ACS Macro Letters最新文献

{"title":"Effect of Confinement on the Structure-Conductivity Relationship in PEO/LiTFSI Electrolytes in 3D Microporous Scaffolds.","authors":"Shreyas Pathreeker, Hyeongjun Koh, Weiwei Kong, Richard Robinson, Gillian Weissman, Eric A Stach, Eric Detsi, Russell J Composto","doi":"10.1021/acsmacrolett.4c00555","DOIUrl":"10.1021/acsmacrolett.4c00555","url":null,"abstract":"<p><p>Because 3D batteries comprise solid polymer electrolytes (SPEs) confined to porous scaffolds with high surface areas, the interplay between polymer confinement and interfacial interactions on SPE total ionic conductivity must be understood. This paper investigates contributions to the structure-conductivity relationship in poly(ethylene oxide) (PEO)-lithium bis(trifluorosulfonylimide) (LiTFSI) complexes confined to microporous nickel scaffolds. For bulk and confined conditions, PEO crystallinity decreases as the salt concentration (Li⁺:EO (<i>r</i>) = 0.0125, 0.0167, 0.025, 0.05) increases. For pure PEO and all <i>r</i> values except 0.05, PEO crystallinity under confinement is lower than in the bulk, whereas the glass transition temperature remains statistically invariant. At 298 K (semicrystalline), total ionic conductivity under confinement is higher than in the bulk at <i>r</i> = 0.0167 but remains invariant at <i>r</i> = 0.05; however, at 350 K (amorphous), total ionic conductivity in confinement is lower than in the bulk for both salt concentrations. Time-of-flight secondary ion mass spectrometry indicates selective migration of ions toward the polymer-scaffold interface. In summary, for the 3D structure studied, polymer crystallinity, interfacial segregation, and tortuosity play important roles in determining total ionic conductivity and, ultimately, the emergence of 3D SPEs as energy storage materials.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":" ","pages":"1577-1583"},"PeriodicalIF":5.1,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574785","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}

{"title":"Modeling of Chain Sequence Length and Distribution in Random Copolyesters","authors":"Yisong Wang, Bingxue Jiang, Zhengqi Peng, Khak Ho Lim, Qingyue Wang, Shengbin Shi, Jieyuan Zheng, Deliang Wang, Xuan Yang, Pingwei Liu, Wen-Jun Wang","doi":"10.1021/acsmacrolett.4c00598","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00598","url":null,"abstract":"The performances and properties of random copolyesters, including biodegradability, mechanical and thermal properties, transparency, etc., are highly influenced by their chain structures. However, obtaining detailed chain sequence information remains a significant challenge. This study introduces a mathematical model based on a probabilistic approach to determine the sequence length and distribution in random copolyesters. Two types of copolyesters, A₁A₁BB-A₂A₂BB, representing poly(butylene adipate-<i>co</i>-terephthalate) (PBAT), and A₁A₁B₁B₁-A₂B₂, using poly(butylene succinate-<i>co</i>-glycolic acid) (PBT–PGA) as an example, are the focus. The predicted sequence lengths of various copolyesters derived from the model are in good agreement with the values reported in the literature. The chain sequence distribution obtained from the model provides better insights into the unique properties of the copolyesters. It is observed that the incorporation of hydroxyl acid units into copolyester chains effectively reduces the sequence length without altering the copolymer composition, offering a strategic approach for enhancing degradation performance while maintaining mechanical properties of random copolyesters. The influence of the number-average sequence length becomes particularly significant when the copolymer composition ranges between 0.7 and 0.9, with a higher copolymer composition required for copolyesters containing hydroxyl acid monomer units. This model represents a powerful tool for researchers, enabling a deeper understanding of the relationship between copolymer composition and its structural characteristics in random copolyesters and facilitating the development of high-performance random copolyesters.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"246 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637492","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}

{"title":"Light-Driven Organocatalyzed Controlled Radical Copolymerization of (Perfluoroalkyl)ethylenes and Vinyl Esters/Amides","authors":"Qianhao Ye,&nbsp;Kaixuan Chen,&nbsp;Chengda Zhou,&nbsp;Mengli Xu and Mao Chen*,&nbsp;","doi":"10.1021/acsmacrolett.4c0073710.1021/acsmacrolett.4c00737","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00737https://doi.org/10.1021/acsmacrolett.4c00737","url":null,"abstract":"<p >Fluoropolymers of well-defined structures exhibit significant potential in a broad range of high-tech applications. However, the controlled synthesis of fluoropolymers from easily available monomers remains difficult. In this work, we report the development of an organocatalyzed controlled radical copolymerization of (perfluoroalkyl)ethylenes (PFAEs) and unconjugated vinyl monomers (UCMs) under light irradiation, which has enabled on-demand access toward side-chain fluorinated polymers under metal-free conditions. This method furnishes a large variety of polymers with diverse fluoroalkyl and ester/amide as pendent groups, tunable molar masses, and low dispersities (ca. <i>Đ</i> = 1.1–1.3), and adjustable fractions of PFAE and UCM units. Obtained fluoropolymers exhibit good chain-end fidelity and activity, allowing chain-extension polymerizations to prepare block copolymers of complicated compositions. Furthermore, the PFAE copolymers exhibit outstanding light transmission and low refractive index.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"13 12","pages":"1640–1646 1640–1646"},"PeriodicalIF":5.1,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843005","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}

{"title":"Modeling of Chain Sequence Length and Distribution in Random Copolyesters","authors":"Yisong Wang,&nbsp;Bingxue Jiang,&nbsp;Zhengqi Peng,&nbsp;Khak Ho Lim,&nbsp;Qingyue Wang,&nbsp;Shengbin Shi,&nbsp;Jieyuan Zheng,&nbsp;Deliang Wang,&nbsp;Xuan Yang,&nbsp;Pingwei Liu and Wen-Jun Wang*,&nbsp;","doi":"10.1021/acsmacrolett.4c0059810.1021/acsmacrolett.4c00598","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00598https://doi.org/10.1021/acsmacrolett.4c00598","url":null,"abstract":"<p >The performances and properties of random copolyesters, including biodegradability, mechanical and thermal properties, transparency, etc., are highly influenced by their chain structures. However, obtaining detailed chain sequence information remains a significant challenge. This study introduces a mathematical model based on a probabilistic approach to determine the sequence length and distribution in random copolyesters. Two types of copolyesters, A₁A₁BB-A₂A₂BB, representing poly(butylene adipate-<i>co</i>-terephthalate) (PBAT), and A₁A₁B₁B₁-A₂B₂, using poly(butylene succinate-<i>co</i>-glycolic acid) (PBT–PGA) as an example, are the focus. The predicted sequence lengths of various copolyesters derived from the model are in good agreement with the values reported in the literature. The chain sequence distribution obtained from the model provides better insights into the unique properties of the copolyesters. It is observed that the incorporation of hydroxyl acid units into copolyester chains effectively reduces the sequence length without altering the copolymer composition, offering a strategic approach for enhancing degradation performance while maintaining mechanical properties of random copolyesters. The influence of the number-average sequence length becomes particularly significant when the copolymer composition ranges between 0.7 and 0.9, with a higher copolymer composition required for copolyesters containing hydroxyl acid monomer units. This model represents a powerful tool for researchers, enabling a deeper understanding of the relationship between copolymer composition and its structural characteristics in random copolyesters and facilitating the development of high-performance random copolyesters.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"13 12","pages":"1647–1654 1647–1654"},"PeriodicalIF":5.1,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843120","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}

{"title":"Circular Cross-Linked Polyethylene Enabled by In-Chain Ketones","authors":"Tobias O. Morgen,&nbsp; and ,&nbsp;Stefan Mecking*,&nbsp;","doi":"10.1021/acsmacrolett.4c0066010.1021/acsmacrolett.4c00660","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00660https://doi.org/10.1021/acsmacrolett.4c00660","url":null,"abstract":"<p >Cross-linked polyethylenes (PEs) are widely employed, but the permanent links between the chains impede recycling. We show that via imine formation with diamines keto-functionalized polyethylenes from both free-radical (keto-low-density PE, keto-LDPE) and catalytic (keto-high-density PE, keto-HDPE) nonalternating ethylene-CO copolymerization can be cross-linked efficiently in the melt, resulting in gel fractions of the formed cross-linked PEs of up to 85% and improved tensile properties. The imine-based cross-links in the material can be hydrolyzed at 140 °C to recycle up to 97% of the initial thermoplastic keto-polyethylene. Low keto contents of ≤1.5 mol % are found ideal to retain PE-like thermal properties, achieve sufficient cross-link density, and maintain circular recyclability.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"13 12","pages":"1655–1661 1655–1661"},"PeriodicalIF":5.1,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmacrolett.4c00660","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843004","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}

{"title":"Light-Driven Organocatalyzed Controlled Radical Copolymerization of (Perfluoroalkyl)ethylenes and Vinyl Esters/Amides","authors":"Qianhao Ye, Kaixuan Chen, Chengda Zhou, Mengli Xu, Mao Chen","doi":"10.1021/acsmacrolett.4c00737","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00737","url":null,"abstract":"Fluoropolymers of well-defined structures exhibit significant potential in a broad range of high-tech applications. However, the controlled synthesis of fluoropolymers from easily available monomers remains difficult. In this work, we report the development of an organocatalyzed controlled radical copolymerization of (perfluoroalkyl)ethylenes (PFAEs) and unconjugated vinyl monomers (UCMs) under light irradiation, which has enabled on-demand access toward side-chain fluorinated polymers under metal-free conditions. This method furnishes a large variety of polymers with diverse fluoroalkyl and ester/amide as pendent groups, tunable molar masses, and low dispersities (ca. <i>Đ</i> = 1.1–1.3), and adjustable fractions of PFAE and UCM units. Obtained fluoropolymers exhibit good chain-end fidelity and activity, allowing chain-extension polymerizations to prepare block copolymers of complicated compositions. Furthermore, the PFAE copolymers exhibit outstanding light transmission and low refractive index.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"162 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637494","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}

{"title":"High-Resolution Total Internal Reflection-Based Structural Coloration by Electrohydrodynamic Jet Printing of Transparent Polyethylene Glycol Microdomes","authors":"Dongho Lee,&nbsp;Doyoung Byun* and Dae-Hyun Cho*,&nbsp;","doi":"10.1021/acsmacrolett.4c0051210.1021/acsmacrolett.4c00512","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00512https://doi.org/10.1021/acsmacrolett.4c00512","url":null,"abstract":"<p >Total internal reflection (TIR)-based structural coloration is a brilliant strategy to overcome the need for periodic nanostructures and complex fabrication processes. Light entering the microdome structure undergoes TIR, and owing to varying reflection paths, it exhibits a color that changes with the microdome size. Although solution-based printing techniques have been proposed to achieve this effect, they fall short of full-color realization owing to resolution limitations. Herein, we achieved 3628 dpi of full-color and high-resolution structural color images by printing transparent microdome structures with 1.2–9.9 μm diameter using electrohydrodynamic (EHD) jet printing. Additionally, high-resolution EHD jet-printed structural color images display complex encoded information, enhancing the anticounterfeiting effectiveness through their fabrication simplicity and precise control over the microdome size. Because of these advantages, this TIR-based structural coloration technique with EHD jet printing is highly suitable for anticounterfeiting applications.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"13 12","pages":"1634–1639 1634–1639"},"PeriodicalIF":5.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843106","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}

{"title":"Catalytic Syntheses of Thiol-End-Functionalized ROMP Polymers","authors":"Ankita Mandal,&nbsp;Ijaj Ahmed and Andreas F. M. Kilbinger*,&nbsp;","doi":"10.1021/acsmacrolett.4c0057110.1021/acsmacrolett.4c00571","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00571https://doi.org/10.1021/acsmacrolett.4c00571","url":null,"abstract":"<p >Thiol-functionalized polymers have become a crucial class of materials due to their distinct chemical properties and versatile reactivity, leading to a broad spectrum of applications. Herein, we report the straightforward syntheses of a wide range of thiol-end-functionalized ring-opening metathesis polymerization (ROMP) polymers exploiting our previously reported catalytic ROMP mechanisms using suitable chain transfer agents. All the synthesized polymers were characterized via SEC, ¹H NMR spectroscopy and MALDI-ToF mass spectrometry techniques. Furthermore, the existence of thiol groups on the polymer chains was verified through the well-established thiol coating reaction on gold nanoparticle surfaces. We believe this method of synthesizing thiol-end-functionalized ROMP polymers (using a reduced amount of ruthenium metal compared to conventional living ROMP) will be of great importance to materials science and biochemical research.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"13 12","pages":"1627–1633 1627–1633"},"PeriodicalIF":5.1,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850028","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}

{"title":"Catalytic Syntheses of Thiol-End-Functionalized ROMP Polymers","authors":"Ankita Mandal, Ijaj Ahmed, Andreas F. M. Kilbinger","doi":"10.1021/acsmacrolett.4c00571","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00571","url":null,"abstract":"Thiol-functionalized polymers have become a crucial class of materials due to their distinct chemical properties and versatile reactivity, leading to a broad spectrum of applications. Herein, we report the straightforward syntheses of a wide range of thiol-end-functionalized ring-opening metathesis polymerization (ROMP) polymers exploiting our previously reported catalytic ROMP mechanisms using suitable chain transfer agents. All the synthesized polymers were characterized via SEC, ¹H NMR spectroscopy and MALDI-ToF mass spectrometry techniques. Furthermore, the existence of thiol groups on the polymer chains was verified through the well-established thiol coating reaction on gold nanoparticle surfaces. We believe this method of synthesizing thiol-end-functionalized ROMP polymers (using a reduced amount of ruthenium metal compared to conventional living ROMP) will be of great importance to materials science and biochemical research.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"11 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601641","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}

{"title":"Generating Tooth Organoids Using Defined Bioorthogonally Cross-Linked Hydrogels","authors":"Xuechen Zhang, Nicola Contessi Negrini, Rita Correia, Paul T. Sharpe, Adam D. Celiz, Ana Angelova Volponi","doi":"10.1021/acsmacrolett.4c00520","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00520","url":null,"abstract":"Generating teeth <i>in vitro</i> requires mimicking tooth developmental processes. Biomaterials are essential to support 3D tooth organoid formation, but their properties must be finely tuned to achieve the required biomimicry for tooth development. For the first time, we used bioorthogonally cross-linked hydrogels as defined 3D matrixes for tooth developmental engineering, and we highlighted how their properties play a pivotal role in enabling 3D tooth organoid formation <i>in vitro</i>. We prepared hydrogels by mixing gelatin precursors modified either with tetrazine (Tz) or norbornene (Nb) moieties. We tuned the hydrogel properties (<i>E</i> = 2–7 kPa; <i>G</i>′ = 500–1500 Pa) by varying the gelatin concentration (8% vs 12% w/V) and stoichiometric ratio (Tz:Nb = 1 vs 0.5). We encapsulated dental epithelial-mesenchymal cell pellets in a library of hydrogels and identified a hydrogel formulation that enabled successful growth kinetics and morphogenesis of tooth germs, introducing a defined tunable platform for tooth organoid engineering and modeling.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"38 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601642","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}