Yuheng Fu, Bingbing Xie, Miaoxia Liu, Shaojuan Hou, Qunyan Zhu, Alexander Kuhn, Lin Zhang, Wensheng Yang, Neso Sojic
Electrochemiluminescence (ECL) has emerged as a valuable tool for understanding multiphasic and compartmentalized systems, which have crucial wide-ranging applications across diverse fields. However, ECL reactions are limited to the vicinity of the electrode surface due to spatial constraints of electron transfer and the short lifetime of radical species, making ECL emission in bulk multiphasic solution challenging. To address this limitation, we propose a novel bipolar electrochemistry (BPE) approach for wireless dual-color ECL emission at the water/oil (w/o) interface. Firstly, amphiphilic glass carbon (GC) microbeads with distinct hydrophilic and hydrophobic regions are prepared by bipolar electrografting of hydrophobic trifluoromethyl diazonium salt, then the resulting Janus beads are positioned at the w/o interface. Subsequently, two model ECL systems containing luminol and H2O2 in the aqueous phase, and [Ru(bpy)3]²⁺ and benzoyl peroxide (BPO) in the organic phase, are selected based on their solubility to confine light-emitting reactions to their respective phases. Upon application of an electric field perpendicular to the interface, the Janus microbeads get polarized, triggering simultaneous oxidative blue ECL (425 nm) and reductive red ECL (620 nm) in the aqueous and organic phases, respectively. Taking advantage of ECL imaging, the potential gradient distribution on the GC microbead at the w/o interface is revealed, indicating a "pseudo-closed" bipolar system due to limited ion transfer between phases. We also investigate the effect of changing the electric field direction parallel to the interface, which alters the ECL emission area from a hemisphere to a quarter of the microbead's surface. This bipolar ECL approach at the w/o interface not only offers opportunities for imaging the aqueous phase and organic phase simultaneously, but also enables ECL imaging and light generation in the bulk solution, thus overcoming the usual spatial limitation requiring proximity to the electrode surface.
{"title":"Bipolar Electrochemiluminescence at the Water/Organic Interface","authors":"Yuheng Fu, Bingbing Xie, Miaoxia Liu, Shaojuan Hou, Qunyan Zhu, Alexander Kuhn, Lin Zhang, Wensheng Yang, Neso Sojic","doi":"10.1039/d4sc06103a","DOIUrl":"https://doi.org/10.1039/d4sc06103a","url":null,"abstract":"Electrochemiluminescence (ECL) has emerged as a valuable tool for understanding multiphasic and compartmentalized systems, which have crucial wide-ranging applications across diverse fields. However, ECL reactions are limited to the vicinity of the electrode surface due to spatial constraints of electron transfer and the short lifetime of radical species, making ECL emission in bulk multiphasic solution challenging. To address this limitation, we propose a novel bipolar electrochemistry (BPE) approach for wireless dual-color ECL emission at the water/oil (w/o) interface. Firstly, amphiphilic glass carbon (GC) microbeads with distinct hydrophilic and hydrophobic regions are prepared by bipolar electrografting of hydrophobic trifluoromethyl diazonium salt, then the resulting Janus beads are positioned at the w/o interface. Subsequently, two model ECL systems containing luminol and H2O2 in the aqueous phase, and [Ru(bpy)3]²⁺ and benzoyl peroxide (BPO) in the organic phase, are selected based on their solubility to confine light-emitting reactions to their respective phases. Upon application of an electric field perpendicular to the interface, the Janus microbeads get polarized, triggering simultaneous oxidative blue ECL (425 nm) and reductive red ECL (620 nm) in the aqueous and organic phases, respectively. Taking advantage of ECL imaging, the potential gradient distribution on the GC microbead at the w/o interface is revealed, indicating a \"pseudo-closed\" bipolar system due to limited ion transfer between phases. We also investigate the effect of changing the electric field direction parallel to the interface, which alters the ECL emission area from a hemisphere to a quarter of the microbead's surface. This bipolar ECL approach at the w/o interface not only offers opportunities for imaging the aqueous phase and organic phase simultaneously, but also enables ECL imaging and light generation in the bulk solution, thus overcoming the usual spatial limitation requiring proximity to the electrode surface.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580757","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}
Laurent Knerr, Thomas Cogswell, Marie. Ahlqvist, Richard James Lewis, Anneli Nordqvist, Christian Sköld
Conformational control of drug candidates to engineer improved potency and ADME properties is an ongoing area of research. Macrocyclic rings tend to offer a greater degree of rigidity than non-cyclised small molecules, and, as a result they are perfect platforms to instil conformational controls. In this study, the difluoroalkoxyphenyl moiety is examined as a tool to alter the conformation of macrocycles. A fluorinated and non-fluorinated macrocyclic matched pair is compared in terms of conformation preferences and related ADME properties. The synthesised macrocycles are found to give similar major conformations exhibiting a trans amide in the macrocyclic backbone. However, for the fluorinated macrocycle, the major trans amide conformation is in equilibrium with a cis amide minor conformation, seen by 1H NMR in a 4:1 ratio of trans/cis. The conformational fits for the minor fluorinated isomer demonstrate the out of plane preference of the difluoroalkoxy system encouraging the amide within the macrocycle backbone to adopt a cis conformation. A dramatic reduction in metabolic stability was found for the fluorinated macrocycle compared to the non-fluorinated and is postulated to be a result of the interconversion of trans amide to the cis amide, which may be more readily metabolised.
{"title":"The Effect of gem-Difluorination on the Conformation and Properties of a Model Macrocyclic System","authors":"Laurent Knerr, Thomas Cogswell, Marie. Ahlqvist, Richard James Lewis, Anneli Nordqvist, Christian Sköld","doi":"10.1039/d4sc05424e","DOIUrl":"https://doi.org/10.1039/d4sc05424e","url":null,"abstract":"Conformational control of drug candidates to engineer improved potency and ADME properties is an ongoing area of research. Macrocyclic rings tend to offer a greater degree of rigidity than non-cyclised small molecules, and, as a result they are perfect platforms to instil conformational controls. In this study, the difluoroalkoxyphenyl moiety is examined as a tool to alter the conformation of macrocycles. A fluorinated and non-fluorinated macrocyclic matched pair is compared in terms of conformation preferences and related ADME properties. The synthesised macrocycles are found to give similar major conformations exhibiting a trans amide in the macrocyclic backbone. However, for the fluorinated macrocycle, the major trans amide conformation is in equilibrium with a cis amide minor conformation, seen by 1H NMR in a 4:1 ratio of trans/cis. The conformational fits for the minor fluorinated isomer demonstrate the out of plane preference of the difluoroalkoxy system encouraging the amide within the macrocycle backbone to adopt a cis conformation. A dramatic reduction in metabolic stability was found for the fluorinated macrocycle compared to the non-fluorinated and is postulated to be a result of the interconversion of trans amide to the cis amide, which may be more readily metabolised.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580753","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}
N-Perfluoro-tert-butyl (N-PFtB) secondary amines, harboring a unique 19F-reporting moiety linked directly to nitrogen, are highly attractive due to their diverse potential applications. However, their mild and facile synthesis remains a significant challenge. Herein, we present a safe and efficient strategy for the direct synthesis of N-perfluoro-tert-butyl secondary amines from readily available N-trifluoromethyl secondary amines. Experiments and theoretical calculations demonstrate that this novel protocol encompasses three main processes: the elimination of hydrogen fluoride from the N-trifluoromethyl precursor, consecutive addition-elimination conversion of difluoromethyl imine (R-N=CF2) to hexafluoropropyl imine (R-N=C(CF3)2), and final addition of R-N=C(CF3)2 with the in situ generated fluoroform (HCF3). Key advantages of this reaction include the utilization of a single trifluoromethyl source and the N-trifluoromethyl starting material itself as the hydrogen source. Notably, the elimination of hydrogen fluoride, facilitated by CsF, is critical for the success of this approach. This method is compatible with a broad range of functional groups, including heterocyclic compounds. 19F MRI experiments suggest promising prospects for PFtB-labeled secondary amines as 19F MRI contrast agents.
{"title":"Direct synthesis of N-perfluoro-tert-butyl secondary amines from N-trifluoromethyl secondary amines","authors":"leibing Wang, Zhongyu Feng, Zhen Luo, Zihao Guo, Jieping Wang, WenBin Yi","doi":"10.1039/d4sc06335j","DOIUrl":"https://doi.org/10.1039/d4sc06335j","url":null,"abstract":"N-Perfluoro-tert-butyl (N-PFtB) secondary amines, harboring a unique 19F-reporting moiety linked directly to nitrogen, are highly attractive due to their diverse potential applications. However, their mild and facile synthesis remains a significant challenge. Herein, we present a safe and efficient strategy for the direct synthesis of N-perfluoro-tert-butyl secondary amines from readily available N-trifluoromethyl secondary amines. Experiments and theoretical calculations demonstrate that this novel protocol encompasses three main processes: the elimination of hydrogen fluoride from the N-trifluoromethyl precursor, consecutive addition-elimination conversion of difluoromethyl imine (R-N=CF2) to hexafluoropropyl imine (R-N=C(CF3)2), and final addition of R-N=C(CF3)2 with the in situ generated fluoroform (HCF3). Key advantages of this reaction include the utilization of a single trifluoromethyl source and the N-trifluoromethyl starting material itself as the hydrogen source. Notably, the elimination of hydrogen fluoride, facilitated by CsF, is critical for the success of this approach. This method is compatible with a broad range of functional groups, including heterocyclic compounds. 19F MRI experiments suggest promising prospects for PFtB-labeled secondary amines as 19F MRI contrast agents.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580760","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}
Li Li, Wenhan Xu, Guanchun Rui, Shixian Zhang, Qiming Zhang, Qing Wang
Electrostatic capacitors (ECs) are critical components in advanced electronics and electric power systems due to their rapid charge-discharge rate and high power density. While polymers are ideal for ECs due to their high voltage tolerance and mechanical flexibility, their low dielectric constants (K) and limited energy density remain significant limitations. Traditional polymer nanocomposites, which incorporate high-K ceramic fillers, have shown promise in enhancing dielectric properties but often at the cost of electric breakdown strength and scalability. In this Perspective, we explore a pioneering approach that utilizes ultralow loadings of small-sized inorganic nanofillers to significantly improve dielectric constants without compromising other key properties. We delve into the unconventional effects observed in these polymer nanocomposites, including dielectric enhancements, charge trapping, mechanical reinforcements, and microstructural changes, and highlight the impressive energy storage performance achieved with minimal filler contents. We discuss innovative design strategies from viewpoints of polymer and filler structures and showcase recent advancements in nanoscale characterizations and theoretical modelling for understanding the crucial role of polymer-filler interfaces. Finally, we stress fundamental challenges and prospects, providing insights into the transformative potential of these nanocomposites for next-generation energy storage applications.
静电电容器（EC）因其快速充放电速率和高功率密度而成为先进电子和电力系统的关键元件。虽然聚合物具有高耐压性和机械灵活性，是静电电容器的理想材料，但其低介电常数（K）和有限的能量密度仍然是其显著的局限性。传统的聚合物纳米复合材料加入了高 K 陶瓷填料，在增强介电性能方面大有可为，但往往要以电击穿强度和可扩展性为代价。在本《视角》中，我们探讨了一种开创性的方法，即利用超低负载的小尺寸无机纳米填料来显著提高介电常数，同时不影响其他关键性能。我们深入探讨了在这些聚合物纳米复合材料中观察到的非常规效应，包括介电增强、电荷捕获、机械增强和微观结构变化，并重点介绍了在填料含量极低的情况下实现的令人印象深刻的储能性能。我们从聚合物和填料结构的角度讨论了创新设计策略，并展示了纳米级表征和理论建模方面的最新进展，以了解聚合物-填料界面的关键作用。最后，我们强调了基本挑战和前景，为这些纳米复合材料在下一代储能应用中的变革潜力提供了见解。
{"title":"Dilute nanocomposites for capacitive energy storage: progress, challenges and prospects","authors":"Li Li, Wenhan Xu, Guanchun Rui, Shixian Zhang, Qiming Zhang, Qing Wang","doi":"10.1039/d4sc05437g","DOIUrl":"https://doi.org/10.1039/d4sc05437g","url":null,"abstract":"Electrostatic capacitors (ECs) are critical components in advanced electronics and electric power systems due to their rapid charge-discharge rate and high power density. While polymers are ideal for ECs due to their high voltage tolerance and mechanical flexibility, their low dielectric constants (K) and limited energy density remain significant limitations. Traditional polymer nanocomposites, which incorporate high-K ceramic fillers, have shown promise in enhancing dielectric properties but often at the cost of electric breakdown strength and scalability. In this Perspective, we explore a pioneering approach that utilizes ultralow loadings of small-sized inorganic nanofillers to significantly improve dielectric constants without compromising other key properties. We delve into the unconventional effects observed in these polymer nanocomposites, including dielectric enhancements, charge trapping, mechanical reinforcements, and microstructural changes, and highlight the impressive energy storage performance achieved with minimal filler contents. We discuss innovative design strategies from viewpoints of polymer and filler structures and showcase recent advancements in nanoscale characterizations and theoretical modelling for understanding the crucial role of polymer-filler interfaces. Finally, we stress fundamental challenges and prospects, providing insights into the transformative potential of these nanocomposites for next-generation energy storage applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580755","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}
The hierarchical assembly of liposomes into interconnected networks forms the basis for creating rudimentary artificial multicellular systems. Each vesicle performs specialized functions both temporally and spatially, replicating the complexity of living tissues. Controlling the size and number of liposomes in artificial multicellular systems and their dynamic interactions are necessary for quantitative bioprocesses but remain challenging. Here, we develop a satellite-parent liposome network—a central parent liposome surrounded by smaller satellite liposomes. This structure spontaneously forms during the dewetting transition of microfluidically prepared complex double emulsions. Intriguingly, the adhesion strength between the satellites and the parent liposome can be tuned using environmental stimuli. The varying numbers of satellite liposomes provide an excellent platform for studying quantitative microreactions. To illustrate, we first explore the differences in molecular affinity between parent and satellite liposomes to achieve directional molecular transfer against concentration gradients. Then, we mimic quantitative signal transfer by performing enzymatic reactions, supplying substrates from different numbers of satellites to the parent liposomes. After the reaction, the satellites can be separated from the parent liposome on demand upon osmotic stimuli. This work showcases an exceptional dynamic liposome network that will facilitate the mimicry of the complexity of multicellular systems in vitro.
{"title":"Dynamic satellite-parent liposome networks for quantitative microreactions","authors":"Jia-Qi Tian, Nan-Nan Deng","doi":"10.1039/d4sc04925j","DOIUrl":"https://doi.org/10.1039/d4sc04925j","url":null,"abstract":"The hierarchical assembly of liposomes into interconnected networks forms the basis for creating rudimentary artificial multicellular systems. Each vesicle performs specialized functions both temporally and spatially, replicating the complexity of living tissues. Controlling the size and number of liposomes in artificial multicellular systems and their dynamic interactions are necessary for quantitative bioprocesses but remain challenging. Here, we develop a satellite-parent liposome network—a central parent liposome surrounded by smaller satellite liposomes. This structure spontaneously forms during the dewetting transition of microfluidically prepared complex double emulsions. Intriguingly, the adhesion strength between the satellites and the parent liposome can be tuned using environmental stimuli. The varying numbers of satellite liposomes provide an excellent platform for studying quantitative microreactions. To illustrate, we first explore the differences in molecular affinity between parent and satellite liposomes to achieve directional molecular transfer against concentration gradients. Then, we mimic quantitative signal transfer by performing enzymatic reactions, supplying substrates from different numbers of satellites to the parent liposomes. After the reaction, the satellites can be separated from the parent liposome on demand upon osmotic stimuli. This work showcases an exceptional dynamic liposome network that will facilitate the mimicry of the complexity of multicellular systems in vitro.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580765","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}
Alvaro Valdés-Maqueda, Manuel Plaza, Carlos Valdes
The reactions of cyclic α,β-unsaturated N-tosylhydrazones and alkylboronic acids promoted by 370-390 nm light in the presence of a base give rise to allylic boronic acids that can be trapped as the corresponding pinacolboronates by treatment with pinacol. This reaction features wide scope regarding both coupling partners and functional group tolerance, allowing for the incorporation of a variety of natural product-derived fragments. The allylic boronic acids can be also reacted in a one-pot process with aldehydes, to produce homoallylic alcohols with very high diastereoselectivity. A three-component one-pot procedure has been developed revealing that the methodology is a powerful tool for the generation of structural diversity that is accomplished by incorporation of an ample variety of each of the three elements. Moreover, from a synthetic perspective, in the reaction, the formation of two C-C bonds, at the carbonyl and the β positions of a α,β-unsaturated carbonyl, has been achieved in the three-component reaction.
{"title":"Photochemical Carboborylation and Three-component Difunctionalization of α,β-unsaturated Ketones with Boronic Acids via Tosylhydrazones","authors":"Alvaro Valdés-Maqueda, Manuel Plaza, Carlos Valdes","doi":"10.1039/d4sc06537a","DOIUrl":"https://doi.org/10.1039/d4sc06537a","url":null,"abstract":"The reactions of cyclic α,β-unsaturated N-tosylhydrazones and alkylboronic acids promoted by 370-390 nm light in the presence of a base give rise to allylic boronic acids that can be trapped as the corresponding pinacolboronates by treatment with pinacol. This reaction features wide scope regarding both coupling partners and functional group tolerance, allowing for the incorporation of a variety of natural product-derived fragments. The allylic boronic acids can be also reacted in a one-pot process with aldehydes, to produce homoallylic alcohols with very high diastereoselectivity. A three-component one-pot procedure has been developed revealing that the methodology is a powerful tool for the generation of structural diversity that is accomplished by incorporation of an ample variety of each of the three elements. Moreover, from a synthetic perspective, in the reaction, the formation of two C-C bonds, at the carbonyl and the β positions of a α,β-unsaturated carbonyl, has been achieved in the three-component reaction.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580754","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}
Herein, we present a straightforward CuBr-mediated surface-initiated controlled radical polymerization (SI-CRP) method for fabricating polymer brushes using microliter volumes of reaction solution in air and at room temperature. The key advantage of this method is its ability to rapidly grow polymer brushes with oxygen tolerance, driven by the controlled disproportionation of CuI into CuII and Cu0 by CuBr and ligand. We demonstrate the successful preparation of homo-, block, patterned, and wafer-scale polymer brushes. Additionally, the catalyst in CuBr-mediated SI-CRP is reusable, long-lasting, and compatible with various monomers. This work broadens the potential of CuBr for polymer brush growth, making it accessible to both experts and non-experts.
{"title":"CuBr-mediated surface-initiated controlled radical polymerization in air","authors":"Menglu Chen, Shuai You, Tingting Guo, Haohao Ren, Longzu Zhu, Peize Wang, Wenbo Sheng, Chenliang Gong, Wei Li","doi":"10.1039/d4sc06012a","DOIUrl":"https://doi.org/10.1039/d4sc06012a","url":null,"abstract":"Herein, we present a straightforward CuBr-mediated surface-initiated controlled radical polymerization (SI-CRP) method for fabricating polymer brushes using microliter volumes of reaction solution in air and at room temperature. The key advantage of this method is its ability to rapidly grow polymer brushes with oxygen tolerance, driven by the controlled disproportionation of CuI into CuII and Cu0 by CuBr and ligand. We demonstrate the successful preparation of homo-, block, patterned, and wafer-scale polymer brushes. Additionally, the catalyst in CuBr-mediated SI-CRP is reusable, long-lasting, and compatible with various monomers. This work broadens the potential of CuBr for polymer brush growth, making it accessible to both experts and non-experts.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580758","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}
Tayyaba Najam, Syed Shoaib Ahmad Shah, Hanqing Yin, Xin Xiao, Shamraiz Talib, Qianqian Ji, Yonggui Deng, Muhammad Sufyan Javed, Jie Hu, Ruo Zhao, Aijun Du, Xingke Cai, Qiang Xu
Correction for ‘Second-shell modulation on porphyrin-like Pt single atom catalysts for boosting oxygen reduction reaction’ by Tayyaba Najam et al., Chem. Sci., 2024, https://doi.org/10.1039/d4sc03369h.
{"title":"Correction: Second-shell modulation on porphyrin-like Pt single atom catalysts for boosting oxygen reduction reaction","authors":"Tayyaba Najam, Syed Shoaib Ahmad Shah, Hanqing Yin, Xin Xiao, Shamraiz Talib, Qianqian Ji, Yonggui Deng, Muhammad Sufyan Javed, Jie Hu, Ruo Zhao, Aijun Du, Xingke Cai, Qiang Xu","doi":"10.1039/d4sc90219j","DOIUrl":"https://doi.org/10.1039/d4sc90219j","url":null,"abstract":"Correction for ‘Second-shell modulation on porphyrin-like Pt single atom catalysts for boosting oxygen reduction reaction’ by Tayyaba Najam <em>et al.</em>, <em>Chem. Sci.</em>, 2024, https://doi.org/10.1039/d4sc03369h.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588559","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}
Minhye Kim, Heekyoung Choi, Minjoo Kim, Seonghan Kim, Seohyeon Yun, Eunji Lee, Jaeheung Cho, Sung Ho Jung, Jong Hwa Jung
Understanding the pathway complexity of supramolecular polymerization in biomimetic systems has been a challenging issue due to its importance in the development of rationally controlled materials and insight into self-assembly in nature. We herein report a kinetic trapping strategy as a new methodology on how to control the pathway of metallosupramolecular polymerization by employing secondary metal ions and/or ligands which form competitive complex species. For this, we proposed monoalkynylplatinum(II) metalloligand (Pt-L1) derived from a bis(amideterpyridine) receptor with one unoccupied terpyridyl terminal as a coordination site for the secondary metal ion (Ag+ or Fe2+). The inherent pathway complexity intrinsic to the Pt-L1-anchored supramolecular polymerization has been modulated through the incorporation of Ag+ or Fe2+. During the supramolecular polymerization of Pt-L1 in the presence of Ag+ and Fe2+, the added secondary ligand bpy (4,4'-dimethyl-2,2'-bipyridine) or DA18C6 (1,14-diaza-18-crown-6) form complexes as kinetic species, thereby inhibiting spontaneous polymerizations. The supramolecular polymer (SP-I), with a spherical structure composed of Pt-L1 in the absence of metal ions as a kinetic product, did not transform into the thermodynamic product, namely supramolecular polymer (SP-III) with a left-handed fiber structure, due to a high energy barrier. However, the supramolecular polymer (SP-II) with a left-handed fiber structure, which was formed by Pt-L1 in the presence of AgNO3, converted to SP-III upon the addition of NaCl. Additionally, SP-II transformed into supramolecular polymer (SP-IV) upon the addition of Fe(BF4)2, through an on-pathway process. Both the morphological and emissive characteristics of the resulting supramolecular polymers can be fine-tuned via the Pt···Pt or Ag···Ag interactions as well as through the changes of the coordination geometry depending on the existing Ag+ or Fe2+ ions. The present results have important implications in expanding the scope of pathway complexity to produce a variety of products via kinetically controlled processes involving secondary metal ions and ligands.
{"title":"Pathway control in metallosupramolecular polymerization of a monoalkynylplatinum(II) terpyridine complex through competitive complex formation","authors":"Minhye Kim, Heekyoung Choi, Minjoo Kim, Seonghan Kim, Seohyeon Yun, Eunji Lee, Jaeheung Cho, Sung Ho Jung, Jong Hwa Jung","doi":"10.1039/d4sc06083k","DOIUrl":"https://doi.org/10.1039/d4sc06083k","url":null,"abstract":"Understanding the pathway complexity of supramolecular polymerization in biomimetic systems has been a challenging issue due to its importance in the development of rationally controlled materials and insight into self-assembly in nature. We herein report a kinetic trapping strategy as a new methodology on how to control the pathway of metallosupramolecular polymerization by employing secondary metal ions and/or ligands which form competitive complex species. For this, we proposed monoalkynylplatinum(II) metalloligand (Pt-<strong>L<small><sup>1</sup></small></strong>) derived from a bis(amideterpyridine) receptor with one unoccupied terpyridyl terminal as a coordination site for the secondary metal ion (Ag+ or Fe2+). The inherent pathway complexity intrinsic to the Pt-<strong>L<small><sup>1</sup></small></strong>-anchored supramolecular polymerization has been modulated through the incorporation of Ag<small><sup>+</sup></small> or Fe<small><sup>2+</sup></small>. During the supramolecular polymerization of Pt-<strong>L<small><sup>1</sup></small></strong> in the presence of Ag<small><sup>+</sup></small> and Fe<small><sup>2+</sup></small>, the added secondary ligand bpy (4,4'-dimethyl-2,2'-bipyridine) or DA18C6 (1,14-diaza-18-crown-6) form complexes as kinetic species, thereby inhibiting spontaneous polymerizations. The supramolecular polymer (SP-<strong>I</strong>), with a spherical structure composed of Pt-<strong>L<small><sup>1</sup></small></strong> in the absence of metal ions as a kinetic product, did not transform into the thermodynamic product, namely supramolecular polymer (SP-<strong>III</strong>) with a left-handed fiber structure, due to a high energy barrier. However, the supramolecular polymer (SP-<strong>II</strong>) with a left-handed fiber structure, which was formed by Pt-<strong>L<small><sup>1</sup></small></strong> in the presence of AgNO<small><sub>3</sub></small>, converted to SP-<strong>III</strong> upon the addition of NaCl. Additionally, SP-<strong>II</strong> transformed into supramolecular polymer (SP-<strong>IV</strong>) upon the addition of Fe(BF<small><sub>4</sub></small>)<small><sub>2</sub></small>, through an on-pathway process. Both the morphological and emissive characteristics of the resulting supramolecular polymers can be fine-tuned via the Pt···Pt or Ag···Ag interactions as well as through the changes of the coordination geometry depending on the existing Ag<small><sup>+</sup></small> or Fe<small><sup>2+</sup></small> ions. The present results have important implications in expanding the scope of pathway complexity to produce a variety of products via kinetically controlled processes involving secondary metal ions and ligands.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580756","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}
Shengen Gong, Meihua Zhu, Yan Zhou, Ru-Nan Li, Jianhua Zhang, Xiaoteng Jia, Danming Chao, Caiyun Wang
Organic materials are promising cathodes for aqueous zinc-ion batteries (AZIBs) due to their cost-effectiveness, environmental friendliness, and tunable structures. However, the energy density of AZIBs remains limited by the inherently low capacity and output voltage of organic cathode materials. To address this challenge, we develop a Mn ion--doped polyaniline (PAM) by harnessing the joint merits of the highly reversible doping process of conjugated backbone, as well as the unique dissolution-deposition behavior of Mn2+ in ZnSO4 electrolyte. The incorporation of Mn2+ into the PANI backbone facilitates the stabilization of PAM at high potentials by lowering the lowest unoccupied molecular orbital (LUMO) energy level, resulting in enhanced output voltage and cycling stability. This new interactive dual energy storage mechanism, illustrated by the density functional theory calculation and ex-situ characterizations, contributes to the improved capacity by employing a dissolution-deposition storage mechanism. The battery showcases a maximum specific capacity of 496.7 mAh g-1 at an ultra-high working voltage of 2.4 V. And the capacity is 213.2 mAh g-1 when the current density reaches 20 A g-1. This molecular design of the pre-doped PANI cathode and the insight into groundbreaking dual energy storage mechanism offers a new host alternative for high-performance Zn-organic batteries.
有机材料因其成本效益高、环境友好和结构可调而成为水性锌离子电池（AZIB）的理想阴极。然而，有机阴极材料固有的低容量和低输出电压限制了 AZIB 的能量密度。为了应对这一挑战，我们利用共轭骨架的高可逆掺杂过程以及 Mn2+ 在 ZnSO4 电解质中的独特溶解沉积行为的共同优点，开发出了掺杂锰离子的聚苯胺 (PAM)。在 PANI 骨架中掺入 Mn2+，可通过降低最低未占分子轨道（LUMO）能级，促进 PAM 在高电位下的稳定，从而提高输出电压和循环稳定性。密度泛函理论计算和原位特性分析表明，这种新型交互式双能量存储机制采用了溶解沉积存储机制，有助于提高电池容量。该电池在 2.4 V 超高工作电压下的最大比容量为 496.7 mAh g-1。当电流密度达到 20 A g-1 时，容量为 213.2 mAh g-1。这种预掺杂 PANI 阴极的分子设计以及对开创性双重储能机制的深入了解，为高性能 Zn 有机电池提供了一种新的主机替代方案。
{"title":"An Interactive Dual Energy Storage Mechanism Boosts High-Performance Aqueous Zinc-Ion Batteries","authors":"Shengen Gong, Meihua Zhu, Yan Zhou, Ru-Nan Li, Jianhua Zhang, Xiaoteng Jia, Danming Chao, Caiyun Wang","doi":"10.1039/d4sc05710d","DOIUrl":"https://doi.org/10.1039/d4sc05710d","url":null,"abstract":"Organic materials are promising cathodes for aqueous zinc-ion batteries (AZIBs) due to their cost-effectiveness, environmental friendliness, and tunable structures. However, the energy density of AZIBs remains limited by the inherently low capacity and output voltage of organic cathode materials. To address this challenge, we develop a Mn ion--doped polyaniline (PAM) by harnessing the joint merits of the highly reversible doping process of conjugated backbone, as well as the unique dissolution-deposition behavior of Mn2+ in ZnSO4 electrolyte. The incorporation of Mn2+ into the PANI backbone facilitates the stabilization of PAM at high potentials by lowering the lowest unoccupied molecular orbital (LUMO) energy level, resulting in enhanced output voltage and cycling stability. This new interactive dual energy storage mechanism, illustrated by the density functional theory calculation and ex-situ characterizations, contributes to the improved capacity by employing a dissolution-deposition storage mechanism. The battery showcases a maximum specific capacity of 496.7 mAh g-1 at an ultra-high working voltage of 2.4 V. And the capacity is 213.2 mAh g-1 when the current density reaches 20 A g-1. This molecular design of the pre-doped PANI cathode and the insight into groundbreaking dual energy storage mechanism offers a new host alternative for high-performance Zn-organic batteries.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580210","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}
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