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Committors without Descriptors 没有描述符的提交器
IF 5.5 1区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-11 DOI: 10.1021/acs.jctc.5c01848
Peilin Kang,Jintu Zhang,Enrico Trizio,TingJun Hou,Michele Parrinello
The study of rare events is one of the major challenges in atomistic simulations, and several enhanced sampling methods toward its solution have been proposed. Recently, it has been suggested that the use of the committor, which provides a precise formal description of rare events, could be of use in this context. We have recently followed up on this suggestion and proposed a committor-based method that promotes frequent transitions between the metastable states of the system and allows extensive sampling of the process transition state ensemble. One of the strengths of our approach is being self-consistent and semiautomatic, exploiting a variational criterion to iteratively optimize a neural-network-based parametrization of the committor, which uses a set of physical descriptors as input. Here, we further automate this procedure by combining our previous method with the expressive power of graph neural networks, which can directly process atomic coordinates rather than descriptors. Besides applications on benchmark systems, we highlight the advantages of a graph-based approach in describing the role of solvent molecules in systems, such as ion pair dissociation or ligand binding.
稀有事件的研究是原子模拟的主要挑战之一,已经提出了几种解决稀有事件的增强采样方法。最近,有人建议在这种情况下使用committor,它提供了对罕见事件的精确的正式描述。我们最近跟进了这一建议,并提出了一种基于提交者的方法,该方法促进了系统亚稳态之间的频繁转换,并允许对过程转换状态集合进行广泛的采样。我们方法的优点之一是自一致和半自动,利用变分标准迭代地优化基于神经网络的提交者参数化,它使用一组物理描述符作为输入。在这里,我们通过将我们之前的方法与图神经网络的表达能力相结合,进一步自动化这个过程,图神经网络可以直接处理原子坐标而不是描述符。除了在基准系统上的应用,我们还强调了基于图的方法在描述溶剂分子在系统中的作用方面的优势,例如离子对解离或配体结合。
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引用次数: 0
PEGylated Cross-Linked Amphiphilic Micellar Network for Fouling Release and Antibiofouling Ultrafiltration Membranes 聚乙二醇交联两亲性胶束网络用于污垢释放和抗生素污垢超滤膜
IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-11 DOI: 10.1021/acs.langmuir.5c06220
Arka Biswas,Suresh K. Jewrajka
We report the development of a membrane surface featuring both fouling release and antimicrobial properties, incorporating biocidal and fouling release structural motifs. The ultrafiltration membrane surface is modified by the PEGylated cross-linked micelles of partially alkylated poly(vinyl imidazole) followed by brief solvent evaporation to obtain an interconnected micelles network via intra- and intermicellar cross-linking and alkyl chain entanglement. The resulting PEGylated micellar coating endows the membrane surface with strong antimicrobial and biofilm inhibition activity. The modified membrane (MUF-PEG2k) displays good antifouling/antibiofouling performance during the separation of emulsified oil, protein, and bacteria with flux recovery ratios of 86.6%, 86%, and 93%, respectively, after total 40 h of test. The combined effects of low-surface-energy alkyl and polar hydrophilic PEG chains promote fouling release activity, while quaternized amine groups and lipophilic alkyl segments provide antimicrobial and biofilm inhibition properties. Glass and 96-cell well surfaces are also modified by this process. This strategy offers a platform for engineering robust, multifunctional membrane surfaces toward sustainable separation and biofouling mitigation.
我们报道了一种具有污垢释放和抗菌特性的膜表面的发展,结合了生物杀灭和污垢释放结构基元。通过部分烷基化聚(乙烯基咪唑)的聚乙二醇化交联胶束对超滤膜表面进行修饰,然后进行短暂的溶剂蒸发,通过胶束内和胶束间交联和烷基链缠结获得相互连接的胶束网络。由此产生的聚乙二醇胶束涂层赋予膜表面很强的抗菌和生物膜抑制活性。经过40 h的实验,改性膜(MUF-PEG2k)在乳化油、蛋白质和细菌的分离中表现出良好的防污/抗菌性能,通量回收率分别为86.6%、86%和93%。低表面能烷基和极性亲水性PEG链的联合作用促进污垢释放活性,而季铵化胺基和亲脂性烷基段提供抗菌和生物膜抑制性能。玻璃和96孔井表面也可以通过该工艺进行修饰。该策略为设计坚固、多功能的膜表面提供了一个平台,以实现可持续的分离和生物污染缓解。
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引用次数: 0
Access to Chiral Sulfoxides by Enantioselective Imine Condensation 通过对映选择性亚胺缩合获得手性亚砜
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-11 DOI: 10.1021/acs.orglett.6c00403
Jiong Xu Ng,Gang Liao,Yu Zhao
Chiral sulfoxides are highly important structural motifs that find wide application in asymmetric synthesis and the pharmaceutical industry. While traditional access to chiral sulfoxides mainly relies on asymmetric oxidation of the sulfide center, innovation in catalytic strategy can lead to new and valuable analogs. Herein, we present an unprecedented enantioselective imine condensation approach, resulting in efficient kinetic resolution of sulfoxide molecules bearing an aldehyde functionality with selectivity factor up to >100. Using this chiral acid-catalyzed process with an operationally simple procedure, chiral sulfoxides could be accessed in good yields and excellent enantioselectivities. The resultant chiral sulfoxides could be further transformed via a one-step derivatization to previously inaccessible bifunctional molecules with great potential in asymmetric synthesis.
手性亚砜是一种非常重要的结构基序,在不对称合成和制药工业中有着广泛的应用。虽然传统的手性亚砜主要依赖于硫化物中心的不对称氧化,但催化策略的创新可以产生新的有价值的类似物。在此,我们提出了一种前所未有的对映选择性亚胺缩合方法,导致具有醛基功能的亚砜分子的有效动力学分辨率,选择性因子高达bbb100。该方法操作简单,手性亚砜的产率高,对映选择性好。所得的手性亚砜可以通过一步衍生进一步转化为以前难以获得的双功能分子,具有很大的不对称合成潜力。
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引用次数: 0
Dynamic Anode/Cathode–Electrolyte Interface Induced through Polymer Evolution for Durable Lithium Metal Batteries 聚合物演化诱导的耐用锂金属电池动态阳极/阴极-电解质界面
IF 15 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-11 DOI: 10.1021/jacs.5c18082
Wanru Lin,Kang Zhou,Chao Yang,Huayu Huang,Jian Lan,Hao Peng,Songzhi Zheng,Tianpeng Jiao,Shiwen Wang,Jianming Zheng,Wanwisa Limphirat,Ling Huang,Shi-Gang Sun,Ya-Ping Deng
Fine-tuning the solid–electrolyte interface (SEI) on the Li anode has been widely developed to break through the cyclability bottleneck of Li metal batteries (LMBs). Meanwhile, the cycling behavior of LMBs is also dependent on cathode stability, and hence, it is promising to develop strategies that simultaneously constrain Li dendrite growth and cathode particle distortion. Herein, through copolymerization of maleic anhydride (MA) and hexafluorobutyl acrylate (HFA) monomers, an artificial interface (noted as MAF) is constructed on the Li anode. Such an MAF layer establishes hybrid SEI components consisting of an inorganic-rich interior and a polymer exterior. Its bifunctional contributions on the Li anode and the LiFePO4 (LFP) or LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode are validated by virtue of its dynamic polymer evolution upon LMB cycling. Besides providing lithophilic sites for even Li+ plating, the fluorinated oligomers within the MAF exterior further evolve under an ethylene carbonate (EC)-based electrolyte, inducing dynamic maturation of the LiF-rich cathode–electrolyte interface (CEI). As a result, Li||Li symmetric cells perform for over 900 h of cycling at 1 mA cm–2, while Li||LFP and Li||NCM811 cells maintain capacity retentions of 90.2% after 1500 cycles and 80.6% after 350 cycles at their respective 1 C rate.
为了突破锂金属电池的可循环瓶颈,锂阳极固液界面(SEI)的微调得到了广泛的发展。同时,lmb的循环行为也依赖于阴极稳定性,因此,开发同时抑制Li枝晶生长和阴极颗粒畸变的策略是有希望的。本文通过马来酸酐(MA)和六氟丙烯酸丁酯(HFA)单体的共聚,在锂阳极上构建了一个人工界面(MAF)。这样的MAF层建立了由富无机内部和聚合物外部组成的杂化SEI组分。其在锂阳极和LiFePO4 (LFP)或LiNi0.8Co0.1Mn0.1O2 (NCM811)阴极上的双功能贡献通过其在LMB循环过程中的动态聚合物演化得到验证。除了为均匀的Li+电镀提供亲石位点外,MAF外部的氟化低聚物在基于碳酸乙烯(EC)的电解质下进一步演化,诱导富锂阴极-电解质界面(CEI)的动态成熟。结果表明,Li||Li对称电池在1 mA cm-2下的循环时间超过900小时,而Li||LFP和Li||NCM811电池在各自的1℃速率下,在1500次循环后和350次循环后的容量保持率分别为90.2%和80.6%。
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引用次数: 0
Chaos of Active Site Structure as a Ladder to Climbing the Apex of the 2e–ORR Volcano Plot 活跃场地结构的混沌作为攀爬2orr火山地块顶点的阶梯
IF 15 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-11 DOI: 10.1021/jacs.5c15908
Jiannan Du,Guokang Han,Xin Zhang,Dongyue Xin,Yuqi Yan,Xiaodan Wen,Hua Huo,Geping Yin,Yong Shuai,Chunyu Du
Two-electron oxygen reduction reaction (2e–ORR) in neutral media offers an eco-friendly and practical strategy for efficient synthesis of hydrogen peroxide (H2O2), yet limited understanding of electrocatalytic mechanisms and poor catalyst activity hinder its development. We propose a strategic design principle for high-performance four-coordinated Co single-atom catalysts based on atomic entropy fluctuation by both geometric and electronic modifications, quantitatively described by the descriptor φ, which is able to capture the impact of local entropy fluctuations on catalytic performance. φ serves as an effective metric for elucidating the relationship between ORR activity and the coordination environment in Co single-atom catalyst systems, thereby elucidating the origin of the high activity of CoN3S, which lies close to the apex of the volcano peak. Based on the prediction, the as-synthesized Co–N3SC catalyst achieved a 97% selectivity for H2O2 electrosynthesis at low overpotentials in neutral electrolytes. Impressively, Co–N3SC exhibited remarkable stability and delivered a cumulative yield of 10.58 g of H2O2 in flow cell devices (110 h @0.18A). In a solid-state electrolyte electrolyzer, it achieved a production rate of 10.25 mol gcat–1 h–1, enabling the direct synthesis of high-purity urea peroxide. This work offers not only strategies for designing highly active and selective 2e–ORR catalysts but deep insights into coordination environment–activity regulation and validation of practical catalyst applications.
中性介质中的双电子氧还原反应(2e-ORR)为高效合成过氧化氢(H2O2)提供了一种环保实用的策略,但对电催化机理的了解有限,催化剂活性差,阻碍了其发展。我们提出了一种基于原子熵波动的高性能四配位Co单原子催化剂的策略设计原则,通过几何和电子修饰,用描述符φ定量描述,能够捕捉局部熵波动对催化性能的影响。φ可以作为解释Co单原子催化剂体系中ORR活性与配位环境之间关系的有效度量,从而解释了CoN3S高活性的来源,它位于靠近火山顶点的位置。基于预测,合成的Co-N3SC催化剂在中性电解质中低过电位下电合成H2O2的选择性达到97%。令人印象深刻的是,Co-N3SC表现出了显著的稳定性,在流动电池装置中(110 h @0.18A)累计产H2O2量为10.58 g。在固态电解质电解槽中,其产率达到10.25 mol gcat-1 h-1,可直接合成高纯度过氧化脲。这项工作不仅为设计高活性和选择性的2 - orr催化剂提供了策略,而且为协调环境-活性调节和实际催化剂应用的验证提供了深刻的见解。
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引用次数: 0
Development of Prostate-Specific Lysosome-Targeting Degraders 前列腺特异性溶酶体靶向降解物的研究进展
IF 15 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-11 DOI: 10.1021/jacs.5c18594
Deqin Cai,Xuankun Chen,Yaxian Zhou,Malick Bio Idrissou,Reinier Hernandez,Weiping Tang
Targeted protein degradation (TPD) technologies have emerged as transformative therapeutic modality for treating cancers and other diseases. While significant progress has been achieved in intracellular protein degradation, degradation of membrane proteins and extracellular targets remains in an early stage. In this study, we developed a prostate-specific lysosome-targeting degradation strategy using a prostate-specific membrane antigen (PSMA) as a lysosome-targeting receptor (LTR). We demonstrated that both extracellular and membrane proteins can be selectively degraded in prostate cancer cells via the lysosome pathway. These PSMA TArgeting Chimeras (PTACs) were shown to facilitate lysosomal degradation in a selective, potent, rapid, and sustained manner. Notably, Ctx-L3 and Atz-L5 exhibited exceptional degradation potencies in LNCaP cells, with DC50 values of 4.3 pM for EGFR and 2 pM for PD-L1, respectively─among the most potent degraders reported to date. Furthermore, the application of PTACs to degrade PD-L1, using both antibody- and small-molecule-based formats, highlights the versatility of this platform. Collectively, this work advances the application of TPD technology and offers promising avenues for precision medicine in prostate-related diseases.
靶向蛋白降解(TPD)技术已成为治疗癌症和其他疾病的变革性治疗方式。虽然在细胞内蛋白降解方面取得了重大进展,但膜蛋白和细胞外靶点的降解仍处于早期阶段。在这项研究中,我们开发了一种前列腺特异性溶酶体靶向降解策略,使用前列腺特异性膜抗原(PSMA)作为溶酶体靶向受体(LTR)。我们证明了细胞外蛋白和膜蛋白都可以通过溶酶体途径在前列腺癌细胞中选择性地降解。这些PSMA靶向嵌合体(PTACs)被证明以选择性、有效、快速和持续的方式促进溶酶体降解。值得注意的是,Ctx-L3和Atz-L5在LNCaP细胞中表现出异常的降解能力,EGFR和PD-L1的DC50值分别为4.3 pM和2 pM,是迄今为止报道的最有效的降解物。此外,利用基于抗体和小分子的形式,PTACs降解PD-L1的应用凸显了该平台的多功能性。总之,这项工作推进了TPD技术的应用,为前列腺相关疾病的精准医学提供了有希望的途径。
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引用次数: 0
Multidimensional design of silicon anode binders: from molecular interactions to macroscopic functionality 硅阳极粘结剂的多维设计:从分子相互作用到宏观功能
IF 20.6 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-02-11 DOI: 10.1016/j.ccr.2026.217686
Siqi Zhu, Panpan Li, Tongyu He, Xuanxuan Fu, Hu Tian, Yuan Du, Yongxin Wang, Kangning Li, Buyin Shi, Xiaojiao Yang, Xiaofei Lou, Kunyu Lv, Hui Zhang
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引用次数: 0
Organic frameworks-based optical sensors for uranyl ions: Unveiling mechanisms and applications 基于有机框架的铀酰离子光学传感器:揭示机制和应用
IF 20.6 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-02-11 DOI: 10.1016/j.ccr.2026.217685
Chengze Song, Hongbo Gou, Yapeng Huo, Kai Li, Qiyang Gu, Jiaqi He, Sha Liu
{"title":"Organic frameworks-based optical sensors for uranyl ions: Unveiling mechanisms and applications","authors":"Chengze Song, Hongbo Gou, Yapeng Huo, Kai Li, Qiyang Gu, Jiaqi He, Sha Liu","doi":"10.1016/j.ccr.2026.217685","DOIUrl":"https://doi.org/10.1016/j.ccr.2026.217685","url":null,"abstract":"","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"99 1","pages":""},"PeriodicalIF":20.6,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146153138","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
Dual-mode PEF/SERS detection of Riboflavin based on TA-AuNSF/AgNS@PVA plasmonic hybridized substrate 基于TA-AuNSF/AgNS@PVA等离子体杂交底物的核黄素双模PEF/SERS检测
IF 8.4 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-11 DOI: 10.1016/j.snb.2026.139647
Ziheng Song, Wenxuan Liu, Wenjie Hu, Yingying Deng, Meiqin Ni, Yingdong Han, Qingru Wang, Dong Zhang
{"title":"Dual-mode PEF/SERS detection of Riboflavin based on TA-AuNSF/AgNS@PVA plasmonic hybridized substrate","authors":"Ziheng Song, Wenxuan Liu, Wenjie Hu, Yingying Deng, Meiqin Ni, Yingdong Han, Qingru Wang, Dong Zhang","doi":"10.1016/j.snb.2026.139647","DOIUrl":"https://doi.org/10.1016/j.snb.2026.139647","url":null,"abstract":"","PeriodicalId":425,"journal":{"name":"Sensors and Actuators B: Chemical","volume":"99 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146153226","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
Contra-electronegativity transmetallation unlocks alkene carbomagnesiation to access quaternary stereocentres 反电负性金属转化使烯烃碳镁化反应进入季立体中心
IF 21.8 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-11 DOI: 10.1038/s41557-026-02073-1
Xiaodong Ye, Bo Sun, Shi-Liang Shi
Grignard reagents—cornerstones of synthetic chemistry—are hindered by enduring limitations in accessing complex architectures, which poses a persistent synthetic bottleneck. Meanwhile, quaternary carbon (stereo)centres, ubiquitous in bioactive molecules and natural products, remain formidable synthetic targets despite decades of research. Here we introduce a nickel-catalysed carbomagnesiation strategy that simultaneously overcomes these challenges through a rare contra-electronegativity transmetallation (Ni to Mg). This approach enables the efficient and modular synthesis of β-quaternary Grignard reagents via carbomagnesiation of 1,1-disubstituted alkenes and 1,3-dienes, employing aryl triflate and PhMgBr as carbon and magnesium sources, respectively. The resulting organomagnesium reagents undergo one-pot reactions with diverse electrophiles, delivering stereochemically complex quaternary centres with high precision. Mechanistically, bulky N-heterocyclic carbene (NHC)-based catalysts divert classical cross-coupling pathways, enforcing a counterintuitive Ni-to-Mg transmetallation that defies conventional electronegativity trends while achieving exceptional regio- and enantiocontrol. This contra-electronegativity transmetallation demonstrates substantial potential to advance carbometallation reactions and open new avenues for cross-coupling chemistry.
格氏试剂——合成化学的基石——在获取复杂结构方面受到了持久的限制,这构成了一个持续的合成瓶颈。与此同时,在生物活性分子和天然产物中无处不在的季碳(立体)中心,尽管经过了几十年的研究,仍然是令人生畏的合成目标。在这里,我们介绍了一种镍催化的碳镁化策略,通过一种罕见的反电负性金属转化(Ni到Mg),同时克服了这些挑战。该方法采用三氟化芳基和PhMgBr分别作为碳源和镁源,通过碳镁化1,1-二取代烯烃和1,3-二烯,实现了β-季格氏试剂的高效模块化合成。所得的有机镁试剂与不同的亲电试剂进行一锅反应,以高精度提供立体化学复杂的四元中心。从机理上说,体积庞大的n -杂环碳(NHC)基催化剂改变了经典的交叉偶联途径,实现了违反直觉的Ni-to-Mg金属化,这违背了传统的电负性趋势,同时实现了特殊的区域和对映体控制。这种反电负性金属转化在推进碳金属化反应和开辟交叉偶联化学的新途径方面显示出巨大的潜力。
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引用次数: 0
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