ACS Macro Letters最新文献_第3页

Mechanochromic Break Points Control the Toughness of Entangled Polyphenylenes

IF 5.8

ACS Macro Letters Pub Date : 2025-02-10 DOI: 10.1021/acsmacrolett.4c00810

Annina Missikewitsch, Hartmut Komber, Till Biskup, Michael Sommer

引用次数: 0

Correction to “Antibacterial Iodine-Releasing Coatings of Cross-Linked Poly(N-vinylpyrrolidone) Synthesized by Solvent-Free Initiated Chemical Vapor Deposition”

IF 5.8

ACS Macro Letters Pub Date : 2025-02-10 DOI: 10.1021/acsmacrolett.5c00071

Qing Song, Zihan Xiao, Tong Liu, Haijun Gao, Ximan Chen, Qingyan Jia, Peng Li, Dahai Wei

引用次数: 0

Cation Chemistry and Molecular Weight Effects on the Ion Conductivity in PEO-based Electrolytes

IF 5.1

ACS Macro Letters Pub Date : 2025-02-10 DOI: 10.1021/acsmacrolett.4c0080210.1021/acsmacrolett.4c00802

Chrysostomos Papamichail, Olympia Techlemtzi, Georgia Nikolakakou and Emmanouil Glynos*,

{"title":"Cation Chemistry and Molecular Weight Effects on the Ion Conductivity in PEO-based Electrolytes","authors":"Chrysostomos Papamichail, Olympia Techlemtzi, Georgia Nikolakakou and Emmanouil Glynos*, ","doi":"10.1021/acsmacrolett.4c0080210.1021/acsmacrolett.4c00802","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00802https://doi.org/10.1021/acsmacrolett.4c00802","url":null,"abstract":"This study investigates the fundamental influence of cation chemistry on the ionic conductivity of PEO-based electrolytes, with implications for advancing polymer electrolyte design. Two PEO systems─high molecular weight (Mw = 100 kg/mol) and low molecular weight (Mw = 0.35 kg/mol)─were blended with LiTFSI and NaTFSI salts to explore ion transport mechanisms. In the high-Mw PEO, where ion hopping dominates, smaller Li+ ions exhibit higher conductivity (σLiTFSI > σNaTFSI). In contrast, the low-Mw PEO, where ion diffusion is the primary mechanism, shows higher conductivity for larger Na+ ions (σNaTFSI > σLiTFSI). In the former, rheology measurements indicate that larger Na+ cations form more transient EO:Na+ contact, hindering cation hopping and reducing conductivity. In the latter, the stronger EO:Li+ interactions lead to a larger hydrodynamic radius and slower diffusion. Notably, PEO-0.35K:NaTFSI exhibits a room-temperature conductivity of σNaTFSI ≈ 4 × 10–4 S/cm, meeting the requirements for practical applications. These findings highlight the potential of low-Mw PEO and Na-based electrolytes for the development of efficient Na-ion batteries.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"14 2","pages":"225–230 225–230"},"PeriodicalIF":5.1,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmacrolett.4c00802","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143428309","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Cation Chemistry and Molecular Weight Effects on the Ion Conductivity in PEO-based Electrolytes

IF 5.8

ACS Macro Letters Pub Date : 2025-02-10 DOI: 10.1021/acsmacrolett.4c00802

Chrysostomos Papamichail, Olympia Techlemtzi, Georgia Nikolakakou, Emmanouil Glynos

{"title":"Cation Chemistry and Molecular Weight Effects on the Ion Conductivity in PEO-based Electrolytes","authors":"Chrysostomos Papamichail, Olympia Techlemtzi, Georgia Nikolakakou, Emmanouil Glynos","doi":"10.1021/acsmacrolett.4c00802","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00802","url":null,"abstract":"This study investigates the fundamental influence of cation chemistry on the ionic conductivity of PEO-based electrolytes, with implications for advancing polymer electrolyte design. Two PEO systems─high molecular weight (Mw = 100 kg/mol) and low molecular weight (Mw = 0.35 kg/mol)─were blended with LiTFSI and NaTFSI salts to explore ion transport mechanisms. In the high-Mw PEO, where ion hopping dominates, smaller Li+ ions exhibit higher conductivity (σLiTFSI > σNaTFSI). In contrast, the low-Mw PEO, where ion diffusion is the primary mechanism, shows higher conductivity for larger Na+ ions (σNaTFSI > σLiTFSI). In the former, rheology measurements indicate that larger Na+ cations form more transient EO:Na+ contact, hindering cation hopping and reducing conductivity. In the latter, the stronger EO:Li+ interactions lead to a larger hydrodynamic radius and slower diffusion. Notably, PEO-0.35K:NaTFSI exhibits a room-temperature conductivity of σNaTFSI ≈ 4 × 10–4 S/cm, meeting the requirements for practical applications. These findings highlight the potential of low-Mw PEO and Na-based electrolytes for the development of efficient Na-ion batteries.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"31 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375240","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Engineering Lithium–Magnesium Selectivity in Hydrated Polymer Membranes through Polymer Backbone Rigidity

IF 5.8

ACS Macro Letters Pub Date : 2025-02-05 DOI: 10.1021/acsmacrolett.4c00828

Paul R. Irving, Grace Sam, Soham Rane, Nikhil Thirumalai, Nico Marioni, Geoffrey M. Geise, Benny D. Freeman, Venkat Ganesan

{"title":"Engineering Lithium–Magnesium Selectivity in Hydrated Polymer Membranes through Polymer Backbone Rigidity","authors":"Paul R. Irving, Grace Sam, Soham Rane, Nikhil Thirumalai, Nico Marioni, Geoffrey M. Geise, Benny D. Freeman, Venkat Ganesan","doi":"10.1021/acsmacrolett.4c00828","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00828","url":null,"abstract":"Using computer simulations and experiments, we demonstrate that polymer backbone rigidity can be used to tune selectivities and permeabilities of lithium over magnesium in hydrated polymer membranes. Coarse-grained molecular dynamics (CGMD) simulations suggest a strong dependence of cation diffusion coefficients on polymer segmental dynamics and cation-solvent coordination strength, with water content and backbone dynamics having distinct effects on transport properties. Experimentally, we synthesized 2-hydroxyethyl acrylate-co-ethyl acrylate (HEA-co-EA) and 2-hydroxyethyl methacrylate-co-methyl methacrylate (HEMA-co-MMA) membranes. These polymers have different levels of backbone flexibility while maintaining similar chemistry. LiCl and MgCl2 salt permeabilities and sorption coefficients were measured for membranes with varying water content. Magnesium chloride permeability and diffusion coefficients show a stronger dependence on backbone dynamics than lithium chloride, whereas backbone dynamics has a minor impact on salt sorption. Overall, these factors allow permeability and selectivity of LiCl relative to MgCl2 to be increased simultaneously by increasing both water content and backbone rigidity.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"40 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124327","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Engineering Lithium–Magnesium Selectivity in Hydrated Polymer Membranes through Polymer Backbone Rigidity

IF 5.1

ACS Macro Letters Pub Date : 2025-02-05 DOI: 10.1021/acsmacrolett.4c0082810.1021/acsmacrolett.4c00828

Paul R. Irving, Grace Sam, Soham Rane, Nikhil Thirumalai, Nico Marioni, Geoffrey M. Geise, Benny D. Freeman* and Venkat Ganesan*,

{"title":"Engineering Lithium–Magnesium Selectivity in Hydrated Polymer Membranes through Polymer Backbone Rigidity","authors":"Paul R. Irving, Grace Sam, Soham Rane, Nikhil Thirumalai, Nico Marioni, Geoffrey M. Geise, Benny D. Freeman* and Venkat Ganesan*, ","doi":"10.1021/acsmacrolett.4c0082810.1021/acsmacrolett.4c00828","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00828https://doi.org/10.1021/acsmacrolett.4c00828","url":null,"abstract":"Using computer simulations and experiments, we demonstrate that polymer backbone rigidity can be used to tune selectivities and permeabilities of lithium over magnesium in hydrated polymer membranes. Coarse-grained molecular dynamics (CGMD) simulations suggest a strong dependence of cation diffusion coefficients on polymer segmental dynamics and cation-solvent coordination strength, with water content and backbone dynamics having distinct effects on transport properties. Experimentally, we synthesized 2-hydroxyethyl acrylate-co-ethyl acrylate (HEA-co-EA) and 2-hydroxyethyl methacrylate-co-methyl methacrylate (HEMA-co-MMA) membranes. These polymers have different levels of backbone flexibility while maintaining similar chemistry. LiCl and MgCl2 salt permeabilities and sorption coefficients were measured for membranes with varying water content. Magnesium chloride permeability and diffusion coefficients show a stronger dependence on backbone dynamics than lithium chloride, whereas backbone dynamics has a minor impact on salt sorption. Overall, these factors allow permeability and selectivity of LiCl relative to MgCl2 to be increased simultaneously by increasing both water content and backbone rigidity.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"14 2","pages":"161–168 161–168"},"PeriodicalIF":5.1,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143428521","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Enzymatically Covalent and Noncovalent Weaving toward Highly Efficient Synthesis of 2D Monolayered Molecular Fabrics

IF 5.1

ACS Macro Letters Pub Date : 2025-02-03 DOI: 10.1021/acsmacrolett.5c0001710.1021/acsmacrolett.5c00017

Zhenzhu Wang, Yunpeng Ge, Wencan Li, Chenyang Zhang and Zeyuan Dong*,

{"title":"Enzymatically Covalent and Noncovalent Weaving toward Highly Efficient Synthesis of 2D Monolayered Molecular Fabrics","authors":"Zhenzhu Wang, Yunpeng Ge, Wencan Li, Chenyang Zhang and Zeyuan Dong*, ","doi":"10.1021/acsmacrolett.5c0001710.1021/acsmacrolett.5c00017","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00017https://doi.org/10.1021/acsmacrolett.5c00017","url":null,"abstract":"Molecular fabrics with fascinating physical characteristics, such as structural flexibility and single-layered thinness, have attracted much attention. Chemists worldwide have been working on building unique molecularly woven structures in two dimensions. However, the synthesis of two-dimensional molecular weaving remains a challenging task, especially in water. Herein, we propose a straightforward and practical method to construct 2D molecular fabrics by enzymatically covalent and noncovalent syntheses in water. In particular, aromatic helical pentamers with two-terminal tyrosine residues (Penta-Tyr) can spontaneously dimerize via π–π interactions into double-helical interlocking structure, and the two-terminal tyrosine moieties of Penta-Tyr can undergo oxidative polymerization catalyzed by horseradish peroxidase (HRP) and hydrogen peroxide (H2O2) for effective covalent cross-linking. The 2D monolayered molecular fabrics can be readily prepared by the catalysis of HRP and H2O2 under mild conditions, which exhibit concentration-dependent weaving behavior. This work not only demonstrates an enzyme-catalyzed approach for the highly efficient synthesis of 2D monolayered molecular fabrics for the first time but also will promote the controllable preparation and application of water-soluble 2D molecular fabrics.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"14 2","pages":"201–206 201–206"},"PeriodicalIF":5.1,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143428593","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Surface Nanostructure Fabrication by Initiated Chemical Vapor Deposition and Its Combined Technologies

IF 5.8

ACS Macro Letters Pub Date : 2025-02-03 DOI: 10.1021/acsmacrolett.4c00793

Qing Song, Haijun Gao, Lin Cheng, Zihan Xiao, Deli Li, Yue Wang, Meizhen Xie, Nathan A. Fuller, Mengfan Zhu

{"title":"Surface Nanostructure Fabrication by Initiated Chemical Vapor Deposition and Its Combined Technologies","authors":"Qing Song, Haijun Gao, Lin Cheng, Zihan Xiao, Deli Li, Yue Wang, Meizhen Xie, Nathan A. Fuller, Mengfan Zhu","doi":"10.1021/acsmacrolett.4c00793","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00793","url":null,"abstract":"Initiated chemical vapor deposition (iCVD) is a versatile technique that enables the direct growth of nanostructures and surface modification of such structures. Unlike traditional CVD methods, iCVD operates under mild conditions, allowing for damage-free processing of delicate substrates. It can produce highly uniform polymer layers, with thicknesses ranging from over 15 μm to sub-10 nm, conformally coating intricate geometries. The broad range of polymer compositions achievable with iCVD offers precise control of surface chemistry. In this Viewpoint, we present iCVD’s mechanisms and the principles for controlling the composition and morphology of deposited layers. We summarize various surface nanostructures including nanodomes, nanocones, nanowrinkles, nanoparticles, and nanoporous structures that are directly fabricated using iCVD. We also demonstrate the integration of iCVD with other advanced methods, such as photo, soft, and nanoimprint lithography; template-assisted growth; and thermal CVD, to leverage the advantages of multiple methods and overcome individual limitations in nanofabrication. Through these combined strategies, we show the iCVD’s potential for creating multifunctional nanostructures with broad applications across engineering and biomedical fields.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"12 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084132","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Surface Nanostructure Fabrication by Initiated Chemical Vapor Deposition and Its Combined Technologies

IF 5.1

ACS Macro Letters Pub Date : 2025-02-03 DOI: 10.1021/acsmacrolett.4c0079310.1021/acsmacrolett.4c00793

Qing Song*, Haijun Gao, Lin Cheng, Zihan Xiao, Deli Li, Yue Wang, Meizhen Xie, Nathan A. Fuller and Mengfan Zhu*,

{"title":"Surface Nanostructure Fabrication by Initiated Chemical Vapor Deposition and Its Combined Technologies","authors":"Qing Song*, Haijun Gao, Lin Cheng, Zihan Xiao, Deli Li, Yue Wang, Meizhen Xie, Nathan A. Fuller and Mengfan Zhu*, ","doi":"10.1021/acsmacrolett.4c0079310.1021/acsmacrolett.4c00793","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00793https://doi.org/10.1021/acsmacrolett.4c00793","url":null,"abstract":"Initiated chemical vapor deposition (iCVD) is a versatile technique that enables the direct growth of nanostructures and surface modification of such structures. Unlike traditional CVD methods, iCVD operates under mild conditions, allowing for damage-free processing of delicate substrates. It can produce highly uniform polymer layers, with thicknesses ranging from over 15 μm to sub-10 nm, conformally coating intricate geometries. The broad range of polymer compositions achievable with iCVD offers precise control of surface chemistry. In this Viewpoint, we present iCVD’s mechanisms and the principles for controlling the composition and morphology of deposited layers. We summarize various surface nanostructures including nanodomes, nanocones, nanowrinkles, nanoparticles, and nanoporous structures that are directly fabricated using iCVD. We also demonstrate the integration of iCVD with other advanced methods, such as photo, soft, and nanoimprint lithography; template-assisted growth; and thermal CVD, to leverage the advantages of multiple methods and overcome individual limitations in nanofabrication. Through these combined strategies, we show the iCVD’s potential for creating multifunctional nanostructures with broad applications across engineering and biomedical fields.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"14 2","pages":"214–224 214–224"},"PeriodicalIF":5.1,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143428558","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Versatile and Controlled Synthesis of Degradable, Water-Soluble Bottlebrush Polymers with Poly(disulfide) Backbones Derived from α-Lipoic Acid

IF 5.8

ACS Macro Letters Pub Date : 2025-02-03 DOI: 10.1021/acsmacrolett.4c00839

Ivan O. Levkovsky, Lucca Trachsel, Hironobu Murata, Krzysztof Matyjaszewski

{"title":"Versatile and Controlled Synthesis of Degradable, Water-Soluble Bottlebrush Polymers with Poly(disulfide) Backbones Derived from α-Lipoic Acid","authors":"Ivan O. Levkovsky, Lucca Trachsel, Hironobu Murata, Krzysztof Matyjaszewski","doi":"10.1021/acsmacrolett.4c00839","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00839","url":null,"abstract":"Bottlebrush (BB) polymers, with their densely grafted side chains and unique architecture, are highly advantageous for drug delivery due to their high functional group density for drug conjugation, unimolecular nature, and enhanced biodistribution properties. These attributes enable extended blood circulation half-life, improved tumor tissue penetration, and high tumoral drug accumulation. However, the typically nondegradable, all-carbon backbones of most BB polymers limit their suitability for applications requiring controlled clearance and biodegradability. To address this, we developed degradable BB polymers with poly(disulfide) backbones synthesized via reversible addition–fragmentation chain transfer (RAFT) copolymerization of α-lipoic acid (LA), a renewable and readily available compound, with acrylate-based inimers. These copolymers feature degradable backbones and initiating sites for subsequent BB synthesis. Using an atom transfer radical polymerization (ATRP) grafting-from methodology, we synthesized BB polymers with relatively low dispersities (Đ = 1.30–1.53), high backbone degrees of polymerization (DPbb), and high molar masses (Mn,MALS = 650–2700 kg/mol). The easily cleavable disulfide bonds enabled backbone degradation under mild reducing conditions. Beyond hydrophilic BB with tri(ethylene glycol) methyl ether acrylate (TEGA) side chains, we synthesized BB with cationic, anionic, and zwitterionic side chains, demonstrating broad monomer compatibility. This scalable approach produces water-soluble, degradable BB polymers with tunable architectures and predictable molecular weights. By addressing the need for degradability in BB polymers, this work advances their potential for drug delivery, offering enhanced functionality, biocompatibility, and sustainability.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"123 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084133","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0