Chemical Science最新文献_第8页

High-Throughput Electronic Property Prediction of Cyclic Molecules with 3D-Enhanced Machine Learning 基于3d增强机器学习的循环分子高通量电子性质预测

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-02 DOI: 10.1039/d5sc04079e

Peikun Zheng, Olexandr Isayev

{"title":"High-Throughput Electronic Property Prediction of Cyclic Molecules with 3D-Enhanced Machine Learning","authors":"Peikun Zheng, Olexandr Isayev","doi":"10.1039/d5sc04079e","DOIUrl":"https://doi.org/10.1039/d5sc04079e","url":null,"abstract":"Complex organic molecules play a pivotal role in bioactive compounds and organic functional materials, yet existing molecular datasets lack structural diversity for such systems, limiting the generalizability of machine learning (ML) models. This study introduces a high-quality dataset, Ring Vault, comprising 201,546 cyclic molecules, including monocyclic, bicyclic, and tricyclic systems, spanning 11 non-metallic elements. This dataset covers a wide chemical space and provides a robust foundation for molecular property prediction. Leveraging quantum mechanical (QM) calculations on a subset (36,000 molecules), we trained three ML models (Graph Attention Network, Chemprop, and AIMNet2) to predict five key electronic properties: HOMO-LUMO gap, ionization potential (IP), electron affinity (EA), and redox potentials (Eox, Ered). The fine-tuned AIMNet2 model, incorporating 3D conformational information, outperformed 2D-based models, achieving R² values exceeding 0.95 and reducing mean absolute errors (MAEs) by over 30%. Principal component analysis (PCA) of AIMNet2 embeddings revealed intrinsic correlations between electronic properties and structural features, such as conjugation extent and functional group effects. This work establishes a robust framework for high-throughput screening and rational design of cyclic molecules, with applications spanning drug discovery, organic electronics, and energy materials. The dataset and methodology provide a foundation for exploring complex structure-property relationships and accelerating functional molecule discovery.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"94 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209876","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

Unveilling photoinduced electron transfers in photosensitized polyoxometalates for solar energy conversion. 揭示光敏多金属氧酸盐中用于太阳能转换的光诱导电子转移。

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-02 DOI: 10.1039/d5sc04351d

Christian Cariño, Anna Proust, Geoffroy Guillemot, Ludivine K/Bidi, Sébastien Blanchard, Elizabeth Gibson, Guillaume Izzet

{"title":"Unveilling photoinduced electron transfers in photosensitized polyoxometalates for solar energy conversion.","authors":"Christian Cariño, Anna Proust, Geoffroy Guillemot, Ludivine K/Bidi, Sébastien Blanchard, Elizabeth Gibson, Guillaume Izzet","doi":"10.1039/d5sc04351d","DOIUrl":"https://doi.org/10.1039/d5sc04351d","url":null,"abstract":"Artificial photosynthesis faces the challenge of developing visible-light-driven strategies for converting and storing solar energy in the form of fuels and high-value chemicals. In such an approach, selective fuel production often depends on the accumulation of multiple electrons at a catalytic site. However, this process is constrained by the rapid recombination of photogenerated charges and the inherently slow kinetics of multi-electron catalytic reactions, which hinder efficient charge buildup and utilization. Polyoxometalates (POMs), a tunable class of nanoscale metal oxides, have emerged as promising multi-electron acceptors due to their redox versatility and stability. Their electron storage capabilities make them attractive as both reservoirs and catalysts. In most cases, their UV-limited absorption necessitates pairing of the POM with visible-light-absorbing antennas. Advances in photosensitized POM derivatives —via electrostatic assembly, covalent bonding, or band-gap engineering—are herein detailed. Covalent hybrids, in particular, allow precise control over electron transfer. Still, a detailed understanding of photoinduced electron transfer kinetics remains limited. This Perspective article explores the potentials of POMs in solar fuel generation, emphasizing the need for kinetic insight to design efficient, visible-light-driven photocatalysts and photoelectrochemical devices.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"91 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203590","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

A Photochemical Strategy for Aromatic Nitrogen ortho- Isomerization 芳香族氮邻位异构化的光化学策略

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-02 DOI: 10.1039/d5sc05329c

Alessandro Ruffoni, Daniele Leonori, Giovanni Lenardon, Xheila Yzeiri, Gael Le Berre, Dilara Berna Yildiz

引用次数: 0

A reflection on ketoABNO: the crossing point between organic synthesis and protein modification 酮abno：有机合成与蛋白质修饰的交叉点

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-02 DOI: 10.1039/d5sc90203g

Moe Toyobe, Motomu Kanai

引用次数: 0

Multi-region mapping of ligand binding and structural changes in the β-1 adrenergic receptor using carbene footprinting and mass spectrometry 利用碳足迹和质谱技术对β-1肾上腺素能受体的配体结合和结构变化进行多区域定位

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-01 DOI: 10.1039/d5sc05107j

James Lloyd, Arppana Sara Varughese, Parth Kapoor, Katharina Duerr, Hsin-Yung Yen, Ali Jazayeri, Jonathan Hopper, Neil J Oldham

引用次数: 0

Cerium-mediated site-selective cysteine functionalization 铈介导的选择性半胱氨酸功能化

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-01 DOI: 10.1039/d5sc04538j

Jaewon Lee, Woon Ju Song

引用次数: 0

Elucidating the reaction kernel and probing the effect of anharmonicity in the ring-closing reaction of fulgide single crystals 阐明了反应核，探讨了不调和性对氟化物单晶合环反应的影响

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-01 DOI: 10.1039/d5sc03764f

Soumyajit Mitra, Ming Zhang, Simon Felix Bittmann, Jianxin Cai, Xiaolong Dong, R. Scott Murphy, Zheng Li, D. Miller

{"title":"Elucidating the reaction kernel and probing the effect of anharmonicity in the ring-closing reaction of fulgide single crystals","authors":"Soumyajit Mitra, Ming Zhang, Simon Felix Bittmann, Jianxin Cai, Xiaolong Dong, R. Scott Murphy, Zheng Li, D. Miller","doi":"10.1039/d5sc03764f","DOIUrl":"https://doi.org/10.1039/d5sc03764f","url":null,"abstract":"Chemistry involves dynamics that transform chemical structures from one form to another. However, among the vast milieu of quantum vibrations in a molecule, it boils down to a few key motions that drive the system across the transition state. It is the anharmonicity at the transition state or barrier-crossing region that couples normal modes, leading to localized motions and reduced dimensionality. The interplay of strongly anharmonic local modes collectively drives the system across the barrier-crossing region. Ultrafast broadband transient absorption spectroscopy has observed the effect of reduced dimensionality in a prototypical ring-closing reaction in fulgide single crystals. The relatively large anharmonicity at the reactive crossing and the strong reaction forces experienced during the chemical transformation provide a significant driving force for the vibrational modes, revealing a new mechanism of coherent vibrational energy transfer between molecular modes. This effect is observed as a non-impulsive growth of modulation amplitude of an 80 cm-1 mode coupled to the reaction coordinate. Our study sheds light on the lattice-coupled reaction dynamics owing to specific system-bath interactions and provides new insight into utilizing lattice alignment for chemical transformation in a solid-state crystalline environment.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"45 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195316","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

AI-driven rational design of promiscuous and selective plastic-binding peptides 人工智能驱动的混杂和选择性塑料结合肽的合理设计

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-01 DOI: 10.1039/d5sc04903b

Vinamr Jain, Michael T. Bergman, Carol K. Hall, Fengqi You

{"title":"AI-driven rational design of promiscuous and selective plastic-binding peptides","authors":"Vinamr Jain, Michael T. Bergman, Carol K. Hall, Fengqi You","doi":"10.1039/d5sc04903b","DOIUrl":"https://doi.org/10.1039/d5sc04903b","url":null,"abstract":"Microplastic pollution is challenging to remediate due to the small size and heterogeneous composition of microplastic particles. Remediation efforts would benefit from tools that either bind to the many components of microplastic pollution (promiscuous binding) to facilitate quantitation and capture, or bind to certain components of pollution (selective binding) to facilitate separation or degradation. Such a role could be filled by polypeptides, which can bind selectively or promiscuously to biomolecules or materials. While methods exist to design plastic-binding peptides (PBPs) for a single plastic, the design of promiscuous plastic-binding peptides has received scant attention, and there are no methods to design selective plastic-binding peptides. Here, we present a minimalist yet high-performing framework integrating Long Short-Term Memory (LSTM) models with simulated annealing (SA) to design promiscuous plastic-binding or selective plastic-binding peptides. Our approach learns sequence–function relationships governing peptide affinity for different plastics from PepBD data, a biophysical modeling program. The learned relationship enables rapid design of peptides with tailored binding properties for arbitrary combinations of plastics. We use our LSTM-SA framework to engineer (1) promiscuous plastic-binding peptides with affinity for five plastics (polyethylene, polypropylene, PET, polyvinyl chloride, and nylon), and (2) selective plastic-binding peptides that bind preferentially to one plastic (polypropylene) over another (PET). Notably, the promiscuous plastic-binding peptides are the first reported designs intended to bind to nylon and PVC. Molecular dynamics simulations validate that our designed peptides exhibit the predicted binding behaviors, where high affinity is linked to strong van der Waals interactions. The framework's modularity can be readily adapted to optimize peptide selectivity or promiscuity for different combinations of plastics. More broadly, the architecture may be useful for designing peptides that bind to other solid materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195320","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

Photoactivable Ru(II) Polypyridyl Complexes as Dual Action Modulators of Amyloid-Beta Peptide Aggregation and Cu Redox Cycling 光活化Ru（II）多吡啶配合物作为淀粉样蛋白- β肽聚集和Cu氧化还原循环的双作用调节剂

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-01 DOI: 10.1039/d5sc05593h

Grace Leech, Alfredo Lopez Acosta, Samyadeb Mahato, Patrick C. Barrett, Rachel O Hodges, Sherri Ann McFarland, Tim Storr

{"title":"Photoactivable Ru(II) Polypyridyl Complexes as Dual Action Modulators of Amyloid-Beta Peptide Aggregation and Cu Redox Cycling","authors":"Grace Leech, Alfredo Lopez Acosta, Samyadeb Mahato, Patrick C. Barrett, Rachel O Hodges, Sherri Ann McFarland, Tim Storr","doi":"10.1039/d5sc05593h","DOIUrl":"https://doi.org/10.1039/d5sc05593h","url":null,"abstract":"The misfolding and aggregation of the amyloid-β (Aβ) peptide is a major hallmark of Alzheimer's disease (AD), yet therapeutic strategies targeting this process have faced long-standing challenges related to efficacy and specificity. Here, we investigate two photoactivatable Ru(II) polypyridyl complexes (RuP) that operate as dual-action modulators of AD pathology by addressing both Aβ aggregation and Cu-Aβ associated ROS generation. The RuP complexes contain an extended planar imidazo[4,5-f] [1,10]phenanthroline ligand, which is important for pre-association with the Aβ peptide via hydrophobic and π-π interactions, as well as sterically hindered ligands 6,6'-dimethyl-2,2'-bipyridyl (6,6′-dmb) for RuP1 and 2,9-dimethyl-1,10-phenanthroline (2,9-dmp) for RuP2, which cause steric strain at the metal center. Photoactivation of the RuP complexes results in loss of either a 6,6′-dmb or 2,9-dmp ligand exposing cis-exchangeable coordination sites for binding to the Aβ peptide, which immediately redirects the Aβ peptide away from its β-sheet-rich fibrillization pathway, promoting the formation of amorphous, off-pathway aggregates that exhibit increased sensitivity to proteolytic degradation. We find that the photoactivated RuP complexes are closely associated with the amorphous aggregates, and that this is a common endpoint regardless of Aβ peptide aggregation state (monomer, oligomer, or fibril). Importantly, we show that the ejected ligands also inhibit the redox cycling and ROS generation of Cu-Aβ species. Together, these results highlight the potential of photoactivatable RuP complexes as multifunctional therapeutic candidates, offering a rational approach to intercepting Aβ aggregation and Cu-mediated oxidative stress, and advancing the design of light-responsive treatments for neurodegenerative diseases.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"31 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203644","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 homocoupling of allenylic alcohols through divergent cooperative catalysis 通过发散协同催化的烯醇对映选择性均偶联

IF 8.4 1区化学

Chemical Science Pub Date : 2025-09-30 DOI: 10.1039/d5sc02831k

Aditya Chakrabarty, Ritwika Chatterjee, Santanu Mukherjee

{"title":"Enantioselective homocoupling of allenylic alcohols through divergent cooperative catalysis","authors":"Aditya Chakrabarty, Ritwika Chatterjee, Santanu Mukherjee","doi":"10.1039/d5sc02831k","DOIUrl":"https://doi.org/10.1039/d5sc02831k","url":null,"abstract":"An enantioselective homocoupling of branched allenylic alcohols is developed under cooperative iridium and Lewis acid catalysis. In this reaction, racemic allenylic alcohol is transformed, under Lewis acidic Sc(OTf)3, into an alpha,beta-unsaturated enol (cross dienol) through a Meyer-Schuster-type 1,3-hydroxy transposition. In an independent cycle, catalyzed by a combination of an Ir(I)/(phosphoramidite,olefin) complex and Sc(OTf)3, allenylic alcohol is proposed to produce an η2-Ir(I)-bound allenylic carbocation intermediate, which is intercepted by the in situ generated cross dienol. Overall, starting from racemic branched allenylic alcohols, α′-allenylic alpha,beta-unsaturated ketones are produced, without using any preformed carbon nucleophile, in moderate to good yields with excellent enantioselectivities. This strategy may be termed as divergent cooperative catalysis, where a single substrate is converted into two transient intermediates of complementary polarity under the influence of two different catalysts. The selective coupling of these two polarity-matched intermediates results in the desired product. Mechanistic details are unraveled through experimental studies and density functional theory (DFT) calculations.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"17 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189246","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