Chemical Science最新文献_第6页

Non-radical pathways control methane sulfonation versus oxygenation C–H functionalization selectivity with Hg(II) and Au(III) catalysis 在Hg（II）和Au（III）催化下，非自由基途径控制甲烷磺化与氧合C-H功能化的选择性

IF 8.4 1区化学

Chemical Science Pub Date : 2026-04-23 DOI: 10.1039/d6sc01628f

Anjaneyulu Koppaka, Caz Cullimore, Jyothish Joy, Alex Kraus, Roy A. Periana, Daniel H. Ess

{"title":"Non-radical pathways control methane sulfonation versus oxygenation C–H functionalization selectivity with Hg(II) and Au(III) catalysis","authors":"Anjaneyulu Koppaka, Caz Cullimore, Jyothish Joy, Alex Kraus, Roy A. Periana, Daniel H. Ess","doi":"10.1039/d6sc01628f","DOIUrl":"https://doi.org/10.1039/d6sc01628f","url":null,"abstract":"Methane C–H functionalization by radical pathways is often unselective and not desirable. Transition metal catalyzed C–H functionalization of methane to methanesulfonic acid (sulfonation) in sulfuric acid has generally been interpreted as resulting from a radical mechanism whereas functionalization to methyl bisulfate (oxygenation) has been proposed to occur by both radical and non-radical pathways. For HgII and AuIII catalysis, formation of either methanesulfonic acid or methyl bisulfate depends on whether 98% sulfuric acid or oleum (SO3 added) is used. Here we report new experiments combined with density functional theory calculations that have revealed that selectivity is determined by non-radical pathways where a HgII/AuIII-methyl intermediate can undergo either an electrophilic substitution pathway (SE2) with SO3 to form methanesulfonic acid or a nucleophilic substitution pathway (SN2) with bisulfate to form methyl bisulfate. The favored pathway is determined by the electrophilicity/reduction potential of the metal and the sulfuric acid to SO3/H2O equilibrium. Overall, this new selectivity model provides a straightforward understanding of product selectivity and does not require a functionalization mechanism involving radicals.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"134 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147744091","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

Oscillator-qubit generalized quantum signal processing: a case study of uracil cation vibronic model 振子-量子比特广义量子信号处理：以尿嘧啶阳离子振动模型为例

IF 8.4 1区化学

Chemical Science Pub Date : 2026-04-23 DOI: 10.1039/d5sc09606e

Jungsoo Hong, Seong Ho Kim, Seung Kyu Min, Joonsuk Huh

{"title":"Oscillator-qubit generalized quantum signal processing: a case study of uracil cation vibronic model","authors":"Jungsoo Hong, Seong Ho Kim, Seung Kyu Min, Joonsuk Huh","doi":"10.1039/d5sc09606e","DOIUrl":"https://doi.org/10.1039/d5sc09606e","url":null,"abstract":"Hybrid oscillator-qubit processors have recently demonstrated high-fidelity control of both continuous- and discrete-variable information processing. However, most quantum algorithms remain limited to homogeneous quantum architectures. Here, we present a compiler for hybrid oscillator-qubit processors that implements state preparation and time evolution. In this setting, the compiler invokes generalized quantum signal processing (GQSP) to synthesize arbitrary analytic bosonic phase gates in a constructive manner with circuit depth scaling as O(log(1/ε)). The approximation cost scales with the Fourier bandwidth of the target bosonic phase, rather than by the degree of nonlinearity. Armed with OQ-GQSP, multi-state vibronic coupling Hamiltonian dynamics can be decomposed into state-dependent arbitrary-phase potential propagators, which also enable the extension to multi-state systems through the parity-measurement technique. Compared to fully discrete encodings, our approach avoids the overhead of truncating continuous variables, resulting in linear dependence on the number of vibrational modes. We validate our method on the uracil cation, a canonical system whose accurate modeling requires anharmonic vibronic models, and estimate the cost of state preparation and time evolution.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"19 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147736136","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

Chemoproteomics Unveils the Antibacterial Mechanism of Silver Ions: Inhibiting Peptidoglycan Synthesis via Targeting Mur Family Proteins in Staphylococcus aureus 化学蛋白质组学揭示银离子在金黄色葡萄球菌中的抗菌机制：通过靶向Mur家族蛋白抑制肽聚糖合成

IF 8.4 1区化学

Chemical Science Pub Date : 2026-04-23 DOI: 10.1039/d6sc00255b

Li-run Zhou, Ying Zhang, Yajian Li, Tong Yang, Zheng Chu, Qianyu Zhang, Hechen Tang, Ang Ma, Peng Gao, Chen Wang, Yin-Kwan Wong, Cui Liu, Shengnan Shen, Junzhe Zhang, Qiaoli Shi, Huan Tang, Jigang Wang

{"title":"Chemoproteomics Unveils the Antibacterial Mechanism of Silver Ions: Inhibiting Peptidoglycan Synthesis via Targeting Mur Family Proteins in Staphylococcus aureus","authors":"Li-run Zhou, Ying Zhang, Yajian Li, Tong Yang, Zheng Chu, Qianyu Zhang, Hechen Tang, Ang Ma, Peng Gao, Chen Wang, Yin-Kwan Wong, Cui Liu, Shengnan Shen, Junzhe Zhang, Qiaoli Shi, Huan Tang, Jigang Wang","doi":"10.1039/d6sc00255b","DOIUrl":"https://doi.org/10.1039/d6sc00255b","url":null,"abstract":"Silver ions (Ag+) have long been employed as natural antimicrobial agents, yet their precise mechanism of action remains unclear. In this study, we show that Ag++ displays strong antibacterial activity against Staphylococcus aureus (S. aureus), including methicillin-resistant strains (MRSA). Using chemoproteomic analysis, we identified MurB, MurC, and MurD as direct coordinate covalent targets of Ag+ in S. aureus, with binding occurring at cysteine residues Cys224, Cys368, and Cys221, respectively. This interaction leads to a reduction in MurB and MurD expression and inhibits MurC enzymatic activity, ultimately disrupting peptidoglycan synthesis and compromising bacterial cell wall integrity. Consequently, Ag+ treatment results in bacterial membrane leakage, altered membrane potential, and inhibited biofilm formation. Additionally, Ag+ reduces bacterial adhesion and invasion, alleviating the inflammatory response in host cells. Notably, Ag+ exhibits a low resistance frequency compared to conventional antibiotics, underscoring its potential as an effective antimicrobial agent. Its distinct mechanism of action and reduced likelihood of resistance development indicate that it may serve not only as an effective therapeutic strategy, but also as a probe for elucidating the mechanism of bacterial peptidoglycan biosynthesis. These results offer new insights for the development of antibiotics targeting Mur family proteins.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147736137","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

Singlet machine learning photodynamics reveal competing inversion paths of methylated cyclooctatetrathiophene 单线态机器学习光动力学揭示甲基化环四噻吩的竞争反转路径

IF 8.4 1区化学

Chemical Science Pub Date : 2026-04-23 DOI: 10.1039/d6sc00969g

Christian Salguero, Steven A. Lopez

{"title":"Singlet machine learning photodynamics reveal competing inversion paths of methylated cyclooctatetrathiophene","authors":"Christian Salguero, Steven A. Lopez","doi":"10.1039/d6sc00969g","DOIUrl":"https://doi.org/10.1039/d6sc00969g","url":null,"abstract":"We used state-of-the-art machine-learning nonadiabatic molecular dynamics to investigate the stereochemical inversion reaction of a methylated thiophene-fused cyclooctatetraene derivative, MeCOTh. Minimum energy path calculations suggest that the pseudo-dominant pathway of MeCOTh is towards a non-productive fluorescence decay pathway. Our machine learning photodynamics calculations revealed that relative stereochemical inversion occurs mainly on the S1 surface (74% of trajectories), and we identified two competing inversion pathways. The first and main mechanistic pathway, seen in 62% of trajectories, showcases a \"crown\" structure with unidirectional sulfurs resulting from S-S closed-shell repulsions. The second pathway is the previously proposed inversion mechanism, which proceeds through a planar geometry of MeCOTh, and appeared in only 8% of trajectories. Our photodynamic simulations show that although excited-state Baird aromaticity contributes to the relative stereochemical inversion mechanism of MeCOTh, it is not the only electronic effect. Instead, the overall inversion mechanism is primarily governed by the interplay between Baird aromaticity and the S-S closed-shell repulsions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"21 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147736132","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

Enantioselective Synthesis of Configurationally Stable [5]helicenes Containing 1,2-Azaborine Units 含有1,2-氮杂环嘌呤的构型稳定[5]螺旋烯的对映选择性合成

IF 8.4 1区化学

Chemical Science Pub Date : 2026-04-23 DOI: 10.1039/d6sc02344d

Catherine Olguin, Christian Tabacaru, Lennart Besse, Martin Simon, Christopher Golz, Marcos Humanes, Manuel A. Fernandez-Rodriguez, Patricia García-García, Maike Mücke, Ricardo A Mata, Manuel Alcarazo

{"title":"Enantioselective Synthesis of Configurationally Stable [5]helicenes Containing 1,2-Azaborine Units","authors":"Catherine Olguin, Christian Tabacaru, Lennart Besse, Martin Simon, Christopher Golz, Marcos Humanes, Manuel A. Fernandez-Rodriguez, Patricia García-García, Maike Mücke, Ricardo A Mata, Manuel Alcarazo","doi":"10.1039/d6sc02344d","DOIUrl":"https://doi.org/10.1039/d6sc02344d","url":null,"abstract":"Two different families of BN-doped [5]helicenes have been efficiently synthesized through a highly enantioselective, intramolecular, Au-catalyzed alkyne hydroarylation reaction. Key for the success of the method is the use of BINOL-derived cationic phosphonites as ancillary ligands (BINOL: 1,1-Bi-2-naphthol). The inversion barriers of the structures obtained have been determined both experimentally and theoretically, and are essentially identical to those reported for non-dopped carbo[5]helicenes of otherwise identical structure. Contrarily, the newly prepared BN-doped helicenes exhibit intensified absorption spectra at long wavelength (λ ≈ 400 nm) and fluorescence when compared with their only-carbon counterparts. These effects are particularly pronounced for the naphtho[2,1-c]phenanthro[1,2-e][1,2]azaborinine series, in which the BN-unit is located at the rim of the helix. Preliminary studies on the post-synthetic functionalization of these structures are also described; specifically, the naphtho[2,1-c]phenanthro[1,2-e][1,2]azaborinine structure can be site-selective brominated at position 4. In addition, the unprecedented deborilation of these helices to afford axially chiral anilines has been observed by treatment with DDQ.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"2 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147736134","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

Beyond the Three-State Picture: When Higher-Lying Excited States Become Quantitatively Indispensable 超越三态图：当高激发态在数量上不可或缺时

IF 8.4 1区化学

Chemical Science Pub Date : 2026-04-23 DOI: 10.1039/d6sc01726f

Yue He, Daniel Escudero

{"title":"Beyond the Three-State Picture: When Higher-Lying Excited States Become Quantitatively Indispensable","authors":"Yue He, Daniel Escudero","doi":"10.1039/d6sc01726f","DOIUrl":"https://doi.org/10.1039/d6sc01726f","url":null,"abstract":"Higher-lying excited states beyond S1 and T1 are widely recognized in many photophysical systems, including thermally activated delayed fluorescence (TADF). However, their explicit and quantitative impact on photophysical observables such as photoluminescence quantum yields (PLQY) and lifetimes is difficult to be attained experimentally and it has not been systematically assessed within a fully ab initio kinetic modeling framework. To address this gap, we developed KinLuv, a multistate excited state kinetic model that includes higher-lying excited states (S2, T2) and all possible monomolecular interconversion processes between all the electronic states, whose rate constants were computed using Fermi’s golden rule (FGR) explicitly including the Herzberg-Teller (HT) vibronic coupling effect. We applied KinLuv to prototypical multi-resonance TADF (MR-TADF) emitters and their derivatives, as well as other representative organic chromophores, demonstrating its broad applicability across diverse photophysical playgrounds beyond TADF. The resulting simulations quantitatively reproduce key experimental observables, including PLQY and prompt/delayed fluorescence lifetimes. Beyond its predictive power, the present results establish clear criteria for identifying when higher-lying excited states influence the excited-state decay and when simplified models remain adequate. This framework enables rational selection of minimal kinetic models that balance physical insight with numerical robustness, with direct implications for the in silico design of high-performance organic emitters.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"25 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147736135","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

Enantioselective organocatalytic radical alkylation enabled by photoexcitation 通过光激发实现对映选择性有机催化自由基烷基化

IF 8.4 1区化学

Chemical Science Pub Date : 2026-04-23 DOI: 10.1039/d6sc00272b

Yanji Song, Ruifeng Wang, Xi Lu, Yuqiao Zhou, Xiaoming Feng, Weidi Cao, Xiaohua Liu

引用次数: 0

Light-regulated templated self-assembly of bilayered nanotoroids 双层纳米环的光调节模板自组装

IF 8.4 1区化学

Chemical Science Pub Date : 2026-04-22 DOI: 10.1039/d6sc02354a

Kintaro Miyamoto, Sota Mihara, Hiroki Itabashi, Sougata Datta, Hiroki Hanayama, Shiki Yagai

{"title":"Light-regulated templated self-assembly of bilayered nanotoroids","authors":"Kintaro Miyamoto, Sota Mihara, Hiroki Itabashi, Sougata Datta, Hiroki Hanayama, Shiki Yagai","doi":"10.1039/d6sc02354a","DOIUrl":"https://doi.org/10.1039/d6sc02354a","url":null,"abstract":"Controlled molecular self-assembly driven by noncovalent interactions provides access to ordered architectures beyond the molecular scale. Yet the precise construction of higher-order assemblies remains difficult because directionality of noncovalent interactions progressively decreases as structural hierarchy increases. Here we show that bilayered toroids can be generated by introducing trans-azobenzene units into a scissor-shaped diphenylnaphthalene dyad that otherwise forms toroidal assemblies. Rapid evaporation of a toluene solution of the azobenzene-appended dyad affords monolayered toroids, whereas slow evaporation yields bilayered toroids, indicating that the trans-azobenzene unit promotes formation of a second toroidal layer. Consistent with their distinct dimensions, both monolayered and bilayered toroids organize on a substrate into two-dimensional hexagonal arrays with distinct lattice parameters while the bilayered toroids further exhibit stacking along the z axis. In a less polar medium, this hierarchical stacking proceeds to give corrugated cylinders composed of approximately 10 bilayered toroids. The role of azobenzene units in forming the bilayered structure can be demonstrated by slow evaporation of a toluene solution of the photogenerated cis isomer, which affords only monolayered toroids, supporting the conclusion that the trans-azobenzene unit serves as a structural scaffold for bilayer formation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"2 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147736139","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

Living single-cell metabolomics via mass spectrometry: state of the art and perspective 通过质谱分析的单细胞代谢组学：现状和前景

IF 8.4 1区化学

Chemical Science Pub Date : 2026-04-22 DOI: 10.1039/d6sc00482b

Xianzhe Shi, Jiajun Peng, Chunxiu Hu, Muyingnan You, Xin Lu, Xinyu Liu, Guowang Xu

{"title":"Living single-cell metabolomics via mass spectrometry: state of the art and perspective","authors":"Xianzhe Shi, Jiajun Peng, Chunxiu Hu, Muyingnan You, Xin Lu, Xinyu Liu, Guowang Xu","doi":"10.1039/d6sc00482b","DOIUrl":"https://doi.org/10.1039/d6sc00482b","url":null,"abstract":"Cellular heterogeneity is an inherent feature of biological systems, and living single-cell metabolomics (SCM) has emerged as a powerful approach to probe this diversity—a dimension often lost in conventional bulk analyses. Currently, mass spectrometry (MS)-based living SCM techniques are driving a revolution toward higher throughput, sensitivity, and coverage, enabling the identification of rare cell subpopulations and expanding applications across various biological fields. Nevertheless, several bottlenecks remain, including limited metabolome coverage, insufficient throughput, batch effects, instrumental constraints, and challenges in processing large-scale datasets. Future efforts should focus on all stages of SCM, prioritizing the development of microfluidics-integrated living-cell analysis platforms, enhanced ionization sources, in situ chemical derivatizations, AI-powered data processing pipelines, and integrated multi-omics analyses at the single-cell level. Despite existing hurdles, continuous progress in technology, data science, and interdisciplinary collaboration is expected to bring transformative breakthroughs in MS-based living SCM, ultimately advancing our understanding of dynamic biological processes and accelerating biomedical discovery.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147732210","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

Precise construction of symmetrically coordinated triatomic zirconium catalyst for efficient oxygen reduction 高效氧还原对称配位三原子锆催化剂的精确构造

IF 8.4 1区化学

Chemical Science Pub Date : 2026-04-22 DOI: 10.1039/d6sc01335j

Anaer Husile, Tianmi Tang, Li-Yuan Xiao, Xue Bai, Zhenlu Wang, Jingqi Guan

{"title":"Precise construction of symmetrically coordinated triatomic zirconium catalyst for efficient oxygen reduction","authors":"Anaer Husile, Tianmi Tang, Li-Yuan Xiao, Xue Bai, Zhenlu Wang, Jingqi Guan","doi":"10.1039/d6sc01335j","DOIUrl":"https://doi.org/10.1039/d6sc01335j","url":null,"abstract":"Developing an environmentally friendly, highly efficient, and stable electrocatalyst for the oxygen reduction reaction (ORR) holds critical importance for advancing the commercial viability of zinc-air batteries (ZABs). The d-band electronic structure of metal atoms in triatomic catalysts (TACs) can be precisely regulated to achieve the optimal adsorption energy for oxygen intermediates (*OOH, *O and *OH). Here, a TAC Zr3/NG with Zr3O1N6 active sites has been successfully synthesized by a Joule heating method for the ORR. The Zr3/NG demonstrates a half-wave potential (E1/2) of 0.857 V, better than single-atom Zr1/NG and commercial Pt/C. Furthermore, the ZAB based on Zr3/NG can achieve maximum peak power density of 164.3 mW cm-2 and maintains stable operation for over 175 h. Theoretical studies reveal that the Zr3O1N6 coordination configuration shifts the d-band center of zirconium toward the Fermi level, effectively adjusting the adsorption energy of the oxygen intermediate by elongating the O-O bond through bridge adsorption, thereby effectively promoting the breaking of the bond. This study reveals the synergistic effect of triatomic zirconium active centers for improving the ORR performance.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"9 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147732265","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