Chemical Science最新文献

{"title":"Interplay between conformational dynamics and substrate binding regulates enzymatic activity: a single-molecule FRET study","authors":"David Scheerer, Dorit Levy, Remi Casier, Inbal Riven, Hisham Mazal, Gilad Haran","doi":"10.1039/d4sc06819j","DOIUrl":"https://doi.org/10.1039/d4sc06819j","url":null,"abstract":"Proteins often harness extensive motions of domains and subunits to promote their function. Deciphering how these movements impact activity is key for understanding life’s molecular machinery. The enzyme adenylate kinase is an intriguing example for this relationship; it ensures efficient catalysis by large-scale domain motions that lead to the enclosure of the bound substrates ATP and AMP. Surprisingly, the enzyme is activated by urea, a compound commonly acting as a denaturant. We utilize this phenomenon to decipher the involvement of conformational dynamics in the mechanism of action of the enzyme. Combining single-molecule FRET spectroscopy and enzymatic activity studies, we find that urea promotes the open conformation of the enzyme, aiding the proper positioning of the substrates. Further, urea decreases AMP affinity, paradoxically facilitating a more efficient progression towards the catalytically active complex. These results allow us to define a complete kinetic scheme that includes the open/close transitions of the enzyme and to unravel the important interplay between conformational dynamics and chemical steps, a general property of enzymes. State-of-the-art tools, such as single-molecule fluorescence spectroscopy, offer new insights into how enzymes balance different conformations to regulate activity.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"22 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020353","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":"Photo-Crosslinking of Doped Magic-size Nanocluster for the Construction of Enhanced Electrochemiluminescence Biosensors","authors":"Junjun Ge, tengyue yin, Haoyang Zhang, Yue Cao, Juan Liu, Jun-Jie Zhu, Yang Zhou, Yuanyuan Wang","doi":"10.1039/d4sc07800d","DOIUrl":"https://doi.org/10.1039/d4sc07800d","url":null,"abstract":"Semiconductor magic-size nanoclusters (MSCs) possess atomic-level compositional precision and ultrasmall dimensions, allowing accurate modulation of electrochemiluminescence (ECL) properties, essential for advanced bioanalytical applications. However, low intrinsic ECL intensity and poor stability in bipolar electrode (BPE)-ECL systems hinder their broader use. In this work, we addressed these limitations through doping and direct optical crosslinking strategies, achieving a 24-fold boost in ECL signal and a fivefold stability increase for doped (CdS)34:Ag MSCs compared with original (CdS)34 MSCs . The resulting BPE-ECL biosensing platform was used for the sensitive detection of glucose with a linear detection range of 10 μM to 1 mM and a detection limit of 3.64 μM. This approach provides a robust strategy to enhance MSC-based ECL biosensing, paving the way for ultrasensitive, stable biosensors for clinical diagnostics and bioanalysis.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"11 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020344","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":"Metal-Ligand Cooperativity Enables Zero-Valent Metal Transfer","authors":"Martin Riu, Jing-Ran Shan, K. N. Houk, Matthew Nava","doi":"10.1039/d4sc07938h","DOIUrl":"https://doi.org/10.1039/d4sc07938h","url":null,"abstract":"Group 13 TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl) complexes of the form (L)E(TEMPO)<small>₃</small> (L=THF (tetrahydrofuran) or Py (pyridine); E = Al, Ga, In) were prepared and structurally characterized. The complexes (THF)Ga(TEMPO)<small>₃</small> (<strong>1</strong>·THF) and (Py)In(TEMPO)<small>₃</small> (<strong>2</strong>·Py) are shown to heterolytically cleave H<small>₂</small> under mild conditions (3 atm, 20 ◦C, t ≤ 1 h). <strong>1</strong>·THF reacts reversibly with H<small>₂</small> to form a formal H<small>₂</small>-adduct that bears a Ga(III) hydride center and a protonated TEMPO ligand with concomitant loss of THF, consistent with Ga(III) and TEMPO functioning as Lewis acid and base, respectively. Conversely, <strong>2</strong>·Py is reduced by H<small>₂</small> to form an intermediate dimer complex of monovalent {In(TEMPO)}<small>₂</small>, which undergoes further reactivity with H<small>₂</small> to form elemental indium as determined by powder X-ray diffraction. Treatment of <strong>2</strong>·Py with H<small>₂</small> and Ph<small>₃</small>PSe forms binary InSe, in addition to Ph<small>₃</small>P and TEMPOH, demonstrating that <strong>2</strong>·Py functions as a molecular source of zerovalent indium under mildly reducing conditions. Computational studies support an intramolecular metal-ligand cooperativity pathway in the heterolytic cleavage of H<small>₂</small>.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"29 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020823","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":"Rapid access to functionalized nanographenes through a palladium-catalyzed multi-annulation sequence","authors":"Takehisa Maekawa, Kenichiro Itami","doi":"10.1039/d4sc07995g","DOIUrl":"https://doi.org/10.1039/d4sc07995g","url":null,"abstract":"Nanographenes and polycyclic aromatic hydrocarbons exhibit many intriguing physical properties and have potential applications across a range of scientific fields, including electronics, catalysis, and biomedicine. To accelerate the development of such applications, efficient and reliable methods for accessing functionalized analogs are required. Herein, we report the efficient synthesis of functionalized small nanographenes from readily available iodobiaryl and diarylacetylene derivatives <em>via</em> a one-pot, multi-annulation sequence catalyzed by a single palladium catalyst. This method enables the preparation of small nanographenes bearing various polar functional groups, such as hydroxy, amino, and pyridinic nitrogen atoms, which are otherwise difficult to incorporate. These functional groups provide valuable sites for further derivatization, allowing the modulation of small nanographenes' solubility, optoelectronic properties, and photochromic and vapochromic behaviors. Our new method thus provides a platform for facile access to novel carbon-based materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"84 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990974","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":"Enhancing Organic Cathodes of Aqueous Zinc-Ion Batteries via Nitro Group Modification","authors":"Donghong Wang, Mengxuan Qin, Changyou Zhang, Mengxue Li, Chao Peng, Chunyi Zhi, Qing Li, Lei Zhu","doi":"10.1039/d4sc08514k","DOIUrl":"https://doi.org/10.1039/d4sc08514k","url":null,"abstract":"Organic compounds present promising options for sustainable zinc battery electrodes. Nevertheless, the electrochemical properties of current organic electrodes still lag behind those of their inorganic counterparts. In this study, nitro groups were incorporated into pyrene-4, 5, 9, 10-tetraone (PTO), resulting in an elevated discharge voltage due to their strong electron-withdrawing capabilities. Additionally, a novel electrochemical conversion of nitro to azo groups was observed in aqueous electrolytes. This transformation can be leveraged to enhance cycling stability, especially at low current densities. The electrochemical process of nitro-PTO during discharge comprises three distinct steps. Initially, two stages of H+/Zn2+ coordination to the carbonyl groups led to a high capacity of ~284 mAh g−1 above 0.80 V—significantly higher than that of PTO. Further discharge irreversibly transformed -NO2 groups into N=N bonds, resulting in exceptionally high specific capacities of approximately 695 mAh g−1 and 905 mAh g−1 for PTO decorated with single and double -NO2 groups, respectively. As -NO2 was continuously reduced to N=N, the resultant azo-conjugated PTO (PTO-Azo) demonstrated reversible H+/Zn2+ co-storage and release during subsequent charge/discharge cycles, with improved capacity retention and higher kinetics. This work, therefore, elucidates the impact of nitro group chemistry on the electrochemical performance of carbonyl-rich organic electrodes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"102 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990973","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":"Synthesis of Precisely Functionalized Nano-confinement: a Bottom-up Approach to the Evolution of Selective Molecular Receptors","authors":"Ya-Mei Tan, Lu-Mei Zhang, Qixia Bai, Zhe Zhang, Pingshan Wang, Qi Zhang","doi":"10.1039/d4sc08176e","DOIUrl":"https://doi.org/10.1039/d4sc08176e","url":null,"abstract":"<strong>Abstract</strong>: Precise molecular recognition depends on the delicate interplay between a guest molecule and a host possessing complementary functional groups. De novo design of selective artificial receptors remains a formidable challenge, given the complexity of predicting these interactions. We present herein a bottom-up approach to the evolution of selective molecular receptor through precise endo-functionalization of a supramolecular cage. Internal functional groups were introduced within the heteroleptic palladium coordination cage in a site-precise fashion. With just five different functional groups, we successfully created a library of 32 isoreticular nano-cages, each featuring unique micro-environments, by varying the nature, location and combination of endo-functional groups. The nano-cage exhibited adaptive recognition ability towards guest molecules of distinct geometries and hydrogen bonding capabilities. Titration experiments demonstrated that the binding affinity for a specific guest can be finely tuned and optimized by changing the endo-functional groups. As a proof of principle, by strategically screening our nano-cage library, we identified a receptor with high affinity and specificity for the dihydrogen phosphate guest. X-ray analysis and DFT calculation highlighted the pivotal role of the synergistic interactions among distinct endo-functional groups in achieving high-fidelity molecular recognition. This study is expected to provide a versatile solution for the bottom-up construction of tailor-made molecular receptors.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"198 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990193","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":"Surface immobilization of single atoms on heteroatom-doped carbon nanospheres through phenolic-mediated interfacial anchoring for highly efficient biocatalysis","authors":"Yajing Zhang, Yunxiang He, Yun Jiao, Guobin Yang, Yiran Pu, Zhangmin Wan, Shuyun Li, Yan-Chao Wu, Wen Liao, Junling Guo","doi":"10.1039/d4sc07775j","DOIUrl":"https://doi.org/10.1039/d4sc07775j","url":null,"abstract":"Single-atom catalysts (SACs) dispersed on support materials exhibit exceptional catalytic properties that can be fine-tuned through interactions between the single atoms and the support. However, selectively controlling the spatial location of single metal atoms while simultaneously harmonizing their coordination environment remains a significant challenge. Here, we present a phenolic-mediated interfacial anchoring (PIA) strategy to prepare SACs with Fe single atoms anchored on the surface of heteroatom-doped carbon nanospheres. Briefly, by exploiting the metal-phenolic networks (MPNs) for the surface coating and phloroglucinol-induced polymerization for the support precursor formation, we successfully anchored Fe single atoms at the interface between the MPN layer and the support surface. Moreover, this anchoring strategy effectively prevents Fe species from clustering or migrating toward the interior of the support during thermal treatment, resulting in atomically dispersed FeN<small>₃</small>P-SAC exhibits a high metallic utilization efficiency and comparable peroxidase-like catalytic activity and kinetics to natural enzymes. As a proof-of-concept demonstration, FeN<small>₃</small>P-SAC could effectively block the growth of tumor cells in vitro by combining excellent tumor penetration and the ability to activate chemodynamic and photothermal effects synergistically. This work advances the development of highly active SACs with MPN-based nanotechnology, providing a promising approach for nanocatalytic tumor therapy.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"20 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990197","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":"Rational pore engineering reveals the relative contribution of enzymatic sites and self-assembly towards rapid ferroxidase activity and mineralization: Impact of electrostatic guiding and cage-confinement in bacterioferritin","authors":"Akankshika Parida, Gargee Bhattacharyya, Swagatika Mallik, Rabindra K Behera","doi":"10.1039/d4sc07021f","DOIUrl":"https://doi.org/10.1039/d4sc07021f","url":null,"abstract":"The self-assembled ferritin protein nanocage plays a pivotal role during oxidative stress, iron metabolism, and host-pathogen interaction by executing rapid iron uptake, oxidation and its safe-storage. Self-assembly creates a nanocompartment and various pores/channels for the uptake of charged substrates (Fe2+) and develops a concentration gradient across the protein shell. This phenomenon fuels the rapid ferroxidase activity by an upsurge in the substrate concentration at the catalytic sites. However, it is difficult to segregate the relative contribution of the catalytic sites and self-assembly towards rapid ferroxidase/mineralization activity owing to the inherent self-assembly propensity of ferritins. In the current work, 3-fold pore electrostatics of bacterioferritin from Mycobacterium tuberculosis was rationally altered by site-directed mutagenesis to generate self-assembled (E121A, E121Q) and assembly-defective (E121K, E121F) variants. In comparison to autoxidation of Fe2+ in buffer, the assembly-defective variants exhibited a significantly faster ferroxidase/mineralization activity and O2 consumption kinetics due to their functional catalytic sites, but failed to level-up with the self-assembled variants even at 100-fold higher Fe2+ concentration. Only the self-assembled variants exhibited cooperativity in iron oxidation, maintained biomineral solubility, and protected DNA against Fenton reaction. This report highlights the concerted effect of self-assembly and ferroxidase sites that propels the rapid Fe2+ uptake, its oxidation and biomineralization in bacterioferritin. The findings also establish the importance of electrostatic guiding and nanoconfinement offered by ferritin self-assembly towards its enzymatic activity and antioxidative property. Moreover, this work identifies the key electrostatic interactions (“hot-spots”) at the subunit contact points that control the cage/pore formation, impart cage stability and influences ferritin’s natural functions. Manipulation of hot-spot residues can be further extended towards encapsulation of cargo, for various bio-medical applications, by strategically inducing its disassembly and subsequent reassembly by adjustments in the ionic strength. This would bypass the need for extreme/harsh reaction conditions and minimize the loss of cargo/protein.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"8 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990156","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":"Colloidally Uniform Single Crystal Precursors Enable Uniform FAPbI3 Films for Efficient Perovskite Submodules","authors":"Yugang Liang, Yingping Fan, Zhixiao Qin, Lei Lu, Haifei Wang, Meng Ren, Fang Liu, Yanfeng Miao, Yuetian Chen, Yixin Zhao","doi":"10.1039/d4sc07759h","DOIUrl":"https://doi.org/10.1039/d4sc07759h","url":null,"abstract":"With the unprecedent research development on lead halide perovskite photovoltaics, scaling up the fabrication while comprehensively understanding the properties of cost-effective and highly uniform precursor film has become critical for their applicational promotion. When enlarging the device area, good precursor purity serves as the first step on ensuring the uniformity of perovskite film. Chemical purity and the colloidal uniformity in precursor solution all play important roles on dictating the film uniformity and defect density. Here we, for the first time, explore the colloidal behavior of FAPbI<small>₃</small> precursor using different preparatory materials of varied costs but with similar metal purity. As the regular PbI<small>₂</small>+FAI powder precursors’ colloidal size increases compared to PbI<small>₂</small> colloids, the FAPbI<small>₃</small> single crystal precursor synthesized from low-purity chemicals exhibits a generally smaller and more uniform colloid size, which yields perovskite films of improved uniformity and reduced defect density at lower expenses. The colloidally uniform single crystal precursors lead to photovoltaics with higher power conversion efficiency and better long-term operational stability. More importantly, the uniformity in precursor and film is beneficial for large-area fabrication, where the scaling-up production of 30 cm × 30 cm perovskite submodules based on single crystal precursors achieve an impressive 20.7% efficiency.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"80 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990158","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":"Biomimetic Thiyl Radical Formation From Diphenyl Disulfide with The Low Valent Ni(I) State of A Cofactor F430 Model","authors":"Samira Amini, Kerstin Oppelt, Olivier Blacque, Mikhail Agrachev, Gunnar Jeschke, Felix Zelder","doi":"10.1039/d4sc08416k","DOIUrl":"https://doi.org/10.1039/d4sc08416k","url":null,"abstract":"Cofactor F430 is a nickel-containing hydrocorphinato complex that plays important roles in the enzymatic formation and oxidation of methane. In methanotrophic bacteria, F430-dependent methyl-coenzyme M reductase (MCR) catalyses the endergonic conversion of the heterodisulfide adduct of coenzymes M and B with methane to methyl-coenzyme M and coenzyme B. In a radical mechanism, the Ni(I)-induced formation of a transient thiyl radical of coenzyme B from the heterodisulfide has been proposed. Herein, we introduce a new semi-artificial Ni-complex derived from vitamin B12 as functional model of F430. We demonstrate with electrochemical studies that the low valent Ni(I) complex cleaves the biomimetic model compound diphenyl disulfide into approx. 0.5 equivalents of thiophenol and a transient thiophenyl radical at a potential of -1.65 V vs. Fc/Fc+. The thiyl radical is trapped in solution with phenylacetylene as thiophenyl-substituted olefins, but also leads to degradation of the Ni-complex.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"100 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990194","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}