Hoyun Kim, Dokyeong Lee, Young Jae Jung, Sung Ho Yang, Hye Jin Lee, Hong-In Lee, Jungkyu K. Lee
{"title":"Visible-Light Photoredox Catalysis of Polydopamine with Triethanolamine in Water","authors":"Hoyun Kim, Dokyeong Lee, Young Jae Jung, Sung Ho Yang, Hye Jin Lee, Hong-In Lee, Jungkyu K. Lee","doi":"10.1039/d5sc04938e","DOIUrl":"https://doi.org/10.1039/d5sc04938e","url":null,"abstract":"Polydopamine (PDA), a synthetic melanin, has recently emerged as a photoreactive material, contrasting with its conventional role in photoprotection. Especially, its photochemical reactivity under visible light offers new perspective on the role of melanin and opens up potential applications in biomedical engineering and energy conversion. However, the mechanism of the visible light-induced reactions is still not well understood, necessitating further systematic investigation. To address this challenge, we carefully investigated its photoredox catalysis under visible-light irradiation, focusing on electron transfer processes in the presence of triethanolamine as an electron donor. We explored various aspects, including its size-dependent reactivity, electrochemical and photophysical properties, and the characterization of generated radical species. Furthermore, we sought to optimize photoinitiated polymerization under various reaction conditions, such as different concentrations, monomers, and atmospheres. The use of water as a solvent is generally considered as safe and poses minimal risk to human health and safety compared to many organic solvents. These results are crucial for advancing the understanding of melanin’s photoredox catalytic mechanism and for developing innovative biocompatible photoreactive materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"143 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144677782","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}
{"title":"A Pair of Strongly Reductive and Oxidative Photocatalysts for the General Upcycling of Biomass Derivatives and Plastic Wastes","authors":"Hao Cui, Xiang Chen, Xiong She, Wen-Xin Su, Shi-Chao Chen, Xiao Zhang","doi":"10.1039/d5sc03457d","DOIUrl":"https://doi.org/10.1039/d5sc03457d","url":null,"abstract":"Tailoring photocatalysts to achieve both strongly reductive and oxidative properties from a common scaffold remains challenging. Herein, we report the development of a pair of photocatalysts, isothiatruxene (ITS) and isosulfonyltruxene (ITSO2), by modulating the valence states of heteroatoms. ITS exhibits highly reducing power, facilitating selective cleavage of C-O bonds in biomass derivatives despite their negative redox potentials. Upon oxidation of ITS, the resultant ITSO2 demonstrates strongly oxidizing capacity, enabling metal-free and acid-free upcycling of plastic wastes even with their high redox potentials. By immobilizing ITS and ITSO2 on polystyrene and oxidized lignin supports, respectively, we have developed recyclable photocatalysts that drive multiple catalytic cycles with high efficiency. Gram-scale upcycling of plastic is achieved by integrating photoredox catalysis with flow chemistry. Mechanistic studies reveal that the excited states of ITS and ITSO2 can directly activate inert substrates, correlating with their strong redox properties. The newly introduced pair of photocatalysts, characterized by their metal-free nature, concise synthesis via trimerization, and dual photocatalytic capabilities encompassing both strongly reducing and oxidizing properties, show great potential for a wide range of applications. Furthermore, this study presents a sustainable catalytic strategy for synthesizing high-value aromatic compounds directly from biomass derivatives and plastic wastes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"28 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144677829","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}
Jun Tian, Lei Zhang, Ze Lin, Shizhong Mao, Zeyuan Dong
{"title":"Helical foldamers replicating membrane-spanning gramicidin a with pH responsiveness and ultrafast potassium permeability","authors":"Jun Tian, Lei Zhang, Ze Lin, Shizhong Mao, Zeyuan Dong","doi":"10.1039/d5sc01362c","DOIUrl":"https://doi.org/10.1039/d5sc01362c","url":null,"abstract":"Structural simulation of natural ion channels remains a challenging topic. To fabricate artificial ion channels structurally resembling natural gramicidin A (gA), we prepared a type of precise hollow helical molecular channel by means of a modular synthesis strategy. Helical molecules are able to form 2.9 nm membrane-spanning channels through dimeric π-stacking assembly and efficiently accelerate ion transmembrane transport, with ultrahigh transport activity of up to 28 nM. Among these molecular channels with transmembrane structures similar to gA, one of them significantly exceeds natural gA for potassium ion transport, while another one exhibits the same proton transport activity as natural gA under identical conditions. Moreover, we found that the positive charges near the entrance of the channel reduce the potassium transport rate of the channel but significantly promote proton transport. In addition, a molecular channel with terminal amine groups shows pH-regulated ion transport function. This is the first example of structural replication of natural gA, in which helically folded molecules with assembled dimeric structure yield fantastic ion transport properties.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"110 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144677827","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}
Soumalya Bhattacharyya, Martin R. Black, Ben S. Pilgrim
{"title":"Encapsulation of reactive species within metal-organic cages","authors":"Soumalya Bhattacharyya, Martin R. Black, Ben S. Pilgrim","doi":"10.1039/d5sc02081f","DOIUrl":"https://doi.org/10.1039/d5sc02081f","url":null,"abstract":"Reactivity under confinement often differs greatly from reactivity in the bulk. Metal-organic cages (MOCs) are a class of discrete, solution-processable container molecules encompassing well-defined nanospaces, which can be rapidly constructed in modular fashion via self-assembly. Supramolecular chemists have created an extensive library of MOCs and demonstrated their ability to serve as molecular flasks, with cavities tailored to bind guests of interest. In this review, we cover selected examples of the encapsulation and relative stabilisation of reactive species within MOCs, from early reports to the most recent developments. Most reactive species are not inherently unstable; but they persist only as long as they do not encounter a partner with whom they can react. MOCs can prevent or reduce the rate of this deletrious reactivity through acting as a shield and providing a physical barrier between an encapsulated reactive guest and other system components regularly encountered in the bulk environment, including air, water, solvent, light, another molecule of itself, or a co-reactant. Thus, MOCs can extend the lifetime of these short-lived reactive species enhancing their study, or allowing for different reactivity to be explored. Examples have been segregated based on the nature of stabilisation (i.e., with what partner a reaction has been prevented). We believe this analysis will help provide more nuanced understanding of what types of highly reactive species can be tolerated within a dynamic MOC system to enable MOCs to find use in a wider variety of real-world applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"98 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144677780","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}
Wenjie Ma, Yakun Tang, Yue Zhang, Xiaohui Li, Lang Liu, Xueting Wang, Yuliang Cao
{"title":"Promoting cationic redox and stabilizing lattice oxygen in an Fe-based DRX cathode by the synergy of initial Li deficiency and 3D hierarchical porous architecture","authors":"Wenjie Ma, Yakun Tang, Yue Zhang, Xiaohui Li, Lang Liu, Xueting Wang, Yuliang Cao","doi":"10.1039/d5sc03335g","DOIUrl":"https://doi.org/10.1039/d5sc03335g","url":null,"abstract":"Anionic and cationic redox chemistries boost the ultrahigh specific capacity of Fe-based disordered rock salt (DRX) Li<small><sub>2</sub></small>FeTiO<small><sub>4</sub></small>. However, the sluggish kinetics and high O redox activity result in continuous capacity decay and poor rate performance. Herein, 3D hierarchical porous Li<small><sub>2</sub></small>FeTiO<small><sub>4</sub></small> (H-Ca-LFT) with initial Li-deficiency is successfully prepared using an acid-assisted CaCO<small><sub>3</sub></small> template method. By introducing Li deficiency, the local electronic structure of Li<small><sub>2</sub></small>FeTiO<small><sub>4</sub></small> is modulated to facilitate Li<small><sup>+</sup></small> diffusion and regulate the redox activity. Specifically, Li deficiency reduces the density of states in the O 2p band, Li<small><sup>+</sup></small> diffusion barrier, and band gap, thereby suppressing the high activity of oxygen and improving transport dynamics and electron conductivity. Moreover, the 3D hierarchical porous structure provides abundant channels and active sites for ion diffusion and electrochemical reaction. The synergistic effect of Li deficiency and the 3D hierarchical porous structure is revealed by various <em>in</em>/<em>ex situ</em> characterizations and DFT calculations, which promotes cationic redox and stabilizes anionic redox. Consequently, H-Ca-LFT demonstrates a high initial capacity (209.3 mA h g<small><sup>−1</sup></small> at 50 mA g<small><sup>−1</sup></small>), remarkable rate capability (130.4 mA h g<small><sup>−1</sup></small> at 1 A g<small><sup>−1</sup></small>), and outstanding long-term cycling stability. This work offers a new insight into stabilizing anionic redox through the design of initial Li deficiency and 3D hierarchical porous architecture for high-performance DRX cathodes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"62 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144669983","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}
Fitri Nur Indah Sari, Ping-Chang Chuang, Shih-Ching Huang, Chia-Yu Lin, Yi-Hsuan Lai
{"title":"Photoelectrochemical valorisation of organic waste for the cogeneration of solar fuels and value-added chemicals","authors":"Fitri Nur Indah Sari, Ping-Chang Chuang, Shih-Ching Huang, Chia-Yu Lin, Yi-Hsuan Lai","doi":"10.1039/d5sc03146j","DOIUrl":"https://doi.org/10.1039/d5sc03146j","url":null,"abstract":"Rapid industrialisation has resulted in severe greenhouse gas emissions through extensive fossil fuel extraction and an increasing volume of solid waste disposal. This perspective review examines the photoelectrochemical (PEC) valorisation of organic waste as a promising solution for addressing the energy crisis and environmental pollution. The current stage of PEC organic valorisation has yet to meet industrial requirements, hindered by its relatively low efficiency, limited robustness, and poor scalability compared to conventional technologies. A better understanding of the working principle of the PEC reaction mechanism, the properties of state-of-the-art photoelectrodes, and the organic waste pre-treatment process is required to pave the path toward practical implementation. In this perspective review, we demonstrate that the strategies employed in the design of photoanodes, including doping, heterojunction formation, co-catalyst modification, nanostructuring, and crystal facet engineering, have different effects on activity, selectivity, and stability. In addition to the hydrogen evolution reaction, selected organic reduction reactions for the synthesis of value-added chemicals in a PEC cell are also discussed, followed by recent progress on integrated PEC cells and their practical assessment for solar fuel and value-added chemical production. Since stability and scalability are also essential parameters beyond efficiency for assessing the techno-economic feasibility of a PEC organic valorisation system, we additionally addressed stability, scalability and the compatibility of photoelectrodes in organic waste valorisation. Finally, conclusions and future perspectives on feasible strategies for PEC valorisation are discussed. We hope this review will serve as a helpful guide in designing effective, robust, and scalable PEC organic waste valorisation systems, making it a viable technology for real-world applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"76 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144670007","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}
Rongjie Zhang, Yueyang Liu, Rujing Yin, Fangfang Ma, Deming Xia, Jingwen Chen, Hongbin Xie, Joseph S Francisco
{"title":"Significance of Halogen Bonding in the Synergistic Nucleation of Iodine Oxoacids and Iodine Oxides","authors":"Rongjie Zhang, Yueyang Liu, Rujing Yin, Fangfang Ma, Deming Xia, Jingwen Chen, Hongbin Xie, Joseph S Francisco","doi":"10.1039/d5sc02517f","DOIUrl":"https://doi.org/10.1039/d5sc02517f","url":null,"abstract":"Congeneric iodine oxoacids and iodine oxides, key nucleating vapours in the marine atmosphere, have been reported to nucleate individually. However, whether they can nucleate together remains unknown. Here, we provide molecular-level evidence that I2O4, the iodine oxide with the highest nucleation potential towards iodine oxoacids, can synergistically nucleate with HIO3-HIO2. The nucleation rate of HIO3-HIO2-I2O4 is 1.5 to 6.8 times higher than that of the known most efficient iodine-associated two-component (HIO3-HIO2) nucleation at 278.15 K, enhancing the role of iodine-containing species in marine atmospheric particle formation. Microscopic analysis of the three-component cluster configurations revealed that an unexpected acid‒base reaction between I2O4 and HIO2/HIO3 is a key driver of this efficient synergistic nucleation, besides hydrogen bonds and halogen bonds. We identified halogen bond-induced basicity enhancement as the chemical nature of I2O4 behaving as a base in the nucleation process with HIO2/HIO3. Such a basicity enhancement effect can be extended to other iodine-containing species, e.g., HIO2 and the more acidic HIO3, suggesting a common feature in interactions between iodine-containing species. Our findings clarify the synergistic nucleation of iodine oxoacids and iodine oxides and highlight the necessity of considering the effect of halogen bond-induced basicity enhancement on the formation of iodine-containing particles.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"102 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144669978","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}
Liangtao Xiong, Chengbin Fu, Jiaxin Tian, Yubo Geng, Lixin Han, Han Zhang, Haoyuan Li
{"title":"Intrinsic Mechanical Properties of Two-Dimensional Covalent Organic Frameworks","authors":"Liangtao Xiong, Chengbin Fu, Jiaxin Tian, Yubo Geng, Lixin Han, Han Zhang, Haoyuan Li","doi":"10.1039/d5sc02180d","DOIUrl":"https://doi.org/10.1039/d5sc02180d","url":null,"abstract":"Understanding the mechanical properties of two-dimensional covalent organic frameworks (2D COFs) is critical to their design for flexible devices, energy storage and catalysis applications. To date, only a limited number of 2D COFs have been examined, leaving the material design principles largely undefined. Furthermore, the measured results are often complicated by various extrinsic factors, causing difficulties in deciphering the underlying relationships. Here, we establish rules governing the intrinsic mechanical properties of 2D COFs based on molecular simulations of 86 structures under uniaxial tensile stress. Interestingly, we found that the mechanical properties of these nanoscale structures can be comprehended through principles traditionally applied to macroscopic objects. This enables quantitatively predicting the mechanical properties of 2D COFs based on their chemical linkage, topology, and pore dimensions, thereby facilitating material design. Counterintuitively, integrating rigid molecular groups into a 2D framework can potentially compromise overall mechanical strength by inducing imbalanced local strain. These findings pave the way for designing robust 2D COFs for diverse applications and serve as a solid foundation for fully unraveling the roles of various extrinsic factors in the future.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"102 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144670000","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}
Huan Li, Qi Zhou, Yu Zhang, Jun Luo, Tianjiao Hou, Zhenxin Yi, Gui-Xiang Wang, Long Zhu, Yuan Gao
{"title":"Impact of Stereochemistry in 3D Energetic Materials Science: A Case Based on Peripheral Editing of 2,4,10-Trioxaadamantane Backbone","authors":"Huan Li, Qi Zhou, Yu Zhang, Jun Luo, Tianjiao Hou, Zhenxin Yi, Gui-Xiang Wang, Long Zhu, Yuan Gao","doi":"10.1039/d5sc02800k","DOIUrl":"https://doi.org/10.1039/d5sc02800k","url":null,"abstract":"Stereoisomerism has not garnered widespread attention in energetic materials. Herein, two series of energetic stereoisomers, including four diastereomers of 2,4,10-trioxaadamantane-6,8,9-triyl trinitrate and three diastereomers of 9,9-dinitro-2,4,10-trioxaadamantane-6,8-diyl dinitrate, are synthesized based on the systematic alteration of stereochemistry. This study has generated the first cage-like energetic materials that incorporate considerations of configurational isomerism. Notably, despite having the same molecular formulas and functional group positions, these stereoisomers exhibit some differences in density, stability and detonation performance. These results suggest that rationally designed stereochemical editing can serve as an effective strategy for further development of high-performance energetic materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"31 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144670001","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}
Bailey Bouley, Dae Young Bae, Sagnik Chakrabarti, Mari Rosen, Robert D. Kennedy, Liviu M. Mirica
{"title":"Insights into the Mechanism of Active Catalyst Generation for the PdII(acac)2/PPh3 System in the Context of Telomerization of 1,3-Butadiene","authors":"Bailey Bouley, Dae Young Bae, Sagnik Chakrabarti, Mari Rosen, Robert D. Kennedy, Liviu M. Mirica","doi":"10.1039/d5sc02171e","DOIUrl":"https://doi.org/10.1039/d5sc02171e","url":null,"abstract":"The mechanism by which Pd<small><sup>II</sup></small> precursors are reduced to catalytically active low-valent Pd species has been a subject of interest for developing better catalysts. This process is well understood for catalytic systems employing a combination of palladium(II) acetate [Pd(OAc)<small><sub>2</sub></small>] and tertiary phosphines. However, the mechanism of reduction of palladium(II) acetylacetonate [Pd(acac)<small><sub>2</sub></small>] in the presence of phosphines has not been thoroughly investigated. This is especially important in the context of Pd-catalyzed butadiene telomerization process, which uses a combination of Pd(acac)<small><sub>2</sub></small> and tertiary phosphines in methanol to produce 1-methoxyoctadiene (MOD-1). In this work, we elucidate the steps for generating the active Pd<small><sup>0</sup></small> species for this reaction using a combination of Pd(acac)<small><sub>2</sub></small> and triphenylphosphine (PPh<small><sub>3</sub></small>). The investigations presented in this study provide the following key insights: (a) unification of the steps involved in the generation of the active precatalyst [Pd<small><sup>II</sup></small>(acac)(PPh<small><sub>3</sub></small>)<small><sub>2</sub></small>]<small><sup>+</sup></small>; (b) elucidation of the mechanism of reduction of the precatalyst to Pd<small><sup>0</sup></small> without MOD-1, which parallels the chemistry of the Pd(OAc)<small><sub>2</sub></small>/PPh<small><sub>3</sub></small>; and (c) the generation of Pd<small><sup>II</sup></small>-octadienyl species from the reaction between the precatalyst and MOD-1, the product of the telomerization reaction. A reversible C-O bond cleavage process was identified that leads to the formation of the Pd<small><sup>II</sup></small> π-octadienyl species as the active catalyst in the commercial telomerization process. These studies provide important insights into the reduction of Pd(acac)<small><sub>2</sub></small> into active Pd<small><sup>0</sup></small> species or Pd<small><sup>II</sup></small> π-allyl species, which have wide implications for both cross-coupling catalysis as well as the telomerization reaction.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"17 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144670005","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}