ACS Central Science最新文献_第5页

Mechanism of O2 Activation and Cysteine Oxidation by the Unusual Mononuclear Cu(I) Active Site of the Formylglycine-Generating Enzyme 甲酰基甘氨酸生成酶异常单核Cu(I)活性位点对O2活化和半胱氨酸氧化的机理

IF 12.7 1区化学

ACS Central Science Pub Date : 2025-04-04 DOI: 10.1021/acscentsci.5c0018310.1021/acscentsci.5c00183

Ioannis Kipouros, Hyeongtaek Lim, Mason J. Appel, Katlyn K. Meier, Britt Hedman, Keith O. Hodgson, Carolyn R. Bertozzi* and Edward I. Solomon*,

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引用次数: 0

A Source of the Mysterious m/z 36 Ions Identified: Implications for the Stability of Water and Unusual Chemistry in Microdroplets 神秘的m/z 36离子的来源确定：对水的稳定性和微滴中不寻常化学的影响

IF 12.7 1区化学

ACS Central Science Pub Date : 2025-04-04 DOI: 10.1021/acscentsci.5c0030610.1021/acscentsci.5c00306

Casey J. Chen, and , Evan R. Williams*,

{"title":"A Source of the Mysterious m/z 36 Ions Identified: Implications for the Stability of Water and Unusual Chemistry in Microdroplets","authors":"Casey J. Chen,  and , Evan R. Williams*, ","doi":"10.1021/acscentsci.5c0030610.1021/acscentsci.5c00306","DOIUrl":"https://doi.org/10.1021/acscentsci.5c00306https://doi.org/10.1021/acscentsci.5c00306","url":null,"abstract":"Many unusual reactions involving aqueous microdroplets have been reported, including nitrogen fixation at room temperature, production of abundant hydrogen peroxide, and formation of an ion at m/z 36, attributed to (H2O–OH2)+•, (H3O + OH)+•, or (H2O)2+•, which was used to support the hypothesis of spontaneous production of hydroxyl radicals. Here, m/z 36 ions and extensive hydrated clusters of this ion are formed using either nanoelectrospray ionization or a vibrating mesh nebulizer that produces water droplets ranging from ∼100 nm to ∼20 μm. Exhalation of a single breath near the droplets leads to a substantial increase in the abundance of this ion series, whereas purging the source with N2 gas leads to its near complete disappearance. Accurate mass measurements show that m/z 36 ions formed from pure water are NH4+(H2O) and not (H2O)2+•. Both the high sensitivity to trace levels of gaseous ammonia (unoptimized detection limit of low parts-per-billion) in these experiments and the likely misidentification of the m/z 36 ion in many previous experiments indicate that many results that have been used to support hypotheses about unusual chemistry and the effects of high intrinsic electric fields at microdroplet surfaces may require a more thorough evaluation.Accurate mass measurements show that a m/z 36 ion that is sometimes formed from aqueous microdroplets is NH4+(H2O), not (H2O)2+•, and is abundant when droplets are exposed to human breath.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 4","pages":"622–628 622–628"},"PeriodicalIF":12.7,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.5c00306","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858394","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

Mechanism of O₂ Activation and Cysteine Oxidation by the Unusual Mononuclear Cu(I) Active Site of the Formylglycine-Generating Enzyme. 甲酰基甘氨酸生成酶异常单核Cu(I)活性位点对O2活化和半胱氨酸氧化的机理

IF 12.7 1区化学

ACS Central Science Pub Date : 2025-04-04 eCollection Date: 2025-05-28 DOI: 10.1021/acscentsci.5c00183

Ioannis Kipouros, Hyeongtaek Lim, Mason J Appel, Katlyn K Meier, Britt Hedman, Keith O Hodgson, Carolyn R Bertozzi, Edward I Solomon

{"title":"Mechanism of O2 Activation and Cysteine Oxidation by the Unusual Mononuclear Cu(I) Active Site of the Formylglycine-Generating Enzyme.","authors":"Ioannis Kipouros, Hyeongtaek Lim, Mason J Appel, Katlyn K Meier, Britt Hedman, Keith O Hodgson, Carolyn R Bertozzi, Edward I Solomon","doi":"10.1021/acscentsci.5c00183","DOIUrl":"10.1021/acscentsci.5c00183","url":null,"abstract":"The formylglycine-generating enzyme (FGE) catalyzes the selective oxidation of a peptidyl-cysteine to form formylglycine, a critical cotranslational modification for type I sulfatase activation and a useful bioconjugation handle. Previous studies have shown that the substrate peptidyl-cysteine binds to the linear bis-thiolate Cu-(I) site of FGE to form a trigonal planar tris-thiolate Cu-(I) structure that activates O2 for the oxidation of the Cβ-H of the cysteine substrate via an unknown mechanism. Here, we employed a combination of stopped-flow kinetic, spectroscopic (UV-vis absorption, XAS, and EPR), and computational (DFT/TD-DFT calculations) methods to observe and characterize the key intermediates in this reaction for FGE from Streptomyces coelicolor . Our results define the reaction coordinate of FGE, which involves H-atom abstraction from the Cβ-H bond of the cysteine substrate by a reactive Cu-(II)-O2 •- species to form the now experimentally observed Cu-(I)-OOH intermediate bound to a peptidyl-thioaldehyde, which proceeds to oxidize one of the protein-derived cysteine residues to a sulfenate that is end-on O-coordinated to Cu-(I). These results provide fundamental insights into how the unusual mononuclear Cu-(I) site of FGE activates O2 for cysteine oxidation and stores oxidizing equivalents during catalysis by employing a Cu-(I)-sulfenate intermediate with an end-on O-coordination that is unprecedented in biology.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 5","pages":"683-693"},"PeriodicalIF":12.7,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12123546/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144197694","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

A Source of the Mysterious m/z 36 Ions Identified: Implications for the Stability of Water and Unusual Chemistry in Microdroplets. 神秘的m/z 36离子的来源确定：对水的稳定性和微滴中不寻常化学的影响。

IF 12.7 1区化学

ACS Central Science Pub Date : 2025-04-04 eCollection Date: 2025-04-23 DOI: 10.1021/acscentsci.5c00306

Casey J Chen, Evan R Williams

{"title":"A Source of the Mysterious m/z 36 Ions Identified: Implications for the Stability of Water and Unusual Chemistry in Microdroplets.","authors":"Casey J Chen, Evan R Williams","doi":"10.1021/acscentsci.5c00306","DOIUrl":"https://doi.org/10.1021/acscentsci.5c00306","url":null,"abstract":"Many unusual reactions involving aqueous microdroplets have been reported, including nitrogen fixation at room temperature, production of abundant hydrogen peroxide, and formation of an ion at m/z 36, attributed to (H2O-OH2)+•, (H3O + OH)+•, or (H2O)2 +•, which was used to support the hypothesis of spontaneous production of hydroxyl radicals. Here, m/z 36 ions and extensive hydrated clusters of this ion are formed using either nanoelectrospray ionization or a vibrating mesh nebulizer that produces water droplets ranging from ∼100 nm to ∼20 μm. Exhalation of a single breath near the droplets leads to a substantial increase in the abundance of this ion series, whereas purging the source with N2 gas leads to its near complete disappearance. Accurate mass measurements show that m/z 36 ions formed from pure water are NH4 +(H2O) and not (H2O)2 +•. Both the high sensitivity to trace levels of gaseous ammonia (unoptimized detection limit of low parts-per-billion) in these experiments and the likely misidentification of the m/z 36 ion in many previous experiments indicate that many results that have been used to support hypotheses about unusual chemistry and the effects of high intrinsic electric fields at microdroplet surfaces may require a more thorough evaluation.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 4","pages":"622-628"},"PeriodicalIF":12.7,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12022912/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143950817","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

Leveraging Prompt Engineering in Large Language Models for Accelerating Chemical Research. 利用大型语言模型中的提示工程加速化学研究。

IF 12.7 1区化学

ACS Central Science Pub Date : 2025-04-02 eCollection Date: 2025-04-23 DOI: 10.1021/acscentsci.4c01935

Feifei Luo, Jinglang Zhang, Qilong Wang, Chunpeng Yang

{"title":"Leveraging Prompt Engineering in Large Language Models for Accelerating Chemical Research.","authors":"Feifei Luo, Jinglang Zhang, Qilong Wang, Chunpeng Yang","doi":"10.1021/acscentsci.4c01935","DOIUrl":"https://doi.org/10.1021/acscentsci.4c01935","url":null,"abstract":"Artificial intelligence (AI) using large language models (LLMs) such as GPTs has revolutionized various fields. Recently, LLMs have also made inroads in chemical research even for users without expertise in coding. However, applying LLMs directly may lead to \"hallucinations\", where the model generates unreliable or inaccurate information and is further exacerbated by limited data set and inherent complexity of chemical reports. To counteract this, researchers have suggested prompt engineering, which can convey human ideas formatively and unambiguously to LLMs and simultaneously improve LLMs' reasoning capability. So far, prompt engineering remains underutilized in chemistry, with many chemists barely acquainted with its principle and techniques. In this Outlook, we delve into various prompt engineering techniques and illustrate relevant examples for extensive research from metal-organic frameworks and fast-charging batteries to autonomous experiments. We also elucidate the current limitations of prompt engineering with LLMs such as incomplete or biased outcomes and constraints imposed by closed-source limitations. Although LLM-assisted chemical research is still in its early stages, the application of prompt engineering will significantly enhance accuracy and reliability, thereby accelerating chemical research.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 4","pages":"511-519"},"PeriodicalIF":12.7,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12022906/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143951404","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

Leveraging Prompt Engineering in Large Language Models for Accelerating Chemical Research 利用大型语言模型中的提示工程加速化学研究

IF 12.7 1区化学

ACS Central Science Pub Date : 2025-04-02 DOI: 10.1021/acscentsci.4c0193510.1021/acscentsci.4c01935

Feifei Luo, Jinglang Zhang, Qilong Wang* and Chunpeng Yang*,

{"title":"Leveraging Prompt Engineering in Large Language Models for Accelerating Chemical Research","authors":"Feifei Luo, Jinglang Zhang, Qilong Wang* and Chunpeng Yang*, ","doi":"10.1021/acscentsci.4c0193510.1021/acscentsci.4c01935","DOIUrl":"https://doi.org/10.1021/acscentsci.4c01935https://doi.org/10.1021/acscentsci.4c01935","url":null,"abstract":"Artificial intelligence (AI) using large language models (LLMs) such as GPTs has revolutionized various fields. Recently, LLMs have also made inroads in chemical research even for users without expertise in coding. However, applying LLMs directly may lead to “hallucinations”, where the model generates unreliable or inaccurate information and is further exacerbated by limited data set and inherent complexity of chemical reports. To counteract this, researchers have suggested prompt engineering, which can convey human ideas formatively and unambiguously to LLMs and simultaneously improve LLMs’ reasoning capability. So far, prompt engineering remains underutilized in chemistry, with many chemists barely acquainted with its principle and techniques. In this Outlook, we delve into various prompt engineering techniques and illustrate relevant examples for extensive research from metal–organic frameworks and fast-charging batteries to autonomous experiments. We also elucidate the current limitations of prompt engineering with LLMs such as incomplete or biased outcomes and constraints imposed by closed-source limitations. Although LLM-assisted chemical research is still in its early stages, the application of prompt engineering will significantly enhance accuracy and reliability, thereby accelerating chemical research.AI using large language models creates an unprecedented opportunity for chemical discovery and prompt engineering hopefully unleashes their true potential for accelerating chemical research.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 4","pages":"511–519 511–519"},"PeriodicalIF":12.7,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.4c01935","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858351","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

Deciphering Desorption Pathways and Mechanisms of Peptide Supramolecular Structures Thermodynamically and Kinetically by High-Speed AFM. 高速原子力显微镜解析多肽超分子结构的热动力学解吸途径和机理。

IF 12.7 1区化学

ACS Central Science Pub Date : 2025-04-02 eCollection Date: 2025-05-28 DOI: 10.1021/acscentsci.5c00215

Linhao Sun, Jinhua Hu, Yurtsever Ayhan, Chen Chen

{"title":"Deciphering Desorption Pathways and Mechanisms of Peptide Supramolecular Structures Thermodynamically and Kinetically by High-Speed AFM.","authors":"Linhao Sun, Jinhua Hu, Yurtsever Ayhan, Chen Chen","doi":"10.1021/acscentsci.5c00215","DOIUrl":"10.1021/acscentsci.5c00215","url":null,"abstract":"Studying molecule desorption from solids has attracted much interest in crude oil exploitation, self-cleaning nanotechnology, and biomedicine. Much work on polymer/biopolymer desorption has addressed the effect of pH, salts, and others on desorption features fitted by established models. However, molecular desorption pathways and mechanisms are still poorly understood due to lack of (i) a good model directly revealing nano- to microscale desorption characteristics and (ii) a powerful nanotool enabling the capture of every detail within sufficient spatiotemporal resolution. We utilized well-organized peptide supramolecular arrays (pSMAs) as a model system and high-speed AFM to investigate molecular desorption pathways and the mechanism in thermodynamics and kinetics. Temperature as a key parameter affects both peptide desorption and diffusion processes, leading to changes of pSMA coverage and ordered-to-disordered structures. Significantly, we found distinct desorption pathways of pSMAs in kinetics, including no desorption, one- or double-end desorption, and middle desorption of nanowires (NWs). Therefore, we proposed a \"stop-to-activate\" mechanism. Besides, the desorption characteristics of single NWs and pSMAs were well fitted by an exponential curve following classic desorption models. This work provides a good guideline for studying other molecules' or assemblies' desorption and sheds light on investigating drug effects on disassembly of amyloid protein fibrils in treating neurodegenerative diseases.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 5","pages":"672-682"},"PeriodicalIF":12.7,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12123461/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144197670","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

Amino Acid Sequence Controls Enhanced Electron Transport in Heme-Binding Peptide Monolayers. 氨基酸序列控制血红素结合肽单分子层中增强的电子传递。

IF 12.7 1区化学

ACS Central Science Pub Date : 2025-04-02 eCollection Date: 2025-04-23 DOI: 10.1021/acscentsci.4c01849

Hao Yang, Xiaolin Liu, Moeen Meigooni, Li Zhang, Jitong Ren, Qian Chen, Mark Losego, Emad Tajkhorshid, Jeffrey S Moore, Charles M Schroeder

{"title":"Amino Acid Sequence Controls Enhanced Electron Transport in Heme-Binding Peptide Monolayers.","authors":"Hao Yang, Xiaolin Liu, Moeen Meigooni, Li Zhang, Jitong Ren, Qian Chen, Mark Losego, Emad Tajkhorshid, Jeffrey S Moore, Charles M Schroeder","doi":"10.1021/acscentsci.4c01849","DOIUrl":"https://doi.org/10.1021/acscentsci.4c01849","url":null,"abstract":"Metal-binding proteins have the exceptional ability to facilitate long-range electron transport in nature. Despite recent progress, the sequence-structure-function relationships governing electron transport in heme-binding peptides and protein assemblies are not yet fully understood. In this work, the electronic properties of a series of heme-binding peptides inspired by cytochrome bc 1 are studied using a combination of molecular electronics experiments, molecular modeling, and simulation. Self-assembled monolayers (SAMs) are prepared using sequence-defined heme-binding peptides capable of forming helical secondary structures. Following monolayer formation, the structural properties and chemical composition of assembled peptides are determined using atomic force microscopy and X-ray photoelectron spectroscopy, and the electronic properties (current density-voltage response) are characterized using a soft contact liquid metal electrode method based on eutectic gallium-indium alloys (EGaIn). Our results show a substantial 1000-fold increase in current density across SAM junctions upon addition of heme compared to identical peptide sequences in the absence of heme, while maintaining a constant junction thickness. These findings show that amino acid composition and sequence directly control enhancements in electron transport in heme-binding peptides. Overall, this study demonstrates the potential of using sequence-defined synthetic peptides inspired by nature as functional bioelectronic materials.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 4","pages":"612-621"},"PeriodicalIF":12.7,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12022913/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143950884","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

Amino Acid Sequence Controls Enhanced Electron Transport in Heme-Binding Peptide Monolayers 氨基酸序列控制血红素结合肽单分子层中增强的电子传递

IF 12.7 1区化学

ACS Central Science Pub Date : 2025-04-02 DOI: 10.1021/acscentsci.4c0184910.1021/acscentsci.4c01849

Hao Yang, Xiaolin Liu, Moeen Meigooni, Li Zhang, Jitong Ren, Qian Chen, Mark Losego, Emad Tajkhorshid*, Jeffrey S. Moore* and Charles M. Schroeder*,

{"title":"Amino Acid Sequence Controls Enhanced Electron Transport in Heme-Binding Peptide Monolayers","authors":"Hao Yang, Xiaolin Liu, Moeen Meigooni, Li Zhang, Jitong Ren, Qian Chen, Mark Losego, Emad Tajkhorshid*, Jeffrey S. Moore* and Charles M. Schroeder*, ","doi":"10.1021/acscentsci.4c0184910.1021/acscentsci.4c01849","DOIUrl":"https://doi.org/10.1021/acscentsci.4c01849https://doi.org/10.1021/acscentsci.4c01849","url":null,"abstract":"Metal-binding proteins have the exceptional ability to facilitate long-range electron transport in nature. Despite recent progress, the sequence-structure–function relationships governing electron transport in heme-binding peptides and protein assemblies are not yet fully understood. In this work, the electronic properties of a series of heme-binding peptides inspired by cytochrome bc1 are studied using a combination of molecular electronics experiments, molecular modeling, and simulation. Self-assembled monolayers (SAMs) are prepared using sequence-defined heme-binding peptides capable of forming helical secondary structures. Following monolayer formation, the structural properties and chemical composition of assembled peptides are determined using atomic force microscopy and X-ray photoelectron spectroscopy, and the electronic properties (current density–voltage response) are characterized using a soft contact liquid metal electrode method based on eutectic gallium–indium alloys (EGaIn). Our results show a substantial 1000-fold increase in current density across SAM junctions upon addition of heme compared to identical peptide sequences in the absence of heme, while maintaining a constant junction thickness. These findings show that amino acid composition and sequence directly control enhancements in electron transport in heme-binding peptides. Overall, this study demonstrates the potential of using sequence-defined synthetic peptides inspired by nature as functional bioelectronic materials.Self-assembled peptide monolayers show a 1000-fold increase in electronic conductivity upon heme binding, demonstrating that electronic properties in bioelectronic materials can be tuned by controlling peptide sequence and composition.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 4","pages":"612–621 612–621"},"PeriodicalIF":12.7,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.4c01849","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858349","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

Deciphering Desorption Pathways and Mechanisms of Peptide Supramolecular Structures Thermodynamically and Kinetically by High-Speed AFM 高速原子力显微镜解析多肽超分子结构的热动力学解吸途径和机理

IF 12.7 1区化学

ACS Central Science Pub Date : 2025-04-01 DOI: 10.1021/acscentsci.5c0021510.1021/acscentsci.5c00215

Linhao Sun*, Jinhua Hu, Yurtsever Ayhan and Chen Chen*,

{"title":"Deciphering Desorption Pathways and Mechanisms of Peptide Supramolecular Structures Thermodynamically and Kinetically by High-Speed AFM","authors":"Linhao Sun*, Jinhua Hu, Yurtsever Ayhan and Chen Chen*, ","doi":"10.1021/acscentsci.5c0021510.1021/acscentsci.5c00215","DOIUrl":"https://doi.org/10.1021/acscentsci.5c00215https://doi.org/10.1021/acscentsci.5c00215","url":null,"abstract":"Studying molecule desorption from solids has attracted much interest in crude oil exploitation, self-cleaning nanotechnology, and biomedicine. Much work on polymer/biopolymer desorption has addressed the effect of pH, salts, and others on desorption features fitted by established models. However, molecular desorption pathways and mechanisms are still poorly understood due to lack of (i) a good model directly revealing nano- to microscale desorption characteristics and (ii) a powerful nanotool enabling the capture of every detail within sufficient spatiotemporal resolution. We utilized well-organized peptide supramolecular arrays (pSMAs) as a model system and high-speed AFM to investigate molecular desorption pathways and the mechanism in thermodynamics and kinetics. Temperature as a key parameter affects both peptide desorption and diffusion processes, leading to changes of pSMA coverage and ordered-to-disordered structures. Significantly, we found distinct desorption pathways of pSMAs in kinetics, including no desorption, one- or double-end desorption, and middle desorption of nanowires (NWs). Therefore, we proposed a “stop-to-activate” mechanism. Besides, the desorption characteristics of single NWs and pSMAs were well fitted by an exponential curve following classic desorption models. This work provides a good guideline for studying other molecules’ or assemblies’ desorption and sheds light on investigating drug effects on disassembly of amyloid protein fibrils in treating neurodegenerative diseases.High-speed atomic force microscopy reveals desorption pathways and mechanisms of well-organized peptide supramolecular nanostructures at soft interfaces in thermodynamic and kinetic conditions.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 5","pages":"672–682 672–682"},"PeriodicalIF":12.7,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.5c00215","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144146402","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