Chemical Science最新文献_第7页

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

Supramolecular covalency of halogen bond revealed by NMR contact shift in paramagnetic cocrystals 顺磁共晶中接触位移揭示的卤素键的超分子共价

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-02 DOI: 10.1039/d5sc05769h

Anagha Sasikumar, Jan Novotny, Jan Chyba, Libor Kobera, Radek Marek

引用次数: 0

The interplay of antiaromaticity and diradical character in diarenoindacenes and diindenoarenes 二茚二烯和二茚二烯的抗芳性和双自由基性的相互作用

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-02 DOI: 10.1039/d5sc05050b

Efrain Vidal, Gabrielle I. Warren, Joshua E. Barker, Michael M. Haley

{"title":"The interplay of antiaromaticity and diradical character in diarenoindacenes and diindenoarenes","authors":"Efrain Vidal, Gabrielle I. Warren, Joshua E. Barker, Michael M. Haley","doi":"10.1039/d5sc05050b","DOIUrl":"https://doi.org/10.1039/d5sc05050b","url":null,"abstract":"Over the past ∼15 years our group has performed multiple structure/properties relationship studies to assess how logical structural refinement can affect the antiaromaticity/diradicaloid continuum. Using precision organic synthesis, we can alter the chemical composition of both the pro-aromatic core and the outer fused arene groups. The rational design of antiaromatic diareno-fused s-indacene derivatives leads to pronounced variation of molecule paratropicity, i.e., the HOMO–LUMO energy gap, as determined experimentally (NMR, CV, UV-Vis, X-ray data) and computationally (NICS-XY scans, NICS2BC, bond current plots). Successive benzinterposition within the core motif affords diindenoarene structures where compound paratropicity is minimized yet diradicaloid character emerges. Using the same techniques of changing outer ring fusion with aromatic carbocycles and heterocycles created a series of structures where the diradical character and thus the singlet–triplet energy gap of the molecule could be varied in a controlled, predictable manner, as determined experimentally (NMR, CV, UV-Vis, X-ray, SQUID data) and computationally using high-level quantum chemical calculations. Arising from these fundamental studies, we have demonstrated that diarenoindacenes and diindenoarenes can act as the active layer in OFETs, often showing ambipolar charge characteristics with hole mobilities as high as 7 cm2 V−1 s−1. We also established that our quinoidal/diradicaloid compounds possess large, atypical anti-ohmic conductance enhancement of their transport properties at longer molecular lengths, which suggests that this class of organic materials is a promising candidate for creating highly conductive and tunable nanoscale wires. Taken as a whole, our studies show that traditional physical organic chemistry concepts can be readily applied to modern organic materials research.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"38 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203587","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

Ligand-mediated asymmetric dicopper sites for robust catecholase-mimicking catalysis and selective sensing 配体介导的不对称二铜位点用于稳健的儿茶酚酶模拟催化和选择性传感

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-02 DOI: 10.1039/d5sc05472a

Bojin Li, Meng Yuan, Nan Nan Xia, Xun Hu, Fei He

{"title":"Ligand-mediated asymmetric dicopper sites for robust catecholase-mimicking catalysis and selective sensing","authors":"Bojin Li, Meng Yuan, Nan Nan Xia, Xun Hu, Fei He","doi":"10.1039/d5sc05472a","DOIUrl":"https://doi.org/10.1039/d5sc05472a","url":null,"abstract":"Fabricating dicopper centers in nanozymes offered a promising route to mimic catecholase-like catalysis. However, some dicopper centers often suffered from symmetric configurations, which was prone to weaken the O-O bond polarization, thereby limiting O2 activation. This resulted in the unsatisfied intrinsic activities of nanozymes, thus hindering their potential sensing applications. Here, we reported a CO-like nanozyme (DTD-Cu) engineered with proximal and asymmetrically coordinated dicopper centers via a N/S-rich ligand. The unique asymmetric N4Cu-CuN4S configuration facilitated the preferential O2 adsorption/activation and the O-O bond polarization as well as subsequent 4-electron reduction to H2O via a H2O2 intermediate, thus endowing DTD-Cu with dramatically enhanced intrinsic activity, as evidenced by orders-of-magnitude improvements in Km and Kcat/Km over most reported CO-like nanozymes and artificial enzymes. Capitalizing on this superior activity, we achieved highly selective and sensitive detection of the cytotoxic tris(2-carboxyethyl)phosphine (TCEP) with a detection limit of 98.6 ppb via a synergistic dual-inhibition mechanism involving both TCEP-induced reduction of the oxidized substrate/ROS and direct TCEP-dominated chelation to the Cu sites.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"95 2 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203591","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

Monitoring Structural Change and Drug Release of Responsive Nanoparticles Using Polarity-Sensitive Fluorophores. 利用极性敏感荧光团监测响应性纳米颗粒的结构变化和药物释放。

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-02 DOI: 10.1039/d5sc03803k

Yanting Gao, Peter William McDonald, Chris Ritchie, Georgina Kate Such

{"title":"Monitoring Structural Change and Drug Release of Responsive Nanoparticles Using Polarity-Sensitive Fluorophores.","authors":"Yanting Gao, Peter William McDonald, Chris Ritchie, Georgina Kate Such","doi":"10.1039/d5sc03803k","DOIUrl":"https://doi.org/10.1039/d5sc03803k","url":null,"abstract":"Stimuli-responsive polymeric nanoparticles have the potential to radically enhance the delivery of therapeutic cargo including peptides, proteins, RNA, DNA, and other biomacromolecules. To improve the efficiency of these drug delivery systems, accurate knowledge of their structural dynamics, disassembly process, and loading/release behavior is vital. Amongst a myriad of fluorescent probes utilized for this purpose, environmentally responsive fluorophores demonstrate distinctive advantages due to significant changes in fluorescence intensity, lifetime and/or emission wavelength with variation in their environment. In this work, we designed a series of novel multifunctional probe molecules, isoquinoline betaines (IQBs), with exquisite solvatofluorochromic properties. Through both a steady absorption signal in the visible wavelength range, and an environmentally dependent emission, these IQBs are a powerful tool for simultaneously tracking multiple key processes, including nanoparticle formation and disassembly, the loading and distribution of drug molecules, and the responsive release of drugs. This novel fluorescent probe was covalently conjugated to a pH-responsive nanoparticle and successfully probed the nanoparticle’s internal structural rearrangement while also monitoring its drug-release activity of a model peptide in real-time. This IQB fluorescent probe system enhances our understanding of how nanoparticles interact with both their cargo and microenvironment and thus represents an important step forward in the development of more efficient drug delivery systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"37 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203589","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

Constructing Photoferroelectric Semiconductor by Regulating Non-Covalent Interactions through Halogen Substitution 通过卤素取代调节非共价相互作用构建光铁电半导体

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-02 DOI: 10.1039/d5sc05946a

Yueyue He, Shufang Wu, Xiaofei Li, Qi Wang, Ruifang Zhao, Lin Pan, Chengbing Qin, Xianming Zhang, Dongying Fu

{"title":"Constructing Photoferroelectric Semiconductor by Regulating Non-Covalent Interactions through Halogen Substitution","authors":"Yueyue He, Shufang Wu, Xiaofei Li, Qi Wang, Ruifang Zhao, Lin Pan, Chengbing Qin, Xianming Zhang, Dongying Fu","doi":"10.1039/d5sc05946a","DOIUrl":"https://doi.org/10.1039/d5sc05946a","url":null,"abstract":"The advantages of molecular ferroelectrics lie in the \"designability\" and \"multifunctionality\", and the molecular-level regulation ability has opened up a brand-new dimension for ferroelectric materials. Non-covalent interactions play a crucial role in the construction of molecular ferroelectrics. However, there remain significant challenges in balancing the strength and reversibility of non-covalent interactions, as well as achieving long-range ordered arrangements. Therefore, a systematic study of non-covalent interactions in the structure is the key to construct high-performance molecular ferroelectrics. Here, we introduced halogenated amines with large dipole moments into adjacent inorganic layers to regulate the non-covalent interactions in the structure, thereby inducing the generation of ferroelectricity. Through a halogen substitution strategy to introduce chlorine (Cl) atom on PA+ (n-propylaminium) cation, hybrid perovskite photoferroelectric semiconductor (Cl-PA)2PbBr4 (Cl-PA+ is 3-chloropropylaminiu) with large piezoelectric response (d33 = 36 pC/N) and high Curie temperature (Tc = 365 K) was obtained. Compared with non-ferroelectric (PA)2PbBr4 (μPA = 1.2 D), the larger dipole moment (μCl-PA = 3.3 D) and the directional ordered arrangement of Cl-PA+ in (Cl-PA)2PbBr4 synergistically induce its ferroelectricity. More importantly, when Cl replaces H, it affects the hydrogen bonds network between the organic cation and the inorganic layer, enhancing the dynamic freedom of the Cl-PA+ cations, making the structure of (Cl-PA)2PbBr4 more prone to phase transitions when the temperature changes. The hydrogen bonding and halogen-halogen interactions in (Cl-PA)2PbBr4 leads to the directional and ordered arrangement of Cl-PA+ cations, breaking the centrosymmetric structure and synergistically promoting the generation of ferroelectricity. This work has confirmed the significance of non-covalent interactions in the construction of ferroelectrics.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"54 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203826","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