Chemistry - A European Journal最新文献_第2页

Room-Temperature Paramagnetic-to-Diamagnetic Switching Behavior in an Open-Shell Ionic Liquid with a Tetracyanoquinodimethane Radical Anion Salt. 含四氰喹诺二甲烷自由基阴离子盐的开壳离子液体的室温顺磁-反磁开关行为。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-10-22 DOI: 10.1002/chem.202501449

Ruifeng Shu, Takeshi Naota, Masatoshi Kozaki, Daisuke Shiomi, Shuichi Suzuki

{"title":"Room-Temperature Paramagnetic-to-Diamagnetic Switching Behavior in an Open-Shell Ionic Liquid with a Tetracyanoquinodimethane Radical Anion Salt.","authors":"Ruifeng Shu, Takeshi Naota, Masatoshi Kozaki, Daisuke Shiomi, Shuichi Suzuki","doi":"10.1002/chem.202501449","DOIUrl":"https://doi.org/10.1002/chem.202501449","url":null,"abstract":"An ionic liquid consisting of a 7,7,8,8-tetracyanoquinodimethane (TCNQ) radical anion and a tetra-n-octylphosphonium ion, 1+•TCNQ•-, undergoes a transformation near room temperature from paramagnetic liquid to diamagnetic solid accompanied by significant changes in photophysical properties. A blue solid of 1+•TCNQ•- melts upon heating above 328 K, yielding a green liquid. The green liquid exhibits a magnetic susceptibility of 5 × 10-4 emu mol- 1. Upon cooling, the liquid retains its paramagnetic properties until the temperature reaches approximately 300 K. Upon further cooling below 300 K, the paramagnetic liquid reverts to the initial blue solid. The solid form of 1+•TCNQ•- exhibits near-zero magnetic susceptibility. The thermal hysteresis loop with magnetic bistability is observed without decomposition over the temperature range from 300 to 328 K. Crystal structure analysis, electron spin resonance (ESR), and electronic spectra indicate that the drastic changes in magnetic properties are attributable to the reversible π-dimerization of TCNQ• - species during the solid-liquid/liquid-solid phase transitions. Additionally, the association/dissociation behaviors of the TCNQ• - dimers also induce significant changes in photophysical properties, especially in the short-wave infrared region (1000-2500 nm), suggesting the potential application of 1+•TCNQ•- as a bifunctional material.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e01449"},"PeriodicalIF":3.7,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145342316","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Substitution of CH₃ by CH₂F in 2-Methylerythritol Cyclodiphosphate Triggers Potent Inhibition of IspG with Concomitant Fluoride Ion Expulsion. 2-甲基赤藓糖醇环二磷酸中CH3被CH2F取代触发IspG的有效抑制并伴随氟离子排出。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-10-22 DOI: 10.1002/chem.202502471

Clea Witjaksono, Vivien Herrscher, Hannah Jobelius, Nathan Noël, Fabien Massicot, Jean-Luc Vasse, Jean-Bernard Behr, Myriam Seemann

{"title":"Substitution of CH3 by CH2F in 2-Methylerythritol Cyclodiphosphate Triggers Potent Inhibition of IspG with Concomitant Fluoride Ion Expulsion.","authors":"Clea Witjaksono, Vivien Herrscher, Hannah Jobelius, Nathan Noël, Fabien Massicot, Jean-Luc Vasse, Jean-Bernard Behr, Myriam Seemann","doi":"10.1002/chem.202502471","DOIUrl":"https://doi.org/10.1002/chem.202502471","url":null,"abstract":"IspG (also known as GcpE) is a key [4Fe-4S] metalloenzyme that catalyzes the penultimate step of the methylerythritol phosphate (MEP) pathway, a well-established target for the development of new antimicrobials. This oxygen-sensitive enzyme mediates the reductive dehydroxylation of 2-C-methyl-d-erythritol 2,4-cyclodiphosphate (MEcPP) to (E)-4-hydroxy-3-methylbut-2-en-1-yl diphosphate (HMBPP), requiring electron transfer proteins to deliver two electrons needed for catalysis. To probe the mechanism of IspG and access new mechanism-based inhibitors, we synthesized a substrate analogue, monofluoromethyl-d-erythritol cyclodiphosphate, in which the natural methyl group of MEcPP is replaced by a CH2F group. This analogue proved to be a potent inhibitor of IspG. This study also demonstrates that electron capture is a prerequisite for inhibition and that the inhibitor leads to fluoride release in the IspG-catalyzed reaction. Together, these results provide further support for the involvement of a carbanionic intermediate in the IspG mechanism.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02471"},"PeriodicalIF":3.7,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145342296","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Asymmetric Ligand Field Effects in Electron-Rich Heterometallic Extended Metal Atom Chain Compounds. 富电子杂金属延伸金属原子链化合物中的不对称配体场效应。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-10-22 DOI: 10.1002/chem.202502090

Rebecca K Walde, Trey C Pankratz, Amelia M Wheaton, Milton Acosta, John F Berry

{"title":"Asymmetric Ligand Field Effects in Electron-Rich Heterometallic Extended Metal Atom Chain Compounds.","authors":"Rebecca K Walde, Trey C Pankratz, Amelia M Wheaton, Milton Acosta, John F Berry","doi":"10.1002/chem.202502090","DOIUrl":"https://doi.org/10.1002/chem.202502090","url":null,"abstract":"In heterometallic systems, electron donation from the ligands may influence the metal atoms in either a symmetric or asymmetric way, with the expected case being that the more electronegative metal is favored. Here, we describe a systematic study of heterometallic compounds where this expectation is not observed. In this study, we use a modification of the symmetric 2,2'-dipyridylamine (dpa) ligand with electron donating ethyl groups, the 4,4'-diethyl-2,2'-dipyridylamine ligand (dedpa), to prepare heterometallic extended metal atom chain (HEMAC) complexes with formula Mo2M'(dedpa)4Cl2 (M' = Cr, Mn, Fe, Co, Ni). The effects of the electron donating substituents were studied through techniques including crystallography, magnetometry, cyclic voltammetry, EPR, Mössbauer, electronic absorption spectroscopy, and DFT calculations. We find that the new HEMACs are indeed more electron rich, easier to oxidize, and, most interestingly, the impact of the ethyl substituents is not applied equally to all the metals in the chain. The ligand field is stronger at the Mo2 site, but is surprisingly weaker at the M' center when compared to Mo2M'(dpa)4Cl2 complexes. We also find that changing the ligand field allows for previously unassigned electronic transitions to become visible, including excitations tentatively assigned to a triplet δ-δ* state within the Mo2 unit.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02090"},"PeriodicalIF":3.7,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145342283","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Photo-enabled α-C(sp³)-H Functionalization of Sulfides. 硫化物的光使能α-C(sp3)-H功能化。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-10-21 DOI: 10.1002/chem.202502638

Peng Cheng, Jie Ding, Zhenda Tan

引用次数: 0

NIR-II Organic Phototheranostics: Matching Rotatable Donors and Shielding Acceptors for Enhanced Imaging and Phototherapy by Stabilized Triplet Excitons and Optimized Radiative Decay. NIR-II有机光疗：通过稳定的三重态激子和优化的辐射衰变，为增强成像和光疗匹配可旋转供体和屏蔽受体。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-10-21 DOI: 10.1002/chem.202502527

Jianye Gong, Yue Zhang, Jianguo Wang, Guoyu Jiang

{"title":"NIR-II Organic Phototheranostics: Matching Rotatable Donors and Shielding Acceptors for Enhanced Imaging and Phototherapy by Stabilized Triplet Excitons and Optimized Radiative Decay.","authors":"Jianye Gong, Yue Zhang, Jianguo Wang, Guoyu Jiang","doi":"10.1002/chem.202502527","DOIUrl":"https://doi.org/10.1002/chem.202502527","url":null,"abstract":"Second near-infrared (NIR-II) organic phototheranostic agents (OPTAs) have received significant interests in cancer treatment by enabling precise positioning of deep-seated lesions and highly efficient ablation of tumors. However, competition between radiative and nonradiative pathways of the excitons sets great obstacles for obtaining robust OPTAs. Herein, we propose to fabricate high-performance NIR-II OPTAs through molecular engineering of acceptor shielding units as well as manipulating molecular conformations by donor rotation. Accordingly, two series of OPTAs (BPN series: 4,4'-(ethene-1,1-diyl)bis(N,N-dimethylaniline) as rotatable donor and butadiene as π-bridge, BPTQ series: julolidine as donor and 2-vinylthiophene as π-bridge) with different acceptor shielding units were designed. Photophysical data and theoretical calculations verified the introduction of rotatable donors can help to realize highly twisted molecular conformations, resulting in enhanced NIR-II emission and photothermal conversion efficiency (PCE). Moreover, the adoption of acceptor shielding units is advantageous for stabilizing triplet excitons for radical reactive oxygen species (ROS) generation. As a result, a balance was achieved for BPN-P nanoparticles (NPs) in the BPN series, which exhibited high NIR-II emission, good radical ROS generation and highest PCE of 63%. BPN-P NPs achieved both high-resolution NIR-II angiography and imaging-guided synergistic photodynamic/photothermal cancer treatment in live mice model, showcasing the effectiveness of the strategy.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02527"},"PeriodicalIF":3.7,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145342260","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

π-π Conjugated g-C₁₆N₁₉ Skeleton-Supported Single-Atom Catalyst for Nitrogen Reduction Reaction: A "Lock and Key" Coevaluation of Activity and Selectivity Involved in Constant Potential and pH Effect. 氮还原反应用π-π共轭g-C16N19骨架支撑单原子催化剂：恒电位和pH效应中活性和选择性的“锁与钥匙”共同评价

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-10-21 DOI: 10.1002/chem.202502611

Yali Lu, Zongjin Hu, Qiang Zhang, Chenglong Shi, Qingjun Zhou, Yuling Song

{"title":"π-π Conjugated g-C16N19 Skeleton-Supported Single-Atom Catalyst for Nitrogen Reduction Reaction: A \"Lock and Key\" Coevaluation of Activity and Selectivity Involved in Constant Potential and pH Effect.","authors":"Yali Lu, Zongjin Hu, Qiang Zhang, Chenglong Shi, Qingjun Zhou, Yuling Song","doi":"10.1002/chem.202502611","DOIUrl":"https://doi.org/10.1002/chem.202502611","url":null,"abstract":"The efficient development of electrocatalysts for the nitrogen reduction reaction (NRR) under ambient conditions has been greatly challenging due to the high stability of the N≡N bond and the competitive interference from the hydrogen evolution reaction (HER). This work innovatively designs a graphitic carbon nitride substrate (g-C16N19) with a super-large pore structure based on the self-doping strategy and first-principles calculations, and constructs TM@g-C16N19 (TM = Ti ∼ Au) single-atom catalyst systems. By establishing a \"Four-Step\" screening model, it is found that W@g-C16N19 exhibits the best NRR catalytic performance, with an ultralow limiting potential (UL) of -0.23 V. Combining electron structure analyses such as charge density difference, ICOHP value, Bader charge, and spin magnetic moment, the micro-mechanism of W@g-C16N19 effectively activating the σ/π bonds of N2 molecules through strong d-p orbital hybridization is revealed. Furthermore, based on the pH- and potential-dependent adsorption-free energy results calculated by the constant potential model, pH-potential coupling analysis shows that the configuration has a decisive influence on activity: the E-I/S-V mode dominates in alkaline media, while the E-O/S-O pathway is predominant under acidic conditions. In the E-I configuration, the energy barrier of the rate-determining step (PDS) of NRR decreases with the decrease of the electrode potential; conversely, the energy barrier of the PDS of NRR in the E-O/S-V/S-O configuration increases with the decrease of the electrode potential.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02611"},"PeriodicalIF":3.7,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145342314","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Metal-Free [3 + 3] and [4 + 2] Cascade Cyclization of Dihydroisoquinolines and Ene-Yne-Oxazolones: Synthesis of Indenoisoquinolinoquinolinamides. 无金属[3 + 3]和[4 + 2]级联环化二氢异喹啉和烯-炔-恶唑酮：吲哚异喹啉喹啉酰胺的合成。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-10-21 DOI: 10.1002/chem.202502380

Rattana Worayuthakarn, Phum Tachachartvanich, Rapeepat Sangsuwan, Somsak Ruchirawat, Nopporn Thasana

引用次数: 0

Toward Non-Isocyanate Polyurethanes: Green Synthesis Routes and Recycling Technologies. 迈向非异氰酸酯聚氨酯：绿色合成路线和回收技术。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-10-21 DOI: 10.1002/chem.202502319

Xiaohuan Qin, Xin Wang, Zhengbiao Zhang

{"title":"Toward Non-Isocyanate Polyurethanes: Green Synthesis Routes and Recycling Technologies.","authors":"Xiaohuan Qin, Xin Wang, Zhengbiao Zhang","doi":"10.1002/chem.202502319","DOIUrl":"https://doi.org/10.1002/chem.202502319","url":null,"abstract":"Polyurethanes (PUs) are extensively utilized polymers known for their excellent properties. However, the conventional synthesis of PUs heavily depends on toxic isocyanates, creating significant environmental and health risks. To mitigate these issues, research has increasingly focused on synthesizing non-isocyanate polyurethanes (NIPUs). This review systematically discusses the primary green synthesis routes for NIPUs: (1) Bis(dialkyl carbonate) route, (2) Transurethanization route, (3) Cyclic carbonate route, and (4) Ring-opening polymerization (ROP) route. While PUs exhibit superior mechanical and chemical performance, their disposal at the end of life remains a major challenge. Currently, the main recovery methods include chemical degradation (or raw material recycling) and mechanical recycling, with chemical recycling offering potential for a closed-loop process. This review briefly summarizes these disposal strategies, aiming to encourage sustainable practices. It highlights recent advancements in green synthesis and recycling technologies, focusing on pathways for creating environmentally friendly and recyclable NIPUs. In light of increasing environmental and regulatory pressures to minimize the use of isocyanates due to their toxicity, this paper comprehensively reviews current advances and future prospects in the synthesis and recycling of NIPUs, focusing on sustainable and environmentally friendly approaches. The review delves into innovative synthesis methodologies for NIPUs, highlighting green pathways while also addressing challenges related to end-of-life polyurethane management, with a focus on advancements in chemical recycling technologies.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02319"},"PeriodicalIF":3.7,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145342268","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

γ-Cyclodextrin-Imidazolium Salt-Based Bioinspired Nanoreactor: Enantioselective Rhodium-Catalyzed Arylation of Unprotected Isatin with Arylboronic Acids. γ-环糊精-咪唑盐基生物启发纳米反应器：铑催化无保护Isatin与芳基硼酸的对映选择性芳基化。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-10-21 DOI: 10.1002/chem.202502481

Susumu Tsuda, Narumichi Nozawa, Ryoji Ueda, Reo Ikeda, Tatsuo Yajima, Shin-Ichi Fujiwara, Nobuaki Kambe, Yutaka Nishiyama

{"title":"γ-Cyclodextrin-Imidazolium Salt-Based Bioinspired Nanoreactor: Enantioselective Rhodium-Catalyzed Arylation of Unprotected Isatin with Arylboronic Acids.","authors":"Susumu Tsuda, Narumichi Nozawa, Ryoji Ueda, Reo Ikeda, Tatsuo Yajima, Shin-Ichi Fujiwara, Nobuaki Kambe, Yutaka Nishiyama","doi":"10.1002/chem.202502481","DOIUrl":"https://doi.org/10.1002/chem.202502481","url":null,"abstract":"The optically active 3-aryl-3-hydroxy-2-oxindole skeleton is a promising pharmacophore in drug design and has led to the development of metal-catalyzed asymmetric reactions using designed chiral ligands for synthesizing 3-aryl-3-hydroxy-2-oxindoles from isatins (2,3-oxindoles), 3-aryl-2-oxindoles, and α-ketoamides. Although the arylation of isatins is vital for convergent synthesis, most studies have used N-protected isatins, requiring the removal of protecting groups to obtain the desired bioactive products. Despite limited success in the direct high-enantioselective arylation of unprotected isatins (NH isatins), such arylation holds significant potential for improving atomic and synthetic efficiencies. In aqueous media, cyclodextrins (CDs) with hydrophobic and chiral cavities can selectively include organic compounds, making them potential nanoreactors for asymmetric reactions. In this study, imidazolium salts bearing a γ-CD were applied as N-heterocyclic carbene (NHC) ligands for the Rh-catalyzed asymmetric arylation of NH isatins in environmentally benign aqueous ethanol. The arylation was successfully achieved in high yield and enantioselectivity using our γ-CD-NHC-Rh catalyst. This suggests that the arylation proceeds in the γ-CD cavity (host) through the self-inclusion of NHC─Rh complex intermediates (guests). These bio-inspired transition metal catalysts based on host-guest linkage systems are expected to contribute significantly to the development of efficient organic synthesis reactions with high enantioselectivity.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02481"},"PeriodicalIF":3.7,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145342270","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Helical Polymer-Based Polycarboxylate as Chiral Ligands in Cu-Catalyzed Enantioselective Diels-Alder Reaction in Water. 基于螺旋聚合物的聚羧酸盐作为手性配体在cu催化的对映选择性diols - alder水中的反应。

IF 3.7 2区化学

Chemistry - A European Journal Pub Date : 2025-10-21 DOI: 10.1002/chem.202502697

Naoaki Kamiya, Takeshi Yamamoto, Michinori Suginome

{"title":"Helical Polymer-Based Polycarboxylate as Chiral Ligands in Cu-Catalyzed Enantioselective Diels-Alder Reaction in Water.","authors":"Naoaki Kamiya, Takeshi Yamamoto, Michinori Suginome","doi":"10.1002/chem.202502697","DOIUrl":"https://doi.org/10.1002/chem.202502697","url":null,"abstract":"Water-soluble poly(quinoxaline-2,3-diyl)s (PQXlac) bearing chiral carboxylic acid side chains derived from l-lactic acid were used for Cu-catalyzed enantioselective Diels-Alder reaction in water. The reaction of azachalcone with cyclopentadiene in the presence of PQXlac (1000mer, 1 mol% monomer unit) and Cu(NO3)2 (1 mol% Cu) proceeded at 5 °C in good yield with high enantioselectivity up to 99% ee. The utilization of the corresponding oligomers shorter than 10mer resulted in low chemical yield with low enantioselectivity, suggesting that a tight helical structure is essential for the formation of an effective catalyst. A comparison of the random and block copolymer of PQXlac and PQXteg, which has achiral tetra(ethylene glycol) side chains, indicated that block copolymer, in which the carboxylate groups are more densely packed, showed higher chemical yields along with higher enantioselectivity. These results suggest that the active catalyst has a copper dicarboxylate structure in which two carboxylate groups on every other monomer unit coordinate to the Cu center to form an effective chiral reaction environment.","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02697"},"PeriodicalIF":3.7,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145342318","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0