Bin Li, Ludi Wang, Yu Kang, Hong Cao, Yaoyang Liu, Qiange He, Zhongfeng Li, Xiaoyan Tang, Jing Chen, Li Wang, Chao Xu
Hydrophilic actinide masking agents are believed to be efficient alternatives to circumvent the extensive hazardous organic solvents/diluents typically employed in the liquid–liquid extraction for nuclear waste management. However, the practical application of hydrophilic ligands faces significant challenges in both synthetic/purification procedures and, more importantly, the acid resistance of the ligands themselves. Herein, we have demonstrated the combination of phenanthroline diimide framework with a biomotif of histidine flanking parts could achieve efficient separation of trivalent lanthanides/actinides (also actinides/actinides) under high acidity of over 1 M HNO3. This approach leverages the soft–hard coordination properties of N, O-hybrid ligands, as well as the energetically favored imides for metal coordination and the multiple protonation of histidine. These factors collectively contribute to the synthesis of an easily accessible, highly water-soluble, superior selective, and acid-resistant Am(III) masking agent. Thus, we have shown in this paper, by proper combination of synthetic N, O-hybrid ligand with amino acid, trivalent lanthanide and actinide separation could be efficiently fulfilled in a more sustainable manner.
亲水性锕系元素掩蔽剂被认为是一种有效的替代品，可以避免在核废料管理的液液萃取过程中通常使用的大量有害有机溶剂/稀释剂。然而，亲水配体的实际应用在合成/纯化程序方面面临着巨大挑战，更重要的是配体本身的耐酸性。在本文中，我们证明了菲罗啉二亚胺框架与组氨酸侧翼部分的生物特征相结合，可以在超过 1 M HNO3 的高酸度条件下实现三价镧系元素/锕系元素（也包括锕系元素/锕系元素）的高效分离。这种方法利用了 N、O-杂化配体的软硬配位特性，以及在能量上有利于金属配位的酰亚胺和组氨酸的多重质子化。这些因素共同促成了一种易于获得、水溶性强、选择性高且耐酸的 Am（III）掩蔽剂的合成。因此，我们在本文中表明，通过将合成的 N、O-杂化配体与氨基酸适当结合，可以以更可持续的方式有效实现三价镧系和锕系元素的分离。
{"title":"Amino Acid Decorated Phenanthroline Diimide as Sustainable Hydrophilic Am(III) Masking Agent with High Acid Resistance","authors":"Bin Li, Ludi Wang, Yu Kang, Hong Cao, Yaoyang Liu, Qiange He, Zhongfeng Li, Xiaoyan Tang, Jing Chen, Li Wang, Chao Xu","doi":"10.1021/jacsau.4c00659","DOIUrl":"https://doi.org/10.1021/jacsau.4c00659","url":null,"abstract":"Hydrophilic actinide masking agents are believed to be efficient alternatives to circumvent the extensive hazardous organic solvents/diluents typically employed in the liquid–liquid extraction for nuclear waste management. However, the practical application of hydrophilic ligands faces significant challenges in both synthetic/purification procedures and, more importantly, the acid resistance of the ligands themselves. Herein, we have demonstrated the combination of phenanthroline diimide framework with a biomotif of histidine flanking parts could achieve efficient separation of trivalent lanthanides/actinides (also actinides/actinides) under high acidity of over 1 M HNO<sub>3</sub>. This approach leverages the soft–hard coordination properties of <i>N, O</i>-hybrid ligands, as well as the energetically favored imides for metal coordination and the multiple protonation of histidine. These factors collectively contribute to the synthesis of an easily accessible, highly water-soluble, superior selective, and acid-resistant Am(III) masking agent. Thus, we have shown in this paper, by proper combination of synthetic <i>N, O</i>-hybrid ligand with amino acid, trivalent lanthanide and actinide separation could be efficiently fulfilled in a more sustainable manner.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"5 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142214390","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shuo Wang, Xue-Yuan Gong, Ming-Xin Li, Ming-Hua Li, Jin-Song Hu
Perovskite solar cells (PSCs) are recognized as one of the most promising next-generation photovoltaics, primarily due to their exceptional power conversion efficiency, ease of processing, and cost-effectiveness. Despite these advantages, challenges remain in achieving high-quality films and ensuring the long-term stability of PSCs, which hinder their widespread commercialization. Polymers, characterized by multifunctional groups, superior thermal stability, flexible long chains, and cross-linking capabilities, offer significant potential to enhance the performance and reliability of PSCs. This review comprehensively presents the multifaceted roles that polymers play in PSCs. Through carefully controlling interactions between polymers and perovskites, crucial aspects such as film crystallization kinetics, carrier transport process, ion migration issues, and mechanical properties under bending can be effectively regulated to maximize the device performance. Furthermore, the hydrophobic properties and strong chelated cross-linking networks of polymers significantly enhance the stability of PSCs under various environmental conditions while effectively mitigating lead leakage, thereby addressing environmental concerns and long-term durability. Moreover, this Perspective identifies potential pathways for further advancing polymer-based strategies in PSC applications.
{"title":"Polymers for Perovskite Solar Cells","authors":"Shuo Wang, Xue-Yuan Gong, Ming-Xin Li, Ming-Hua Li, Jin-Song Hu","doi":"10.1021/jacsau.4c00615","DOIUrl":"https://doi.org/10.1021/jacsau.4c00615","url":null,"abstract":"Perovskite solar cells (PSCs) are recognized as one of the most promising next-generation photovoltaics, primarily due to their exceptional power conversion efficiency, ease of processing, and cost-effectiveness. Despite these advantages, challenges remain in achieving high-quality films and ensuring the long-term stability of PSCs, which hinder their widespread commercialization. Polymers, characterized by multifunctional groups, superior thermal stability, flexible long chains, and cross-linking capabilities, offer significant potential to enhance the performance and reliability of PSCs. This review comprehensively presents the multifaceted roles that polymers play in PSCs. Through carefully controlling interactions between polymers and perovskites, crucial aspects such as film crystallization kinetics, carrier transport process, ion migration issues, and mechanical properties under bending can be effectively regulated to maximize the device performance. Furthermore, the hydrophobic properties and strong chelated cross-linking networks of polymers significantly enhance the stability of PSCs under various environmental conditions while effectively mitigating lead leakage, thereby addressing environmental concerns and long-term durability. Moreover, this Perspective identifies potential pathways for further advancing polymer-based strategies in PSC applications.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"277 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142214395","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xinmin Zhao, Hongzhen Peng, Jun Hu, Lihua Wang, Feng Zhang
This Perspective elucidates the transformative impacts of advanced nanotechnology and dynamic energy systems on the polymer chain reaction (PCR), a cornerstone technique in biomedical research and diagnostic applications. Since its invention, the optimization of PCR─specifically its efficiency, specificity, cycling rate, and detection sensitivity─has been a focal point of scientific exploration. Our analysis spans the modulation of PCR from both material and energetic perspectives, emphasizing the intricate interplay between PCR components and externally added entities such as molecules, nanoparticles (NPs), and optical microcavities. We begin with a foundational overview of PCR, detailing the basic principles of PCR modulation through molecular additives to highlight material-level interactions. Then, we delve into how NPs, with their diverse material and surface properties, influence PCR through interface interactions and hydrothermal conduction, drawing parallels to molecular behaviors. Additionally, this Perspective ventures into the energetic regulation of PCR, examining the roles of electromagnetic radiation and optical resonators. We underscore the advanced capabilities of optical technologies in PCR regulation, characterized by their ultrafast, residue-free, and noninvasive nature, alongside label-free detection methods. Notably, optical resonators present a pioneering approach to control PCR processes even in the absence of light, targeting the often-overlooked water component in PCR. By integrating discussions on photocaging and vibrational strong coupling, this review presents innovative methods for the precise regulation of PCR processes, envisioning a new era of PCR technology that enhances both research and clinical diagnostics. The synergy between nanotechnological enhancements and energy dynamics not only enriches our understanding of PCR but also opens new avenues for developing rapid, accurate, and efficient PCR systems. We hope that this Perspective will inspire further innovations in PCR technology and guide the development of next-generation clinical detection instruments.
{"title":"Nanotechnology-Enabled PCR with Tunable Energy Dynamics","authors":"Xinmin Zhao, Hongzhen Peng, Jun Hu, Lihua Wang, Feng Zhang","doi":"10.1021/jacsau.4c00570","DOIUrl":"https://doi.org/10.1021/jacsau.4c00570","url":null,"abstract":"This Perspective elucidates the transformative impacts of advanced nanotechnology and dynamic energy systems on the polymer chain reaction (PCR), a cornerstone technique in biomedical research and diagnostic applications. Since its invention, the optimization of PCR─specifically its efficiency, specificity, cycling rate, and detection sensitivity─has been a focal point of scientific exploration. Our analysis spans the modulation of PCR from both material and energetic perspectives, emphasizing the intricate interplay between PCR components and externally added entities such as molecules, nanoparticles (NPs), and optical microcavities. We begin with a foundational overview of PCR, detailing the basic principles of PCR modulation through molecular additives to highlight material-level interactions. Then, we delve into how NPs, with their diverse material and surface properties, influence PCR through interface interactions and hydrothermal conduction, drawing parallels to molecular behaviors. Additionally, this Perspective ventures into the energetic regulation of PCR, examining the roles of electromagnetic radiation and optical resonators. We underscore the advanced capabilities of optical technologies in PCR regulation, characterized by their ultrafast, residue-free, and noninvasive nature, alongside label-free detection methods. Notably, optical resonators present a pioneering approach to control PCR processes even in the absence of light, targeting the often-overlooked water component in PCR. By integrating discussions on photocaging and vibrational strong coupling, this review presents innovative methods for the precise regulation of PCR processes, envisioning a new era of PCR technology that enhances both research and clinical diagnostics. The synergy between nanotechnological enhancements and energy dynamics not only enriches our understanding of PCR but also opens new avenues for developing rapid, accurate, and efficient PCR systems. We hope that this Perspective will inspire further innovations in PCR technology and guide the development of next-generation clinical detection instruments.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"63 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142226851","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sreeahila Retnadhas, Daniel C. Ducat, Eric L. Hegg
Synthetic plastics have become integral to our daily lives, yet their escalating production, limited biodegradability, and inadequate waste management contribute to environmental contamination. Biological plastic degradation is one promising strategy to address this pollution. The inherent chemical and physical properties of synthetic plastics, however, pose challenges for microbial enzymes, hindering the effective degradation and the development of a sustainable biological recycling process. This Perspective explores alternative, nature-inspired strategies designed to overcome some key limitations in currently available plastic-degrading enzymes. Nature’s refined degradation pathways for natural polymers, such as cellulose, present a compelling framework for the development of efficient technologies for enzymatic plastic degradation. By drawing insights from nature, we propose a general strategy of employing substrate binding domains to improve targeting and multienzyme scaffolds to overcome enzymatic efficiency limitations. As one potential application, we outline a multienzyme pathway to upcycle polyethylene into alkenes. Employing nature-inspired strategies can present a path toward sustainable solution to the environmental impact of synthetic plastics.
{"title":"Nature-Inspired Strategies for Sustainable Degradation of Synthetic Plastics","authors":"Sreeahila Retnadhas, Daniel C. Ducat, Eric L. Hegg","doi":"10.1021/jacsau.4c00388","DOIUrl":"https://doi.org/10.1021/jacsau.4c00388","url":null,"abstract":"Synthetic plastics have become integral to our daily lives, yet their escalating production, limited biodegradability, and inadequate waste management contribute to environmental contamination. Biological plastic degradation is one promising strategy to address this pollution. The inherent chemical and physical properties of synthetic plastics, however, pose challenges for microbial enzymes, hindering the effective degradation and the development of a sustainable biological recycling process. This Perspective explores alternative, nature-inspired strategies designed to overcome some key limitations in currently available plastic-degrading enzymes. Nature’s refined degradation pathways for natural polymers, such as cellulose, present a compelling framework for the development of efficient technologies for enzymatic plastic degradation. By drawing insights from nature, we propose a general strategy of employing substrate binding domains to improve targeting and multienzyme scaffolds to overcome enzymatic efficiency limitations. As one potential application, we outline a multienzyme pathway to upcycle polyethylene into alkenes. Employing nature-inspired strategies can present a path toward sustainable solution to the environmental impact of synthetic plastics.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"96 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142214394","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiaomeng Dou, Kailang Li, Kun Zhang, Chaofeng Zhu, Debora M. Meira, Yang Song, Peng He, Liang Zhang, Lichen Liu
Selective activation of light alkanes is an essential reaction in the petrochemical industry for producing commodity chemicals, such as light olefins and aromatics. Because of the much higher intrinsic activities of noble metals in comparison to non-noble metals, it is desirable to employ solid catalysts with low noble metal loadings to reduce the cost of catalysts. Herein, we report the introduction of a tiny amount of Pt (at levels of hundreds of ppm) as a promoter of the Ga2O3 clusters encapsulated in ZSM-5 zeolite, which leads to ∼20-fold improvement in the activity for ethane dehydrogenation reaction. A combination of experimental and theoretical studies shows that the isolated Pt atoms stabilized by small Ga2O3 clusters are the active sites for activating the inert C–H bonds in ethane. The synergy of atomically dispersed Pt and Ga2O3 clusters confined in the 10MR channels of ZSM-5 can serve as a bifunctional catalyst for the direct ethane–benzene coupling reaction for the production of ethylbenzene, surpassing the performances of the counterpart catalysts made with PtGa nanoclusters and nanoparticles.
{"title":"Isolated Pt Atoms Stabilized by Ga2O3 Clusters Confined in ZSM-5 for Nonoxidative Activation of Ethane","authors":"Xiaomeng Dou, Kailang Li, Kun Zhang, Chaofeng Zhu, Debora M. Meira, Yang Song, Peng He, Liang Zhang, Lichen Liu","doi":"10.1021/jacsau.4c00480","DOIUrl":"https://doi.org/10.1021/jacsau.4c00480","url":null,"abstract":"Selective activation of light alkanes is an essential reaction in the petrochemical industry for producing commodity chemicals, such as light olefins and aromatics. Because of the much higher intrinsic activities of noble metals in comparison to non-noble metals, it is desirable to employ solid catalysts with low noble metal loadings to reduce the cost of catalysts. Herein, we report the introduction of a tiny amount of Pt (at levels of hundreds of ppm) as a promoter of the Ga<sub>2</sub>O<sub>3</sub> clusters encapsulated in ZSM-5 zeolite, which leads to ∼20-fold improvement in the activity for ethane dehydrogenation reaction. A combination of experimental and theoretical studies shows that the isolated Pt atoms stabilized by small Ga<sub>2</sub>O<sub>3</sub> clusters are the active sites for activating the inert C–H bonds in ethane. The synergy of atomically dispersed Pt and Ga<sub>2</sub>O<sub>3</sub> clusters confined in the 10MR channels of ZSM-5 can serve as a bifunctional catalyst for the direct ethane–benzene coupling reaction for the production of ethylbenzene, surpassing the performances of the counterpart catalysts made with PtGa nanoclusters and nanoparticles.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"118 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142214392","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Liver fibrosis is a life-threatening disease that currently lacks clinically effective therapeutic agents. Given the close correlation between dysregulated intracellular K+ homeostasis and the progression of liver fibrosis, developing artificial K+ transporters mimicking the essential function of their natural counterparts in regulating intracellular K+ levels might offer an appealing yet unexplored treatment strategy. Here, we present an unconventional class of artificial K+ transporters involving the “motional” collaboration between two K+ transporter molecules. In particular, 6C6 exhibits an impressive EC50 value of 0.28 μM (i.e., 0.28 mol % relative to lipid) toward K+ and an exceptionally high K+/Na+ selectivity of 15.5, representing one of the most selective artificial K+ transporters reported to date. Most importantly, our study demonstrates, for the first time, the potential therapeutic effect of K+-selective artificial ion transporters in reversing liver fibrosis both in vitro and in vivo.
{"title":"Highly Selective Artificial K+ Transporters Reverse Liver Fibrosis In Vivo","authors":"Qiuping Zhang, Qinghong Liang, Guijiang Wang, Xiaopan Xie, Yin Cao, Nan Sheng, Zhiping Zeng, Changliang Ren","doi":"10.1021/jacsau.4c00521","DOIUrl":"https://doi.org/10.1021/jacsau.4c00521","url":null,"abstract":"Liver fibrosis is a life-threatening disease that currently lacks clinically effective therapeutic agents. Given the close correlation between dysregulated intracellular K<sup>+</sup> homeostasis and the progression of liver fibrosis, developing artificial K<sup>+</sup> transporters mimicking the essential function of their natural counterparts in regulating intracellular K<sup>+</sup> levels might offer an appealing yet unexplored treatment strategy. Here, we present an unconventional class of artificial K<sup>+</sup> transporters involving the “motional” collaboration between two K<sup>+</sup> transporter molecules. In particular, <b>6C6</b> exhibits an impressive EC<sub>50</sub> value of 0.28 μM (i.e., 0.28 mol % relative to lipid) toward K<sup>+</sup> and an exceptionally high K<sup>+</sup>/Na<sup>+</sup> selectivity of 15.5, representing one of the most selective artificial K<sup>+</sup> transporters reported to date. Most importantly, our study demonstrates, for the first time, the potential therapeutic effect of K<sup>+</sup>-selective artificial ion transporters in reversing liver fibrosis both <i>in vitro</i> and <i>in vivo</i>.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"36 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142214391","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ji Hyeon Kim, Jieun Lee, Kyung-Woo Lee, Hao Xiong, Mingle Li, Jong Seung Kim
Aldehyde dehydrogenase (ALDH) is an enzyme responsible for converting aldehyde functional groups into carboxylate metabolites. Elevated ALDH activity is a characteristic feature of cancer stem-like cells (CSCs). As a novel approach to target the CSC trait of overexpressing ALDH, we aimed to utilize ALDH activity for the selective accumulation of a photosensitizer in ALDHHigh CSCs. A novel ALDH substrate photosensitizer, SCHO, with thionylated coumarin and N-ethyl-4-(aminomethyl)benzaldehyde was developed to achieve this goal. Our study demonstrated the efficient metabolism of the aldehyde unit of SCHO into carboxylate, leading to its accumulation in ALDHHigh MDA-MB-231 cells. Importantly, we established the selectivity of SCHO as an ALDHHigh cell photosensitizer as it is not a substrate for ABC transporters. SCHO-based photodynamic therapy triggers apoptosis and pyroptosis in MDA-MB-231 cells and further reduces the characteristics of CSCs. Our study presents a novel strategy to target CSCs by exploiting their cellular metabolism to enhance photosensitizer accumulation, highlighting the potential of photodynamic therapy as a powerful tool for eliminating ALDHHigh CSCs.
{"title":"Trapped in Cells: A Selective Accumulation Approach for Type-I Photodynamic Ablation of Cancer Stem–like Cells","authors":"Ji Hyeon Kim, Jieun Lee, Kyung-Woo Lee, Hao Xiong, Mingle Li, Jong Seung Kim","doi":"10.1021/jacsau.4c00642","DOIUrl":"https://doi.org/10.1021/jacsau.4c00642","url":null,"abstract":"Aldehyde dehydrogenase (ALDH) is an enzyme responsible for converting aldehyde functional groups into carboxylate metabolites. Elevated ALDH activity is a characteristic feature of cancer stem-like cells (CSCs). As a novel approach to target the CSC trait of overexpressing ALDH, we aimed to utilize ALDH activity for the selective accumulation of a photosensitizer in ALDH<sup>High</sup> CSCs. A novel ALDH substrate photosensitizer, <b>SCHO</b>, with thionylated coumarin and <i>N</i>-ethyl-4-(aminomethyl)benzaldehyde was developed to achieve this goal. Our study demonstrated the efficient metabolism of the aldehyde unit of <b>SCHO</b> into carboxylate, leading to its accumulation in ALDH<sup>High</sup> MDA-MB-231 cells. Importantly, we established the selectivity of <b>SCHO</b> as an ALDH<sup>High</sup> cell photosensitizer as it is not a substrate for ABC transporters. <b>SCHO</b>-based photodynamic therapy triggers apoptosis and pyroptosis in MDA-MB-231 cells and further reduces the characteristics of CSCs. Our study presents a novel strategy to target CSCs by exploiting their cellular metabolism to enhance photosensitizer accumulation, highlighting the potential of photodynamic therapy as a powerful tool for eliminating ALDH<sup>High</sup> CSCs.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"4 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142214396","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The development of robust NMR methodologies to probe dynamics on the atomic scale is vital to elucidate the close relations between structure, motion, and function in biological systems. Here, we present an automated protocol to measure, using magic-angle spinning NMR, the effective 13C–15N dipolar coupling constants between multiple spin pairs simultaneously with high accuracy. We use the experimental dipolar coupling constants to quantify the order parameters of multiple C–N bonds in the thousands of identical copies of the coat protein in intact fd-Y21M filamentous bacteriophage virus and describe its overall dynamics on the submillisecond time scale. The method is based on combining three pseudo three-dimensional NMR experiments, where a rotational echo double resonance (REDOR) dephasing block, designed to measure internuclear distances, is combined with three complementary 13C–13C mixing schemes: dipolar-assisted rotational resonance, through-bond transfer-based double quantum/single quantum correlation, and radio frequency driven recoupling. These mixing schemes result in highly resolved carbon spectra with correlations that are created by different transfer mechanisms. We show that the helical part of the coat protein undergoes a uniform small (∼30°) amplitude motion, while the N-terminus is highly flexible. In addition, our results suggest that the reduced mobility of lysine sidechains at the C-terminus are a signature of binding to the single stranded DNA.
开发强大的核磁共振方法来探测原子尺度上的动力学，对于阐明生物系统中结构、运动和功能之间的密切关系至关重要。在这里，我们提出了一种自动化方案，利用魔角旋转 NMR 同时高精度测量多个自旋对之间的有效 13C-15N 双极耦合常数。我们利用实验得到的偶极耦合常数来量化完整的 fd-Y21M 丝状噬菌体病毒数千个相同拷贝的衣壳蛋白中多个 C-N 键的阶次参数，并描述其在亚毫秒级时间尺度上的整体动态。该方法基于三个伪三维核磁共振实验的结合，其中旋转回波双共振（REDOR）去相位块旨在测量核间距，与三个互补的 13C-13C 混合方案相结合：双极性辅助旋转共振、基于通键转移的双量子/单量子相关性和射频驱动的再耦合。这些混合方案产生了高分辨率的碳光谱，其相关性由不同的转移机制产生。我们的研究表明，衣壳蛋白的螺旋部分会发生均匀的小振幅（∼30°）运动，而 N 端则具有高度柔性。此外，我们的研究结果表明，C 端赖氨酸侧链移动性的降低是与单链 DNA 结合的标志。
{"title":"Dynamics in the Intact fd Bacteriophage Revealed by Pseudo 3D REDOR-Based Magic Angle Spinning NMR","authors":"Orr Simon Lusky, Dvir Sherer, Amir Goldbourt","doi":"10.1021/jacsau.4c00549","DOIUrl":"https://doi.org/10.1021/jacsau.4c00549","url":null,"abstract":"The development of robust NMR methodologies to probe dynamics on the atomic scale is vital to elucidate the close relations between structure, motion, and function in biological systems. Here, we present an automated protocol to measure, using magic-angle spinning NMR, the effective <sup>13</sup>C–<sup>15</sup>N dipolar coupling constants between multiple spin pairs simultaneously with high accuracy. We use the experimental dipolar coupling constants to quantify the order parameters of multiple C–N bonds in the thousands of identical copies of the coat protein in intact fd-Y21M filamentous bacteriophage virus and describe its overall dynamics on the submillisecond time scale. The method is based on combining three pseudo three-dimensional NMR experiments, where a rotational echo double resonance (REDOR) dephasing block, designed to measure internuclear distances, is combined with three complementary <sup>13</sup>C–<sup>13</sup>C mixing schemes: dipolar-assisted rotational resonance, through-bond transfer-based double quantum/single quantum correlation, and radio frequency driven recoupling. These mixing schemes result in highly resolved carbon spectra with correlations that are created by different transfer mechanisms. We show that the helical part of the coat protein undergoes a uniform small (∼30°) amplitude motion, while the N-terminus is highly flexible. In addition, our results suggest that the reduced mobility of lysine sidechains at the C-terminus are a signature of binding to the single stranded DNA.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"21 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142214393","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The formation of a hexagonal diamond represents one of the most intriguing questions in materials science. Under shock conditions, the graphite basal plane tends to slide and pucker to form diamond. However, how the shock strength determines the phase selectivity remains unclear. In this work, using a DFT-trained carbon global neural network model, we studied the shock-induced graphite transition. The poor sliding caused by scarce sliding time under high-strength shock leads to metastable hexagonal diamond with an orientation relationship of (001)G//(100)HD+[010]G//[010]HD, while under low-strength shock due to long sliding distance cubic diamond forms with the orientation (001)G//(111)CD+[100]G//[110]CD, unveiling the strength-dependent graphite transition mechanism. We for the first time provide computational evidence of the strength-dependent graphite transition from first-principles, clarifying the long-term unresolved shock-induced hexagonal diamond formation mechanism and the structural source of the strength-dependent trend, which facilitates the hexagonal diamond synthesis via controlled experiment.
{"title":"The Transformation Mechanism of Graphite to Hexagonal Diamond under Shock Conditions","authors":"Gu-Wen Chen, Sheng-Cai Zhu, Liang Xu, Yao-Min Li, Zhi-Pan Liu, Yanglong Hou, Ho-kwang Mao","doi":"10.1021/jacsau.4c00523","DOIUrl":"https://doi.org/10.1021/jacsau.4c00523","url":null,"abstract":"The formation of a hexagonal diamond represents one of the most intriguing questions in materials science. Under shock conditions, the graphite basal plane tends to slide and pucker to form diamond. However, how the shock strength determines the phase selectivity remains unclear. In this work, using a DFT-trained carbon global neural network model, we studied the shock-induced graphite transition. The poor sliding caused by scarce sliding time under high-strength shock leads to metastable hexagonal diamond with an orientation relationship of (001)<sub>G</sub>//(100)<sub>HD</sub>+[010]<sub>G</sub>//[010]<sub>HD</sub>, while under low-strength shock due to long sliding distance cubic diamond forms with the orientation (001)<sub>G</sub>//(111)<sub>CD</sub>+[100]<sub>G</sub>//[110]<sub>CD</sub>, unveiling the strength-dependent graphite transition mechanism. We for the first time provide computational evidence of the strength-dependent graphite transition from first-principles, clarifying the long-term unresolved shock-induced hexagonal diamond formation mechanism and the structural source of the strength-dependent trend, which facilitates the hexagonal diamond synthesis via controlled experiment.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"96 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142214490","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hojeong Lee, Seontaek Kwon, Namgyoo Park, Sun Gwan Cha, Eunyoung Lee, Tae-Hoon Kong, Jihoo Cha, Youngkook Kwon
The electrochemical CO2 reduction (eCO2R) in membrane electrode assemblies (MEAs) has brought e-chemical production one step closer to commercialization because of its advantages of minimized ohmic resistance and stackability. However, the current performance of reported eCO2R in MEAs is still far below the threshold for economic feasibility where low overall cell voltage (<2 V) and extensive stability (>5 years) are required. Furthermore, while the production cost of e-chemicals heavily relies on the carbon capture and product separation processes, these areas have received much less attention compared to CO2 electrolysis, itself. In this perspective, we examine the current status of eCO2R technologies from both academic and industrial points of view. We highlight the gap between current capabilities and commercialization standards and offer future research directions for eCO2R technologies with the hope of achieving industrially viable e-chemical production.
{"title":"Scalable Low-Temperature CO2 Electrolysis: Current Status and Outlook","authors":"Hojeong Lee, Seontaek Kwon, Namgyoo Park, Sun Gwan Cha, Eunyoung Lee, Tae-Hoon Kong, Jihoo Cha, Youngkook Kwon","doi":"10.1021/jacsau.4c00583","DOIUrl":"https://doi.org/10.1021/jacsau.4c00583","url":null,"abstract":"The electrochemical CO<sub>2</sub> reduction (eCO<sub>2</sub>R) in membrane electrode assemblies (MEAs) has brought e-chemical production one step closer to commercialization because of its advantages of minimized ohmic resistance and stackability. However, the current performance of reported eCO<sub>2</sub>R in MEAs is still far below the threshold for economic feasibility where low overall cell voltage (<2 V) and extensive stability (>5 years) are required. Furthermore, while the production cost of e-chemicals heavily relies on the carbon capture and product separation processes, these areas have received much less attention compared to CO<sub>2</sub> electrolysis, itself. In this perspective, we examine the current status of eCO<sub>2</sub>R technologies from both academic and industrial points of view. We highlight the gap between current capabilities and commercialization standards and offer future research directions for eCO<sub>2</sub>R technologies with the hope of achieving industrially viable e-chemical production.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"25 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142214397","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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