Yin-Ying Ting, Ben Breitung, Simon Schweidler, Junbo Wang, Michael Eikerling, Piotr M. Kowalski, Olivier Guillon, Payam Kaghazchi
Li-rich layered oxides can potentially provide high capacity, thereby enhancing energy density as cathode materials in Li-ion batteries. However, one of the main drawbacks is their low cycling stability. It has been proposed that the structural stability of a solid solution compound might be enhanced by exploiting the high-entropy concept. Here, we studied two Li-rich layered oxide cathode materials with multiple cations in their transition metal sites, categorized as medium or high entropy: Li(Li0.2Co0.18Ni0.18Mn0.44)O2 and Li(Li0.2Co0.18Ni0.18Mn0.18Ti0.26)O2. The synthesized materials, however, experienced a large capacity loss during the first charge/discharge cycle. We performed first-principles calculations to understand the mechanism behind the capacity fading and discovered significant structural changes in both systems. Specifically, we observed extensive Li/Ni interchange, migration of transition metal ions to Li sites, and formation of secondary phases. For the Ti-containing material, which shows a larger capacity fade than the other system, we even observed the formation of a spinel phase. The computed enthalpies of secondary phase formation reactions exhibit large negative values. However, the estimated (maximum) configurational entropy contributions to the free energies of these reactions are much smaller and therefore not determining factors. This study provides crucial insights into degradation mechanisms in Li-rich high-entropy systems, aiding the future design and development of advanced cathode materials for next-generation lithium-ion batteries.
富锂层状氧化物作为锂离子电池的阴极材料，有可能提供高容量，从而提高能量密度。然而，其主要缺点之一是循环稳定性较低。有人提出，可以通过利用高熵概念来增强固溶体化合物的结构稳定性。在此，我们研究了两种富含锂的层状氧化物阴极材料，它们的过渡金属位点中含有多个阳离子，被归类为中熵或高熵：Li(Li0.2Co0.18Ni0.18Mn0.44)O2 and Li(Li0.2Co0.18Ni0.18Mn0.18Ti0.26)O2.然而，合成的材料在第一个充放电周期中出现了较大的容量损失。我们进行了第一原理计算，以了解容量衰减背后的机理，并发现这两种体系都发生了显著的结构变化。具体来说，我们观察到了广泛的锂/镍交换、过渡金属离子向锂位迁移以及次生相的形成。含钛材料的容量衰减比其他体系更大，我们甚至观察到尖晶石相的形成。计算得出的次生相形成反应焓呈现较大的负值。然而，这些反应的自由能的估计（最大）构型熵贡献要小得多，因此不是决定性因素。这项研究为富锂高熵体系的降解机制提供了重要见解，有助于未来新一代锂离子电池先进正极材料的设计和开发。
{"title":"Delithiation-induced secondary phase formation in Li-rich cathode materials","authors":"Yin-Ying Ting, Ben Breitung, Simon Schweidler, Junbo Wang, Michael Eikerling, Piotr M. Kowalski, Olivier Guillon, Payam Kaghazchi","doi":"10.1039/d4ta06030j","DOIUrl":"https://doi.org/10.1039/d4ta06030j","url":null,"abstract":"Li-rich layered oxides can potentially provide high capacity, thereby enhancing energy density as cathode materials in Li-ion batteries. However, one of the main drawbacks is their low cycling stability. It has been proposed that the structural stability of a solid solution compound might be enhanced by exploiting the high-entropy concept. Here, we studied two Li-rich layered oxide cathode materials with multiple cations in their transition metal sites, categorized as medium or high entropy: Li(Li<small><sub>0.2</sub></small>Co<small><sub>0.18</sub></small>Ni<small><sub>0.18</sub></small>Mn<small><sub>0.44</sub></small>)O<small><sub>2</sub></small> and Li(Li<small><sub>0.2</sub></small>Co<small><sub>0.18</sub></small>Ni<small><sub>0.18</sub></small>Mn<small><sub>0.18</sub></small>Ti<small><sub>0.26</sub></small>)O<small><sub>2</sub></small>. The synthesized materials, however, experienced a large capacity loss during the first charge/discharge cycle. We performed first-principles calculations to understand the mechanism behind the capacity fading and discovered significant structural changes in both systems. Specifically, we observed extensive Li/Ni interchange, migration of transition metal ions to Li sites, and formation of secondary phases. For the Ti-containing material, which shows a larger capacity fade than the other system, we even observed the formation of a spinel phase. The computed enthalpies of secondary phase formation reactions exhibit large negative values. However, the estimated (maximum) configurational entropy contributions to the free energies of these reactions are much smaller and therefore not determining factors. This study provides crucial insights into degradation mechanisms in Li-rich high-entropy systems, aiding the future design and development of advanced cathode materials for next-generation lithium-ion batteries.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"35 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610090","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nanping Deng, Yilong Wang, Qiang Zeng, Yang Feng, Gang Wang, Hao Chi, Weimin Kang, Bowen Cheng
Highly efficiency, excellent stability and low-cost catalysts equipping with uniform distribution and enough active sites are rather important for zinc-air batteries (ZABs). In this study, inspired by hollow bubble structured carbon materials and heterostructure characteristics, the hierarchically porous carbon nanofibers with 3D network structure including heterojunction FeCu/FeF3 active nanoparticles and enriched N, F co-doping (FeCu/FeF3@HPCNFs) are prepared for oxygen reduction/evolution reaction (ORR/OER). The hierarchically porous structure inside the nanofibers combining with the hollow bubble structured carbon outside the nanofibers together can increase the specific surface area and carbon edge defects of the composite materials, thus effectively accelerating mass transfer at three-phase interfaces. Meanwhile, the heterojunction FeCu/FeF3 and unique heteroatoms co-doping can reduce charge transport resistance and accelerate catalytic reaction rate. Thus the FeCu/FeF3@HPCNFs display exceedingly good electrocatalytic performance for ORR (EORR, 1/2 = 0.87 V vs. RHE) and OER (ηOER, 10 = 377 mV at 10 mA cm−2). More importantly, both the aqueous rechargeable ZABs and flexible foldable solid-state ZABs assembled with the FeCu/FeF3@HPCNFs catalyst reveal a outstanding maximum power density and excellent long-term cycling stability. In addition, the theoretical analysis also reveals the FeCu/FeF3@HPCNFs electrocatalyst can reasonably adjust the electron distribution, effectively lower the reaction barrier of intermediate and greatly reduce OER/ORR overpotential. All in all, the work will open up a new avenue for facile construction of highly active, structurally stable and cost-effective bi-functional catalysts for ZABs.
具有均匀分布和足够活性位点的高效率、高稳定性和低成本催化剂对于锌空气电池（ZAB）而言相当重要。本研究受空心气泡结构碳材料和异质结构特点的启发，制备了具有三维网络结构的分层多孔碳纳米纤维，其中包括异质结合的 FeCu/FeF3 活性纳米颗粒和富含 N、F 的共掺杂（FeCu/FeF3@HPCNFs），用于氧还原/进化反应（ORR/OER）。纳米纤维内部的分层多孔结构与纳米纤维外部的中空气泡结构碳相结合，可增加复合材料的比表面积和碳边缘缺陷，从而有效加速三相界面的传质。同时，FeCu/FeF3 的异质结和独特的杂原子共掺杂可以降低电荷传输阻力，加快催化反应速率。因此，FeCu/FeF3@HPCNFs 在 ORR（EORR，1/2 = 0.87 V vs. RHE）和 OER（ηOER，10 = 377 mV，10 mA cm-2）方面表现出了极好的电催化性能。更重要的是，使用 FeCu/FeF3@HPCNFs 催化剂组装的水性可充电 ZAB 和柔性可折叠固态 ZAB 都具有出色的最大功率密度和长期循环稳定性。此外，理论分析还表明，FeCu/FeF3@HPCNFs 电催化剂能合理调节电子分布，有效降低中间反应势垒，大大降低 OER/ORR 过电位。总之，这项工作将为简便地构建高活性、结构稳定和经济高效的 ZAB 双功能催化剂开辟一条新途径。
{"title":"Facile construction of hierarchically porous carbon nanofibers modified by FeCu/FeF3 heterojunction for oxygen electrocatalysis in liquid and flexible Zn-air batteries","authors":"Nanping Deng, Yilong Wang, Qiang Zeng, Yang Feng, Gang Wang, Hao Chi, Weimin Kang, Bowen Cheng","doi":"10.1039/d4ta05503a","DOIUrl":"https://doi.org/10.1039/d4ta05503a","url":null,"abstract":"Highly efficiency, excellent stability and low-cost catalysts equipping with uniform distribution and enough active sites are rather important for zinc-air batteries (ZABs). In this study, inspired by hollow bubble structured carbon materials and heterostructure characteristics, the hierarchically porous carbon nanofibers with 3D network structure including heterojunction FeCu/FeF3 active nanoparticles and enriched N, F co-doping (FeCu/FeF3@HPCNFs) are prepared for oxygen reduction/evolution reaction (ORR/OER). The hierarchically porous structure inside the nanofibers combining with the hollow bubble structured carbon outside the nanofibers together can increase the specific surface area and carbon edge defects of the composite materials, thus effectively accelerating mass transfer at three-phase interfaces. Meanwhile, the heterojunction FeCu/FeF3 and unique heteroatoms co-doping can reduce charge transport resistance and accelerate catalytic reaction rate. Thus the FeCu/FeF3@HPCNFs display exceedingly good electrocatalytic performance for ORR (EORR, 1/2 = 0.87 V vs. RHE) and OER (ηOER, 10 = 377 mV at 10 mA cm−2). More importantly, both the aqueous rechargeable ZABs and flexible foldable solid-state ZABs assembled with the FeCu/FeF3@HPCNFs catalyst reveal a outstanding maximum power density and excellent long-term cycling stability. In addition, the theoretical analysis also reveals the FeCu/FeF3@HPCNFs electrocatalyst can reasonably adjust the electron distribution, effectively lower the reaction barrier of intermediate and greatly reduce OER/ORR overpotential. All in all, the work will open up a new avenue for facile construction of highly active, structurally stable and cost-effective bi-functional catalysts for ZABs.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"73 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610092","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Developing a new generation of increased energy, stability, and easily applicable N-rich energetic materials to replace RDX and HMX has posed significant challenges over the past decade. This work presents the design and synthesis of a series of novel N-rich energetic materials (N1 to N3 series) based on the triazole–tetrazole system. Among these, the N3 series demonstrates exceptional detonation performance and stability. It is noteworthy that the N3-3 molecule has achieved the best overall performance among N-rich energetic materials, with an onset decomposition temperature of 302 °C and a detonation velocity of 9341 m s−1, which significantly surpasses that of HMX. Additionally, structural studies of the N1 molecule reveal that the positioning effect of the nitro group and steric hindrance within the molecule disrupt the planar characteristics of the triazole–tetrazole system. In contrast, the amino group in the N3 series enhances molecular planarity, facilitating the formation of large conjugated systems and extensive hydrogen bond networks in N-rich energetic materials. This approach effectively enhances the stability of energetic material molecules and offers valuable insights for the development and design of stable N-rich energetic compounds.
过去十年来，开发新一代能量更高、更稳定、更易于应用的富 N 高能材料以取代 RDX 和 HMX 一直是一项重大挑战。本研究以三唑-四唑体系为基础，设计并合成了一系列新型富 N 高能材料（N1 至 N3 系列）。其中，N3 系列具有优异的引爆性能和稳定性。值得注意的是，N3-3 分子的起爆分解温度为 302 ℃，起爆速度为 9341 m s-1，大大超过了 HMX，是富 N 高能材料中综合性能最好的。此外，对 N1 分子的结构研究表明，硝基的定位效应和分子内的立体阻碍破坏了三唑-四唑体系的平面特性。相反，N3 系列中的氨基增强了分子的平面性，有利于在富含 N 的高能材料中形成大型共轭体系和广泛的氢键网络。这种方法有效提高了高能材料分子的稳定性，为开发和设计稳定的富 N 高能化合物提供了宝贵的启示。
{"title":"Towards advanced N-rich energetic explosives: based on tetrazole and triazole groups with large conjugated systems and extensive hydrogen bonds","authors":"Guofeng Zhang, Xue Hao, Yongbin Zou, Shichang Liu, Junjie Wei, Zhen Dong, Zhiwen Ye","doi":"10.1039/d4ta06447j","DOIUrl":"https://doi.org/10.1039/d4ta06447j","url":null,"abstract":"Developing a new generation of increased energy, stability, and easily applicable N-rich energetic materials to replace RDX and HMX has posed significant challenges over the past decade. This work presents the design and synthesis of a series of novel N-rich energetic materials (<strong>N1</strong> to <strong>N3</strong> series) based on the triazole–tetrazole system. Among these, the <strong>N3</strong> series demonstrates exceptional detonation performance and stability. It is noteworthy that the <strong>N3-3</strong> molecule has achieved the best overall performance among N-rich energetic materials, with an onset decomposition temperature of 302 °C and a detonation velocity of 9341 m s<small><sup>−1</sup></small>, which significantly surpasses that of HMX. Additionally, structural studies of the <strong>N1</strong> molecule reveal that the positioning effect of the nitro group and steric hindrance within the molecule disrupt the planar characteristics of the triazole–tetrazole system. In contrast, the amino group in the <strong>N3</strong> series enhances molecular planarity, facilitating the formation of large conjugated systems and extensive hydrogen bond networks in N-rich energetic materials. This approach effectively enhances the stability of energetic material molecules and offers valuable insights for the development and design of stable N-rich energetic compounds.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"7 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610577","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-14DOI: 10.1016/j.envint.2024.109076
Stephanie C. Hammel, Vivi Schlünssen, David Hope, Mike Dereviankin, Courtney D. Sandau, Karin Sørig Hougaard, Harald W. Meyer, Pete Kines, Keld Alstrup Jensen, Marie Frederiksen
Several buildings in a Danish social housing estate exceeded indoor air guidance values for polychlorinated biphenyls (PCBs), leading to their demolition. Here, we conducted a biomonitoring study among the workers on-site (n = 24) to evaluate their exposure to all 209 PCBs across the two-year demolition. We compared their PCB serum concentrations and accumulation to those of demolition workers at other worksites (n = 21) and office workers (n = 17). Demolition workers were provided with personal protective equipment according to risk assessments for PCB-related work. Serum PCBs were measured from baseline and up to two annual follow-up visits using gas chromatography high-resolution mass spectrometry. Forty-six peaks representing 58 PCBs were detected in > 60 % of serum samples; eight congeners were found in every sample. PCB-153 was the most abundant congener (median = 22.1 ng/g lipid). After adjusting for age and smoking status, demolition workers after one year on the contaminated site experienced more than a four-fold increase in all lower chlorinated PCBs compared to office workers at baseline, with increases most prominent for tri- and tetra-CBs (10β = 6.2 and 9.2, p < 0.01). Nine PCBs were significantly elevated from baseline to year 1 in only contaminated-site demolition workers, with the largest increase observed for PCB-66/80. For higher chlorinated PCBs, levels remained consistent or decreased slightly over the three samples from these workers. Those who worked in active demolition for at least 4 years at baseline experienced a 40 % increase (95 % CI: 10 %, 90 %) in the WHO-12 PCB sum. Age significantly predicted increases in PCBs, which tracked closely with logKow values. Our study showed that despite safety measures, demolition workers who worked on a PCB-contaminated site experienced increased and accumulating internal exposure to lower chlorinated PCBs compared to general demolition and office workers. Consequently, workers’ safety should be carefully considered to reduce exposures among this high risk group.
{"title":"Lower chlorinated PCBs accumulate in demolition workers while working on a contaminated worksite","authors":"Stephanie C. Hammel, Vivi Schlünssen, David Hope, Mike Dereviankin, Courtney D. Sandau, Karin Sørig Hougaard, Harald W. Meyer, Pete Kines, Keld Alstrup Jensen, Marie Frederiksen","doi":"10.1016/j.envint.2024.109076","DOIUrl":"https://doi.org/10.1016/j.envint.2024.109076","url":null,"abstract":"Several buildings in a Danish social housing estate exceeded indoor air guidance values for polychlorinated biphenyls (PCBs), leading to their demolition. Here, we conducted a biomonitoring study among the workers on-site (n = 24) to evaluate their exposure to all 209 PCBs across the two-year demolition. We compared their PCB serum concentrations and accumulation to those of demolition workers at other worksites (n = 21) and office workers (n = 17). Demolition workers were provided with personal protective equipment according to risk assessments for PCB-related work. Serum PCBs were measured from baseline and up to two annual follow-up visits using gas chromatography high-resolution mass spectrometry. Forty-six peaks representing 58 PCBs were detected in > 60 % of serum samples; eight congeners were found in every sample. PCB-153 was the most abundant congener (median = 22.1 ng/g lipid). After adjusting for age and smoking status, demolition workers after one year on the contaminated site experienced more than a four-fold increase in all lower chlorinated PCBs compared to office workers at baseline, with increases most prominent for tri- and tetra-CBs (10<sup>β</sup> = 6.2 and 9.2, p < 0.01). Nine PCBs were significantly elevated from baseline to year 1 in only contaminated-site demolition workers, with the largest increase observed for PCB-66/80. For higher chlorinated PCBs, levels remained consistent or decreased slightly over the three samples from these workers. Those who worked in active demolition for at least 4 years at baseline experienced a 40 % increase (95 % CI: 10 %, 90 %) in the WHO-12 PCB sum. Age significantly predicted increases in PCBs, which tracked closely with logK<sub>ow</sub> values. Our study showed that despite safety measures, demolition workers who worked on a PCB-contaminated site experienced increased and accumulating internal exposure to lower chlorinated PCBs compared to general demolition and office workers. Consequently, workers’ safety should be carefully considered to reduce exposures among this high risk group.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"17 1","pages":""},"PeriodicalIF":11.8,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609827","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Muhammad Muzakir, Karnan Manickavasakam, Eric Jianfeng Cheng, Fangling Yang, Ziyun Wang, Hao Li, Xinyu Zhang, Jiaqian Qin
The development of fast synthesis methods and accurate engineering of the shapes and characteristics of inorganic solid electrolytes has been substantially aided by the advancement of science and technology in electrolyte engineering. The goal of this development is to meet the strict requirements for high-performance ASSBs, or all-solid-state batteries. The synthesis methods and electrochemical characteristics of inorganic solid electrolytes (ISEs), such as NASICON-based oxide, sulfide, hydroborate, anti-perovskite, and halide, as well as their uses in ASSBs, are covered in this review along with recent discoveries. ASSB problems, such as poor ISE-electrode compatibility and the potential for adverse reactions at the electrode interface, may be resolved by using ISEs in composite cathodes and solid interface layers. This illustrates the variety of applications for the ISEs class in the creation of complex ASSB models. In conclusion, we showcase existing ASSB models and forthcoming tactics to advance the advancement of ASSB development for the next generation.
电解质工程科学和技术的发展极大地推动了无机固体电解质快速合成方法和精确形状与特性工程学的发展。这一发展的目标是满足对高性能 ASSB 或全固态电池的严格要求。本综述将介绍无机固态电解质（ISE）的合成方法和电化学特性，如基于 NASICON 的氧化物、硫化物、硼酸盐、反透镜石和卤化物，以及它们在 ASSB 中的用途和最新发现。通过在复合阴极和固体界面层中使用 ISE，可以解决 ASSB 存在的问题，如 ISE 与电极的兼容性差以及电极界面可能发生不良反应。这说明了 ISE 类在创建复杂 ASSB 模型中的各种应用。最后，我们展示了现有的 ASSB 模型和即将推出的策略，以推动下一代 ASSB 的发展。
{"title":"Inorganic solid electrolytes for all-solid-state sodium/lithium-ion batteries: recent development and applications","authors":"Muhammad Muzakir, Karnan Manickavasakam, Eric Jianfeng Cheng, Fangling Yang, Ziyun Wang, Hao Li, Xinyu Zhang, Jiaqian Qin","doi":"10.1039/d4ta06117a","DOIUrl":"https://doi.org/10.1039/d4ta06117a","url":null,"abstract":"The development of fast synthesis methods and accurate engineering of the shapes and characteristics of inorganic solid electrolytes has been substantially aided by the advancement of science and technology in electrolyte engineering. The goal of this development is to meet the strict requirements for high-performance ASSBs, or all-solid-state batteries. The synthesis methods and electrochemical characteristics of inorganic solid electrolytes (ISEs), such as NASICON-based oxide, sulfide, hydroborate, anti-perovskite, and halide, as well as their uses in ASSBs, are covered in this review along with recent discoveries. ASSB problems, such as poor ISE-electrode compatibility and the potential for adverse reactions at the electrode interface, may be resolved by using ISEs in composite cathodes and solid interface layers. This illustrates the variety of applications for the ISEs class in the creation of complex ASSB models. In conclusion, we showcase existing ASSB models and forthcoming tactics to advance the advancement of ASSB development for the next generation.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"22 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610089","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-14DOI: 10.1158/1078-0432.ccr-24-0049
James B. Reinecke, Leyre Jimenez Garcia, Amy C. Gross, Maren Cam, Matthew V. Cannon, Matthew J. Gust, Jeffrey P. Sheridan, Berkley E. Gryder, Ruben Dries, Ryan D. Roberts
Purpose: Lung metastasis is responsible for most deaths caused by osteosarcoma. How malignant bone cells coerce the lung microenvironment to support metastatic growth remains unclear. We sought to identify metastasis-specific therapeutic vulnerabilities by delineating the cellular and molecular mechanisms essential to metastatic niche formation in the lung. Experimental design: We used single-cell transcriptomics (scRNA-seq) to characterize molecular changes induced within lung tissues by disseminated osteosarcoma cells. We then evaluated the ability of nintedanib to reverse metastasis-specific changes in both immunocompetent mouse and immunodeficient xenograft models. Molecular pharmacodynamic studies used single-nucleus and spatial transcriptomics to define the tumor-intrinsic and -extrinsic changes induced by the drug. Results: Osteosarcoma cells induced acute alveolar epithelial injury upon lung dissemination. scRNA-seq demonstrated that the surrounding lung stroma adopts a chronic, non-resolving wound-healing phenotype similar to diseases associated with lung injury. Accordingly, metastasis-associated lung demonstrated marked fibrosis, likely due to the accumulation of pathogenic, pro-fibrotic, partially differentiated epithelial intermediates and macrophages. Our data suggested that nintedanib prevented metastatic progression in multiple murine and human xenograft models by inhibiting osteosarcoma-induced fibrosis. Conclusions: Fibrosis is essential to osteosarcoma lung metastasis and represents a targetable vulnerability. Our data support a model where interactions between osteosarcoma and epithelial cells induce the deposition of extracellular matrix proteins—a reaction disrupted by the anti-fibrotic TKI nintedanib. Our data shed light on the non-cell autonomous effects of TKIs on metastasis and provide a roadmap for using single-cell and spatial transcriptomics to define the mechanism of action of TKIs on metastases in animal models.
{"title":"Aberrant activation of wound healing programs within the metastatic niche facilitates lung colonization by osteosarcoma cells","authors":"James B. Reinecke, Leyre Jimenez Garcia, Amy C. Gross, Maren Cam, Matthew V. Cannon, Matthew J. Gust, Jeffrey P. Sheridan, Berkley E. Gryder, Ruben Dries, Ryan D. Roberts","doi":"10.1158/1078-0432.ccr-24-0049","DOIUrl":"https://doi.org/10.1158/1078-0432.ccr-24-0049","url":null,"abstract":"Purpose: Lung metastasis is responsible for most deaths caused by osteosarcoma. How malignant bone cells coerce the lung microenvironment to support metastatic growth remains unclear. We sought to identify metastasis-specific therapeutic vulnerabilities by delineating the cellular and molecular mechanisms essential to metastatic niche formation in the lung. Experimental design: We used single-cell transcriptomics (scRNA-seq) to characterize molecular changes induced within lung tissues by disseminated osteosarcoma cells. We then evaluated the ability of nintedanib to reverse metastasis-specific changes in both immunocompetent mouse and immunodeficient xenograft models. Molecular pharmacodynamic studies used single-nucleus and spatial transcriptomics to define the tumor-intrinsic and -extrinsic changes induced by the drug. Results: Osteosarcoma cells induced acute alveolar epithelial injury upon lung dissemination. scRNA-seq demonstrated that the surrounding lung stroma adopts a chronic, non-resolving wound-healing phenotype similar to diseases associated with lung injury. Accordingly, metastasis-associated lung demonstrated marked fibrosis, likely due to the accumulation of pathogenic, pro-fibrotic, partially differentiated epithelial intermediates and macrophages. Our data suggested that nintedanib prevented metastatic progression in multiple murine and human xenograft models by inhibiting osteosarcoma-induced fibrosis. Conclusions: Fibrosis is essential to osteosarcoma lung metastasis and represents a targetable vulnerability. Our data support a model where interactions between osteosarcoma and epithelial cells induce the deposition of extracellular matrix proteins—a reaction disrupted by the anti-fibrotic TKI nintedanib. Our data shed light on the non-cell autonomous effects of TKIs on metastasis and provide a roadmap for using single-cell and spatial transcriptomics to define the mechanism of action of TKIs on metastases in animal models.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"6 1","pages":""},"PeriodicalIF":11.5,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610297","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Piezoelectric and triboelectric nanogenerators are at the forefront of converting ambient mechanical energy into electricity. They have experienced a significant leap in functionality and autonomy through integration with artificial intelligence (AI). This integration not only boosts nanogenerator performance for autonomous operations by improving mechanical-to-electrical energy conversion efficiency but also forges new pathways in robotics and intelligent systems. It enhances the responsiveness and adaptability of these devices. Looking ahead, combining nanogenerators with AI is set to play a crucial role in promoting sustainable and eco-friendly energy solutions. Their dual contribution to advancing the capabilities of intelligent systems and promoting environmental sustainability marks a significant advancement in the use of nanogenerators in robotics. This review underscores the essential role of AI in refining nanogenerators, highlighting a path toward achieving energy autonomy and sustainability.
{"title":"Artificial Intelligence Assisted Nanogenerator Applications","authors":"Shumao Xu, Farid Manshaii, Xiao Xiao, Jun Chen","doi":"10.1039/d4ta07127a","DOIUrl":"https://doi.org/10.1039/d4ta07127a","url":null,"abstract":"Piezoelectric and triboelectric nanogenerators are at the forefront of converting ambient mechanical energy into electricity. They have experienced a significant leap in functionality and autonomy through integration with artificial intelligence (AI). This integration not only boosts nanogenerator performance for autonomous operations by improving mechanical-to-electrical energy conversion efficiency but also forges new pathways in robotics and intelligent systems. It enhances the responsiveness and adaptability of these devices. Looking ahead, combining nanogenerators with AI is set to play a crucial role in promoting sustainable and eco-friendly energy solutions. Their dual contribution to advancing the capabilities of intelligent systems and promoting environmental sustainability marks a significant advancement in the use of nanogenerators in robotics. This review underscores the essential role of AI in refining nanogenerators, highlighting a path toward achieving energy autonomy and sustainability.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"20 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610095","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-14DOI: 10.1016/j.envint.2024.109128
Hiroki Andoa, Kelly A. Reynolds
Estimating effective reproduction number (Re) and predicting disease incidences are essential to formulate effective strategies for disease control. Although recent studies developed models for inferring Re from wastewater-based data, they require information on shedding dynamics. Here, we proposed a framework of Re estimation and prediction without shedding information. The framework consists of a space-state model for smoothing wastewater-based data and a renewal equation modified for wastewater-based data. The applicability of the framework was tested with simulated data and real-world data on Influenza A virus (IAV) and SARS-CoV-2 concentration in 2022/2023 season in the USA. We confirmed the state-space model effectively fits various simulated epidemic curves and accurately fits real-world data. In simulations, we found wastewater-based Re (Reww) closely aligns with instantaneous clinical Re when shedding dynamics are rapid. For more prolonged shedding, Reww approximates a smoothed Re over time. We also observed the necessary sampling frequency to trace dynamics of wastewater concentration and Reww accurately in the framework varies depending on the precision of detection methods, the epidemic status, the transmissibility of infectious diseases, and shedding dynamics. By applying our framework to real-world data, we found Reww for SARS-CoV-2 showed similar trend and values to clinically-based Re. Reww for IAV ranged from 0.66 to 1.52 with a clear peak in the winter season, which agrees with previously reported Re. We also succeeded in predicting wastewater concentration in a few weeks from available wastewater-based data. These results indicate that our framework potentially enables real-time approximations of Re and prediction of infectious disease dynamics through wastewater surveillance, which limits the delay between infection and reporting. Our framework is useful especially for regions where reliable clinical surveillance is not available and notifiable surveillance is abolished, and can be expanded to multiple infectious diseases that have been detected from wastewater without shedding information.
估算有效繁殖数（Re）和预测疾病发病率对于制定有效的疾病控制策略至关重要。尽管最近的研究开发了从废水数据中推断 Re 的模型，但它们需要脱落动态信息。在此，我们提出了一个无需脱落信息的 Re 估计和预测框架。该框架由用于平滑废水数据的空间状态模型和针对废水数据修改的更新方程组成。该框架的适用性通过模拟数据和美国 2022/2023 年甲型流感病毒（IAV）和 SARS-CoV-2 浓度的实际数据进行了测试。我们证实，状态空间模型有效地拟合了各种模拟流行病曲线，并准确地拟合了真实世界的数据。在模拟中，我们发现当脱落动态较快时，基于废水的 Re（Reww）与瞬时临床 Re 非常接近。在脱落时间较长的情况下，Reww 近似于随时间变化的平滑 Re。我们还观察到，在框架中准确追踪废水浓度和 Reww 动态所需的采样频率因检测方法的精度、流行状况、传染病的传播性和脱落动态而异。通过将我们的框架应用于真实世界的数据，我们发现 SARS-CoV-2 的 Reww 显示出与基于临床的 Re 相似的趋势和数值。IAV 的 Reww 值从 0.66 到 1.52 不等，在冬季有一个明显的峰值，这与之前报告的 Re 值一致。我们还利用现有的废水数据在几周内成功预测了废水浓度。这些结果表明，我们的框架有可能通过废水监测实时逼近 Re 值和预测传染病动态，从而限制感染与报告之间的延迟。我们的框架尤其适用于没有可靠的临床监测和取消了应申报监测的地区，并可扩展到从废水中检测到的多种传染病，而无需脱落信息。
{"title":"Wastewater-based effective reproduction number and prediction under the absence of shedding information","authors":"Hiroki Andoa, Kelly A. Reynolds","doi":"10.1016/j.envint.2024.109128","DOIUrl":"https://doi.org/10.1016/j.envint.2024.109128","url":null,"abstract":"Estimating effective reproduction number (Re) and predicting disease incidences are essential to formulate effective strategies for disease control. Although recent studies developed models for inferring Re from wastewater-based data, they require information on shedding dynamics. Here, we proposed a framework of Re estimation and prediction without shedding information. The framework consists of a space-state model for smoothing wastewater-based data and a renewal equation modified for wastewater-based data. The applicability of the framework was tested with simulated data and real-world data on Influenza A virus (IAV) and SARS-CoV-2 concentration in 2022/2023 season in the USA. We confirmed the state-space model effectively fits various simulated epidemic curves and accurately fits real-world data. In simulations, we found wastewater-based Re (Reww) closely aligns with instantaneous clinical Re when shedding dynamics are rapid. For more prolonged shedding, Reww approximates a smoothed Re over time. We also observed the necessary sampling frequency to trace dynamics of wastewater concentration and Reww accurately in the framework varies depending on the precision of detection methods, the epidemic status, the transmissibility of infectious diseases, and shedding dynamics. By applying our framework to real-world data, we found Reww for SARS-CoV-2 showed similar trend and values to clinically-based Re. Reww for IAV ranged from 0.66 to 1.52 with a clear peak in the winter season, which agrees with previously reported Re. We also succeeded in predicting wastewater concentration in a few weeks from available wastewater-based data. These results indicate that our framework potentially enables real-time approximations of Re and prediction of infectious disease dynamics through wastewater surveillance, which limits the delay between infection and reporting. Our framework is useful especially for regions where reliable clinical surveillance is not available and notifiable surveillance is abolished, and can be expanded to multiple infectious diseases that have been detected from wastewater without shedding information.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"79 1","pages":""},"PeriodicalIF":11.8,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610498","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Purpose: Cluster of differentiation 40 (CD40) is expressed on B-cell acute lymphoblastic leukemia (B-ALL) cases. However, the effect of CD40 activation on B-ALL cells has never been tested in vivo. Experimental Design: The aim of our preclinical study was to investigate the therapeutic potential of a CD40 agonist in the treatment of B-ALL using patient-derived xenograft (PDX) mouse models. Results: Intravenous administration of the CD40 agonist significantly impeded B-ALL cell proliferation and growth in vivo, accompanied by rapid activation of the extracellular signal-regulated kinase (ERK) pathway, leading to the induction of apoptosis and disruption of cell cycle progression. Co-treatment with a specific inhibitor of ERK further demonstrated that CD40 stimulation induced the pro-apoptosis of B-ALL cells in an ERK-dependent manner. Proteomic analysis revealed alterations in key signaling pathways associated with B-ALL expansion and maintenance. Moreover, the CD40 agonist markedly reduced the frequency of leukemia-initiating cells and leukemia development in PDX mice. Our study showed that the CD40 agonist can be associated with chemotherapeutic agents such as vincristine and dexamethasone, and this combination showed improved effectiveness. Additionally, the CD40 agonist was more effective on pre-B-ALL (EGIL B-III) that expressed CD40, than on common B-ALL (EGIL B-II) that lacked CD40 expression. Conclusion: These findings suggest that CD40 agonists are promising immunotherapeutic candidates for pediatric B-ALL, warranting further clinical investigations to improve patient outcomes in CD40-expressing B-ALL.
{"title":"CD40 agonist on patient-derived xenograft mice for the treatment of B-cell acute lymphoblastic leukemia","authors":"Pierre-Simon Bellaye, Aleksandra Georgievski, Paola Ballerini, Boutheina Bouslama, Corentin Richard, Romain Boidot, Guillaume Chevreux, Véronique Legros, Julien Guy, Jessica Racine, Bertrand Collin, Carmen Garrido, Ronan Quéré","doi":"10.1158/1078-0432.ccr-24-1391","DOIUrl":"https://doi.org/10.1158/1078-0432.ccr-24-1391","url":null,"abstract":"Purpose: Cluster of differentiation 40 (CD40) is expressed on B-cell acute lymphoblastic leukemia (B-ALL) cases. However, the effect of CD40 activation on B-ALL cells has never been tested in vivo. Experimental Design: The aim of our preclinical study was to investigate the therapeutic potential of a CD40 agonist in the treatment of B-ALL using patient-derived xenograft (PDX) mouse models. Results: Intravenous administration of the CD40 agonist significantly impeded B-ALL cell proliferation and growth in vivo, accompanied by rapid activation of the extracellular signal-regulated kinase (ERK) pathway, leading to the induction of apoptosis and disruption of cell cycle progression. Co-treatment with a specific inhibitor of ERK further demonstrated that CD40 stimulation induced the pro-apoptosis of B-ALL cells in an ERK-dependent manner. Proteomic analysis revealed alterations in key signaling pathways associated with B-ALL expansion and maintenance. Moreover, the CD40 agonist markedly reduced the frequency of leukemia-initiating cells and leukemia development in PDX mice. Our study showed that the CD40 agonist can be associated with chemotherapeutic agents such as vincristine and dexamethasone, and this combination showed improved effectiveness. Additionally, the CD40 agonist was more effective on pre-B-ALL (EGIL B-III) that expressed CD40, than on common B-ALL (EGIL B-II) that lacked CD40 expression. Conclusion: These findings suggest that CD40 agonists are promising immunotherapeutic candidates for pediatric B-ALL, warranting further clinical investigations to improve patient outcomes in CD40-expressing B-ALL.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"216 1","pages":""},"PeriodicalIF":11.5,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610294","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-14DOI: 10.1158/1078-0432.ccr-23-4026
Francesca Sarno, Jair Tenorio, Sofia Perea, Laura Medina, Roberto Pazo-Cid, Ignacio Juez, Rocio Garcia-Carbonero, Jaime Feliu, Carmen Guillen-Ponce, Pedro P. Lopez-Casas, Carmen Guerra, Yolanda Duran, Jose Francisco López-Acosta, Carolina Alonso, Estrella Esquivel, Ana Dopazo, Dipikaa Akshinthala, Senthil K. Muthuswamy, Pablo Lapunzina, Bruno Bockorny, Manuel Hidalgo
Purpose: Pancreatic adenocarcinoma (PDAC) has limited treatment options. We compared the efficacy of comprehensive precision medicine against the conventional treatment in PDAC. Methods: Phase III trial of advanced PDAC where patients were randomized (1:2) to a conventional treatment treated at physician’s discretion (arm A), or to precision medicine (arm B). Subjects randomized to arm B underwent a tumor biopsy for whole exome sequencing (WES) and to generate avatar mouse models and patient derived organoids for phenotypic drug screening, with final treatment recommended by molecular tumor board. The primary objective was median overall survival (OS). Results: 137 patients were enrolled with 125 randomized, 44 to arm A and 81 to Arm B. WES was performed in 80.3% (65/81) patients of arm B, with potentially actionable mutations detected in 21.5% (14/65). Experimental models were generated in 16/81 patients (19.8%). Second-line treatment was administered to 39 patients in the experimental arm, but only 4 (10.2%) received personalized treatment, while 35 could not be receive matched therapy due to rapid clinical deterioration, delays in obtaining study results or absence of actionable targets. Median OS was 8.7 and 8.6 months (p=0.849) and median progression-free survival was 3.8 and 4.3 months (p=0.563) for the conventional and experimental arms, respectively. Notably, the four patients who received personalized treatment had median OS of 19.3 months. Conclusions: Personalized medicine was challenging to implement in most patients with PDAC, limiting the interpretation of intention to treat analysis. Survival was improved in the subset of patients who did receive matched therapy.
目的：胰腺腺癌（PDAC）的治疗方案有限。我们比较了综合精准医疗与传统治疗对 PDAC 的疗效。方法：晚期 PDAC III 期试验晚期 PDAC III 期试验，患者被随机（1:2）分配到由医生决定的常规治疗（A 组）或精准医疗（B 组）。被随机分配到B组的受试者接受肿瘤活检，进行全外显子组测序（WES），并生成阿凡达小鼠模型和患者衍生的器官组织，进行表型药物筛选，最终治疗方案由分子肿瘤委员会推荐。主要目标是中位总生存期（OS）。研究结果B组80.3%（65/81）的患者进行了WES检查，21.5%（14/65）的患者检测到了潜在的可操作突变。16/81（19.8%）名患者建立了实验模型。实验组的 39 例患者接受了二线治疗，但只有 4 例（10.2%）接受了个性化治疗，35 例因临床病情迅速恶化、研究结果迟迟未出或缺乏可作用靶点而无法接受匹配治疗。常规组和实验组的中位生存期分别为8.7个月和8.6个月（P=0.849），中位无进展生存期分别为3.8个月和4.3个月（P=0.563）。值得注意的是，接受个性化治疗的四名患者的中位生存期为 19.3 个月。结论对大多数 PDAC 患者实施个体化治疗具有挑战性，这限制了对意向治疗分析的解释。接受匹配治疗的亚组患者的生存率有所提高。
{"title":"A Phase III Randomized Trial of Integrated Genomics and Avatar Models for Personalized Treatment of Pancreatic Cancer: the AVATAR Trial","authors":"Francesca Sarno, Jair Tenorio, Sofia Perea, Laura Medina, Roberto Pazo-Cid, Ignacio Juez, Rocio Garcia-Carbonero, Jaime Feliu, Carmen Guillen-Ponce, Pedro P. Lopez-Casas, Carmen Guerra, Yolanda Duran, Jose Francisco López-Acosta, Carolina Alonso, Estrella Esquivel, Ana Dopazo, Dipikaa Akshinthala, Senthil K. Muthuswamy, Pablo Lapunzina, Bruno Bockorny, Manuel Hidalgo","doi":"10.1158/1078-0432.ccr-23-4026","DOIUrl":"https://doi.org/10.1158/1078-0432.ccr-23-4026","url":null,"abstract":"Purpose: Pancreatic adenocarcinoma (PDAC) has limited treatment options. We compared the efficacy of comprehensive precision medicine against the conventional treatment in PDAC. Methods: Phase III trial of advanced PDAC where patients were randomized (1:2) to a conventional treatment treated at physician’s discretion (arm A), or to precision medicine (arm B). Subjects randomized to arm B underwent a tumor biopsy for whole exome sequencing (WES) and to generate avatar mouse models and patient derived organoids for phenotypic drug screening, with final treatment recommended by molecular tumor board. The primary objective was median overall survival (OS). Results: 137 patients were enrolled with 125 randomized, 44 to arm A and 81 to Arm B. WES was performed in 80.3% (65/81) patients of arm B, with potentially actionable mutations detected in 21.5% (14/65). Experimental models were generated in 16/81 patients (19.8%). Second-line treatment was administered to 39 patients in the experimental arm, but only 4 (10.2%) received personalized treatment, while 35 could not be receive matched therapy due to rapid clinical deterioration, delays in obtaining study results or absence of actionable targets. Median OS was 8.7 and 8.6 months (p=0.849) and median progression-free survival was 3.8 and 4.3 months (p=0.563) for the conventional and experimental arms, respectively. Notably, the four patients who received personalized treatment had median OS of 19.3 months. Conclusions: Personalized medicine was challenging to implement in most patients with PDAC, limiting the interpretation of intention to treat analysis. Survival was improved in the subset of patients who did receive matched therapy.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"5 1","pages":""},"PeriodicalIF":11.5,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610295","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：