Peroxynitrite (ONOO-) is a key mediator of redox imbalance in inflammation and cancer, with in vivo monitoring of its dynamic behavior still posing a major challenge. Here, we developed a BD@PEG nanoprobe that enabled dual-excitation NIR-II ratiometric imaging with superior biocompatibility, quantitative fidelity, and ONOO- selectivity. When applied to a drug-induced liver injury model, BD@PEG-based NIR-II ratiometric imaging allowed real-time monitoring of hepatic ONOO- dynamics, directly correlating oxidative/nitrosative stress to histopathological alterations, and demonstrating significant attenuation under glutathione treatment. In a CT26 tumor model, the NIR-II ratiometric imaging strategy revealed distinct ONOO- modulation in response to different therapeutic interventions. Furthermore, two-plex imaging by integrating NIR-IIb oxyhemoglobin saturation analysis afforded concurrent assessment of nitrosative stress and vascular oxygenation. We found that the combination of chemotherapy and immunotherapy induced synergistic ONOO- production, enhanced immune cell infiltration, and achieved superior antitumor efficacy. Overall, this study established a versatile imaging platform for dynamic redox monitoring and oxygenation assessment in vivo, providing mechanistic insight into ONOO--mediated pathology and a translational tool for optimizing therapeutic interventions in cancer and inflammation.
{"title":"In Vivo NIR-II Ratiometric Imaging of Peroxynitrite for Tracking Redox Dynamics in Tumor Immunochemotherapy.","authors":"Qikang Hu, Ahmad Eldoksh, Pengfan Lu, Chunyu Xie, Jingrun Yang, Jianming Gu, Yeteng Zhong","doi":"10.1002/smtd.202501888","DOIUrl":"https://doi.org/10.1002/smtd.202501888","url":null,"abstract":"<p><p>Peroxynitrite (ONOO<sup>-</sup>) is a key mediator of redox imbalance in inflammation and cancer, with in vivo monitoring of its dynamic behavior still posing a major challenge. Here, we developed a BD@PEG nanoprobe that enabled dual-excitation NIR-II ratiometric imaging with superior biocompatibility, quantitative fidelity, and ONOO<sup>-</sup> selectivity. When applied to a drug-induced liver injury model, BD@PEG-based NIR-II ratiometric imaging allowed real-time monitoring of hepatic ONOO<sup>-</sup> dynamics, directly correlating oxidative/nitrosative stress to histopathological alterations, and demonstrating significant attenuation under glutathione treatment. In a CT26 tumor model, the NIR-II ratiometric imaging strategy revealed distinct ONOO<sup>-</sup> modulation in response to different therapeutic interventions. Furthermore, two-plex imaging by integrating NIR-IIb oxyhemoglobin saturation analysis afforded concurrent assessment of nitrosative stress and vascular oxygenation. We found that the combination of chemotherapy and immunotherapy induced synergistic ONOO<sup>-</sup> production, enhanced immune cell infiltration, and achieved superior antitumor efficacy. Overall, this study established a versatile imaging platform for dynamic redox monitoring and oxygenation assessment in vivo, providing mechanistic insight into ONOO<sup>-</sup>-mediated pathology and a translational tool for optimizing therapeutic interventions in cancer and inflammation.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01888"},"PeriodicalIF":9.1,"publicationDate":"2025-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145802751","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}
Yerim Kim, Hyunji Ryu, Won-Suk Kim, Shafidah Shafian, Kyungkon Kim
We demonstrate a "dry additive" strategy to enhance fully vacuum-deposited perovskite solar cells (PSCs) by co-evaporating diphenyl sulfoxide (DPSO) as a volatile solid additive during film formation. Vacuum-processed perovskite films often exhibit high nucleation densities and small grain sizes, which limit crystallinity and increase defects. Introducing DPSO-a Lewis base that temporarily binds perovskite precursors and slows their reaction, modulates nucleation, and enables the growth of much larger perovskite domains. DPSO-treated films show improved crystallinity, lower defect density, and enhanced charge-transport pathways due to reduced grain-boundary density. Power conversion efficiency (PCE) gains are modest for thicker films (peak ∼18.0% vs. ∼17.3% for control at 350 nm), but substantial in ultrathin devices, particularly at 200 nm, where high efficiency is maintained despite significant thickness reduction. PSCs with ∼200 nm active layers achieve PCEs around 17% with DPSO, compared to ∼3% without, and even a 150 nm DPSO-assisted film reaches over 11% efficiency. This capability to fabricate ultrathin (∼150-200 nm) layers with competitive efficiencies is important for developing lightweight and semitransparent solar cells. Notably, the DPSO-based approach also yields enhanced device stability-PSCs retain ∼94% of their initial efficiency after 720 h of ambient storage, far outperforming control devices.
{"title":"Improving Performance of Fully Vacuum-Evaporated Perovskite Photovoltaics via Dry Additive Strategy.","authors":"Yerim Kim, Hyunji Ryu, Won-Suk Kim, Shafidah Shafian, Kyungkon Kim","doi":"10.1002/smtd.202501434","DOIUrl":"https://doi.org/10.1002/smtd.202501434","url":null,"abstract":"<p><p>We demonstrate a \"dry additive\" strategy to enhance fully vacuum-deposited perovskite solar cells (PSCs) by co-evaporating diphenyl sulfoxide (DPSO) as a volatile solid additive during film formation. Vacuum-processed perovskite films often exhibit high nucleation densities and small grain sizes, which limit crystallinity and increase defects. Introducing DPSO-a Lewis base that temporarily binds perovskite precursors and slows their reaction, modulates nucleation, and enables the growth of much larger perovskite domains. DPSO-treated films show improved crystallinity, lower defect density, and enhanced charge-transport pathways due to reduced grain-boundary density. Power conversion efficiency (PCE) gains are modest for thicker films (peak ∼18.0% vs. ∼17.3% for control at 350 nm), but substantial in ultrathin devices, particularly at 200 nm, where high efficiency is maintained despite significant thickness reduction. PSCs with ∼200 nm active layers achieve PCEs around 17% with DPSO, compared to ∼3% without, and even a 150 nm DPSO-assisted film reaches over 11% efficiency. This capability to fabricate ultrathin (∼150-200 nm) layers with competitive efficiencies is important for developing lightweight and semitransparent solar cells. Notably, the DPSO-based approach also yields enhanced device stability-PSCs retain ∼94% of their initial efficiency after 720 h of ambient storage, far outperforming control devices.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01434"},"PeriodicalIF":9.1,"publicationDate":"2025-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145802783","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}
Jakub Jurczyk, Leo Brockhuis, Amalio Fernández-Pacheco, Ivo Utke
Recent advances in nanotechnology have created the need to manufacture 3D nanostructures with controlled material composition. Focused Electron Beam Induced Deposition (FEBID) is a nanoprinting technique offering highest spatial resolution combined with the ability to directly 3D-print almost any shape. It relies on local electron-induced dissociation of metal-ligand organometallic molecules adsorbed onto a substrate. So far FEBID continuum modeling involves the surface kinetics of precursor molecules during electron irradiation and succeeds in the prediction of nanoprint shape and growth rate and forms nowadays the basis of software for 3D nano-printing of nanostructures. Here, the model is expanded to the surface kinetics of detached ligands. Involving their dissociation and desorption behavior allows to predict trends in the metallic composition of the nanoprinted material and to define desirable nanoprint process windows as function of electron exposure time and flux. The theoretical foundations of the model is presented, validate it experimentally for chromium and silver precursors, compare calculated values with literature data for various precursors, and discuss its potential to design new experiments. This contribution enhances the understanding of FEBID dynamics and provides a versatile framework for predictive FEBID material nano-printing.
{"title":"Ligand Co-Deposition in Focused Electron Beam Induced Nanoprinting: A Predictive Composition Model.","authors":"Jakub Jurczyk, Leo Brockhuis, Amalio Fernández-Pacheco, Ivo Utke","doi":"10.1002/smtd.202501956","DOIUrl":"https://doi.org/10.1002/smtd.202501956","url":null,"abstract":"<p><p>Recent advances in nanotechnology have created the need to manufacture 3D nanostructures with controlled material composition. Focused Electron Beam Induced Deposition (FEBID) is a nanoprinting technique offering highest spatial resolution combined with the ability to directly 3D-print almost any shape. It relies on local electron-induced dissociation of metal-ligand organometallic molecules adsorbed onto a substrate. So far FEBID continuum modeling involves the surface kinetics of precursor molecules during electron irradiation and succeeds in the prediction of nanoprint shape and growth rate and forms nowadays the basis of software for 3D nano-printing of nanostructures. Here, the model is expanded to the surface kinetics of detached ligands. Involving their dissociation and desorption behavior allows to predict trends in the metallic composition of the nanoprinted material and to define desirable nanoprint process windows as function of electron exposure time and flux. The theoretical foundations of the model is presented, validate it experimentally for chromium and silver precursors, compare calculated values with literature data for various precursors, and discuss its potential to design new experiments. This contribution enhances the understanding of FEBID dynamics and provides a versatile framework for predictive FEBID material nano-printing.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01956"},"PeriodicalIF":9.1,"publicationDate":"2025-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145802748","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}
Chayene Gonçalves Anchieta, Barthélémy Lelotte, Hari Vignesh Ramasamy, Alexander Forster, Ali Coskun, Mario El Kazzi, Dario Ferreira Sanchez
Understanding the dynamics of complex heterogeneous battery materials under realistic operation conditions with micrometer spatial and relevant temporal resolutions remains challenging. This work presents a synchrotron-based operando chemical imaging methodology using microfocus X-ray diffraction (µ-XRD) scanning imaging. The approach is applied to an all-solid-state battery (ASSB) with high-energy lithium-rich nickel manganese cobalt layered oxide (Li-rich NCM) as active cathode material, Li3YCl6 as catholyte, amorphous Li3PS4 separator layer, and metallic lithium as anode. Operando XRD mapping unveils the nature and location of phase transformations along one complete cycle. The ASSB is integrated in the multipurpose custom-designed electrochemical cell, which allows optimal exit solid angle for XRD analysis, permitting the resolution of the local chemistry in time and space across a relatively large field of view. We observed the following phenomena: (i) heterogeneous lithiation and delithiation processes within tens of individual Li-rich NCM particles, indicating intraparticle differential lithium diffusion, (ii) the reversible formation of YCl2(H2O)6Cl, attributed to water residues, and (iii) the irreversible dissolution of Li2S and formation of LiOH parasitic phases. (iii) This study opens new perspectives for broader applications in energy technologies, such as Na-ion, Zinc-Air, Li-air, Li-ion, and Li-S.
{"title":"Unveiling Physical and Chemical Changes in All-Solid-State Battery: An Operando Synchrotron Chemical Imaging Study.","authors":"Chayene Gonçalves Anchieta, Barthélémy Lelotte, Hari Vignesh Ramasamy, Alexander Forster, Ali Coskun, Mario El Kazzi, Dario Ferreira Sanchez","doi":"10.1002/smtd.202501793","DOIUrl":"https://doi.org/10.1002/smtd.202501793","url":null,"abstract":"<p><p>Understanding the dynamics of complex heterogeneous battery materials under realistic operation conditions with micrometer spatial and relevant temporal resolutions remains challenging. This work presents a synchrotron-based operando chemical imaging methodology using microfocus X-ray diffraction (µ-XRD) scanning imaging. The approach is applied to an all-solid-state battery (ASSB) with high-energy lithium-rich nickel manganese cobalt layered oxide (Li-rich NCM) as active cathode material, Li<sub>3</sub>YCl<sub>6</sub> as catholyte, amorphous Li<sub>3</sub>PS<sub>4</sub> separator layer, and metallic lithium as anode. Operando XRD mapping unveils the nature and location of phase transformations along one complete cycle. The ASSB is integrated in the multipurpose custom-designed electrochemical cell, which allows optimal exit solid angle for XRD analysis, permitting the resolution of the local chemistry in time and space across a relatively large field of view. We observed the following phenomena: (i) heterogeneous lithiation and delithiation processes within tens of individual Li-rich NCM particles, indicating intraparticle differential lithium diffusion, (ii) the reversible formation of YCl<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub>Cl, attributed to water residues, and (iii) the irreversible dissolution of Li<sub>2</sub>S and formation of LiOH parasitic phases. (iii) This study opens new perspectives for broader applications in energy technologies, such as Na-ion, Zinc-Air, Li-air, Li-ion, and Li-S.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01793"},"PeriodicalIF":9.1,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145792693","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}
Savithra Jayaraj, Kavyasree Chintalapudi, Abraham Badu-Tawiah
Heterogeneous Catalysis
The immobilization of fullerene C60 on cellulose thread allows heterogeneous photoreaction screening to be achieved through a thread spray mass spectrometry platform. Fullerene C60 is identified to facilitate dehydro-dimerization reactions from amines, including the discovery that norharmane can serve as an efficient precursor of antioxidants to quench singlet oxygen. More in article number 2500911, Badu-Tawiah and co-workers.