Chemical Science最新文献_第10页

A focus on salts dissolved in salts: ionic liquid mixtures – ion pairs, ion pairing and ionic liquids 重点研究溶解在盐中的盐：离子液体混合物——离子对、离子对和离子液体

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-06 DOI: 10.1039/d5sc90213d

Tom Welton

引用次数: 0

Observation of shuttling on the one-second timescale in a [10]cycloparaphenylene/C60 [2]catenane [10]环对苯醚/C60[2]链烷在1秒时间尺度上的穿梭观察

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-03 DOI: 10.1039/d5sc05734e

Fabian M. Steudel, Clara Sabrià, Massimo Delle Piane, Ferran Feixas, Xavi Ribas, Giovanni M. Pavan, Max von Delius

{"title":"Observation of shuttling on the one-second timescale in a [10]cycloparaphenylene/C60 [2]catenane","authors":"Fabian M. Steudel, Clara Sabrià, Massimo Delle Piane, Ferran Feixas, Xavi Ribas, Giovanni M. Pavan, Max von Delius","doi":"10.1039/d5sc05734e","DOIUrl":"https://doi.org/10.1039/d5sc05734e","url":null,"abstract":"[2]Catenanes comprising two identical binding sites are an excellent platform to study the kinetics of non-covalent interactions. In this work, we show that the “shuttling” of the [10]CPP nanohoop between two identical fullerene bis-adduct binding sites occurs with regioisomer-dependent rates of 1–5 s-1 at room temperature, placing these among the slowest π-π and dispersion-based shuttling processes reported to date. The catenanes were accessed via Glaser–Eglinton macrocyclization from fullerene bis-adduct precursors, which were purified by extensive recycling chromatography, and characterized by variable-temperature 1H NMR spectroscopy. Molecular dynamic simulations employing well-tempered metadynamics closely reproduce the experimental activation barrier (ΔG‡ ca. 70 kJ mol-1), offering insight into the nanohoop’s motion and metastable states along the shuttling pathway. The kinetic data were further complemented by thermodynamic binding studies between [10]CPP and different fullerene bis-adduct regioisomers.These findings expand our understanding of the kinetics and thermodynamics of concave/convex π–π interactions and will inform the design of future mechanically interlocked machines and 2D materials with slow response to external stimuli.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"105 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215932","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}

引用次数: 0

Mimicking sMMOH chemistry: trapping the Sc3+-bound nonheme FeIII–O–O–FeIII adduct prior to its conversion into an FeIV2(μ-O)2 core 模拟sMMOH化学：在转化为FeIV2(μ-O)2核之前捕获Sc3+结合的非血红素feii - o - o - feiii加合物

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-03 DOI: 10.1039/d5sc05667e

Patrick M. Crossland, Bittu Chandra, Saikat Banerjee, Chase S. Abelson, Yisong Guo, Marcel Swart, Lawrence Que

{"title":"Mimicking sMMOH chemistry: trapping the Sc3+-bound nonheme FeIII–O–O–FeIII adduct prior to its conversion into an FeIV2(μ-O)2 core","authors":"Patrick M. Crossland, Bittu Chandra, Saikat Banerjee, Chase S. Abelson, Yisong Guo, Marcel Swart, Lawrence Que","doi":"10.1039/d5sc05667e","DOIUrl":"https://doi.org/10.1039/d5sc05667e","url":null,"abstract":"Di-iron systems that activate O2 to form high-valent, oxo-bridged FeIV2 or FeIIIFeIV products are of great interest to bio-inorganic chemists due to their relevance to the chemistry of soluble methane mono-oxygenase (sMMOH), which incorporates both atoms of O2 gas into a diiron(IV) complex with an Fe2O2 diamond core. In this study, the [FeIII2(Me3NTB)2(μ-O)(μ-O 2)]2+ adduct (Me3NTB = tris((1-methyl-1H-benzo[d]imidazole-2-yl)methyl)amine) reacts with two Sc3+ to break the O–O bond that in turn forms the target FeIV(μ-O)2FeIV product. This study provides the first evidence that a Lewis acid can interact directly with a diferric-peroxo complex to initiate O–O bond cleavage, as evidenced via vibrational and X-ray absorption spectroscopy.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"102 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209871","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}

引用次数: 0

N-heterocyclic carbenes as clickable molecular anchors for electrochemical surface functionalization of metals and glassy carbon n -杂环碳烯作为金属和玻璃碳电化学表面功能化的可点击分子锚

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-03 DOI: 10.1039/d5sc03908h

Antoine Juneau, Ahmadreza Nezamzadeh, Béatrice Laberge, Anastasia Messina, Justin Lomax, Thilini M. Suduwella, Jashanpreet Kaur, Vikram Singh, Mark D. Aloisio, Paul J. Ragogna, Cathleen M. Crudden, Janine Mauzeroll

{"title":"N-heterocyclic carbenes as clickable molecular anchors for electrochemical surface functionalization of metals and glassy carbon","authors":"Antoine Juneau, Ahmadreza Nezamzadeh, Béatrice Laberge, Anastasia Messina, Justin Lomax, Thilini M. Suduwella, Jashanpreet Kaur, Vikram Singh, Mark D. Aloisio, Paul J. Ragogna, Cathleen M. Crudden, Janine Mauzeroll","doi":"10.1039/d5sc03908h","DOIUrl":"https://doi.org/10.1039/d5sc03908h","url":null,"abstract":"The potential of alkyne-containing NHCs as anchor molecules for electrochemical surface modification is investigated. Using a combination of X-ray photoelectron spectroscopy, atomic force microscopy, fluorescence tagging, and shell-isolated nanoparticle-enhanced Raman spectroscopy, we demonstrate that these NHCs can bind effectively to multiple surfaces and be functionalized via electrochemical copper-catalyzed azide–alkyne cycloaddition. Notably, we extend the scope of substrates beyond metals by demonstrating successful modification of glassy carbon. Compared to diazonium salts, NHC coatings show comparable resistance to sonication while forming films of only ∼4 nm in thickness. This reduced film thickness leads to lower surface passivation, which could offer advantages for electrochemical applications. The versatility of these NHC as molecular anchors is demonstrated through the attachment of electrochemically active TEMPO˙, the immobilization of streptavidin, and the formation of copper coatings. These findings highlight the potential of NHCs as alternatives to thiols and diazonium salts for the design of functional materials, electrodes, and biosensors.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"37 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209873","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}

引用次数: 0

Isomeric decker metallo-supramolecules with tunable luminescence and chiroptical properties 具有可调发光和热性的同分异构体双层金属超分子

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-03 DOI: 10.1039/d5sc04596g

Ningxu Han, Jianjun Ma, Hao Yu, Junjuan Shi, Manman Dai, Ziteng Guo, Zinuo Gao, Houyu Zhang, Ming Wang

{"title":"Isomeric decker metallo-supramolecules with tunable luminescence and chiroptical properties","authors":"Ningxu Han, Jianjun Ma, Hao Yu, Junjuan Shi, Manman Dai, Ziteng Guo, Zinuo Gao, Houyu Zhang, Ming Wang","doi":"10.1039/d5sc04596g","DOIUrl":"https://doi.org/10.1039/d5sc04596g","url":null,"abstract":"The regulation of interchromophoric interactions in multichromophoric systems is crucial for developing high-performance photofunctional materials. In this study, we present a novel self-assembly strategy to construct isomeric decker complexes, denoted as S1 and S2, which integrate disparate chromophores, achiral BODIPY and chiral binaphthyl moieties. This isomerization results in distinct chromophore packing modes. In the case of S1, the BODIPY and binaphthyl moieties are arranged in a relatively loose manner (~ 6.0 Å), enabling efficient FRET and preserving the strong locally excited (LE) emission (ΦF = 91.3%) characteristic of the BODIPY unit. In contrast, for S2, the denser packing between the BODIPY and binaphthyl moieties (~ 4.8 Å) leads to through-space charge transfer (TSCT) and weak charge transfer (CT) emission (ΦF = 8.6%). Notably, only complex (R)/(S)-S1 shows mirror-image circular dichroism (CD) signals based on chirality transfer and circularly polarized luminescence (CPL), as supported by TD-DFT calculations which reveal that the binaphthyl moiety alter the angle between the electric transition dipole moment (μ) and the magnetic transition dipole moment (m).","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"214 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209872","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}

引用次数: 0

Catalytic asymmetric isomerization/hydroboration of silyl enol ethers 硅烯醇醚的催化不对称异构化/硼化反应

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-03 DOI: 10.1039/d5sc04819b

Yisen Yao, Jintao Sun, Jie Li, Wanxiang Zhao

引用次数: 0

Accessing Homoleptic Neutral and Anionic Five-coordinate Pr(IV) Siloxide Complexes 获得同感性中性和阴离子五坐标Pr（IV）硅氧化物配合物

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-03 DOI: 10.1039/d5sc05500h

Pragati Pandey, Megan Keener, Thayalan Rajeshkumar, Rosario Scopelliti, Andrzej Sienkiewicz, Ivica Zivkovic, Laurent Maron, Marinella Mazzanti

{"title":"Accessing Homoleptic Neutral and Anionic Five-coordinate Pr(IV) Siloxide Complexes","authors":"Pragati Pandey, Megan Keener, Thayalan Rajeshkumar, Rosario Scopelliti, Andrzej Sienkiewicz, Ivica Zivkovic, Laurent Maron, Marinella Mazzanti","doi":"10.1039/d5sc05500h","DOIUrl":"https://doi.org/10.1039/d5sc05500h","url":null,"abstract":"Structurally characterized Pr(IV) complexes are limited to four examples because the ligands and reaction conditions capable of stabilizing Pr(IV) remain elusive. Here we identify reaction conditions allowing the synthesis of Pr(IV) compelxes that were originally thought difficult to isolate. The Pr(IV) complexes of the tris(tert-butoxy)siloxide (–OSi(OtBu)3) and triphenylsiloxide (–OSiPh3) ligands, [PrIV(OSi(OtBu)3)4] (2-PrOtBu), [MPrIV(OSiPh3)5] (5M-PrPh) (M = K, Cs), and [KDB18C6][PrIV(OSiPh3)5], (5[KDB18C6-PrPh]) were isolated and fully characterized upon the oxidation of the tetrakis and pentakis(siloxide)praseodymium(III) ate complexes, [KPrIII(OSi(OtBu)3)4] (1-PrOtBu) and [M2PrIII(OSiPh3)5] (4M-PrPh) (M = K, Cs), using the thianthrene radical cation tetrafluoroborate oxidant, thiaBF4. The crucial role of reagents and reaction conditions, like thiaBF4 over the magic blue oxidant and non-coordinating over coordinating solvents, are demonstrated for the isolation of high valent Pr(IV) complexes. The solid state structural and electrochemical properties were studied and further augmented with theoretical calculations. The Pr(IV) oxidation state was further confirmed by electron paramagnetic resonance (EPR) and SQUID magnetometry measurements. Complexes 5M-PrPh and 5[KDB18C6]-PrPh provide the first example of anionic Ln(IV) complexes demonstrating the possibility of accessing charged Pr(IV) complexes as a tool to manipulate the redox potential and therefore access to more stable complexes with the same ligand.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"40 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209875","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}

引用次数: 0

Macrocycle Formation-Mediated Augmentation in Reactive Oxygen Species Production 大环形成介导的活性氧生成的增强

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-03 DOI: 10.1039/d5sc06637a

Ao Liu, Youtao Xin, Yong-Kang Zhu, Yuan-Hang Jin, Yue Yang, Hongzhu Chen, Meng-Hao Li, Xin-Yue Lou, Xin Wang, Hui Gao, Ying-Wei Yang

{"title":"Macrocycle Formation-Mediated Augmentation in Reactive Oxygen Species Production","authors":"Ao Liu, Youtao Xin, Yong-Kang Zhu, Yuan-Hang Jin, Yue Yang, Hongzhu Chen, Meng-Hao Li, Xin-Yue Lou, Xin Wang, Hui Gao, Ying-Wei Yang","doi":"10.1039/d5sc06637a","DOIUrl":"https://doi.org/10.1039/d5sc06637a","url":null,"abstract":"While the synthesis of methylene-bridged fluorescent macrocycles has attracted significant research interest, their ability to generate reactive oxygen species (ROS) remains relatively unexplored. Herein, we present a strategy for constructing multifunctional macrocycles through backbone functionalization and successfully synthesize a new class of [2]terphenyl-extended pillar[6]arenes. Upon incorporating benzothiadiazole, highly fluorescent macrocycles with aggregation-induced emission enhancement characteristics, i.e., [2]terphenyl-benzothiadiazole-extended pillar[6]arenes, were obtained. Subsequent studies on modulating side-chain modifications have revealed distinct singlet oxygen (1O2) generation capabilities. Notably, quaternary ammonium-functionalized macrocycles show lower quantum yields yet superior 1O2 generation efficiency under light irradiation compared to their ethoxy-modified counterparts and the acyclic building block, while retaining targeted fluorescence imaging capabilities. Significantly, the supramolecular synergy between photodynamic action and ceftizoxime sodium drug complexation drastically enhances antibacterial efficacy compared to individual modalities. This study highlights the potential of quaternary ammonium-functionalized fluorescent macrocycles in 1O2 generation and offers promising new avenues for developing antibacterial drugs for biomedical applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215931","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}

引用次数: 0

Stabilizing the oxygen anionic redox chemistry by Li-deficient and Li-rich biphasic structure for high-energy Li-ion batteries 贫锂和富锂双相结构稳定高能锂离子电池氧阴离子氧化还原化学

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-02 DOI: 10.1039/d5sc04623h

Feng Li, Jiacheng Li, Peiyu Hou, Zezhou Lin, Mohan Dong, Linhui Wang, Hongzhou Zhang, Xijin Xu

{"title":"Stabilizing the oxygen anionic redox chemistry by Li-deficient and Li-rich biphasic structure for high-energy Li-ion batteries","authors":"Feng Li, Jiacheng Li, Peiyu Hou, Zezhou Lin, Mohan Dong, Linhui Wang, Hongzhou Zhang, Xijin Xu","doi":"10.1039/d5sc04623h","DOIUrl":"https://doi.org/10.1039/d5sc04623h","url":null,"abstract":"Li-rich layered oxides (LLOs) with a large specific capacity of ~300 mAh g -1 show promise for developing high-energy Li-ion batteries (LIBs). However, the thermodynamic instability of the oxygen-anionic redox couple leads to lattice oxygen loss and structural transformation, resulting in a rapid decline in voltage and capacity. In this work, we rationally engineer Li-deficient phase formation in LLOs to stabilize oxygen-anionic redox chemistry and improve the structural stability of LLOs. The Li-deficient and Li-rich biphasic intergrowth composite is synthesized via ion exchange from the P3/O3 intermediate mixed-phase oxides. It is found that the incorporation of the Li-deficient phase makes the movement of the O 2p non-bonding energy band toward lower energy, which further alleviates the lattice oxygen release and stabilizes the oxygen-anionic redox chemistry upon Li + de-intercalation. Consequently, the cycling stability is significantly enhanced in the biphasic LLOs, maintaining superior capacity/voltage retention of ~86%/88% after 400 cycles with a low capacity decay rate of 0.034% and voltage decline of 1.06 mV per cycle. The biphasic design offers a simple and feasible strategy for regulating the oxygen-anionic redox chemistry and boosting the structural stability of high-capacity LLOs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"99 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203588","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}

引用次数: 0

Hydroxyl Radical Generation from H2O2 via Liquid-Liquid Contact-Electro-Catalysis 液-液接触电催化H2O2生成羟基自由基

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-02 DOI: 10.1039/d5sc05862g

Hai-Mei Li, Airong Xie, Chengzi Hong, Zichen Wang, Xu Chu, Zhong Lin Wang, Yi Liu, Peng Jiang

{"title":"Hydroxyl Radical Generation from H2O2 via Liquid-Liquid Contact-Electro-Catalysis","authors":"Hai-Mei Li, Airong Xie, Chengzi Hong, Zichen Wang, Xu Chu, Zhong Lin Wang, Yi Liu, Peng Jiang","doi":"10.1039/d5sc05862g","DOIUrl":"https://doi.org/10.1039/d5sc05862g","url":null,"abstract":"Contact-electro-catalysis (CEC) has emerged as a promising strategy for reactive oxygen species (ROS) generation, primarily through water oxidation reactions (WOR) and oxygen reduction reactions (ORR), forming the foundation of contact-electrodynamic therapy (CEDT). However, the high energy barrier of the ORR substantially limits the overall catalytic efficiency. Herein, we propose an alternative hydrogen peroxide (H 2 O 2 ) reduction pathway to replace the ORR pathway, enabling the spontaneous generation of hydroxyl radicals (•OH) without ultrasound assistance. Perfluorocarbon (PFC) nanoemulsions were prepared to construct a PFC-water liquidliquid interface. Contact electrification at the PFC-water interface induces interfacial electron-transfer process, wherein the PFC act as mediators by capturing electrons from hydroxide ions (OH -) and subsequently transferring them to H2O2 , thereby generating •OH. Furthermore, ultrasound can enhance •OH production by increasing the frequency of liquid-liquid contact and facilitating electron release from negatively charged PFC (PFC*) to H 2 O 2 . Importantly, we demonstrate that this H 2 O 2 -based CEC pathway represents a previously unrecognized mechanism underlying CEDT. In tumor microenvironments, where H2O2 is overexpressed, this mechanism leads to enhanced ROS production and tumor cell death. This work uncovers a hidden catalytic route within the CEDT framework and provides new insights into the application of CEC for tumor therapy.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"115 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203592","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}

引用次数: 0