Chemical Science最新文献

{"title":"Accelerated Click Reactions using Boronic Acids for Heterocyclic Synthesis in Microdroplets","authors":"Jyotirmoy Ghosh, R. Graham Cooks","doi":"10.1039/d5sc00851d","DOIUrl":"https://doi.org/10.1039/d5sc00851d","url":null,"abstract":"Click chemistry is important for its simplicity and versatility, however, condensation-based click reactions are limited by the general requirement of high temperatures and catalysts. Here, we report accelerated click reactions using boronic acids in microdroplets under ambient conditions without catalyst. The reaction between 2-formyl phenylboronic acid (2-FPBA) and substituted amines leads to the formation of multi-step click products, including iminoboronates, boroxines, thiazolidines, and diazaborines, depending on the selected amine. The reactions occur during microdroplet flight and are three orders of magnitude faster than the corresponding bulk reactions. MS and NMR spectral analysis confirmed the nature of the products. We suggest that the air-liquid interface of microdroplets serves both as a superacid and as a drying surface, facilitating dehydration by its superacidicity to access these products. We also demonstrate the application of these accelerated reactions as a late-stage functionalization (LSF) tool to access a range of antihistamine drug derivatives.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"11 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813820","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Boosting near-infrared-triggered photon upconversion in optical nanomaterials via lanthanide-doped nanoparticle sensitization†","authors":"Jiangshan Luo, Jun-Jian Shen, Xingwen Cheng, Yan Liu, Xiulian Yin, Tianxi Hu, Guangxin Fan, Jianming Zhang, Wei Zheng, Xueyuan Chen","doi":"10.1039/d5sc00937e","DOIUrl":"https://doi.org/10.1039/d5sc00937e","url":null,"abstract":"A broad spectrum of optical nanomaterials, including organic molecules, quantum dots, and metallic nanoparticles, have attracted great attention in fields such as biological imaging, data storage, solid-state lasers and solar energy conversion owing to their nonlinear optical properties facilitated by the two-photon absorption process. However, their nonlinear optical properties, particularly photon upconversion triggered by near-infrared light, are constrained by a limited multiphoton absorption cross-section, requiring costly pulsed laser with high-density excitation. Herein, we present a straightforward and versatile strategy to enhance upconversion luminescence in various optical nanomaterials via sensitization with lanthanide-doped nanoparticles. This approach not only broadens the near-infrared responsivity of these luminescent nanomaterials but also introduces novel emission profiles to the lanthanide-doped nanoparticles, enabling multidimensional tunability in terms of wavelength, lifetime, and polarization under low-density excitation. Concentration-dependent photoluminescence spectra and decay curves reveal a radiative energy transfer upconversion mechanism. These findings provide a general strategy for controlling photon upconversion in a wide range of luminescent nanomaterials, paving the way for innovative and versatile applications in diverse fields.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"32 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813831","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cooperative promotion of electroreduction of CO to n-propanol by *CO enrichment and proton regulation","authors":"Rongxing Qiu, Linxiao Cui, Li Peng, Olga Syzgantseva, Jiaran Li, Nan Fang, Maria Syzgantseva, Yuan Jiang, Jie Zhang, Bingxing Zhang, Ling-Zhi Ding, Yangyang Dong, Tianwei Xue, Cheng Li, Jin-Chao Dong, Jin-Yu Ye, Isil Akpinar, Shuliang Yang, Jun Li, Jianling Zhang, Jian-Feng Li, Buxing Han","doi":"10.1039/d5sc00274e","DOIUrl":"https://doi.org/10.1039/d5sc00274e","url":null,"abstract":"The CO2/CO electroreduction reaction (CO2RR/CORR) to liquid products presents an enticing pathway to store intermittent renewable electricity. However, the selectivity for desirable high-value C3 products, such as n-propanol, remains unsatisfactory in CO2RR/CORR. Here, we report that *CO enrichment and proton regulation cooperatively enhance C1-C2 coupling by increasing CO pressure and utilizing proton sponge modification, promoting the production of n-propanol over a Cu0/Cu⁺ nanosheet catalyst in the CORR. We obtain an impressive Faradaic efficiency (FE) of 44.0% ± 2.3% for n-propanol at a low potential of −0.44 V vs. reversible hydrogen electrode (RHE) under 3 bar CO. Experimental results demonstrated that *H intermediates could be regulated by proton sponge modification. In situ characterizations combined with density functional theory (DFT) calculations validate that Cu+ species exist stably in proton sponge-modified Cu-based catalysts along with appropriate *CO coverage. This design facilitates the potential-determining C1-C1 and C1-C2 coupling steps and contributes to the n-propanol production.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"217 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813819","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The Impact of Whole-Molecule Disorder on Spin-Crossover in a Family of Isomorphous Molecular Crystals","authors":"Holly E. Sephton, Rhiannon L. Watson, Namrah Shahid, Hari Babu Vasili, Daniel Baker, Dipankar Saha, Izar Capel Berdiell, Christopher M. Pask, Oscar Cespedes, Malcolm Halcrow","doi":"10.1039/d5sc00090d","DOIUrl":"https://doi.org/10.1039/d5sc00090d","url":null,"abstract":"Treatment of 2-(pyrazol-1-yl)-6-fluoropyridine with one equiv of the appropriate 4-substituted 1<em>H</em>-pyrazole in the presence of sodium hydride gives moderate yields of 2-(pyrazol-1-yl)-6-(4-methylpyrazol-1-yl)pyridine (L<small>^Me</small>), 2-(pyrazol-1-yl)-6-(4-fluoropyrazol-1-yl)pyridine (L<small>^F</small>), 2-(pyrazol-1-yl)-6-(4-chloropyrazol-1-yl)pyridine (L<small>^Cl</small>) and 2-(pyrazol-1-yl)-6-(4-bromopyrazol-1-yl)pyridine (L<small>^Br</small>). Single crystals of [Fe(L<small>^R</small>)<small>₂</small>]Z<small>₂</small> (R = Me, F or Br; Z<small>⁻</small> = BF<small>₄</small><small>⁻</small> or ClO<small>₄</small><small>⁻</small>) are often well-formed, but are poor diffractors of X-rays. An analysis of [Fe(L<small>^Me</small>)<small>₂</small>][ClO<small>₄</small>]<small>₂</small> showed non-statistical positional disorder of the methyl substituents, leading to whole molecule disorder in each residue of the asymmetric unit. Single crystals of [Fe(L<small>^Br</small>)<small>₂</small>][BF<small>₄</small>]<small>₂</small> are isomorphous with the L<small>^Me</small> complex, and but less substituent disorder. All the complex salts are isomorphous by powder diffraction, and show thermal spin-transitions whose cooperativity differs from gradual (R = Me) to abrupt and hysteretic (R = Br). Some of the cooperative transitions exhibit irregular, closely spaced discontinuities which do not appear to be caused by crystallographic phase changes, and may reflect local heterogeneities caused by the cation disorder. No aspect of their crystal packing appears to correlate with their spin-transition cooperativity. However, weaker cooperativity may correlate with increased cation disorder in this system, which merits further investigation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"97 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813583","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unraveling the Mechanisms of Ketene Generation and Transformation in Syngas-to-Olefins Conversion over ZnCrOx|SAPO-34 Catalysts","authors":"Zhuo-Yan Yao, Sicong Ma, Zhipan Liu","doi":"10.1039/d5sc01651g","DOIUrl":"https://doi.org/10.1039/d5sc01651g","url":null,"abstract":"Ketene was identified as an intermediate in syngas-to-olefins (STO) conversion catalyzed by metal oxide-zeolite composites, which sparked the hot debate on its formation mechanism and catalytic roles. Here we employed large-scale atomic simulations using global neural network potentials to explore the STO reaction pathways, and microkinetic simulations to couple the reaction kinetics in ZnCrO<small>_x</small>|SAPO-34 composite sites. Our results demonstrate that a majority of ketene (86.1%) originates from the methanol carbonylation-to-ketene route (CH<small>₃</small>OH* + H* -&gt; CH<small>₃</small>* + H<small>₂</small>O -&gt; CH<small>₃</small>* + CO* -&gt; CH<small>₂</small>CO* + H*) nearby zeolite acidic sites, where methanol is produced through conventional syngas-to-methanol on Zn<small>₃</small>Cr<small>₃</small>O<small>₈</small>(0001) surface, while the minority of ketene (13.9%) arises from a direct CHO*-CO* coupling (CHO* + CO* + H* -&gt; CHOCO* + H* -&gt; CH<small>₂</small>CO + O*) on Zn<small>₃</small>Cr<small>₃</small>O<small>₈</small>. The presence of the ketene pathway significantly alters the catalytic performance in zeolite, as methanol carbonylation to ketene is kinetically more efficient in competing with conventional methanol-to-olefins (MTO) and thus predominantly drives the product to ethene. Based on our microkinetic simulation, it is the methanol carbonylation activity in zeolite that dictates the performance of STO catalysts.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"75 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813830","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tuning Covalent Bonding in Znic-Based Hybrid Halides towards Tunable Room-Temperature Phosphorescence","authors":"Yibo Cui, Jiawei Lin, Kunjie Liu, Yuhe Shao, Dong Zhao, Zhongnan Guo, Jing Zhao, Zhiguo Xia, Quanlin Liu","doi":"10.1039/d5sc00931f","DOIUrl":"https://doi.org/10.1039/d5sc00931f","url":null,"abstract":"Organic-inorganic metal halides with tunable and state room-temperature phosphorescence (RTP) properties receive broad interests in advanced luminescent materials. Herein, 2-(methylamino)pyridine (MAP), 2-[(methylamino)methyl]pyridine (MAMP), and 2-(2-methylaminoethyl)pyridine (MAEP) were designed and hybridized with Zn2+ and Cl-/Br-, yielding 11 hybrid materials. MAP-based compounds, with a narrow bandgap (3.57 eV), exhibit limited RTP due to inefficient intersystem crossing (ISC) and unstable triplet excitons. In contrast, MAMP (4.49 eV) and MAEP (4.50 eV)-based compounds achieve enhanced RTP through bandgap alignment with Zn halides, enabling efficient energy transfer, ISC, and triplet exciton stabilization via strong hydrogen bonding and π-conjugation effects. Covalent bonding in MAMP and MAEP compounds provides greater rigidity and exciton stability than hydrogen-bonded systems, resulting in prolonged afterglow durations. While Br- bonding enhances ISC and spin-orbit coupling (SOC), and the weak interactions increase non-radiative decay, further reducing afterglow duration. Density functional theory calculations confirm the enhanced SOC in MAMP and MAEP compounds, further improving RTP efficiency. This work demonstrates the precise control of RTP properties, highlighting the potential in advanced anti-counterfeiting and emerging photonics applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"35 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813825","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Visible-light-mediated site-selective C(sp2)–H alkylation of tropones facilitates semi-synthesis of cephafortunoids A and B","authors":"Qi-Xiang Zeng, Cheng-Yu Zheng, Zhan-Peng Ge, Jin-Xin Zhao, Jian-Min Yue","doi":"10.1039/d5sc01006c","DOIUrl":"https://doi.org/10.1039/d5sc01006c","url":null,"abstract":"The synthesis of functionalized tropones constitutes an underexplored chemical space, primarily due to the intrinsic structural properties of the aromatic nucleus. This predicament has impeded extensive investigation into their potential applications in organic and medicinal chemistry. Here, we report a mild and straightforward visible-light-mediated protocol for the α-site-selective C(sp<small>²</small>)–H alkylation of tropones, employing unactivated secondary amines as alkylating agents. This method yields up to 89% in 48 examples, and is significantly amenable to late-stage functionalization. The utility is showcased by the effective chemical transformation of fortunolide A to cephafortunoids A and B, representing the first synthetic entry to this unique class of C<small>₂₀</small><em>Cephalotaxus</em> troponoids. Significantly, this achievement reinforces the chemical feasibility of the newly hypothesized biosynthesis involving direct methylation via radical <em>S</em>-adenosylmethionine (SAM)-dependent methyltransferases.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"39 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813826","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"O-Trifluoromethylation of ketones: an alternative straightforward route to alkenyl trifluoromethyl ethers","authors":"Chi Gao, Yang Liu, Cheng-Sheng Li, He Guo, Sheng-Han Wang, Cong Xu, Mang Wang","doi":"10.1039/d5sc01073j","DOIUrl":"https://doi.org/10.1039/d5sc01073j","url":null,"abstract":"Here we report an unprecedented O-trifluoromethylation of ketones using chloro(phenyl)trifluoromethyl-λ3-iodane (CPTFI). Our method provides a new strategy for the facile synthesis of various synthetically valuable alkenyl trifluoromethyl ethers, particularly those CF3O-substituted terminal alkenes and cyclic alkenes that have been elusive until now, from simple aromatic, aliphatic, and cyclic ketones. The success of this reaction is attributed to the full utilization of the multifunctionality of CPTFI: 1) its strong Lewis acid activation ability, which enables weak nucleophile such as Cl anion to attack the carbonyl group; 2) its bifunctionality, which allows for the introduction of CF3 and Cl into the carbonyl in one step, thus enabling the obtainment of alkenyl trifluoromethyl ethers by further removal of HCl. The further transformation in the synthesis of CF3O-cyclopropanes, which were previously largely unexplored, reveals the significant potential of alkenyl trifluoromethyl ethers as valuable CF3O-containing building blocks in the discovery of innovative materials, pharmaceuticals, and agrochemicals.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"25 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806228","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Precise positioning of Au islands within mesoporous Pd–Pt nanoparticles for plasmon-enhanced methanol oxidation","authors":"Liyang Zhu, Yunqing Kang, Miharu Eguchi, Yingji Zhao, Dong Jiang, Xiaoqian Wei, Xingtao Xu, Kenta Nakagawa, Toru Asahi, Tokihiko Yokoshima, Yusuke Yamauchi","doi":"10.1039/d4sc07345b","DOIUrl":"https://doi.org/10.1039/d4sc07345b","url":null,"abstract":"Trimetallic systems have garnered considerable attention in (electro)catalysis due to the synergistic effects resulting from the combination of three different metals. However, achieving precise control over the positioning of various metals and understanding the relationship between structure and performance remains challenging. This study introduces an approach for synthesizing Pd@Pt@Au mesoporous nanoparticles (MNPs) with distinct core–shell Pd@Pt structures, featuring well-dispersed isolated Au islands on the outer shell, improving the plasmonic effect. The electrocatalytic performance of Pd@Pt@Au MNPs in the methanol oxidation reaction (MOR) is assessed under light-induced and light-independent conditions. The results indicate significantly enhanced activity compared to commercial Pt black, with catalytic activity during MOR increasing approximately 7.5-fold under light irradiation. The external placement of Au on the shell of Pd@Pt@Au MNPs provides superior plasmonic enhancement, thereby contributing to improved catalytic performance under light irradiation. This investigation sheds light on the controlled synthesis of trimetallic MNPs and their catalytic applications, underscoring the importance of precise Au positioning for optimizing performance.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"75 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806229","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Design of Cellulosic Poly(Ionic Liquid)s with Hydrogen Bond/Ion Dual Regulation Mechanism for Highly Reversible Zn Anode†","authors":"Kui Chen, Yongzhen Xu, Hebang Li, Yue Li, Lihua Zhang, Yuanlong Guo, Qinqin Xu, Yunqi Li, Haibo Xie","doi":"10.1039/d5sc01555c","DOIUrl":"https://doi.org/10.1039/d5sc01555c","url":null,"abstract":"The unstable electrode/electrolyte interface with erratic zinc (Zn) deposition, severe dendritic growth and parasitic side reactions deteriorates the reversibility, tolerance and sustainability of aqueous Zn ion batteries (AZIBs). Herein, a imidazolium-based cellulosic poly(ionic liquid)s ([CellMim]+) additive with hydrogen bond/ion dual regulation mechanism for aqueous electrolyte was designed and prepared via a transesterification reaction by taking the particular solvent properties. The water-rich Zn anode interface significantly optimized by hydrogen bond (HB) formation and preferential adsorption of [CellMim]+. Additionally, the overfed Zn2+ ions are modulated by [CellMim]+ cations though electrostatic repulsion, fostering uniform Zn deposition and solid electrolyte interface (SEI). Notably, the Zn||Zn cells with [CellMim]+ modified Zn(OTf)2 electrolyte exhibit a long cycle life over 1800 h at 1 mA cm-2 and a high cumulative capacity of 3700 mAh cm-2 at 10 mA cm-2 with 56.9% Zn utilization rate (ZUR). Intriguingly, this electrolyte demonstrates a remarkable durability of 260 h at 8 mA cm-2 with 22.77% ZUR for a 9 cm2 pouch cell. These results highlight the great potential of cellulosic derivatives in battery applications and offer valuable insights into the design of sustainable aqueous electrolyte additives for AZIBs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"38 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806231","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}