Chemical Science最新文献

{"title":"Polarizable potential window at soft molecular interfaces as a quantitative descriptor for the water content in organic solvents","authors":"Siqi Jin, Lifang Yang, Sijia He, Taoxiong Fang, Xiaohang Sun, Dandan Cai, Qiong Hu, Xinjian Huang, Haiqiang Deng","doi":"10.1039/d5sc00527b","DOIUrl":"https://doi.org/10.1039/d5sc00527b","url":null,"abstract":"The presence of water in organic solvents is a ubiquitous fact and can affect the reactivity and selectivity of chemical reactions. Traditional physical and chemical methods (IR, NMR, Karl Fischer titration, <em>etc.</em>) for quantitative measurement of water in organic solvents are not very suitable for rapid trace water analysis. Here, we demonstrate that, with hydrated Li<small>⁺</small> and Cl<small>⁻</small> as probes to build polarizable potential windows (PPWs) at interfaces between water and more than twenty organic solvents, we can reflect the water content in organic solvents. This method only requires a scan of a cyclic voltammogram for Li<small>⁺</small> and Cl<small>⁻</small> transfer (a weak-interaction electrochemical method), at a micro-scale polarized water/oil interface. A hybrid modified Born ionic solvation model was employed by us to compute the theoretical PPWs of LiCl at a series of water/oil interfaces, which match with the experimental results to some extent. Experiments and theories jointly confirm a novel and universal relationship: the PPW width correlates with the water content (in a large range) in organic solvents in a negative natural logarithm way. We postulate that when the organic solvent is different, the water fingers, <em>i.e.</em>, ions dragging a string of water molecules, will search for water molecules in the organic phase with different probabilities (or microstate numbers) after crossing the interface. This determines the macroscopic quantities, namely the standard Gibbs free energy of ion transfer and the PPW width. It is envisioned that our work paves the way for a broad spectrum of applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"129 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435385","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":"In Situ Raman Spectroscopic Studies of CO2 Reduction Reactions: From Catalyst Surface Structures to Reaction Mechanisms","authors":"Dongao Zhang, Xuan Liu, Yu Zhao, Hua Zhang, Alexander V. Rudnev, Jian-Feng Li","doi":"10.1039/d5sc00569h","DOIUrl":"https://doi.org/10.1039/d5sc00569h","url":null,"abstract":"<strong>A</strong>\u0000<strong>bstract</strong>The electrochemical CO<small>₂</small> reduction reaction (eCO<small>₂</small>RR) has gained widespread attention as an important technology for carbon cycling and sustainable chemistry. In situ Raman spectroscopy, due to its molecular structure sensitive advantage and real-time monitoring capability, has become an effective tool for studying the reaction mechanisms and structure-performance relationships in eCO<small>₂</small>RR. This article reviews recent advancements in the application of in situ Raman spectroscopy in eCO<small>₂</small>RR research, focusing on its critical role in monitoring reaction intermediates, analyzing catalyst surface states, and optimizing catalyst design. Through systematic studies of different catalysts and reaction conditions, in situ Raman spectroscopy has revealed the formation and transformation pathways of various intermediates, deeply exploring their relationship with the active sites of the catalysts. Furthermore, the review discusses the integration of in situ Raman spectroscopy with other characterization techniques to achieve a more comprehensive understanding of the reaction mechanisms. Finally, we summarize the current challenges and opportunities in this research area and look ahead to the future applications of in situ Raman spectroscopy in the field of eCO<small>₂</small>RR.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"80 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435415","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":"Multiple Effects of Aromatic Substituents on Excited State Properties and Singlet Fission Process in Azaquinodimethane System","authors":"Zhenxiang Zhao, Senhao Wang, Xiaomei Shi, Hongbing Fu, Long Wang","doi":"10.1039/d4sc06494a","DOIUrl":"https://doi.org/10.1039/d4sc06494a","url":null,"abstract":"Singlet fission (SF) could offset thermalization loss of high-energy photons via multiexciton generations, thus holding great potential for improving power conversion efficiency of solar cells. However, the SF-based devices remain basically stagnant so far due to the limited scope of practical SF materials. Therefore, designing and developing practical SF material systems is a imperative but challenging task so far. In this work, we comprehensively investigate the effects of aromatic substituents on excited state properties and SF process in the azaquinodimethane system. The results show that the aromatic substituents have a significant influence on molecular diradical characters and then determine the excited state energetics of SF material system including optical band gaps and triplet energy. Moreover, the aromatic substituents could also influence charge transfer coupling interactions via adjusting molecular packing in aggregate state to shunt the excited state population to exert SF process or trap in excimer species. These outcomes not only offer a deep insight into the multiple regulatory effects of the aromatic substituents on excited state properties and SF process but also provide a practical SF material system, which could lay the foundation for the discovery of new SF-active chromophores and practical applications of new generation light harvesting materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"13 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427009","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":"Correction: Enhancing the antibacterial efficacy of vancomycin analogues: targeting metallo-β-lactamases and cell wall biosynthesis","authors":"Paramita Sarkar, Weipan Xu, Melissa Vázquez-Hernández, Geetika Dhanda, Shubhandra Tripathi, Debajyoti Basak, Hexin Xie, Lea Schipp, Pascal Dietze, Julia E. Bandow, Nisanth N. Nair, Jayanta Haldar","doi":"10.1039/d5sc90040a","DOIUrl":"https://doi.org/10.1039/d5sc90040a","url":null,"abstract":"Correction for ‘Enhancing the antibacterial efficacy of vancomycin analogues: targeting metallo-β-lactamases and cell wall biosynthesis’ by Paramita Sarkar <em>et al.</em>, <em>Chem. Sci.</em>, 2024, <strong>15</strong>, 16307–16320, https://doi.org/10.1039/D4SC03577A.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"12 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427003","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 role of lipid phase and temperature in proton barrier and proton migration on biological membranes","authors":"Ambili Ramanthrikkovil Variyam, Mateusz Rzycki, Ramesh Nandi, Alexei Stuchebrukhov, Dominik Drabik, Nadav Amdursky","doi":"10.1039/d4sc07044e","DOIUrl":"https://doi.org/10.1039/d4sc07044e","url":null,"abstract":"Biological membranes play a major role in diffusing protons on their surfaces between transmembrane protein complexes. The retention of protons on the membrane’s surface is commonly described by a membrane-associated proton barrier that determines the efficiency of protons escaping from surface to bulk, which correlates with the proton diffusion (PD) dimensionality at the membrane’s surface. Here, we explore the role of the membrane's biophysical properties and its ability to accept a proton from a light-triggered proton donor situated on the membrane’s surface and to support PD around the probe. By changing lipid composition and temperature, while going through the melting point of the membrane, we directly investigate the role of the membrane phase in PD. We show that the proton transfer process from the proton donor to the membrane is more efficient in the liquid phase of the membrane than in the gel phase, with very low calculated activation energies that are also dependent on the lipid composition of the membrane. We further show that the liquid phase of the membrane allows higher dimensionalities (close to 3) of PD around the probe, indicating lower membrane proton barriers. In the gel phase, we show that the dimensionality of PD is lower, in some cases reaching values closer to 1, thus implying specific pathways for PD, which results in a higher proton recombination rate with the membrane-tethered probe. Computational simulations indicate that the change in PD between the two phases can be correlated to the membrane’s ‘stiffness’ and ‘looseness’ at each phase.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"20 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427005","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":"Robust Protein-Ligand Interaction Modeling through Integrating Physical Laws and Geometric Knowledge for Absolute Binding Free Energy Calculation","authors":"Qun Su, Jike Wang, Qiaolin Gou, Renling Hu, Linlong Jiang, Hui Zhang, Tianyue Wang, Yifei Liu, Chao Shen, Yu Kang, Chang-Yu Hsieh, Tingjun Hou","doi":"10.1039/d4sc07405j","DOIUrl":"https://doi.org/10.1039/d4sc07405j","url":null,"abstract":"Accurate estimation of protein-ligand (PL) binding free energies is a crucial task in medicinal chemistry and a critical measure of PL interaction modeling effectiveness. However, traditional computational methods are often computationally expensive and prone to errors. Recently, deep learning (DL)-based approaches for predicting PL interactions have gained enormous attention, but their accuracy and generalizability are hindered by data scarcity. In this study, we propose LumiNet, a versatile PL interaction modeling framework that bridges the gap between physics-based models and black-box algorithms. LumiNet utilizes subgraph transformer to extract multiscale information from molecular graphs and employs geometric neural networks to integrate PL information, mapping atomic pair structures into key physical parameters of non-bonded interactions in classical force fields, thereby enhancing accurate absolute binding free energy (ABFE) calculations. LumiNet is designed to be highly interpretable, offering detailed insights into atomic interactions within protein-ligand complexes, pinpointing relatively important atom pairs or groups. Our semi-supervised learning strategy enables LumiNet to adapt to new targets with fewer data points than other data-driven methods, making it more relevant for real-world drug discovery. Benchmarks show that LumiNet outperforms the current state-of-the-art model by 18.5% on the PDE10A dataset, and rivals the FEP+ method in some tests with a speed improvement of several orders of magnitude. We applied LumiNet in the scaffold hopping process, which accurately guided the discovery of the optimal ligands. furthermore, we provide a web service for the research community to test LumiNet. The visualization of predicted inter-molecular energy contributions is expected to provide practical values in drug discovery projects.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"867 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427007","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":"Preparation, single crystal structure and room-temperature phosphorescence of a covalent organic polymer containing Te-O-P bonds","authors":"Miaomiao Xue, Guigui Ye, Lei Zhang, Qiang Dong, Chun-Sing Lee, Zhen Li, Qichun Zhang","doi":"10.1039/d4sc07210c","DOIUrl":"https://doi.org/10.1039/d4sc07210c","url":null,"abstract":"Room-temperature phosphorescent (RTP) single crystals of covalent organic polymers (COPs) are rarely reported due to the huge challenge in preparing single crystals from solutions as well as the difficulty in realizing RTP in metal-free organic molecules. Compared to other main group elements, tellurium is rarely successfully introduced into functional single-crystal COPs. Herein, we prepared colorless single crystals of a COP (<strong>CityU-21</strong>) through the reaction between tellurinyldibenzene and [1,1'-biphenyl]-4,4'-diylbis (phosphonic acid). Single crystal X-ray diffraction (SCXRD) analysis indicates that <strong>CityU-21</strong> is a one-dimensional organic polymer through the covalent connection (Te-O-P bonds) between Te(Ph)<small>₂</small>moieties and [HO<small>₃</small>P-Ph-Ph-PO<small>₃</small>H] units. Due to the existence of one unreacted OH group in each phosphonic acid unit, multiple hydrogen-bonding interactions can be formed between adjacent polymer chains, which stabilizes the structure and promotes <strong>CityU-21</strong> to form a pseudo-two-dimensional framework. Benefiting from the integrated effect of aromatic P=O parts, the heavy atoms (tellurium), and multiple hydrogen bonds, single crystals of <strong>CityU-21</strong> display RTP behavior with a lifetime of 179 ms @540 nm and 158 ms @565 nm, the photoluminescence quantum yield of 84.69% and an afterglow time of 1.2 s. Moreover, <strong>CityU-21</strong> can maintain its crystallinity and RTP characters with an afterglow time of up to 0.8 s after immersed in different solvents for 60 hours, which can address the issue that most single crystals of RTP small molecules lose their crystallinity and RTP properties after solvent treatment.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"49 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427006","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":"Silver-mediated formal [4π + 2σ] cycloaddition reactions of bicyclobutanes with nitrile imines: access to 2,3-diazobicyclo[3.1.1]heptenes","authors":"Huijuan Liao, Jianyang Dong, Xuechen Zhou, Qin Jiang, Zishan Lv, Fang Lei, Dong Xue","doi":"10.1039/d4sc08280j","DOIUrl":"https://doi.org/10.1039/d4sc08280j","url":null,"abstract":"Despite recent advances in the synthesis of aza-bicyclo[3.1.1]heptanes (aza-BCHeps, which have an sp<small>³</small>-hybridized nitrogen atom) and azabicyclo[3.1.1]heptenes (aza-BCHepes, which have an sp<small>²</small>-hybridized nitrogen atom), which are bioisosteres of pyridine, construction of 2,3-diazobicyclo[3.1.1]heptenes (2,3-diazo-BCHepes), which have both sp<small>²</small>- and sp<small>³</small>-hybridized nitrogen atoms, has yet to be achieved. Herein, we disclose a method for silver-enabled formal [4π + 2<em>σ</em>] cycloaddition reactions between bicyclobutanes and nitrile imines (generated from hydrazonyl chlorides) to furnish a diverse array of 2,3-diazo-BCHepes, which feature both sp<small>²</small>- and sp<small>³</small>-hybridized nitrogen atoms embedded in a BCHepe framework. These compounds have the potential to serve as bioisosteres of both pyridines and pyridazines. Owing to the presence of the sp<small>³</small>-hybridized nitrogen, 2,3-diazo-BCHepes can be expected to exhibit geometries similar to those of aza-BCHepes and much better solubility. We demonstrated the synthetic utility of our method by carrying out a scaled-up reaction and diverse postcatalytic transformations.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"64 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427013","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":"Single-Molecule-Level Detection of Interfacial Molecular Structures and Ultrafast Dynamics","authors":"Xiaoxuan Zheng, Junjun Tan, Quanbing Pei, Yi Luo, Shuji Ye","doi":"10.1039/d4sc07863b","DOIUrl":"https://doi.org/10.1039/d4sc07863b","url":null,"abstract":"Elucidating the ultrafast dynamics of interfacial molecules at the single-molecule level is pivotal for advancing our understanding of fundamental chemical and biological processes. Here, for the first time, we realized detection of ultrafast vibrational dynamics by a novel technique that integrates femtosecond sum frequency generation vibrational spectroscopy (SFG-VS) with nanoparticle-on-mirror (NPoM) nanocavities (NPoM-SFG-VS). Using a symmetric stretching vibrational mode of para-nitrothiophenol (ν<small>_NO2</small>) as a probe, we have successfully identified signals from self-assembled monolayers (SAMs) comprising ~60 molecules, demonstrating the single-molecule-level sensitivity of the NPoM-SFG-VS. The dephasing time and vibrational relaxation time of ν<small>_NO2</small> at the single-molecule level were determined to be 0.33 ± 0.01 ps and 2.2 ± 0.2 ps, respectively. By controlling the solution concentration used to prepare SAMs (<em>C</em>), a correlation between peak frequency of ν<small>_NO2</small> and localized concentration is established. It was found that single-molecule-level detection was achieved at <em>C</em> ≤ 10<small>^-10</small> M. With this protocol, microregion distribution of interfacial molecule number can be mapped using NPoM-SFG imaging. This work provides insights into the structures and vibrational dynamics of individual interfacial molecules, aiding in precise engineering of surface properties and reactivity.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"2 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427010","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":"Status and Outlook of Solid Electrolyte Membrane Reactors for Energy, Chemical, and Environmental Applications","authors":"Liangdong Fan, Wanying Luo, Qixun Fan, Qicheng Hu, Yifu Jing, Te-Wei Chiu, Peter D Lund","doi":"10.1039/d4sc08300h","DOIUrl":"https://doi.org/10.1039/d4sc08300h","url":null,"abstract":"Solid electrolyte membrane-based reactors (SEMRs) can be operated at super high temperatures with distinct reaction kinetics, or at reduced temperatures (300-500 oC) for industrial-relevant energy applications (such as solid oxide fuel/electrolysis cells, direct carbon fuel cells, and metal–air batteries), chemical (such as alkanes dehydrogenation, C-C coupling, and NH3 synthesis), environmental (De-NOx, CO2 utilization, and separation), as well as their combined (one-step coupled CO2/H2O co-electrolysis and methanation reaction fields, power and chemical cogeneration) applications. SEMRs can efficiently integrate electrical, chemical, and thermal energy sectors, thereby circumventing thermodynamic constraints and production separation issues. They offer a promising way to achieve carbon neutrality and improve chemical manufacturing processes. This review thoroughly examines SEMRs utilizing various ionic conductors, namely O2-, H+, and hybrid types, with operations in different reactor/cell architectures (such as panel, tubular, single chamber, and porous electrolyte). The reactors operate in various modes including pumping, extraction, reversible, or electrical promoting modes, providing multi-functionalities. The discussion extends to the examination of critical materials for solid-state cells and catalysts essential for specific technologically important reactions, focusing on electrochemical performance, conversion efficiency, and selectivity. The review also serves as a first attempt at work that delves into the potential of process-intensified SEMRs through the integration of photo/solar, thermoelectric, and plasma energy and explores the unique phenomenon of electrochemical promotion of catalysis (EPOC) in membrane reactors. The ultimate goal is to offer insight into ongoing critical scientific and technical challenges like durability and operational cost hindering the widespread industrial implementation of SEMRs while exploring the opportunities in this rapidly growing research domain. Although still in its early stages and with limited large-scale demonstration and application, advances in materials, catalysis science, solid-state ionics, and reactor design, as well as process intensification and/or system integration will reduce the gaps in the current high temperature operation of SEMRs and industrial-relevant applications like sustainable clean chemical production, efficient energy conversion/storage, as well as environmental enhancement.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"11 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427008","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}