The honeycomb lattice is a fundamental two-dimensional (2D) network that gives rise to surprisingly rich electronic properties. While its expansion to 2D supramolecular assembly is conceptually appealing, its realization is not straightforward because of weak intermolecular coupling and the strong influence of a supporting substrate. Here, we show that the application of a triptycene derivative with phenazine moieties, Trip-Phz, solves this problem due to its strong intermolecular π-π pancake bonding and nonplanar geometry. Our scanning tunneling microscopy (STM) measurements demonstrate that Trip-Phz molecules self-assemble on a Ag(111) surface to form chiral and commensurate honeycomb lattices. Electronically, the network can be viewed as a hybrid of honeycomb and kagome lattices. The Dirac and flat bands predicted by a simple tight-binding model are reproduced by total density functional theory (DFT) calculations, highlighting the protection of the molecular bands from the Ag(111) substrate. The present work offers a rational route for creating chiral 2D supramolecules that can simultaneously accommodate pristine Dirac and flat bands.
{"title":"Chiral Honeycomb Lattices of Nonplanar π-Conjugated Supramolecules with Protected Dirac and Flat Bands.","authors":"Ryohei Nemoto, Ryuichi Arafune, Saya Nakano, Masahisa Tsuchiizu, Noriaki Takagi, Rie Suizu, Takashi Uchihashi, Kunio Awaga","doi":"10.1021/acsnano.4c04496","DOIUrl":"https://doi.org/10.1021/acsnano.4c04496","url":null,"abstract":"<p><p>The honeycomb lattice is a fundamental two-dimensional (2D) network that gives rise to surprisingly rich electronic properties. While its expansion to 2D supramolecular assembly is conceptually appealing, its realization is not straightforward because of weak intermolecular coupling and the strong influence of a supporting substrate. Here, we show that the application of a triptycene derivative with phenazine moieties, Trip-Phz, solves this problem due to its strong intermolecular π-π pancake bonding and nonplanar geometry. Our scanning tunneling microscopy (STM) measurements demonstrate that Trip-Phz molecules self-assemble on a Ag(111) surface to form chiral and commensurate honeycomb lattices. Electronically, the network can be viewed as a hybrid of honeycomb and kagome lattices. The Dirac and flat bands predicted by a simple tight-binding model are reproduced by total density functional theory (DFT) calculations, highlighting the protection of the molecular bands from the Ag(111) substrate. The present work offers a rational route for creating chiral 2D supramolecules that can simultaneously accommodate pristine Dirac and flat bands.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hun Park, Ki Hyun Lee, Sung Hyun Noh, Wonsik Eom, Jiaxing Huang, Tae Hee Han
Layered membranes assembled from two-dimensional (2D) building blocks such as graphene oxide (GO) are of significant interest in desalination and osmotic power generation because of their ability to selectively transport ions through interconnected 2D nanochannels between stacked layers. However, architectural defects in the final assembled membranes (e.g., wrinkles, voids, and folded layers), which are hard to avoid due to mechanical compliant issues of the sheets during the membrane assembly, disrupt the ionic channel pathways and degrade the stacking geometry of the sheets. This leads to degraded ionic transport performance and the overall structural integrity. In this study, we demonstrate that introducing in-plane nanopores on GO sheets is an effective way to suppress the formation of such architectural imperfections, leading to a more homogeneous membrane. Stacking of porous GO sheets becomes significantly more compact, as the presence of nanopores makes the sheets mechanically softer and more compliant. The resulting membranes exhibit ideal lamellar microstructures with well-aligned and uniform nanochannel pathways. The well-defined nanochannels afford excellent ionic conductivity with an effective transport pathway, resulting in fast, selective ion transport. When applied as a nanofluidic membrane in an osmotic power generation system, the holey GO membrane exhibits higher osmotic power density (13.15 W m–2) and conversion efficiency (46.6%) than the pristine GO membrane under a KCl concentration gradient of 1000-fold.
由二维（2D）构件（如氧化石墨烯（GO））组装而成的层状膜在海水淡化和渗透发电方面具有重要意义，因为它们能够通过堆叠层之间相互连接的 2D 纳米通道选择性地传输离子。然而，在最终组装的膜中，由于膜组装过程中薄片的机械顺应性问题而难以避免的结构缺陷（如皱褶、空隙和折叠层）会破坏离子通道路径并降低薄片的堆叠几何形状。这导致离子传输性能和整体结构完整性下降。在本研究中，我们证明了在 GO 片上引入面内纳米孔是抑制这种结构缺陷形成的有效方法，从而使膜更加均匀。由于纳米孔的存在，多孔 GO 片材的堆叠变得更加紧凑，使得片材在机械性能上更加柔软、更有顺应性。由此产生的膜呈现出理想的片状微结构，具有排列整齐、均匀的纳米通道。定义明确的纳米通道具有出色的离子传导性和有效的传输途径，从而实现快速、选择性的离子传输。在渗透发电系统中用作纳米流体膜时，在氯化钾浓度梯度为 1000 倍的条件下，孔状 GO 膜比原始 GO 膜表现出更高的渗透功率密度（13.15 W m-2）和转换效率（46.6%）。
{"title":"Holey Sheets Enhance the Packing and Osmotic Energy Harvesting of Graphene Oxide Membranes","authors":"Hun Park, Ki Hyun Lee, Sung Hyun Noh, Wonsik Eom, Jiaxing Huang, Tae Hee Han","doi":"10.1021/acsnano.4c04493","DOIUrl":"https://doi.org/10.1021/acsnano.4c04493","url":null,"abstract":"Layered membranes assembled from two-dimensional (2D) building blocks such as graphene oxide (GO) are of significant interest in desalination and osmotic power generation because of their ability to selectively transport ions through interconnected 2D nanochannels between stacked layers. However, architectural defects in the final assembled membranes (e.g., wrinkles, voids, and folded layers), which are hard to avoid due to mechanical compliant issues of the sheets during the membrane assembly, disrupt the ionic channel pathways and degrade the stacking geometry of the sheets. This leads to degraded ionic transport performance and the overall structural integrity. In this study, we demonstrate that introducing in-plane nanopores on GO sheets is an effective way to suppress the formation of such architectural imperfections, leading to a more homogeneous membrane. Stacking of porous GO sheets becomes significantly more compact, as the presence of nanopores makes the sheets mechanically softer and more compliant. The resulting membranes exhibit ideal lamellar microstructures with well-aligned and uniform nanochannel pathways. The well-defined nanochannels afford excellent ionic conductivity with an effective transport pathway, resulting in fast, selective ion transport. When applied as a nanofluidic membrane in an osmotic power generation system, the holey GO membrane exhibits higher osmotic power density (13.15 W m<sup>–2</sup>) and conversion efficiency (46.6%) than the pristine GO membrane under a KCl concentration gradient of 1000-fold.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":17.1,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463999","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jiwoong Kim, Jihye Lee, Seongwook Choi, Hyori Lee, Jinge Yang, Hyunseo Jeon, Minsik Sung, Won Jong Kim, Chulhong Kim
Photoacoustic computed tomography (PACT), an emerging imaging modality in preclinical cancer research, can provide multiparametric 3D information about structures, physiological functions, and pharmacokinetics. Here, we demonstrate the use of high-definition 3D multiparametric PACT imaging of both primary and metastatic tumors in living mice to noninvasively monitor angiogenesis, carcinogenesis, hypoxia, and pharmacokinetics. The high-definition PACT system with a 1024-element hemispherical ultrasound transducer array provides an isotropic spatial resolution of 380 μm, an effective volumetric field-of-view of 12.8 mm × 12.8 mm × 12.8 mm without scanning, and an acquisition time of <30 s for a whole mouse body. Initially, we monitor the structural progression of the tumor microenvironment (e.g., angiogenesis and vessel tortuosity) after tumor cell inoculation. Then, we analyze the change in oxygen saturation of the tumor during carcinogenesis, verifying induced hypoxia in the tumor’s core region. Finally, the whole-body pharmacokinetics are photoacoustically imaged after intravenous injection of micelle-loaded IR780 dye, and the in vivo PACT results are validated in vivo and ex vivo by fluorescence imaging. By employing the premium PACT system and applying multiparametric analyses to subcutaneous primary tumors and metastatic liver tumors, we demonstrate that this PACT system can provide multiparametric analyses for comprehensive cancer research.
{"title":"3D Multiparametric Photoacoustic Computed Tomography of Primary and Metastatic Tumors in Living Mice","authors":"Jiwoong Kim, Jihye Lee, Seongwook Choi, Hyori Lee, Jinge Yang, Hyunseo Jeon, Minsik Sung, Won Jong Kim, Chulhong Kim","doi":"10.1021/acsnano.3c12551","DOIUrl":"https://doi.org/10.1021/acsnano.3c12551","url":null,"abstract":"Photoacoustic computed tomography (PACT), an emerging imaging modality in preclinical cancer research, can provide multiparametric 3D information about structures, physiological functions, and pharmacokinetics. Here, we demonstrate the use of high-definition 3D multiparametric PACT imaging of both primary and metastatic tumors in living mice to noninvasively monitor angiogenesis, carcinogenesis, hypoxia, and pharmacokinetics. The high-definition PACT system with a 1024-element hemispherical ultrasound transducer array provides an isotropic spatial resolution of 380 μm, an effective volumetric field-of-view of 12.8 mm × 12.8 mm × 12.8 mm without scanning, and an acquisition time of <30 s for a whole mouse body. Initially, we monitor the structural progression of the tumor microenvironment (e.g., angiogenesis and vessel tortuosity) after tumor cell inoculation. Then, we analyze the change in oxygen saturation of the tumor during carcinogenesis, verifying induced hypoxia in the tumor’s core region. Finally, the whole-body pharmacokinetics are photoacoustically imaged after intravenous injection of micelle-loaded IR780 dye, and the in vivo PACT results are validated in vivo and ex vivo by fluorescence imaging. By employing the premium PACT system and applying multiparametric analyses to subcutaneous primary tumors and metastatic liver tumors, we demonstrate that this PACT system can provide multiparametric analyses for comprehensive cancer research.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":17.1,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464020","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The discovery of cuproptosis, a copper-dependent mechanism of programmed cell death, has provided a way for cancer treatment. However, cuproptosis has inherent limitations, including potential cellular harm, the lack of targeting, and insufficient efficacy as a standalone treatment. Therefore, exogenously controlled combination treatments have emerged as key strategies for cuproptosis-based oncotherapy. In this study, a Cu2–xSe@cMOF nanoplatform was constructed for combined sonodynamic/cuproptosis/gas therapy. This platform enabled precise cancer cotreatment, with external control allowing the selective induction of cuproptosis in cancer cells. This approach effectively prevented cancer metastasis and recurrence. Furthermore, Cu2–xSe@cMOF was combined with the antiprogrammed cell death protein ligand-1 antibody (aPD-L1), and this combination maximized the advantages of cuproptosis and immune checkpoint therapy. Additionally, under ultrasound irradiation, the H2Se gas generated from Cu2–xSe@cMOF induced cytotoxicity in cancer cells. Further, it generated reactive oxygen species, which hindered cell survival and proliferation. This study reports an externally controlled system for cuproptosis induction that combines a carbonized metal–organic framework with aPD-L1 to enhance cancer treatment. This precision and reinforced cuproptosis cancer therapy platform could be valuable as an effective therapeutic agent to reduce cancer mortality and morbidity in the future.
{"title":"Multifaceted Carbonized Metal–Organic Frameworks Synergize with Immune Checkpoint Inhibitors for Precision and Augmented Cuproptosis Cancer Therapy","authors":"Chen Zhao, Xiaoying Tang, Xiaoyuan Chen, Zhenqi Jiang","doi":"10.1021/acsnano.4c04022","DOIUrl":"https://doi.org/10.1021/acsnano.4c04022","url":null,"abstract":"The discovery of cuproptosis, a copper-dependent mechanism of programmed cell death, has provided a way for cancer treatment. However, cuproptosis has inherent limitations, including potential cellular harm, the lack of targeting, and insufficient efficacy as a standalone treatment. Therefore, exogenously controlled combination treatments have emerged as key strategies for cuproptosis-based oncotherapy. In this study, a Cu<sub>2–<i>x</i></sub>Se@cMOF nanoplatform was constructed for combined sonodynamic/cuproptosis/gas therapy. This platform enabled precise cancer cotreatment, with external control allowing the selective induction of cuproptosis in cancer cells. This approach effectively prevented cancer metastasis and recurrence. Furthermore, Cu<sub>2–<i>x</i></sub>Se@cMOF was combined with the antiprogrammed cell death protein ligand-1 antibody (aPD-L1), and this combination maximized the advantages of cuproptosis and immune checkpoint therapy. Additionally, under ultrasound irradiation, the H<sub>2</sub>Se gas generated from Cu<sub>2–<i>x</i></sub>Se@cMOF induced cytotoxicity in cancer cells. Further, it generated reactive oxygen species, which hindered cell survival and proliferation. This study reports an externally controlled system for cuproptosis induction that combines a carbonized metal–organic framework with aPD-L1 to enhance cancer treatment. This precision and reinforced cuproptosis cancer therapy platform could be valuable as an effective therapeutic agent to reduce cancer mortality and morbidity in the future.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":17.1,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464024","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Juan A. Allegretto, Gregorio Laucirica, Angel L. Huamani, Michael F. Wagner, Alberto G. Albesa, Maria Eugenia Toimil-Molares, Matías Rafti, Waldemar Marmisollé, Omar Azzaroni
Solid-state nanochannels (SSNs) have emerged as promising platforms for controlling ionic transport at the nanoscale. SSNs are highly versatile, and this feature can be enhanced through their combination with porous materials such as Metal−Organic Frameworks (MOF). By selection of specific building blocks and experimental conditions, different MOF architectures can be obtained, and this can influence the ionic transport properties through the nanochannel. Herein, we study the effects of confined synthesis of Zr-based UiO-66 MOF on the ion transport properties of single bullet-shaped poly(ethylene terephthalate) (PET) nanochannels. We have found that emerging textural properties from the MOF phase play a determinant role in controlling ionic transport through the nanochannel. We demonstrate that a transition from ion current saturation regimes to diode-like regimes can be obtained by employing different synthetic approaches, namely, counterdiffusion synthesis, where MOF precursors are kept separate and forced to diffuse through the nanochannel, and one-pot synthesis, where both precursors are placed at both ends of the channel. Also, by considering the dependence of the charge state of the UiO-66 MOF on the protonation degree, pH changes offered a mechanism to tune the iontronic output (and selectivity) among different regimes, including anion-driven rectification, cation-driven rectification, ion current saturation, and ohmic behavior. Furthermore, Poisson–Nernst–Planck (PNP) simulations were employed to rationalize the different iontronic outputs observed experimentally for membranes modified by different methods. Our results demonstrate a straightforward tool to synthesize MOF-based SSN membranes with tunable ion transport regimes.
{"title":"Manipulating Ion Transport Regimes in Nanomembranes via a “Pore-in-Pore” Approach Enabled by the Synergy of Metal–Organic Frameworks and Solid-State Nanochannels","authors":"Juan A. Allegretto, Gregorio Laucirica, Angel L. Huamani, Michael F. Wagner, Alberto G. Albesa, Maria Eugenia Toimil-Molares, Matías Rafti, Waldemar Marmisollé, Omar Azzaroni","doi":"10.1021/acsnano.4c04435","DOIUrl":"https://doi.org/10.1021/acsnano.4c04435","url":null,"abstract":"Solid-state nanochannels (SSNs) have emerged as promising platforms for controlling ionic transport at the nanoscale. SSNs are highly versatile, and this feature can be enhanced through their combination with porous materials such as Metal−Organic Frameworks (MOF). By selection of specific building blocks and experimental conditions, different MOF architectures can be obtained, and this can influence the ionic transport properties through the nanochannel. Herein, we study the effects of confined synthesis of Zr-based UiO-66 MOF on the ion transport properties of single bullet-shaped poly(ethylene terephthalate) (PET) nanochannels. We have found that emerging textural properties from the MOF phase play a determinant role in controlling ionic transport through the nanochannel. We demonstrate that a transition from ion current saturation regimes to diode-like regimes can be obtained by employing different synthetic approaches, namely, counterdiffusion synthesis, where MOF precursors are kept separate and forced to diffuse through the nanochannel, and one-pot synthesis, where both precursors are placed at both ends of the channel. Also, by considering the dependence of the charge state of the UiO-66 MOF on the protonation degree, pH changes offered a mechanism to tune the iontronic output (and selectivity) among different regimes, including anion-driven rectification, cation-driven rectification, ion current saturation, and ohmic behavior. Furthermore, Poisson–Nernst–Planck (PNP) simulations were employed to rationalize the different iontronic outputs observed experimentally for membranes modified by different methods. Our results demonstrate a straightforward tool to synthesize MOF-based SSN membranes with tunable ion transport regimes.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":17.1,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464037","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ling-Hong Xiong, Langyi Yang, Jiangtao Geng, Ben Zhong Tang, Xuewen He
Currently, specific cancer-responsive fluorogenic probes with activatable imaging and therapeutic functionalities are in great demand in the accurate diagnostics and efficient therapy of malignancies. Herein, an all-in-one strategy is presented to realize fluorescence (FL) imaging-guided and synergetic chemodynamic–photodynamic cancer therapy by using a multifunctional alkaline phosphatase (ALP)-response aggregation-induced emission (AIE) probe, TPE-APP. By responding to the abnormal expression levels of an ALP biomarker in cancer cells, the phosphate groups on the AIE probe are selectively hydrolyzed, accompanied by in situ formation of strong emissive AIE aggregates for discriminative cancer cell imaging over normal cells and highly active quinone methide species with robust chemodynamic–photodynamic activities. Consequently, the activated AIE probes can efficiently destroy cancer cell membranes and lead to the death of cancer cells within 30 min. A superior efficacy in cancer cell ablation is demonstrated in vitro and in vivo. The cancer-associated biomarker response-derived discriminative FL imaging and synergistic chemodynamic–photodynamic therapy are expected to provide a promising avenue for precise image-guided cancer therapy.
{"title":"All-in-One Alkaline Phosphatase-Response Aggregation-Induced Emission Probe for Cancer Discriminative Imaging and Combinational Chemodynamic–Photodynamic Therapy","authors":"Ling-Hong Xiong, Langyi Yang, Jiangtao Geng, Ben Zhong Tang, Xuewen He","doi":"10.1021/acsnano.4c03879","DOIUrl":"https://doi.org/10.1021/acsnano.4c03879","url":null,"abstract":"Currently, specific cancer-responsive fluorogenic probes with activatable imaging and therapeutic functionalities are in great demand in the accurate diagnostics and efficient therapy of malignancies. Herein, an all-in-one strategy is presented to realize fluorescence (FL) imaging-guided and synergetic chemodynamic–photodynamic cancer therapy by using a multifunctional alkaline phosphatase (ALP)-response aggregation-induced emission (AIE) probe, TPE-APP. By responding to the abnormal expression levels of an ALP biomarker in cancer cells, the phosphate groups on the AIE probe are selectively hydrolyzed, accompanied by in situ formation of strong emissive AIE aggregates for discriminative cancer cell imaging over normal cells and highly active quinone methide species with robust chemodynamic–photodynamic activities. Consequently, the activated AIE probes can efficiently destroy cancer cell membranes and lead to the death of cancer cells within 30 min. A superior efficacy in cancer cell ablation is demonstrated in vitro and in vivo. The cancer-associated biomarker response-derived discriminative FL imaging and synergistic chemodynamic–photodynamic therapy are expected to provide a promising avenue for precise image-guided cancer therapy.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":17.1,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464003","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Alzheimer’s disease (AD) starts decades before cognitive symptoms develop. Easily accessible and cost-effective biomarkers that accurately reflect AD pathology are essential for both monitoring and therapeutics of AD. Neurofilament light chain (NfL) levels in blood and cerebrospinal fluid are increased in AD more than a decade before the expected onset, thus providing one of the most promising blood biomarkers for monitoring of AD. The clinical practice of employing single-molecule array (Simoa) technology for routine use in patient care is limited by the high costs. Herein, we developed a microarray chip-based high-throughput screening method and screened an attractive self-assembling peptide targeting NfL. Through directly “imprinting” and further analyzing the sequences, morphology, and affinity of the identified self-assembling peptides, the Pep-NfL peptide nanosheet with high binding affinity toward NfL (KD = 1.39 × 10–9 mol/L), high specificity, and low cost was characterized. The superior binding ability of Pep-NfL was confirmed in AD mouse models and cell lines. In the clinical setting, the Pep-NfL peptide nanosheets hold great potential for discriminating between patients with AD (P < 0.001, n = 37), mild cognitive impairment (P < 0.05, n = 26), and control groups (n = 30). This work provides a high-throughput, high-sensitivity, and economical system for noninvasive tracking of AD to monitor neurodegeneration at different stages of disease. The obtained Pep-NfL peptide nanosheet may be useful for assessing dynamic changes in plasma NfL concentrations to evaluate disease-modifying therapies as a surrogate end point of neurodegeneration in clinical trials.
{"title":"Microarray Chip-Based High-Throughput Screening of Neurofilament Light Chain Self-Assembling Peptide for Noninvasive Monitoring of Alzheimer’s Disease","authors":"Ying Zhou, Guoen Cai, Yuanzhuo Wang, Yuxin Guo, Zhimin Yang, Anqi Wang, Yongshou Chen, Xuejie Li, Xiaochun Chen, Zhiyuan Hu, Zihua Wang","doi":"10.1021/acsnano.3c09642","DOIUrl":"https://doi.org/10.1021/acsnano.3c09642","url":null,"abstract":"Alzheimer’s disease (AD) starts decades before cognitive symptoms develop. Easily accessible and cost-effective biomarkers that accurately reflect AD pathology are essential for both monitoring and therapeutics of AD. Neurofilament light chain (NfL) levels in blood and cerebrospinal fluid are increased in AD more than a decade before the expected onset, thus providing one of the most promising blood biomarkers for monitoring of AD. The clinical practice of employing single-molecule array (Simoa) technology for routine use in patient care is limited by the high costs. Herein, we developed a microarray chip-based high-throughput screening method and screened an attractive self-assembling peptide targeting NfL. Through directly “imprinting” and further analyzing the sequences, morphology, and affinity of the identified self-assembling peptides, the Pep-NfL peptide nanosheet with high binding affinity toward NfL (<i>K</i><sub>D</sub> = 1.39 × 10<sup>–9</sup> mol/L), high specificity, and low cost was characterized. The superior binding ability of Pep-NfL was confirmed in AD mouse models and cell lines. In the clinical setting, the Pep-NfL peptide nanosheets hold great potential for discriminating between patients with AD (<i>P</i> < 0.001, <i>n</i> = 37), mild cognitive impairment (<i>P</i> < 0.05, <i>n</i> = 26), and control groups (<i>n</i> = 30). This work provides a high-throughput, high-sensitivity, and economical system for noninvasive tracking of AD to monitor neurodegeneration at different stages of disease. The obtained Pep-NfL peptide nanosheet may be useful for assessing dynamic changes in plasma NfL concentrations to evaluate disease-modifying therapies as a surrogate end point of neurodegeneration in clinical trials.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":17.1,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464017","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Renan Villarreal, Zviadi Zarkua, Silvan Kretschmer, Vince Hendriks, Jonas Hillen, Hung Chieh Tsai, Felix Junge, Matz Nissen, Tanusree Saha, Simona Achilli, Hans C. Hofsäss, Michael Martins, Giovanni De Ninno, Paolo Lacovig, Silvano Lizzit, Giovanni Di Santo, Luca Petaccia, Steven De Feyter, Stefan De Gendt, Steven Brems, Joris Van de Vondel, Arkady V. Krasheninnikov, Lino M. C. Pereira
Despite its broad potential applications, substitution of carbon by transition metal atoms in graphene has so far been explored only to a limited extent. We report the realization of substitutional Mn doping of graphene to a record high atomic concentration of 0.5%, which was achieved using ultralow-energy ion implantation. By correlating the experimental data with the results of ab initio Born–Oppenheimer molecular dynamics calculations, we infer that direct substitution is the dominant mechanism of impurity incorporation. Thermal annealing in ultrahigh vacuum provides efficient removal of surface contaminants and additional implantation-induced disorder, resulting in Mn-doped graphene that, aside from the substitutional Mn impurities, is essentially as clean and defect-free as the as-grown layer. We further show that the Dirac character of graphene is preserved upon substitutional Mn doping, even in this high concentration regime, making this system ideal for studying the interaction between Dirac conduction electrons and localized magnetic moments. More generally, these results show that ultralow energy ion implantation can be used for controlled functionalization of graphene with substitutional transition-metal atoms, of relevance for a wide range of applications, from magnetism and spintronics to single-atom catalysis.
尽管石墨烯中过渡金属原子对碳的替代具有广泛的应用潜力，但迄今为止，人们对它的探索还很有限。我们报告了利用超低能离子注入法实现石墨烯替代性掺入 0.5% 原子浓度的创纪录高水平。通过将实验数据与 Ab initio Born-Oppenheimer 分子动力学计算结果进行关联，我们推断直接取代是杂质掺入的主要机制。在超高真空中进行热退火可有效去除表面污染物和植入诱导的额外无序性，从而得到掺锰石墨烯，除了取代锰杂质外，该石墨烯基本上与原生长层一样干净、无缺陷。我们还进一步证明，即使在这种高浓度条件下，石墨烯的狄拉克特性在掺入取代态锰之后仍然得以保留，这使得该系统成为研究狄拉克传导电子与局部磁矩之间相互作用的理想选择。更广泛地说，这些结果表明，超低能量离子注入可用于用取代过渡金属原子对石墨烯进行受控功能化，这与从磁学、自旋电子学到单原子催化等广泛应用息息相关。
{"title":"Achieving High Substitutional Incorporation in Mn-Doped Graphene","authors":"Renan Villarreal, Zviadi Zarkua, Silvan Kretschmer, Vince Hendriks, Jonas Hillen, Hung Chieh Tsai, Felix Junge, Matz Nissen, Tanusree Saha, Simona Achilli, Hans C. Hofsäss, Michael Martins, Giovanni De Ninno, Paolo Lacovig, Silvano Lizzit, Giovanni Di Santo, Luca Petaccia, Steven De Feyter, Stefan De Gendt, Steven Brems, Joris Van de Vondel, Arkady V. Krasheninnikov, Lino M. C. Pereira","doi":"10.1021/acsnano.4c03475","DOIUrl":"https://doi.org/10.1021/acsnano.4c03475","url":null,"abstract":"Despite its broad potential applications, substitution of carbon by transition metal atoms in graphene has so far been explored only to a limited extent. We report the realization of substitutional Mn doping of graphene to a record high atomic concentration of 0.5%, which was achieved using ultralow-energy ion implantation. By correlating the experimental data with the results of ab initio Born–Oppenheimer molecular dynamics calculations, we infer that direct substitution is the dominant mechanism of impurity incorporation. Thermal annealing in ultrahigh vacuum provides efficient removal of surface contaminants and additional implantation-induced disorder, resulting in Mn-doped graphene that, aside from the substitutional Mn impurities, is essentially as clean and defect-free as the as-grown layer. We further show that the Dirac character of graphene is preserved upon substitutional Mn doping, even in this high concentration regime, making this system ideal for studying the interaction between Dirac conduction electrons and localized magnetic moments. More generally, these results show that ultralow energy ion implantation can be used for controlled functionalization of graphene with substitutional transition-metal atoms, of relevance for a wide range of applications, from magnetism and spintronics to single-atom catalysis.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":17.1,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464005","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jiatong Li, Guangyue Li, Rui Wang, Qiya He, Wan Liu, Chaoquan Hu, Huigang Zhang, Junfeng Hui, Fengwei Huo
Lithium–sulfur (Li–S) batteries are promising for next-generation high-energy energy storage systems. However, the slow reaction kinetics render mobile polysulfides hardly controlled, yielding shuttling effects and eventually damaging Li metal anodes. To improve the cyclability of Li–S batteries, high-efficiency catalysts are desired to accelerate polysulfide conversion and suppress the shuttling effect. Herein, we studied a doping system with Ni2P and Ni2B as the end members and found a B-doped Ni2P catalyst that demonstrates high activity for Li–S batteries. As anionic dopants, B demonstrates an interesting reverse electron transfer to P and tunes the electronic structure of Ni2P dramatically. The resultant B-doped Ni2P exhibits short Ni–B bonds and strong Ni–S interaction, and the electron donation of B to P further enhances the adsorption of polysulfide on catalysts. The S–S bonds of polysulfides were activated appropriately, therefore decreasing a low energy barrier for conversion reactions.
锂硫（Li-S）电池有望成为下一代高能量储能系统。然而，缓慢的反应动力学使流动的多硫化物难以控制，产生穿梭效应，最终损坏锂金属阳极。为了提高锂-S 电池的循环能力，我们需要高效催化剂来加速多硫化物的转化并抑制穿梭效应。在此，我们研究了以 Ni2P 和 Ni2B 为最终成员的掺杂体系，发现了一种 B 掺杂的 Ni2P 催化剂，该催化剂在锂-S 电池中表现出很高的活性。作为阴离子掺杂剂，B 向 P 进行了有趣的反向电子转移，并极大地调整了 Ni2P 的电子结构。掺杂了 B 的 Ni2P 表现出短的 Ni-B 键和强的 Ni-S 相互作用，B 向 P 的电子捐赠进一步增强了催化剂对多硫化物的吸附。多硫化物的 S-S 键被适当激活，从而降低了转化反应的低能量障碍。
{"title":"Boron-Doped Dinickel Phosphide to Enhance Polysulfide Conversion and Suppress Shuttling in Lithium–Sulfur Batteries","authors":"Jiatong Li, Guangyue Li, Rui Wang, Qiya He, Wan Liu, Chaoquan Hu, Huigang Zhang, Junfeng Hui, Fengwei Huo","doi":"10.1021/acsnano.4c03315","DOIUrl":"https://doi.org/10.1021/acsnano.4c03315","url":null,"abstract":"Lithium–sulfur (Li–S) batteries are promising for next-generation high-energy energy storage systems. However, the slow reaction kinetics render mobile polysulfides hardly controlled, yielding shuttling effects and eventually damaging Li metal anodes. To improve the cyclability of Li–S batteries, high-efficiency catalysts are desired to accelerate polysulfide conversion and suppress the shuttling effect. Herein, we studied a doping system with Ni<sub>2</sub>P and Ni<sub>2</sub>B as the end members and found a B-doped Ni<sub>2</sub>P catalyst that demonstrates high activity for Li–S batteries. As anionic dopants, B demonstrates an interesting reverse electron transfer to P and tunes the electronic structure of Ni<sub>2</sub>P dramatically. The resultant B-doped Ni<sub>2</sub>P exhibits short Ni–B bonds and strong Ni–S interaction, and the electron donation of B to P further enhances the adsorption of polysulfide on catalysts. The S–S bonds of polysulfides were activated appropriately, therefore decreasing a low energy barrier for conversion reactions.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":17.1,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464079","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yue Luo, Ji-Hoon Park, Jiadi Zhu, Michele Tamagnone, Federico Capasso, Tomás Palacios, Jing Kong, William L. Wilson
The optimization of nanoscale optical devices and structures will enable the exquisite control of planar optical fields. Polariton manipulation is the primary strategy in play. In two-dimensional heterostructures, the ability to excite mixed optical modes offers an additional control in device design. Phonon polaritons in hexagonal boron nitride have been a common system explored for the control of near-infrared radiation. Their hybridization with graphene plasmons makes these mixed phonon polariton modes in hexagonal boron nitride more appealing in terms of enabling active control of electrodynamic properties with a reduction of propagation losses. Optical resonators can be added to confine these hybridized plasmon–phonon polaritons deeply into the subwavelength regime, with these structures featuring high quality factors. Here, we show a scalable approach for the design and fabrication of heterostructure nanodisc resonators patterned in chemical vapor deposition-grown monolayer graphene and h-BN sheets. Real-space mid-infrared nanoimaging reveals the nature of hybridized polaritons in the heterostructures. We simulate and experimentally demonstrate localized hybridized polariton modes in heterostructure nanodisc resonators and demonstrate that those nanodiscs can collectively couple to the waveguide. High quality factors for the nanodiscs are measured with nanoscale Fourier transform infrared spectroscopy. Our results offer practical strategies to realize scalable nanophotonic devices utilizing low-loss hybridized polaritons for applications such as on-chip optical components.
{"title":"Highly Confined Hybridized Polaritons in Scalable van der Waals Heterostructure Resonators","authors":"Yue Luo, Ji-Hoon Park, Jiadi Zhu, Michele Tamagnone, Federico Capasso, Tomás Palacios, Jing Kong, William L. Wilson","doi":"10.1021/acsnano.3c13047","DOIUrl":"https://doi.org/10.1021/acsnano.3c13047","url":null,"abstract":"The optimization of nanoscale optical devices and structures will enable the exquisite control of planar optical fields. Polariton manipulation is the primary strategy in play. In two-dimensional heterostructures, the ability to excite mixed optical modes offers an additional control in device design. Phonon polaritons in hexagonal boron nitride have been a common system explored for the control of near-infrared radiation. Their hybridization with graphene plasmons makes these mixed phonon polariton modes in hexagonal boron nitride more appealing in terms of enabling active control of electrodynamic properties with a reduction of propagation losses. Optical resonators can be added to confine these hybridized plasmon–phonon polaritons deeply into the subwavelength regime, with these structures featuring high quality factors. Here, we show a scalable approach for the design and fabrication of heterostructure nanodisc resonators patterned in chemical vapor deposition-grown monolayer graphene and <i>h</i>-BN sheets. Real-space mid-infrared nanoimaging reveals the nature of hybridized polaritons in the heterostructures. We simulate and experimentally demonstrate localized hybridized polariton modes in heterostructure nanodisc resonators and demonstrate that those nanodiscs can collectively couple to the waveguide. High quality factors for the nanodiscs are measured with nanoscale Fourier transform infrared spectroscopy. Our results offer practical strategies to realize scalable nanophotonic devices utilizing low-loss hybridized polaritons for applications such as on-chip optical components.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":17.1,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463984","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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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