Chemical Science最新文献_第10页

Identifying the Superatomic AuCu56 Nanocluster through a Ligand-exchange Coupled Metal-exchange Induced Transformation 通过配体交换耦合金属交换诱导转化鉴定超原子AuCu56纳米团簇

IF 8.4 1区化学

Chemical Science Pub Date : 2025-05-28 DOI: 10.1039/d5sc02515j

SANIYA GRATIOUS, Bo Li, Dipanjana Mondal, Dayona Aleyamma Varghese, Alok Kumar, Jibin Thomas, De-En Jiang, Vinayak B. Kamble, Sukhendu Mandal

{"title":"Identifying the Superatomic AuCu56 Nanocluster through a Ligand-exchange Coupled Metal-exchange Induced Transformation","authors":"SANIYA GRATIOUS, Bo Li, Dipanjana Mondal, Dayona Aleyamma Varghese, Alok Kumar, Jibin Thomas, De-En Jiang, Vinayak B. Kamble, Sukhendu Mandal","doi":"10.1039/d5sc02515j","DOIUrl":"https://doi.org/10.1039/d5sc02515j","url":null,"abstract":"Quantum-sized metal nanoclusters can be viewed as superatoms that mimic the electron-shell closing behaviours of atoms, where these electronic shell configurations often govern their properties. Various superatomic nanoclusters with diverse structures and valence states have been identified over the past few years, but the 1S valence state of atomically precise Au nanoclusters have rarely been seen. Herein, we have achieved the synthesis of a 1S1 superatomic [AuCu56S12(SAdm)20(O3SAdm)12] nanocluster from the eight-electron [Au23(S-c-C6H11)16]- nanocluster via a ligand-exchange coupled metal-exchange induced transformation. Detailed studies through mass spectrometry provided insights into the nanocluster formation, and theoretical studies revealed the superatomic nature of the nanocluster. Moreover, the as-synthesized nanocluster exhibited a broad optical absorption, leading to good photocurrent response under UV illumination. This work introduces a novel doping strategy that enables us to realize a rare superatomic valence state in an alloy cluster and to explore its unique light-induced properties.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"2 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144153981","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

Mining Peptides for Mining Solutions: Evaluation of Calcium-Binding Peptides for Rare Earth Element Separations 为采矿溶液挖掘多肽：稀土元素分离中钙结合多肽的评价

IF 8.4 1区化学

Chemical Science Pub Date : 2025-05-28 DOI: 10.1039/d5sc02315g

Farid Farid Khoury, Bradley S. Heater, Daniel R. Marzolf, Sameera S. Abeyrathna, Jonathan W. Picking, Piyush Kumar, Steven A. Higgins, Randy Jones, Alan T. Lewis, Katarzyna H. Kucharzyk, Scott Banta

{"title":"Mining Peptides for Mining Solutions: Evaluation of Calcium-Binding Peptides for Rare Earth Element Separations","authors":"Farid Farid Khoury, Bradley S. Heater, Daniel R. Marzolf, Sameera S. Abeyrathna, Jonathan W. Picking, Piyush Kumar, Steven A. Higgins, Randy Jones, Alan T. Lewis, Katarzyna H. Kucharzyk, Scott Banta","doi":"10.1039/d5sc02315g","DOIUrl":"https://doi.org/10.1039/d5sc02315g","url":null,"abstract":"Rare earth elements (REEs), which include the 15 lanthanides plus scandium and yttrium, are critical components commonly used in permanent magnets and play a significant role in electronics and green energy technologies. Due to the similarities of these ions, conventional separation processes are chemically- and energy-intensive and generate large quantities of waste. The lanthanides share physical and chemical similarities with calcium ions, which allow REEs to replace calcium in calcium-binding peptides and proteins. In this study, we conducted a bioinformatic search to identify calcium-binding peptides with high affinity to bind and separate REEs. Seven unique domains representing different calcium-binding geometries were selected for evaluation. The results revealed a strong correlation between the charge of the binding loop and its affinity for REEs. We concluded that highly charged, aspartic acid-rich loops exhibit greater electrostatic repulsion, which creates higher affinity due to the increased stabilization effect of ion binding. Binding affinity across the lanthanide series was highest for ions with radii similar to that of calcium (~1 Å), consistent with the evolutionary optimization of calcium-binding proteins for selective ion recognition. While selectivity varied among proteins in solution, immobilized proteins demonstrated higher selectivity toward intermediate REEs. One notable candidate identified in the bioinformatic search was HEW5 from Nocardioides zeae. We leveraged the selectivity of HEW5 in a 7 mL column to demonstrate a single-stage, chelator-free separation of an equimolar lanthanum-neodymium mixture, achieving a high purity (>90%) and yield (90%) of REEs. Additionally, immobilized HEW5 was used to remove non-REE ions from a simulated leachate stream and separate lanthanum (>90% purity) from other REEs in a single separation stage.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144153982","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

The contribution of cyclic imide stereoisomers on cereblon-dependent activity 环亚胺立体异构体对小脑依赖活性的贡献

IF 8.4 1区化学

Chemical Science Pub Date : 2025-05-28 DOI: 10.1039/d5sc01371b

Yuka Amako, Saki Ichikawa, Hannah C. Lloyd, N. Connor Payne, Zhi Lin, Andrew S. Boghossian, Matthew G. Rees, Melissa M. Ronan, Jennifer A. Roth, Qian Zhu, Bogdan Budnik, Ralph Mazitschek, Christina M. Woo

{"title":"The contribution of cyclic imide stereoisomers on cereblon-dependent activity","authors":"Yuka Amako, Saki Ichikawa, Hannah C. Lloyd, N. Connor Payne, Zhi Lin, Andrew S. Boghossian, Matthew G. Rees, Melissa M. Ronan, Jennifer A. Roth, Qian Zhu, Bogdan Budnik, Ralph Mazitschek, Christina M. Woo","doi":"10.1039/d5sc01371b","DOIUrl":"https://doi.org/10.1039/d5sc01371b","url":null,"abstract":"Thalidomide, lenalidomide, and their derivatives mimic glutarimide and aspartimide protein modifications that give rise to a motif recognized by the E3 ligase substrate adapter cereblon (CRBN). These cyclic imides have a chiral center that, given the biological significance of chirality, may influence CRBN's function and therapeutic applications. Here, we systematically examine cyclic imides in small molecules, peptides, and proteins to assess their racemization, CRBN engagement, ternary complex formation in vitro, and resulting degradation outcomes in cells. While the thalidomide-binding domain of CRBN consistently favors the (S)-stereoisomer across all cyclic imide small molecule ligands and engineered proteins, we find that, in some cases, the (R)-stereoisomer can bind to CRBN, either enhancing or hindering the eventual target engagement and degradation. Lenalidomide and its derivatives racemize more rapidly (t50%ee = 4–5 h) than the C-terminal cyclic imide under non-enzymatic conditions. These findings highlight that although the (S)-stereoisomer of the cyclic imide is the primary ligand for the thalidomide-binding domain of CRBN, the (R)-stereoisomer, if present, has the potential to contribute to CRBN-dependent cellular activity.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"148 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154185","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

Response of reaction mechanisms to electric-field catalysis on carbon nanotubes in microfluidic reactors 微流控反应器中电场催化对碳纳米管反应机理的响应

IF 8.4 1区化学

Chemical Science Pub Date : 2025-05-28 DOI: 10.1039/d5sc02934a

M. Ángeles Gutiérrez López, Alenka Marsalek, Naomi Sakai, Stefan Matile

引用次数: 0

Photoabsorption of 1-2 nm Molecular Ce-oxo Nanoclusters Versus Ceria: Intervalence Charge Transfer but No Size Effects. 1- 2nm分子铈氧纳米团簇与铈的光吸收：价间电荷转移但无尺寸效应。

IF 8.4 1区化学

Chemical Science Pub Date : 2025-05-28 DOI: 10.1039/d5sc00905g

Sebastian D Pike, Stephen E Brown

{"title":"Photoabsorption of 1-2 nm Molecular Ce-oxo Nanoclusters Versus Ceria: Intervalence Charge Transfer but No Size Effects.","authors":"Sebastian D Pike, Stephen E Brown","doi":"10.1039/d5sc00905g","DOIUrl":"https://doi.org/10.1039/d5sc00905g","url":null,"abstract":"The absorption spectra of a series of Ce-oxo clusters (molecular nanoparticles) with sizes ranging from 3 to 100 Ce atoms per cluster are reported. The O 2p to Ce 4f charge-transfer absorption onset in these systems is unaffected by size and almost identical to that of 5 nm CeO(2-x) particles and other Ce based materials such as the metal organic framework Ce-UiO-66. This clearly demonstrates that in CeO2 based systems, with highly localized 4f LUMO orbitals, quantum confinement effects are not influential on electronic structure. Importantly, this allows the use of ultrasmall ceria particles in (visible light) photochemical applications without detrimental band-gap enlarging size-effects. Changes in colour in CeO2 materials and these Ce-oxo clusters are instead clearly attributed to the presence of (defective) surface sites. Surface Ce(III) sites in mixed-valence clusters contribute a Ce(III)/Ce(IV) intervalence charge transfer transition in the visible region, which affects their colour. Ce24 clusters with a range of aliphatic and aromatic carboxylate ligands are studied, to compare the effect of surface ligands on the electronic structure. Ligand influence on the absorption spectra is only observed when highly conjugated (napthyl) or strongly electron donating substituents (anisole or aniline) are present.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"5 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154188","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

Correction: Exciton and charge transfer processes within singlet fission micelles 修正：单线态裂变胶束中的激子和电荷转移过程

IF 7.6 1区化学

Chemical Science Pub Date : 2025-05-28 DOI: 10.1039/D5SC90113H

Daniel Malinowski, Guiying He, Bernardo Salcido-Santacruz, Kanad Majumder, Junho Kwon, Matthew Y. Sfeir and Luis M. Campos

引用次数: 0

Privileged Metal Cluster Complexes 特权金属集群综合体

IF 8.4 1区化学

Chemical Science Pub Date : 2025-05-27 DOI: 10.1039/d5sc02924d

Shiquan Lin, Dan Li, Dandan Zhang, Lijun Geng, Yuhan Jia, Weizhe Wang, Longjiu Cheng, Shiv N Khanna, Zhixun Luo

{"title":"Privileged Metal Cluster Complexes","authors":"Shiquan Lin, Dan Li, Dandan Zhang, Lijun Geng, Yuhan Jia, Weizhe Wang, Longjiu Cheng, Shiv N Khanna, Zhixun Luo","doi":"10.1039/d5sc02924d","DOIUrl":"https://doi.org/10.1039/d5sc02924d","url":null,"abstract":"Clusters are a prominent subject of interest in modern chemistry research, bridging atoms and materials or catalysts. Metal coordination and metal-metal bonding are crucial in determining the chemical structures and properties of metal clusters; however, formulating a universal principle for assessing their electronic activity remains challenging. Utilizing self-developed mass spectrometry, this study examines the gas-phase reactions of rhodium and platinum clusters with common ligand molecules in forming metal complexes. We find that the Rhn± (n = 1−35) and Ptn± (n = 3−20) clusters readily react with CO and NO to form highly-selective products of cluster complexes. This illustrates the size-dependent saturable effect of sequential coordination, which is rooted in cluster stability alongside concurrent electron delocalization and local bondings. We introduce a new electronic rule, termed the electronic \"Aā\" rule, to understand the adaptive balance of electron delocalization and averaged local bonding in stabilizing metal clusters, whether they are coordinated with ligands or not.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"67 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144145479","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 Pd Superstructures with Superlattices for Solar-Driven Organic Transformation 太阳驱动有机转化用超晶格Pd超结构的精确构建

IF 8.4 1区化学

Chemical Science Pub Date : 2025-05-27 DOI: 10.1039/d5sc01599e

Henglei Jia, Jingzhao Li, Fu-Kuo Chiang, Hao Wang, Fan Li, Zhongqing Lin, Qifeng Ruan, Chun-Yang Zhang

{"title":"Precise Construction of Pd Superstructures with Superlattices for Solar-Driven Organic Transformation","authors":"Henglei Jia, Jingzhao Li, Fu-Kuo Chiang, Hao Wang, Fan Li, Zhongqing Lin, Qifeng Ruan, Chun-Yang Zhang","doi":"10.1039/d5sc01599e","DOIUrl":"https://doi.org/10.1039/d5sc01599e","url":null,"abstract":"Precisely controlling the spatial arrangement of nanostructures offers unique opportunities for tuning physical and chemical properties, however, it remains a great challenge due to the lack of effective synthetic methods. Herein, we present a wet-chemistry strategy for the synthesis of three-dimensional (3D) Pd superstructures (Pd SSs) by manipulating the growth kinetics. The strategy consists of two steps including (1) the formation of tetrahedron-shaped Pd nanocrystal core and (2) the growth of four legs on each tip of the core. Interestingly, each leg can be built from one, two, or three arrowhead-like Pd nanocrystals. Moreover, superlattices that associate with Pd vacancies are extensively present in Pd SSs, providing active sites for reactant molecule adsorption and activation. The Pd SSs exhibit an excellent catalytic performance toward the oxidation of o-phenylenediamine (OPDA) under visible and near-infrared (NIR) light illumination. Both theoretical and experimental results demonstrate that the superior photocatalytic activity of Pd SSs benefits from the well-ordered 3D architecture, unique superlattice properties, high-index facets, and large local electric field enhancement. This research sheds new light on the rational design and precise construction of 3D nanostructures, with potential promising applications in the fields of catalysis, nanotechnology, and biotechnology.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"56 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144145766","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

Interstitial Nitrogen Modified Rh Nanocrystal for Efficient and CO-Resistant Alkaline Hydrogen Oxidation Electrocatalysis 高效抗co碱性氢氧化电催化的间隙氮修饰Rh纳米晶

IF 8.4 1区化学

Chemical Science Pub Date : 2025-05-27 DOI: 10.1039/d5sc02884a

Jianchao Yue, Chaoyi Yang, Yu Zhang, Qianqian Xiong, Wei Luo

引用次数: 0

GlycanInsight: an open platform for carbohydrate-binding pocket prediction and characterization† GlycanInsight：一个用于碳水化合物结合口袋预测和表征的开放平台

IF 7.6 1区化学

Chemical Science Pub Date : 2025-05-27 DOI: 10.1039/D5SC02262B

Qinyu Chu, Xinheng He, Xinyi Tan, Zhiyong Gu, Yin Luo, Zifu Huang, Mingyue Zheng and Xi Cheng

{"title":"GlycanInsight: an open platform for carbohydrate-binding pocket prediction and characterization†","authors":"Qinyu Chu, Xinheng He, Xinyi Tan, Zhiyong Gu, Yin Luo, Zifu Huang, Mingyue Zheng and Xi Cheng","doi":"10.1039/D5SC02262B","DOIUrl":"10.1039/D5SC02262B","url":null,"abstract":"Carbohydrate–protein interactions underlie key physiological and pathological processes, yet identification of glycan-binding sites remains challenging due to the complexity of glycans and a lack of dedicated computational tools. We present GlycanInsight, a deep learning-based open platform that predicts carbohydrate-binding pockets on protein structures. On the benchmark dataset of experimental structures, GlycanInsight achieves a high Matthews correlation coefficient (MCC) of 0.63, outperforming existing tools, and maintains robust performance on AlphaFold2-predicted structures (MCC = 0.53). GlycanInsight clusters predicted residues into three-dimensional carbohydrate-binding pockets for detailed structural inspection, quantitatively analyzes pocket characteristics, searches for other proteins with similar pockets, and suggests putative binding ligands for the predicted pockets. By integrating precise prediction with automated structural annotation and ligand retrieval, GlycanInsight facilitates mechanistic studies and rational design of glycan-targeted therapeutics. The platform is freely accessible at https://www.glycaninsight.cn/.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" 23","pages":" 10264-10272"},"PeriodicalIF":7.6,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/sc/d5sc02262b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144153983","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0