier, the 3D‐printed nanofibrous scaffold promotes bone tissue regeneration and integration in vivo. Additionally, the facile and versatile chemical modification facilitates the precise tailoring of the scaffold's functionality. Using nanofibrous microspheres with highly biomimetic and versatile modification properties as the foundational constituent in this universal 3D printing methodology enables comprehensive manipulation of scaffolding biological properties, spanning from macroscopic external morphology to molecular‐scale biochemical kinetics, thereby addressing a diverse spectrum of clinical requisites.
{"title":"3D Printing Hierarchical Porous Nanofibrous Scaffold for Bone Regeneration","authors":"Zhiai Hu, Hengyi Lin, Zhenming Wang, Yating Yi, Shujuan Zou, Hao Liu, Xianglong Han, Xin Rong","doi":"10.1002/smll.202405406","DOIUrl":"https://doi.org/10.1002/smll.202405406","url":null,"abstract":"Current limitations in 3D printing pose significant challenges for the fabrication of hierarchical 3D scaffolds with nanofibrous structures that simulate the natural bone extracellular matrix (ECM) for enhanced bone regeneration. This study presents an innovative approach to 3D printing customized hierarchical porous scaffolds with nanofiber structures using biodegradable nanofibrous microspheres as the bio‐ink. In vitro investigations demonstrate that the hierarchical porous architecture substantially enhances cell infiltration and proliferation rates, while the nanofiber topology provides physical cues to guide osteogenic differentiation and ECM deposition. When serving as a cell carrier, the 3D‐printed nanofibrous scaffold promotes bone tissue regeneration and integration in vivo. Additionally, the facile and versatile chemical modification facilitates the precise tailoring of the scaffold's functionality. Using nanofibrous microspheres with highly biomimetic and versatile modification properties as the foundational constituent in this universal 3D printing methodology enables comprehensive manipulation of scaffolding biological properties, spanning from macroscopic external morphology to molecular‐scale biochemical kinetics, thereby addressing a diverse spectrum of clinical requisites.","PeriodicalId":228,"journal":{"name":"Small","volume":"166 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642788","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}
Qian Wang, Jun Du, Fujun Yang, Sijia Wu, Luna Zhu, Xueyu Li, Han Yang, Yuqing Miao, Yuhao Li
The tumor microenvironment (TME) is characterized by hypoxia and low immunogenicity, with a dense and rigid extracellular matrix (ECM) that impedes the diffusion of therapeutic agents and immune cells, thereby limiting the efficacy of immunotherapy. To overcome these challenges, an oxygen defect piezoelectric‐photothermal sensitizer, bismuth vanadate nanorod‐supported platinum nanodots (BVP) is developed. The integration of platinum enhances the photothermal effect and improves charge separation efficiency under ultrasound, leading to increased heat generation and the production of reactive oxygen species (ROS) and oxygen. Platinum also catalyzes the conversion of hydrogen peroxide in the TME to oxygen, which serves as both a ROS source and a means to alleviate tumor hypoxia, thereby reversing the immunosuppressive TME. Moreover, the coordination of bismuth ions with glutathione further amplifies cellular oxidative stress. The generated heat and ROS not only denature the collagen in the ECM, facilitating the deeper penetration of BVP into the tumor but also induce immunogenic cell death in tumor cells. Through the “degeneration and penetration” strategy, photoacoustic therapy effectively activates immune cells, inhibiting both tumor growth and metastasis. This study introduces a pioneering approach in the design of antitumor nanomedicines aimed at reversing the immunosuppressive characteristics of the TME.
{"title":"Charge Separation‐Engineered Piezoelectric Ultrathin Nanorods Modulate Tumor Stromal Microenvironment and Enhance Cell Immunogenicity for Synergistically Piezo‐Thermal‐Immune Therapy","authors":"Qian Wang, Jun Du, Fujun Yang, Sijia Wu, Luna Zhu, Xueyu Li, Han Yang, Yuqing Miao, Yuhao Li","doi":"10.1002/smll.202408038","DOIUrl":"https://doi.org/10.1002/smll.202408038","url":null,"abstract":"The tumor microenvironment (TME) is characterized by hypoxia and low immunogenicity, with a dense and rigid extracellular matrix (ECM) that impedes the diffusion of therapeutic agents and immune cells, thereby limiting the efficacy of immunotherapy. To overcome these challenges, an oxygen defect piezoelectric‐photothermal sensitizer, bismuth vanadate nanorod‐supported platinum nanodots (BVP) is developed. The integration of platinum enhances the photothermal effect and improves charge separation efficiency under ultrasound, leading to increased heat generation and the production of reactive oxygen species (ROS) and oxygen. Platinum also catalyzes the conversion of hydrogen peroxide in the TME to oxygen, which serves as both a ROS source and a means to alleviate tumor hypoxia, thereby reversing the immunosuppressive TME. Moreover, the coordination of bismuth ions with glutathione further amplifies cellular oxidative stress. The generated heat and ROS not only denature the collagen in the ECM, facilitating the deeper penetration of BVP into the tumor but also induce immunogenic cell death in tumor cells. Through the “degeneration and penetration” strategy, photoacoustic therapy effectively activates immune cells, inhibiting both tumor growth and metastasis. This study introduces a pioneering approach in the design of antitumor nanomedicines aimed at reversing the immunosuppressive characteristics of the TME.","PeriodicalId":228,"journal":{"name":"Small","volume":"48 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642964","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}
Shuijing Wang, Tangying Miao, Yang Wang, Jinshan Xu, Fengyuan Jia, Yang Li, Jiahui Kou, Zhongzi Xu
Undersea optical communication (UOC) is vital for ocean exploration and military applications. In the dim-light underwater environment, photodetectors must maximize photon utilization by minimizing optical losses and carrier recombination. This can be achieved by integrating ultrathin metal nanostructures with photocatalysts to form Schottky junctions, which enhance charge separation and injection while mitigating metal-induced light shading. The strategic design of discrete metal nanostructures providing numerous high-depth space charge regions (SCRs) without overlap offers a promising approach to optimize hole transport paths and further suppress recombination. Here, a facile phase-separation lithography technique is explored to fabricate tunable ultrathin Ni nanoislands atop n-Si, yielding high-performance photoelectrochemical photodetectors (PEC PDs) tailored for underwater weak-light environments. This results indicate that key determinant of hole extraction behavior is the relationship between the spacing distance of adjacent Ni nanostructures (ds) and twice the SCR radius (Ws). PEC PDs with optimized 8 nm ultrathin Ni nanostructures featuring closely but non-overlapping SCRs, exhibit a 55-fold increase in photoresponsivity (2.2 mA W−1) and a 128-fold enhancement in detection sensitivity (3.2 × 1011 Jones) at 0 V over Ni film, revealing the exceptional stability. Furthermore, this approach enables effective detection across UV–vis-near infrared spectrum, supporting reliable multispectral UOC and underwater imaging capabilities.
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Triphenylamine‐based Y‐shaped organic sensitizers, specifically TPA‐MN (1), TPA‐CA (2), TPAT‐MN (3), and TPAT‐CA (4), are synthesized and utilized as p‐type self‐assembled monolayers (SAMs) for tin‐based perovskite solar cells (TPSCs). These SAMs are developed using low‐cost starting materials, primarily from triphenylamine (TPA) components. An extensive analysis is conducted to examine the crystalline, morphological, thermal, optical, electrochemical, and optoelectronic characteristics of SAMs 1–4, and the results are compared. A two‐step method is employed to successfully develop tin perovskite layers on all four SAM surfaces. The resulting devices demonstrates PCE in the following order: TPAT‐CA (8.1%) > TPAT‐MN (6.1%) > TPA‐MN (5.0%) > TPA‐CA (4.2%). The TPAT‐CA molecule, which contains a thiophene spacer, performed better than the other three SAMs in terms of rapid hole extraction rate, high hole mobility, and retarded charge recombination. Consequently, SAM TPAT‐CA exhibited the highest device performance with excellent stability over time, retaining ≈90% from the beginning values after storage for 3000 h. The innovative Y‐shaped SAMs describe in this study, characterized by their simple and efficient design, have the potential to contribute significantly to the advancement of perovskite photovoltaics, particularly in the development of cost‐effective TPSC technology.
我们合成了三苯胺基 Y 型有机敏化剂，特别是 TPA-MN (1)、TPA-CA (2)、TPAT-MN (3) 和 TPAT-CA (4)，并将其用作锡基过氧化物太阳能电池 (TPSC) 的 p 型自组装单层 (SAM)。这些 SAM 是使用低成本的起始材料（主要来自三苯胺 (TPA) 成分）开发的。对 SAM 1-4 的结晶、形态、热、光学、电化学和光电特性进行了广泛的分析，并对结果进行了比较。采用两步法成功地在所有四种 SAM 表面上形成了锡包晶层。所得器件按以下顺序显示出 PCE：TPAT-CA（8.1%）；TPAT-MN（6.1%）；TPA-MN（5.0%）；TPA-CA（4.2%）。含有噻吩间隔的 TPAT-CA 分子在快速空穴萃取率、高空穴迁移率和延迟电荷重组方面的表现优于其他三种 SAM。因此，SAM TPAT-CA 表现出最高的器件性能和卓越的长期稳定性，在存储 3000 小时后，其性能仍能保持≈90%的初始值。 本研究中描述的创新型 Y 型 SAM 具有设计简单、效率高的特点，有望为促进过氧化物光伏技术的发展，特别是在开发具有成本效益的 TPSC 技术方面做出重大贡献。
{"title":"Triphenylamine‐Based Y‐Shaped Self‐Assembled Monolayers for Efficient Tin Perovskite Solar Cells","authors":"Shakil N. Afraj, Chun‐Hsiao Kuan, Hsu‐Lung Cheng, Yun‐Xin Wang, Cheng‐Liang Liu, Yun‐Sheng Shih, Jhih‐Min Lin, Yi‐Wei Tsai, Ming‐Chou Chen, Eric Wei‐Guang Diau","doi":"10.1002/smll.202408638","DOIUrl":"https://doi.org/10.1002/smll.202408638","url":null,"abstract":"Triphenylamine‐based Y‐shaped organic sensitizers, specifically TPA‐MN (1), TPA‐CA (2), TPAT‐MN (3), and TPAT‐CA (4), are synthesized and utilized as <jats:italic>p</jats:italic>‐type self‐assembled monolayers (SAMs) for tin‐based perovskite solar cells (TPSCs). These SAMs are developed using low‐cost starting materials, primarily from triphenylamine (TPA) components. An extensive analysis is conducted to examine the crystalline, morphological, thermal, optical, electrochemical, and optoelectronic characteristics of SAMs 1–4, and the results are compared. A two‐step method is employed to successfully develop tin perovskite layers on all four SAM surfaces. The resulting devices demonstrates PCE in the following order: TPAT‐CA (8.1%) > TPAT‐MN (6.1%) > TPA‐MN (5.0%) > TPA‐CA (4.2%). The TPAT‐CA molecule, which contains a thiophene spacer, performed better than the other three SAMs in terms of rapid hole extraction rate, high hole mobility, and retarded charge recombination. Consequently, SAM TPAT‐CA exhibited the highest device performance with excellent stability over time, retaining ≈90% from the beginning values after storage for 3000 h. The innovative Y‐shaped SAMs describe in this study, characterized by their simple and efficient design, have the potential to contribute significantly to the advancement of perovskite photovoltaics, particularly in the development of cost‐effective TPSC technology.","PeriodicalId":228,"journal":{"name":"Small","volume":"9 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642787","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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