Yanjing Gao, Farbod Shirinichi, Audrey Hansrisuk, Runyao Zhu, Sijie Xian, Marya Lieberman, Matthew J. Webber, Yichun Wang
Opioid Detection
Fentanyl and related opioids pose a serious threat to public health and safety. In article number 2407702, Matthew J. Webber, Yichun Wang, and co-workers created an effective sensor system by coupling drug-induced displacement of a fluorescent dye from a supramolecular macrocycle with dye quenching by graphene quantum dot nanomaterials. This sensor can broadly detect fentanyl analogues, even in trace amounts alongside other compounds.
{"title":"A Supramolecular–Quantum Dot System for Broad-Spectrum Detection of Fentanyl Analogs (Small 16/2025)","authors":"Yanjing Gao, Farbod Shirinichi, Audrey Hansrisuk, Runyao Zhu, Sijie Xian, Marya Lieberman, Matthew J. Webber, Yichun Wang","doi":"10.1002/smll.202570120","DOIUrl":"https://doi.org/10.1002/smll.202570120","url":null,"abstract":"<p><b>Opioid Detection</b></p><p>Fentanyl and related opioids pose a serious threat to public health and safety. In article number 2407702, Matthew J. Webber, Yichun Wang, and co-workers created an effective sensor system by coupling drug-induced displacement of a fluorescent dye from a supramolecular macrocycle with dye quenching by graphene quantum dot nanomaterials. This sensor can broadly detect fentanyl analogues, even in trace amounts alongside other compounds.\u0000\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":228,"journal":{"name":"Small","volume":"21 16","pages":""},"PeriodicalIF":13.0,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/smll.202570120","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866049","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Synthesizing 2D nanosheets in a controlled and scalable manner remains a significant challenge. Here, a nanoconfined solvothermal synthesis is presented of metallic phase MoS2 (1T-MoS2) monolayers at kilogram scale. The MoS2 nanosheets exhibit a remarkably high monolayer ratio of 97%, a 1T content of ≈89%, and a well-defined average lateral size ranging from ≈100 nm to 1.0 µm, with a narrow size distribution. Moreover, these nanosheets possesses abundant surface defects, and the defect density can be regulated in situ through changing the reaction conditions. Intriguingly, the monolayer MoS2 nanosheets demonstrate good dispersibility and high stability in various solvents, including water, ethylene glycol, dimethyl formamide and others, with a high concentration of up to 1.0 mg mL−1. They are also proven to be high-performance electrocatalysts for the hydrogen evolution reaction, exhibiting an overpotential of 315 mV at an industrial current density of 1000 mA cm−2 and maintaining constant current densities of 500 mA cm−2 for up to 100 h, surpassing the performance of the commercial 20 wt.% Pt/C. Our strategy represents a significant advancement in the controlled synthesis of monolayer MoS2 at scale, providing a promising avenue for the practical application of 2D materials.
{"title":"Nanoconfined Solvothermal Synthesis of Defective 1T-MoS2 Monolayers with High Electrocatalytic Performance","authors":"Yishu Chen, Yuxin Zhang, Deliang Wang, Kexuan Zhao, Wen-Jun Wang, Bogeng Li, Pingwei Liu","doi":"10.1002/smll.202410087","DOIUrl":"https://doi.org/10.1002/smll.202410087","url":null,"abstract":"Synthesizing 2D nanosheets in a controlled and scalable manner remains a significant challenge. Here, a nanoconfined solvothermal synthesis is presented of metallic phase MoS<sub>2</sub> (1T-MoS<sub>2</sub>) monolayers at kilogram scale. The MoS<sub>2</sub> nanosheets exhibit a remarkably high monolayer ratio of 97%, a 1T content of ≈89%, and a well-defined average lateral size ranging from ≈100 nm to 1.0 µm, with a narrow size distribution. Moreover, these nanosheets possesses abundant surface defects, and the defect density can be regulated in situ through changing the reaction conditions. Intriguingly, the monolayer MoS<sub>2</sub> nanosheets demonstrate good dispersibility and high stability in various solvents, including water, ethylene glycol, dimethyl formamide and others, with a high concentration of up to 1.0 mg mL<sup>−1</sup>. They are also proven to be high-performance electrocatalysts for the hydrogen evolution reaction, exhibiting an overpotential of 315 mV at an industrial current density of 1000 mA cm<sup>−2</sup> and maintaining constant current densities of 500 mA cm<sup>−2</sup> for up to 100 h, surpassing the performance of the commercial 20 wt.% Pt/C. Our strategy represents a significant advancement in the controlled synthesis of monolayer MoS<sub>2</sub> at scale, providing a promising avenue for the practical application of 2D materials.","PeriodicalId":228,"journal":{"name":"Small","volume":"26 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867226","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}
It is difficult for hydrogels to have both excellent stiffness and toughness in conventional polymer networks. Physically entangled hydrogels provide ideas to solve this problem, but the loss of physical entanglement in the swelling process does not effectively utilize the potential of this approach. In this work, the hydrogel is synthesized including two layers of interpenetrating physically entangled networks, the backbone network and the filler network. According to rubberlike elasticity theory, the backbone network inhibits the swelling of the filler network retaining a large amount of physical entanglements, inheriting and enhancing the advantages of physically entanglement hydrogels. The stiffness of the hydrogel reaches 0.33 MPa, and the fracture toughness reaches 1.93 × 104 J m−2, which shows significant advantages over other hydrogels. The removable physical entanglements tend to favor an ideal uniform network after being subjected to cyclic loading, and the toughness and fracture strain improve more than 2 times to 4.2 MJ m−3 and 7.2, respectively. The fatigue threshold reaches 5.41 × 103 J m−2, which is five times higher than the fatigue-resistant hydrogels. The present work perfectly inherits the physically entangled network structure while realizing the anti-swelling property, which provides a way to break the toughness-stiffness conflict intractable in hydrogels.
{"title":"Physically Entangled Hydrogels Constructed Through Pre-Stretched Backbone Provide Excellent Comprehensive Mechanical Properties","authors":"Junyu Wang, Xiaomin Li, Yuhong Liu","doi":"10.1002/smll.202501666","DOIUrl":"https://doi.org/10.1002/smll.202501666","url":null,"abstract":"It is difficult for hydrogels to have both excellent stiffness and toughness in conventional polymer networks. Physically entangled hydrogels provide ideas to solve this problem, but the loss of physical entanglement in the swelling process does not effectively utilize the potential of this approach. In this work, the hydrogel is synthesized including two layers of interpenetrating physically entangled networks, the backbone network and the filler network. According to rubberlike elasticity theory, the backbone network inhibits the swelling of the filler network retaining a large amount of physical entanglements, inheriting and enhancing the advantages of physically entanglement hydrogels. The stiffness of the hydrogel reaches 0.33 MPa, and the fracture toughness reaches 1.93 × 10<sup>4</sup> J m<sup>−2</sup>, which shows significant advantages over other hydrogels. The removable physical entanglements tend to favor an ideal uniform network after being subjected to cyclic loading, and the toughness and fracture strain improve more than 2 times to 4.2 MJ m<sup>−3</sup> and 7.2, respectively. The fatigue threshold reaches 5.41 × 10<sup>3</sup> J m<sup>−2</sup>, which is five times higher than the fatigue-resistant hydrogels. The present work perfectly inherits the physically entangled network structure while realizing the anti-swelling property, which provides a way to break the toughness-stiffness conflict intractable in hydrogels.","PeriodicalId":228,"journal":{"name":"Small","volume":"7 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867211","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}
Potassium–sodium niobate (KNN) ceramics are critical lead‐free piezoelectric materials, offering eco‐friendly alternatives with high performance for sustainable sensor applications. However, how to overcome the theoretical framework of conventional K/Na ratio limitation and achieve property enhancement in extreme composition remains to be fully understood. Herein, by combining density function theory calculation, Rayleigh analysis, and ferroelectric scaling behavior, the origin of property discrepancy in KNN‐based ceramics with extreme K/Na ratio is unveiled. Compared with Na‐rich sample, 2.3‐fold enhanced piezoelectricity can be achieved in K‐rich ceramics, superior to those with similar high K concentration. The deteriorated property in Na‐rich sample comes from the existence of in‐phase oxygen octahedron tilting (M2+) mode, suppressing the polar () mode and leading to a higher energy barrier. Nevertheless, the absence of M2+ mode and the multiphase coexistence with a maze‐like domain, promote polarization rotation and domain switching, resulting in improved piezoelectric response in K‐rich ceramics. A compression‐type accelerometer based on KNN with extreme K/Na ratio is designed and the sensitivity of K‐rich ceramics is also much higher than that of Na‐rich ones, highest in reported KNN‐based piezoelectric accelerometers. The study provides a new paradigm to boost electrical properties and reveals the underlying mechanism of property discrepancy induced by extreme K/Na ratio, beneficial to the development of sensor applications.
{"title":"Revealing the Origin of Property Discrepancy in KNN‐Based Ceramics with Extreme K/Na Ratio for Sensing Application","authors":"Yi Ding, Zhi Tan, Yongqi Pan, Yu Wang, Yangda Dong, Wenbin Liu, Ting Zheng, Jiagang Wu","doi":"10.1002/smll.202502418","DOIUrl":"https://doi.org/10.1002/smll.202502418","url":null,"abstract":"Potassium–sodium niobate (KNN) ceramics are critical lead‐free piezoelectric materials, offering eco‐friendly alternatives with high performance for sustainable sensor applications. However, how to overcome the theoretical framework of conventional K/Na ratio limitation and achieve property enhancement in extreme composition remains to be fully understood. Herein, by combining density function theory calculation, Rayleigh analysis, and ferroelectric scaling behavior, the origin of property discrepancy in KNN‐based ceramics with extreme K/Na ratio is unveiled. Compared with Na‐rich sample, 2.3‐fold enhanced piezoelectricity can be achieved in K‐rich ceramics, superior to those with similar high K concentration. The deteriorated property in Na‐rich sample comes from the existence of in‐phase oxygen octahedron tilting (M<jats:sub>2</jats:sub><jats:sup>+</jats:sup>) mode, suppressing the polar () mode and leading to a higher energy barrier. Nevertheless, the absence of M<jats:sub>2</jats:sub><jats:sup>+</jats:sup> mode and the multiphase coexistence with a maze‐like domain, promote polarization rotation and domain switching, resulting in improved piezoelectric response in K‐rich ceramics. A compression‐type accelerometer based on KNN with extreme K/Na ratio is designed and the sensitivity of K‐rich ceramics is also much higher than that of Na‐rich ones, highest in reported KNN‐based piezoelectric accelerometers. The study provides a new paradigm to boost electrical properties and reveals the underlying mechanism of property discrepancy induced by extreme K/Na ratio, beneficial to the development of sensor applications.","PeriodicalId":228,"journal":{"name":"Small","volume":"35 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866653","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}
Ajeet Singh, Brij Mohan, Vijay Pratap, Wei Sun, Armando J. L. Pombeiro, Bal Chandra Yadav
Formaldehyde is a frequent indoor pollutant that poses a risk to human and environmental health and is suspected to be a carcinogen. However, achieving high sensitivity and selectivity for real‐time applications remains challenging. In this study, a room‐temperature operated formaldehyde chemiresistor is developed by cerium dioxide/indium oxide (CeO2/In2O3) nanocomposite for exclusive detection. The nanocomposite is synthesized using hydrothermal, forming CeO2 nanospheres grown on In2O3 nanocubes. This unique structure enhances the sensing capabilities of CeO2/In2O3, allowing it to detect formaldehyde in the 1–50 ppm range, and a 0.157 ppm detection limit is earned. The sensor exhibits an impressive response of 175.05 at 50 ppm at room temperature and shows responsiveness to various other substances, for instance, methanol, ethanol, aniline, benzene, toluene, acetone, and ammonia. Additionally, the CeO2/In2O3 sensor demonstrated moderate to high selectivity, sensitivity, stability, speedy response/recovery times, and resilience to humidity. This work presents a promising strategy for the detection of formaldehyde.
{"title":"Humidity‐Resistant CeO2/In2O3 Nanocomposite‐Based Chemiresistor for Selective Detection of Formaldehyde","authors":"Ajeet Singh, Brij Mohan, Vijay Pratap, Wei Sun, Armando J. L. Pombeiro, Bal Chandra Yadav","doi":"10.1002/smll.202410023","DOIUrl":"https://doi.org/10.1002/smll.202410023","url":null,"abstract":"Formaldehyde is a frequent indoor pollutant that poses a risk to human and environmental health and is suspected to be a carcinogen. However, achieving high sensitivity and selectivity for real‐time applications remains challenging. In this study, a room‐temperature operated formaldehyde chemiresistor is developed by cerium dioxide/indium oxide (CeO<jats:sub>2</jats:sub>/In<jats:sub>2</jats:sub>O<jats:sub>3</jats:sub>) nanocomposite for exclusive detection. The nanocomposite is synthesized using hydrothermal, forming CeO<jats:sub>2</jats:sub> nanospheres grown on In<jats:sub>2</jats:sub>O<jats:sub>3</jats:sub> nanocubes. This unique structure enhances the sensing capabilities of CeO<jats:sub>2</jats:sub>/In<jats:sub>2</jats:sub>O<jats:sub>3</jats:sub>, allowing it to detect formaldehyde in the 1–50 ppm range, and a 0.157 ppm detection limit is earned. The sensor exhibits an impressive response of 175.05 at 50 ppm at room temperature and shows responsiveness to various other substances, for instance, methanol, ethanol, aniline, benzene, toluene, acetone, and ammonia. Additionally, the CeO<jats:sub>2</jats:sub>/In<jats:sub>2</jats:sub>O<jats:sub>3</jats:sub> sensor demonstrated moderate to high selectivity, sensitivity, stability, speedy response/recovery times, and resilience to humidity. This work presents a promising strategy for the detection of formaldehyde.","PeriodicalId":228,"journal":{"name":"Small","volume":"129 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866654","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}
Tumor tissues exhibit elevated oxidative stress, with the cystine-glutamate transporter xCT solute carrier family 7 member 11 (xCT/SLC7A11) protecting cancer cells from oxidative damage by facilitating cystine uptake for glutathione synthesis. Disulfidptosis, a newly identified form of programmed cell death (PCD), occurs in cells with high xCT/SLC7A11 expression under glucose-deprived conditions. Distinct from other PCD pathways, disulfidptosis is characterized by aberrant disulfide bond formation and cellular dysfunction, ultimately resulting in cancer cell death. This novel mechanism offers remarkable therapeutic potential by targeting the inherent oxidative stress vulnerabilities of rapidly growing cancer cells. Advances in nanotechnology enable the development of nanomaterials capable of inducing reactive oxygen species (ROS) generation, disrupting disulfide bonds. In addition, they are capable to deliver therapeutic agents directly to tumors, thereby improving therapeutic precision and minimizing off-target effects. Moreover, combining disulfidptosis with ROS-induced immunogenic cell death can remodel the tumor microenvironment and enhance anti-tumor immunity. This review explores the mechanisms underlying disulfidptosis, its therapeutic potential in cancer treatment, and the synergistic role of nanotechnology in amplifying its effects. Selective induction of disulfidptosis using nanomaterials represents a promising strategy for achieving more effective, selective, and less toxic cancer therapies.
{"title":"Unlocking the Potential of Disulfidptosis: Nanotechnology-Driven Strategies for Advanced Cancer Therapy","authors":"Wenyao Zhen, Tianzhi Zhao, Xiaoyuan Chen, Jingjing Zhang","doi":"10.1002/smll.202500880","DOIUrl":"https://doi.org/10.1002/smll.202500880","url":null,"abstract":"Tumor tissues exhibit elevated oxidative stress, with the cystine-glutamate transporter <i>x</i>CT solute carrier family 7 member 11 (<i>x</i>CT/SLC7A11) protecting cancer cells from oxidative damage by facilitating cystine uptake for glutathione synthesis. Disulfidptosis, a newly identified form of programmed cell death (PCD), occurs in cells with high <i>x</i>CT/SLC7A11 expression under glucose-deprived conditions. Distinct from other PCD pathways, disulfidptosis is characterized by aberrant disulfide bond formation and cellular dysfunction, ultimately resulting in cancer cell death. This novel mechanism offers remarkable therapeutic potential by targeting the inherent oxidative stress vulnerabilities of rapidly growing cancer cells. Advances in nanotechnology enable the development of nanomaterials capable of inducing reactive oxygen species (ROS) generation, disrupting disulfide bonds. In addition, they are capable to deliver therapeutic agents directly to tumors, thereby improving therapeutic precision and minimizing off-target effects. Moreover, combining disulfidptosis with ROS-induced immunogenic cell death can remodel the tumor microenvironment and enhance anti-tumor immunity. This review explores the mechanisms underlying disulfidptosis, its therapeutic potential in cancer treatment, and the synergistic role of nanotechnology in amplifying its effects. Selective induction of disulfidptosis using nanomaterials represents a promising strategy for achieving more effective, selective, and less toxic cancer therapies.","PeriodicalId":228,"journal":{"name":"Small","volume":"7 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867210","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}
Hui Li, Tianhao Li, Ran Zhao, Hexiang Zhao, Haodong Ji, Fangyuan Chen, Zhurui Shen, Sihui Zhan
Hydroxyl radical (•OH) stemming from dissolved oxygen (O2) via photocatalysis is very attractive, but its poor selectivity and generation efficiency greatly limit its application. Herein, a kind of tungsten single site co-coordinated with O and S atoms (WO3S1) is established on ZnIn2S4 (W-ZIS). The strong interactions in WO3S1 shift the d-band center toward the Fermi level, enhancing the adsorption of O2. These interactions improve the accumulation of photo-generated electrons on WO3S1, facilitating the dissociation of O─O bonds in crucial intermediates and promoting the selective conversion from O2 into •OH. This brings a state-of-the-art selectivity (40.2%) and generation efficiency (1668.90 mmol. g−1. L−1. h−1) of •OH production. Experimental results and theoretical simulations have elucidated that O2 can be reduced by d-orbitals single electron (↑, _, _, _, _, _) of WO3S1 transfer to 2p-orbital O─O pi anti-bonding (π*: px and py), initially activating O2. Additionally, WO3S1 sites facilitate the cleavage of H2O, optimizing proton adsorption through W─O orbital coupling in WO3S1 and promoting the transformation of oxygen-containing intermediates. More importantly, d-orbitals single electron can fill O─O π* bond in •OOH intermediate, weakening the covalency of the O─O bond, mitigating the formation of H2O2 and shortening the pathway for •OH generation.).
{"title":"d-Orbital Single Electron Filling O─O π* Bonds on WO3S1 Sites for Highly Selective Generation of Hydroxyl Radicals","authors":"Hui Li, Tianhao Li, Ran Zhao, Hexiang Zhao, Haodong Ji, Fangyuan Chen, Zhurui Shen, Sihui Zhan","doi":"10.1002/smll.202412234","DOIUrl":"https://doi.org/10.1002/smll.202412234","url":null,"abstract":"Hydroxyl radical (•OH) stemming from dissolved oxygen (O<sub>2</sub>) via photocatalysis is very attractive, but its poor selectivity and generation efficiency greatly limit its application. Herein, a kind of tungsten single site co-coordinated with O and S atoms (WO<sub>3</sub>S<sub>1</sub>) is established on ZnIn<sub>2</sub>S<sub>4</sub> (W-ZIS). The strong interactions in WO<sub>3</sub>S<sub>1</sub> shift the <i>d</i>-band center toward the Fermi level, enhancing the adsorption of O<sub>2</sub>. These interactions improve the accumulation of photo-generated electrons on WO<sub>3</sub>S<sub>1</sub>, facilitating the dissociation of O─O bonds in crucial intermediates and promoting the selective conversion from O<sub>2</sub> into •OH. This brings a state-of-the-art selectivity (40.2%) and generation efficiency (1668.90 mmol. g<sup>−1</sup>. L<sup>−1</sup>. h<sup>−1</sup>) of •OH production. Experimental results and theoretical simulations have elucidated that O<sub>2</sub> can be reduced by <i>d</i>-orbitals single electron (<span style=\"text-decoration:underline\">↑</span>, _, _, _, _, _) of WO<sub>3</sub>S<sub>1</sub> transfer to 2<i>p</i>-orbital O─O pi anti-bonding (<i>π*</i>: <i>p<sub>x</sub></i> and <i>p<sub>y</sub></i>), initially activating O<sub>2</sub>. Additionally, WO<sub>3</sub>S<sub>1</sub> sites facilitate the cleavage of H<sub>2</sub>O, optimizing proton adsorption through W─O orbital coupling in WO<sub>3</sub>S<sub>1</sub> and promoting the transformation of oxygen-containing intermediates. More importantly, <i>d</i>-orbitals single electron can fill O─O <i>π*</i> bond in •OOH intermediate, weakening the covalency of the O─O bond, mitigating the formation of H<sub>2</sub>O<sub>2</sub> and shortening the pathway for •OH generation.).","PeriodicalId":228,"journal":{"name":"Small","volume":"72 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867224","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 Liu, Ye Wu, Anastasiia Sokolova, Xinmin Shi, Stephen V. Kershaw, Yusheng Wu, Lakshminarayana Polavarapu, Xiaoming Li, Andrey L. Rogach
Although bulk crystals of lead-free vacancy-ordered double perovskites demonstrated a highly efficient emission, their nanocrystals (NCs) counterparts exhibit inferior optical performance. To understand the reasons behind this phenomenon, Cs2ZrCl6:Te4+ double perovskite NCs are synthesized, and their optical properties are compared with their bulk powders. Temperature-dependent spectroscopy revealed that the NCs sustain a thermal sensitization of the intermediate trap state, which is located between the self-trapped state of the host (Cs2ZrCl6) and the triplet states of the dopant (Te4+). This opens up a pathway for the non-radiative recombination, and thus decreases the energy transfer efficiency from host to dopant. Importantly, this pathway is suppressed in larger (40 nm) Cs2ZrCl6:Te4+ NCs, resulting in their photoluminescence quantum yield of 24%, as compared to 7% for the 22 nm NCs. Furthermore, the emission spectral range of these double perovskite NCs is shown to extended into near-infrared by incorporating rare-earth ions as additional dopants. The study has established a crucial relation between the optical properties and the size effect in lead-free vacancy-ordered double perovskites and thus lays a foundation for further improvement of their optical performance.
{"title":"Photoluminescence of Te-Doped Double Perovskite Cs2ZrCl6 Nanocrystals Versus Bulk: Insights From Temperature-Dependent Spectroscopy","authors":"Yang Liu, Ye Wu, Anastasiia Sokolova, Xinmin Shi, Stephen V. Kershaw, Yusheng Wu, Lakshminarayana Polavarapu, Xiaoming Li, Andrey L. Rogach","doi":"10.1002/smll.202501342","DOIUrl":"https://doi.org/10.1002/smll.202501342","url":null,"abstract":"Although bulk crystals of lead-free vacancy-ordered double perovskites demonstrated a highly efficient emission, their nanocrystals (NCs) counterparts exhibit inferior optical performance. To understand the reasons behind this phenomenon, Cs<sub>2</sub>ZrCl<sub>6</sub>:Te<sup>4+</sup> double perovskite NCs are synthesized, and their optical properties are compared with their bulk powders. Temperature-dependent spectroscopy revealed that the NCs sustain a thermal sensitization of the intermediate trap state, which is located between the self-trapped state of the host (Cs<sub>2</sub>ZrCl<sub>6</sub>) and the triplet states of the dopant (Te<sup>4+</sup>). This opens up a pathway for the non-radiative recombination, and thus decreases the energy transfer efficiency from host to dopant. Importantly, this pathway is suppressed in larger (40 nm) Cs<sub>2</sub>ZrCl<sub>6</sub>:Te<sup>4+</sup> NCs, resulting in their photoluminescence quantum yield of 24%, as compared to 7% for the 22 nm NCs. Furthermore, the emission spectral range of these double perovskite NCs is shown to extended into near-infrared by incorporating rare-earth ions as additional dopants. The study has established a crucial relation between the optical properties and the size effect in lead-free vacancy-ordered double perovskites and thus lays a foundation for further improvement of their optical performance.","PeriodicalId":228,"journal":{"name":"Small","volume":"69 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867228","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}
Xiaoting Wang, Ning Tang, Yujia Jiang, Min-Hui Li, Jun Hu
Glassy hydrogels, which maintain a distinctive glassy state at ambient temperature, are appealing for engineering applications. Nevertheless, the existing glassy hydrogels often suffer from inferior strength, inadequate stiffness, and environmental stability caused by weak physical cross-linking. Herein, we present an ultrastiff and ultrastrong glassy hydrogel by introducing robust coordination bonds into a network composed of polyacrylic acid (PAA) and polyvinyl alcohol (PVA), using a copper acetate-assisted strategy. The presence of acetate anions creates a relatively alkaline environment, which deprotonates the carboxyl groups of PAA. This deprotonation exposes carboxylate groups that readily coordinate with copper ions, establishing a densely cross-linked network in the glassy state. The resultant glassy hydrogel exhibits record-breaking Young's modulus (469.7 MPa), tensile strength (19.2 MPa), and exceptional environmental stability. Moreover, the reversible softening and vitrification induced by the breakage and reforming of coordination bonds endows glassy hydrogel with structural programmability, allowing for the construction of integrated auxetic hydrogel (IAH). The IAH demonstrates enhanced mechanical properties compared to the auxetic skeleton alone while maintaining a negative Poisson's ratio over a wide strain range of 0–29%. This study provides a promising engineering route for the development of advanced glassy hydrogels.
{"title":"Copper-Coordination Engineered Glassy Hydrogels Featuring Ultrastiffness and Structural Programmability","authors":"Xiaoting Wang, Ning Tang, Yujia Jiang, Min-Hui Li, Jun Hu","doi":"10.1002/smll.202502949","DOIUrl":"https://doi.org/10.1002/smll.202502949","url":null,"abstract":"Glassy hydrogels, which maintain a distinctive glassy state at ambient temperature, are appealing for engineering applications. Nevertheless, the existing glassy hydrogels often suffer from inferior strength, inadequate stiffness, and environmental stability caused by weak physical cross-linking. Herein, we present an ultrastiff and ultrastrong glassy hydrogel by introducing robust coordination bonds into a network composed of polyacrylic acid (PAA) and polyvinyl alcohol (PVA), using a copper acetate-assisted strategy. The presence of acetate anions creates a relatively alkaline environment, which deprotonates the carboxyl groups of PAA. This deprotonation exposes carboxylate groups that readily coordinate with copper ions, establishing a densely cross-linked network in the glassy state. The resultant glassy hydrogel exhibits record-breaking Young's modulus (469.7 MPa), tensile strength (19.2 MPa), and exceptional environmental stability. Moreover, the reversible softening and vitrification induced by the breakage and reforming of coordination bonds endows glassy hydrogel with structural programmability, allowing for the construction of integrated auxetic hydrogel (IAH). The IAH demonstrates enhanced mechanical properties compared to the auxetic skeleton alone while maintaining a negative Poisson's ratio over a wide strain range of 0–29%. This study provides a promising engineering route for the development of advanced glassy hydrogels.","PeriodicalId":228,"journal":{"name":"Small","volume":"72 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867247","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}
Minsu Han, Tomota Nagaura, Ho Ngoc Nam, Zihao Yang, Azhar Alowasheeir, Quan Manh Phung, Takeshi Yanai, Jeonghun Kim, Saad M. Alshehri, Tansir Ahamad, Yoshio Bando, Yusuke Yamauchi
Materials with the same chemical composition can exhibit distinct properties depending on their crystal phases. Here, the synthesis of two types of mesoporous Bi2Se3 films at different reduction potentials is reported and their application in electrochemical glucose sensing. Mesoporous Bi2Se3 is synthesized by incorporating block copolymer micelle assemblies into the deposition solution and applying a reduction potential. To characterize the crystal phases accurately, Bi2Se3 films are heat-treated at 200 °C for 1 h in a nitrogen atmosphere. The results reveal that the Bi2Se3 films synthesized under different conditions exhibit clearly distinct phases: rhombohedral (R-Bi2Se3) and orthorhombic (O-Bi2Se3). The R-Bi2Se3-8 nm, featuring 8 nm pores and synthesized at a more negative reduction potential, outperforms its nonporous counterpart, achieving a glucose sensing sensitivity of 0.143 µA cm−2 µM−1 and a detection limit of 6.2 µM at pH 7.4 in 0.1 M phosphate-buffered saline solution. In contrast, the O-Bi2Se3, prepared at a relatively positive potential, exhibits no glucose-sensing activity. The inactivity of O-Bi2Se3 for glucose oxidation is likely due to the energetically unfavorable intermediates, as predicted by density functional theory calculations. These findings underscore the critical role of crystal phase control in porous nanomaterials and pave the way for developing innovative porous systems.
{"title":"Selective Design of Mesoporous Bi2Se3 Films with Orthorhombic and Rhombohedral Crystals","authors":"Minsu Han, Tomota Nagaura, Ho Ngoc Nam, Zihao Yang, Azhar Alowasheeir, Quan Manh Phung, Takeshi Yanai, Jeonghun Kim, Saad M. Alshehri, Tansir Ahamad, Yoshio Bando, Yusuke Yamauchi","doi":"10.1002/smll.202501534","DOIUrl":"https://doi.org/10.1002/smll.202501534","url":null,"abstract":"Materials with the same chemical composition can exhibit distinct properties depending on their crystal phases. Here, the synthesis of two types of mesoporous Bi<sub>2</sub>Se<sub>3</sub> films at different reduction potentials is reported and their application in electrochemical glucose sensing. Mesoporous Bi<sub>2</sub>Se<sub>3</sub> is synthesized by incorporating block copolymer micelle assemblies into the deposition solution and applying a reduction potential. To characterize the crystal phases accurately, Bi<sub>2</sub>Se<sub>3</sub> films are heat-treated at 200 °C for 1 h in a nitrogen atmosphere. The results reveal that the Bi<sub>2</sub>Se<sub>3</sub> films synthesized under different conditions exhibit clearly distinct phases: rhombohedral (<i>R</i>-Bi<sub>2</sub>Se<sub>3</sub>) and orthorhombic (<i>O</i>-Bi<sub>2</sub>Se<sub>3</sub>). The <i>R</i>-Bi<sub>2</sub>Se<sub>3</sub>-8 nm, featuring 8 nm pores and synthesized at a more negative reduction potential, outperforms its nonporous counterpart, achieving a glucose sensing sensitivity of 0.143 µA cm<sup>−2</sup> µM<sup>−1</sup> and a detection limit of 6.2 µM at pH 7.4 in 0.1 M phosphate-buffered saline solution. In contrast, the <i>O</i>-Bi<sub>2</sub>Se<sub>3</sub>, prepared at a relatively positive potential, exhibits no glucose-sensing activity. The inactivity of <i>O</i>-Bi<sub>2</sub>Se<sub>3</sub> for glucose oxidation is likely due to the energetically unfavorable intermediates, as predicted by density functional theory calculations. These findings underscore the critical role of crystal phase control in porous nanomaterials and pave the way for developing innovative porous systems.","PeriodicalId":228,"journal":{"name":"Small","volume":"14 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867219","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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