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Cluster versus coordination: the chemistry of cyclopentadienyl titanium and vanadium complexes with B- and C-functionalized carborane-thiols, [C2B10H12-n (SH) n ] (n = 2 or 3). 簇与配位:环戊二烯基钛钒配合物与B-和c -官能化碳烷-硫醇[C2B10H12-n (SH) n] (n = 2或3)的化学性质。
IF 7.6 1区 化学
Chemical Science Pub Date : 2025-07-10 DOI: 10.1039/d5sc03562g
Subhash Bairagi, Deepak Kumar Patel, Debipada Chatterjee, Monika Kučeráková, Jan Macháček, Tomas Base, Thalappil Pradeep, Sundargopal Ghosh
{"title":"Cluster <i>versus</i> coordination: the chemistry of cyclopentadienyl titanium and vanadium complexes with B- and C-functionalized carborane-thiols, [C<sub>2</sub>B<sub>10</sub>H<sub>12-<i>n</i></sub> (SH) <sub><i>n</i></sub> ] (<i>n</i> = 2 or 3).","authors":"Subhash Bairagi, Deepak Kumar Patel, Debipada Chatterjee, Monika Kučeráková, Jan Macháček, Tomas Base, Thalappil Pradeep, Sundargopal Ghosh","doi":"10.1039/d5sc03562g","DOIUrl":"10.1039/d5sc03562g","url":null,"abstract":"<p><p>A series of B- and C-functionalized di- and trithiol chelating <i>o</i>-carborane ligands have been employed to explore the coordination chemistry with cyclopentadienyl titanium and vanadium complexes. Treatment of [Cp*TiCl<sub>3</sub>] with [LiBH<sub>4</sub>·THF], followed by thermolysis with a C-functionalized carborane-dithiol ligand [1,2-(SH)<sub>2</sub>-1,2-C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>], yielded octacapped octahedral [(Cp*Ti)<sub>4</sub>{Ti(1,2-(S)<sub>2</sub>-1,2-C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>)}<sub>2</sub>(μ<sub>3</sub>-S)<sub>6</sub>(μ<sub>3</sub>-O)<sub>2</sub>] (1) and hexacapped trigonal bipyramidal [(Cp*Ti)<sub>4</sub>{Ti(1,2-(S)<sub>2</sub>-1,2-C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>)}(μ<sub>3</sub>-S)<sub>6</sub>] (2) clusters. One of the driving forces of these reactions is the cleavage of C-S bonds of carborane-dithiols that resulted in sulfide ligands and subsequently generated clusters 1 and 2. In contrast, a similar reaction with a B-functionalized carborane-dithiol [9,12-(SH)<sub>2</sub>-1,2-C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>] led to B-B bond formation that yielded a κ<sup>2</sup>-hydridoborato complex, [(Cp*Ti){κ<sup>2</sup>-BH<sub>3</sub>(9,12-(S)<sub>2</sub>-1,2-C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>)}] (3). To the best of our knowledge, complex 3 is the first example of a carborane-dithiol functionalized hydridoborato complex. Interestingly, when the reactions of [Cp*TiCl<sub>3</sub>] or [Cp<sub>2</sub>TiCl<sub>2</sub>] were carried out with a B-functionalized carborane-trithiol, [8,9,12-(SH)<sub>3</sub>-1,2-C<sub>2</sub>B<sub>10</sub>H<sub>9</sub>], they led to coordination complexes, [(Cp/Cp*Ti){8,9,12-(S)<sub>3</sub>-1,2-C<sub>2</sub>B<sub>10</sub>H<sub>9</sub>}] (Cp* (4a) and Cp (4b)). Similarly, when [(Cp*VCl<sub>2</sub>)<sub>3</sub>] was employed as a metal precursor, deboronation was observed at the icosahedral cage that resulted in a zwitterionic complex, [(Cp*V){1,5,6-(S)<sub>3</sub>-<i>nido</i>-7,8-C<sub>2</sub>B<sub>9</sub>H<sub>9</sub>}] (5). All the clusters have been characterized by NMR, IR, mass spectrometry, and X-ray diffraction analysis. Furthermore, the theoretical analyses provided valuable insights into the electronic structures of these unusual clusters.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12242837/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144625487","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Synergistic intercalation–conversion reaction mechanism in Prussian blue analogue materials toward enhanced Na-storage 普鲁士蓝模拟材料增强na存储的协同插层-转化反应机理
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-07-10 DOI: 10.1039/d5sc03041b
Na Liu, Xiaohan Wang, Jing Liu, Ningbo Liu, Liubin Wang
{"title":"Synergistic intercalation–conversion reaction mechanism in Prussian blue analogue materials toward enhanced Na-storage","authors":"Na Liu, Xiaohan Wang, Jing Liu, Ningbo Liu, Liubin Wang","doi":"10.1039/d5sc03041b","DOIUrl":"https://doi.org/10.1039/d5sc03041b","url":null,"abstract":"Sodium-ion batteries (SIBs) have emerged as promising candidates for large-scale energy storage systems owing to the abundant and low-cost sodium resources. Among various cathode materials, Prussian blue analogues (PBAs) show great promise due to their three-dimensional open framework and easy synthesis process. However, critical challenges including limited electron transfer, blocked electronic pathways between particles, excessive lattice water content, and structural instability during cycling significantly compromise their electrochemical performance. Herein, we have developed a lead hexacyanoferrate/carbon nanotube composite (PbHCF/CNTs) through rational interface design to improve the electrochemical performance. The PbHCF/CNTs electrode exhibits a four-electron transfer capacity based on the redox reaction of Pb<small><sup>0/2+</sup></small> through a reversible intercalation–conversion mechanism. This innovative configuration delivers a high initial reversible capacity of 161.8 mA h g<small><sup>−1</sup></small> at 20 mA g<small><sup>−1</sup></small> and good cycling stability with 95.8 mA h g<small><sup>−1</sup></small> retained after 250 cycles at 100 mA g<small><sup>−1</sup></small> (64% capacity retention), along with enhanced structural reversibility confirmed by <em>operando</em> XRD analysis. This innovative approach provides a new design concept for high-capacity Prussian blue analogue cathode materials in the realm of high-performance SIBs and beyond.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144630078","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
Synthesis and immunological evaluation of the lipopolysaccharide outer core of Salmonella for potential broad-spectrum protection against multiple Salmonella serovars 沙门氏菌脂多糖外核的合成及其对多种沙门氏菌血清型广谱保护的免疫学评价
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-07-10 DOI: 10.1039/d5sc03944d
Xingling Pan, Ting-An Chen, Fatemeh Shafieichaharberoud, Sharon M. Tennant, Scott M. Baliban, Xuefei Huang
{"title":"Synthesis and immunological evaluation of the lipopolysaccharide outer core of Salmonella for potential broad-spectrum protection against multiple Salmonella serovars","authors":"Xingling Pan, Ting-An Chen, Fatemeh Shafieichaharberoud, Sharon M. Tennant, Scott M. Baliban, Xuefei Huang","doi":"10.1039/d5sc03944d","DOIUrl":"https://doi.org/10.1039/d5sc03944d","url":null,"abstract":"<em>Salmonella</em> species (<em>Salmonella</em> spp.) are a major foodborne pathogen and a leading cause of gastroenteritis in humans. The emergence and continued spread of multidrug-resistant <em>Salmonella</em> spp. suggest the urgent need for novel vaccines to complement antibiotics. Currently, there are no approved vaccines against <em>Salmonella</em> spp. for human use beyond those for <em>Salmonella enterica</em> (<em>S. enterica</em>) serovar Typhi. To address this gap, oligosaccharides corresponding to the lipopolysaccharide (LPS) outer core of <em>S. enterica</em> were investigated as potential antigens that can target multiple pathogenic <em>Salmonella</em> serovars. An efficient chemical synthesis strategy was developed to stereoselectively construct the sterically congested outer core pentasaccharides with five 1,2-<em>cis</em> glycosidic linkages. These synthetic glycan antigens were conjugated to the mutant bacteriophage Qβ, a highly immunogenic carrier system. The resulting constructs elicited strong and durable anti-glycan IgG antibodies, which can robustly bind to <em>Salmonella</em> spp. with truncated LPS (rough strain). For smooth strains bearing long LPS chains, the combination of the antisera with the antimicrobial peptide thanatin, an inhibitor of the LPS transport system, exhibited enhanced cytotoxicity toward multiple serovars of pathogenic <em>Salmonella</em>, suggesting that combination therapy may serve as a strategy for enhancing protection against salmonellosis.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"670 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144630298","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
Unveiling the role of cobalt in the product regulation for CO2 hydrogenation to light olefins over alumina-supported Co–Fe catalysts 揭示了钴在氧化铝负载的Co-Fe催化剂上CO2加氢生成轻烯烃的产物调控中的作用
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-07-10 DOI: 10.1039/d5sc04407c
Zhihao Liu, Wenlong Song, Peipei Zhang, Jiaming Liang, Chengwei Wang, Chufeng Liu, Hanyao Song, Baojian Chen, Kangzhou Wang, Guangbo Liu, Xiaoyu Guo, Yingluo He, Xinhua Gao, Jianli Zhang, Guohui Yang, Noritatsu Tsubaki
{"title":"Unveiling the role of cobalt in the product regulation for CO2 hydrogenation to light olefins over alumina-supported Co–Fe catalysts","authors":"Zhihao Liu, Wenlong Song, Peipei Zhang, Jiaming Liang, Chengwei Wang, Chufeng Liu, Hanyao Song, Baojian Chen, Kangzhou Wang, Guangbo Liu, Xiaoyu Guo, Yingluo He, Xinhua Gao, Jianli Zhang, Guohui Yang, Noritatsu Tsubaki","doi":"10.1039/d5sc04407c","DOIUrl":"https://doi.org/10.1039/d5sc04407c","url":null,"abstract":"CoFe-based catalysts for CO<small><sub>2</sub></small> hydrogenation reactions have been widely studied, but the effects of cobalt on the product regulation remains largely over-looked. In the present study, we report a series of Na-decorated alumina-supported Co–Fe bimetallic catalysts with varying Co/Fe molar ratios for the direct conversion of CO<small><sub>2</sub></small> to light olefins. <em>In situ</em> XRD and Mössbauer spectroscopy reveal that Co doping significantly promotes the reduction and carburization of Fe species, leading to the formation of active CoFe alloy carbides. Furthermore, the DFT results indicate that cobalt decreases the H<small><sub>2</sub></small> adsorption energy, thereby regulating the surface C/H ratio and enhancing the tandem RWGS and Fischer–Tropsch reactions. These effects synergistically improve the formation and desorption of light olefins. As a result, the optimal Co1Fe2 catalyst (Co/Fe = 1/2) achieves a high STY of 315.1 g kg<small><sub>cat</sub></small><small><sup>−1</sup></small> h<small><sup>−1</sup></small> for light olefins with a CO<small><sub>2</sub></small> conversion of 51.9% at 320 °C. This study provides mechanistic insights into cobalt-assisted product selectivity control and offers a promising strategy for designing highly efficient CO<small><sub>2</sub></small>-to-light olefins catalytic systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"21 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144622643","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
Neutral buffered electrolytes guarantee ideal band-edge pinning for semiconductor photoanodes 中性缓冲电解质保证了半导体光电阳极理想的带边固定
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-07-10 DOI: 10.1039/d5sc01816a
Yosuke Kageshima, Hiromu Kumagai, Katsuya Teshima, Kazunari Domen, Hiromasa Nishikiori
{"title":"Neutral buffered electrolytes guarantee ideal band-edge pinning for semiconductor photoanodes","authors":"Yosuke Kageshima, Hiromu Kumagai, Katsuya Teshima, Kazunari Domen, Hiromasa Nishikiori","doi":"10.1039/d5sc01816a","DOIUrl":"https://doi.org/10.1039/d5sc01816a","url":null,"abstract":"The photoelectrochemical (PEC) processes occurring in semiconductor photoelectrodes have been regarded as similar to the physical processes occurring at the semiconductor/metal interfaces. In contrast, the physicochemical processes occurring in the electrolyte have been considered to be unaffected by the (photo)electrode materials that are employed. We found that these “ideal” situations are not always guaranteed during performing the actual PEC reaction. That is, the present study based on impedance and hydrodynamic voltammetry analyses proposes that the band diagram at the interface between a semiconductor photoanode and an electrolyte can be affected by transient physicochemical phenomena in the electrolyte during the PEC oxygen evolution reaction. Specifically, in the case that a neutral unbuffered electrolyte was employed, a local pH gradient was formed during the reaction and produced a positive shift in the flat-band potential. This means the breakdown of the ideal band bending at the Schottky-like junction. Meanwhile, a neutral buffered phosphate-based electrolyte suppressed the formation of this pH gradient and thus guaranteed ideal band-edge pinning at the photoanode/electrolyte interface. This study provides insights demonstrating that PEC water splitting occurring at the semiconductor/electrolyte interface are distinct from simple analogy to the conventional semiconductor physics and to the physicochemical processes in the electrolyte.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"9 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144622644","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
"Node" facilitated thermostable mechanophores for rapid self-strengthening in double network materials. “节点”促进了热稳定机械团在双网材料中的快速自强化。
IF 7.6 1区 化学
Chemical Science Pub Date : 2025-07-10 DOI: 10.1039/d5sc00151j
Julong Jiang, Zhi Jian Wang, Ruben Staub, Yu Harabuchi, Alexandre Varnek, Jian Ping Gong, Satoshi Maeda
{"title":"\"Node\" facilitated thermostable mechanophores for rapid self-strengthening in double network materials.","authors":"Julong Jiang, Zhi Jian Wang, Ruben Staub, Yu Harabuchi, Alexandre Varnek, Jian Ping Gong, Satoshi Maeda","doi":"10.1039/d5sc00151j","DOIUrl":"10.1039/d5sc00151j","url":null,"abstract":"<p><p>Mechanophores are force-sensitive compounds that undergo chemical reactions under force stimuli. The design and discovery of efficient yet thermally stable mechanophores are crucial for developing self-strengthening materials. However, conventional mechanophores are often chemically unstable due to the presence of highly strained rings or weak covalent bonds, making the material sensitive to the change of temperature or UV irradiation. In this study, a comprehensive computational exploration was conducted to discover thermally stable, unconventional mechanophores for self-strengthening materials based on mechanoradical polymerisation. Notably, the computational procedure presented here serves as a general strategy for designing mechanophores intended for various applications. First, a conformational motif called a \"node\" along the force transduction direction was identified, significantly enhancing the force effect. Molecules with bridged rings emerged as ideal candidates for possessing a \"node,\" as the bridged structure helps to fix the key dihedral angle. Simulations predicted that polymers containing camphanediol and pinanediol could readily undergo C-C bond homolysis under force. Subsequently, automated reaction path exploration revealed the fate of the mechanoradicals and suggested that camphanediol could generate long-lived radicals, a crucial feature for self-strengthening materials. Following these computational predictions, we successfully prepared double-network hydrogels containing the camphanediol moiety. Careful experiments were then performed to quantify the concentration of mechanoradicals, and enhanced self-strengthening performance was demonstrated through loading-unloading tests.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12242834/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144625486","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Degradable water-soluble polymer prodrugs for subcutaneous delivery of irritant anticancer drugs. 用于皮下递送刺激性抗癌药物的可降解水溶性高分子前药。
IF 7.6 1区 化学
Chemical Science Pub Date : 2025-07-10 DOI: 10.1039/d5sc02967h
Léa Guerassimoff, Jingming Cao, Michaella Auguste, Amaury Bossion, Chen Zhu, Dao Le, Catherine Cailleau, Safa Mohamed Ismail, Françoise Mercier-Nomé, Julien Nicolas
{"title":"Degradable water-soluble polymer prodrugs for subcutaneous delivery of irritant anticancer drugs.","authors":"Léa Guerassimoff, Jingming Cao, Michaella Auguste, Amaury Bossion, Chen Zhu, Dao Le, Catherine Cailleau, Safa Mohamed Ismail, Françoise Mercier-Nomé, Julien Nicolas","doi":"10.1039/d5sc02967h","DOIUrl":"10.1039/d5sc02967h","url":null,"abstract":"<p><p>Chemotherapy is primarily administered intravenously (IV), but this route poses significant challenges (<i>e.g.</i>, high costs, patient discomfort, logistical difficulties, side effects such as infections from catheter use). Although oral and subcutaneous (SC) routes are preferred for their convenience and have the potential for better patient comfort and cost reduction, oral chemotherapy faces issues like poor bioavailability and adherence, while SC delivery is unsuitable for irritant or vesicant drugs due to local toxicity. To overcome these limitations, the polymer prodrug strategy has been explored, where drugs are linked to a polymer, reducing toxicity and enhancing drug delivery. Recent work has focused on creating water-soluble polymer prodrugs for SC delivery of paclitaxel (Ptx), a hydrophobic and vesicant drug, which was successfully conjugated to polyacrylamide (PAAm), a very hydrophilic biocompatible polymer, resulting in safer SC injection and enhanced therapeutic efficacy in tumor-bearing mice. However, this strategy's potential depends on adapting it to other vesicant anticancer drugs. Making the polymer degradable for facilitated excretion would also be a key improvement. In this work, this approach has been successfully extended to gemcitabine (Gem), a widely used but irritant anticancer drug, and to a degradable PAAm-based promoiety, having cleavable ester groups in the main chain. The resulting Gem-based prodrugs featured upper critical solution temperature to ensure complete solubility at the temperature of the SC tissue, sustained Gem release, significant degradation under physiological conditions, improved systemic toxicity and absence of local toxicity compared to free Gem. Remarkably, Gem-PAAm polymer prodrugs exhibited significant anticancer efficacy in mice bearing Mia Pa-Ca 2 tumors, outperforming Gemzar®, the commercial formulation of Gem. These advances suggest the potential of these hydrophilic polymer prodrugs to transform SC chemotherapy, enabling the use of a broader range of anticancer drugs while reducing side effects and improving patient outcomes.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12243153/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144625489","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Supramolecular "sergeants": in situ and multi-level induction of chirality in helical assemblies of triarylamine trisamide monomers. 超分子“中士”:原位和多层次诱导手性在螺旋组装的三芳胺三酰胺单体。
IF 7.6 1区 化学
Chemical Science Pub Date : 2025-07-10 DOI: 10.1039/d5sc02159f
Antoine Perennes, Quentin Sallembien, Weiwei Fang, Stéphane Grass, Jérôme Lacour, Laurent Bouteiller, Matthieu Raynal
{"title":"Supramolecular \"sergeants\": <i>in situ</i> and multi-level induction of chirality in helical assemblies of triarylamine trisamide monomers.","authors":"Antoine Perennes, Quentin Sallembien, Weiwei Fang, Stéphane Grass, Jérôme Lacour, Laurent Bouteiller, Matthieu Raynal","doi":"10.1039/d5sc02159f","DOIUrl":"10.1039/d5sc02159f","url":null,"abstract":"<p><p>The induction and transmission of chirality across multiple length scales is fundamental to many (bio)chemical processes. For the majority of macromolecular and supramolecular structures adopting a helical configuration, this is harnessed by means of a monomer embedding a stereogenic element, also called a \"sergeant\" because of its ability to transfer its chirality preference to achiral monomers. Herein, we devise a triarylamine trisamide (TATA) monomer embedding a (thio)urea unit able to interact with a chiral phosphate anion through hydrogen bonding. Thanks to the orthogonal nature of the amide and (thio)urea functions, the anion specifically binds to the (thio)urea unit, thus yielding a supramolecular monomer acting as a \"sergeant\" <i>i.e.</i> allowing efficient chirality induction in amide-bonded TATA helical copolymers composed of various types of achiral TATA monomers. Unlike covalent \"sergeants\", chirality can be induced <i>in situ</i> by binding of the chiral anion to pre-formed coassemblies. In addition, the catalytic performance of TATA coassemblies embedding intrinsically achiral phosphine-functionalized TATA monomers has been evaluated: higher enantioselectivities are reached with the supramolecular <i>versus</i> covalent \"sergeant\". Our work may facilitate the design and development of supramolecular \"sergeants\" as a modular approach to induce chirality in supramolecular helical copolymers and catalysts.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12272724/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144674003","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Photo-uncaging of a ferrocene-bridged dinuclear iridium(iii) complex for three-photon photoimmunotherapy against hypoxic melanoma. 二茂铁桥接双核铱(iii)配合物用于三光子光免疫治疗缺氧黑色素瘤的光封包。
IF 7.6 1区 化学
Chemical Science Pub Date : 2025-07-10 DOI: 10.1039/d5sc04006j
Lina Xie, Zhuoli Chen, Tianying Wang, Jinzhe Liang, Qiaoshan Lie, Chengzhi Jin, Xiting Zhang, Yu Chen, Hui Chao
{"title":"Photo-uncaging of a ferrocene-bridged dinuclear iridium(iii) complex for three-photon photoimmunotherapy against hypoxic melanoma.","authors":"Lina Xie, Zhuoli Chen, Tianying Wang, Jinzhe Liang, Qiaoshan Lie, Chengzhi Jin, Xiting Zhang, Yu Chen, Hui Chao","doi":"10.1039/d5sc04006j","DOIUrl":"10.1039/d5sc04006j","url":null,"abstract":"<p><p>The complexity of solid tumors in terms of light scattering, oxygen insufficiency, and redox imbalance complicates the strategic design of photoactivated therapy. In this work, an unprecedented photoactivated homolysis process of ferrocene is driven by the photochemistry of a conjugated cyclometalated iridium(iii) complex upon 970 nm three-photon excitation, exhibiting photo-uncaging, biocatalysis, and an ROS storm all in one moiety. Trapping assays, ultrafast spectroscopy, and DFT calculations reveal the release of Fe<sup>2+</sup> ions, the location of carbon-centered radicals, and the essential single electron transfer (SET) process for their generation. Such a photo-uncaging pattern harnesses peripheral substrates (O<sub>2</sub>, H<sub>2</sub>O<sub>2,</sub> and H<sub>2</sub>O) for ROS generation. It continuously degrades the biomolecule homeostasis (GSH and NADH), inducing high immunogenic ferroptosis and necroptosis in hypoxic melanoma models for long-term photoimmunotherapy. The uncaging of the photostable ferrocene by transition metal photochemistry develops an elegant paradigm for multi-functional molecular photoactivated therapy.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12278504/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144689042","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Single-visible-light performed STORM imaging with activatable photoswitches. 单可见光采用可激活光开关进行STORM成像。
IF 7.6 1区 化学
Chemical Science Pub Date : 2025-07-10 DOI: 10.1039/d5sc03224e
Fanghui Li, Mengqi Li, Yiqi Shi, Xinyun Bian, Ning Lv, Shaomeng Guo, Ying Wang, Weijun Zhao, Wei-Hong Zhu
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