ACS Macro Letters最新文献_第2页

Thermoelectrochemical Method for Quantification of the Micellization Entropy of Redox-Active Polymers 定量氧化还原活性聚合物胶束熵的热电化学方法

IF 5.8

ACS Macro Letters Pub Date : 2025-01-09 DOI: 10.1021/acsmacrolett.4c00773

Mizuha Ujita, Hongyao Zhou, Teppei Yamada

{"title":"Thermoelectrochemical Method for Quantification of the Micellization Entropy of Redox-Active Polymers","authors":"Mizuha Ujita, Hongyao Zhou, Teppei Yamada","doi":"10.1021/acsmacrolett.4c00773","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00773","url":null,"abstract":"Redox-active micelles undergo reversible association and dissociation in response to their redox potential and are promising materials for various applications, such as drug delivery and bioimaging. Evaluation of the micellization entropy is critical in controlling the thermodynamics of micelle formation. However, conventional methods such as isothermal titration calorimetry and surface tensiometry require a long measurement time to observe changes in the heat flow or the surface tension caused by the micellization. Here we report a thermoelectrochemical method to quantify the entropy change produced by redox-active micelles. A set of poly(ethyl glycidyl ether-b-ethylene oxide)phenothiazine (PT-EGE-EO) with varied chain length were synthesized, and their micellization entropy was calculated from the temperature-dependent changes of the equilibrium potential. This thermoelectrochemical method enables a quick evaluation of the micellization entropy with only a single sample preparation and temperature sweep. The obtained results showed a reasonable agreement with the conventional surface tensiometry and isothermal titration calorimetry, indicating that the thermoelectrochemical method is a promising alternative for quantification of the micellization entropy.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"1 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937167","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

Influence of Tacticity on the Self-Assembly of Poly(ethylene glycol)-b-poly(lactic acid) Block Copolymers 弹性对聚乙二醇-聚乳酸嵌段共聚物自组装的影响

IF 5.8

ACS Macro Letters Pub Date : 2025-01-06 DOI: 10.1021/acsmacrolett.4c00758

Sjoerd J. Rijpkema, B. Jelle Toebes, Jules van Vlaenderen, Liban van Haren, Daniela A. Wilson

引用次数: 0

Ordered Photoexfoliation for Polypseudorotaxane Nanosheets 聚聚环氧紫杉烷纳米片的有序光剥

IF 5.8

ACS Macro Letters Pub Date : 2025-01-05 DOI: 10.1021/acsmacrolett.4c00815

Mouwei Liu, Bin Wu, Shen Shen, Hao Sun, Xinyan Gu, Shan Li, Ziran Tang, Jianshuo Cheng, Xiang Ma, Man Zhang, Yifei Xu, Liangliang Zhu

引用次数: 0

Converting a Metal-Coordinating Polymer to a Polymerized Ionic Liquid Improves Li+ Transport 将金属配位聚合物转化为聚合离子液体可改善Li+输运

IF 5.8

ACS Macro Letters Pub Date : 2025-01-03 DOI: 10.1021/acsmacrolett.4c00704

James T. Bamford, Leo W. Gordon, Raphaële J. Clément, Rachel A. Segalman

引用次数: 0

Persistent Toughness and Heat Triggered Plasticization in Polylactide Modified with Poly(ethylene oxide)-block-poly(butylene oxide) 聚（环氧乙烷）-嵌段聚（环氧丁烯）改性聚丙交酯的持久韧性和热触发增塑

IF 5.8

ACS Macro Letters Pub Date : 2025-01-01 DOI: 10.1021/acsmacrolett.4c00678

Jonathan P. Coote, Matthew C. Larson, Frank S. Bates, Christopher J. Ellison

{"title":"Persistent Toughness and Heat Triggered Plasticization in Polylactide Modified with Poly(ethylene oxide)-block-poly(butylene oxide)","authors":"Jonathan P. Coote, Matthew C. Larson, Frank S. Bates, Christopher J. Ellison","doi":"10.1021/acsmacrolett.4c00678","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00678","url":null,"abstract":"Poly(lactide) (PLA) is a promising biodegradable polymer with potential applications in single-use packaging. However, its use is limited by brittleness, and its biodegradability is restricted to industrial compost conditions due in part to an elevated glass transition temperature (Tg). We previously showed that addition of a poly(ethylene-oxide)-block-poly(butylene oxide) diblock copolymer (PEO–PBO) forms macrophase-separated rubbery domains in PLA that can impart significant toughness at only 5 wt %. This work demonstrates that PEO–PBO/PLA blends exhibit substantial toughness for at least nine months, beyond the average lifetime of single-use packaging, even amidst oxidative degradation of PEO–PBO into oligomeric products. Due to the glassy nature of the PLA matrix, these degradation products are confined to macrophase-separated domains, and the blend morphology is preserved. However, modest thermal annealing (∼60 °C) causes these domains to rapidly reduce in area fraction and size from migration and solubilization of the PEO–PBO degradation products into PLA, which plasticizes PLA and reduces the blend Tg. As a result, aged PEO–PBO/PLA blends degrade in just under half the time of similarly aged neat PLA when submerged in artificial seawater at 50 °C. This surprising combination of properties addresses two of PLA’s most significant limitations with a single additive by (1) toughening the PLA during its useful lifetime and then (2) accelerating its degradation rate by heat-triggered plasticization when exposed to elevated temperatures at end-of-life, such as those of industrial (or even home) compost.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"27 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912285","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

Degradable and Chain Extendable Segmented Hyperbranched Copolymers by Wavelength-Selective Photoiniferter Polymerization Using a Trithiocarbonate-Derived Dimethacrylate 波长选择性光干扰聚合的可降解和可扩链分段超支化共聚物

IF 5.8

ACS Macro Letters Pub Date : 2024-12-23 DOI: 10.1021/acsmacrolett.4c00771

Yanwen Chen, Ruiming Wang, Xinxin Sheng, Li Zhang, Jianbo Tan

{"title":"Degradable and Chain Extendable Segmented Hyperbranched Copolymers by Wavelength-Selective Photoiniferter Polymerization Using a Trithiocarbonate-Derived Dimethacrylate","authors":"Yanwen Chen, Ruiming Wang, Xinxin Sheng, Li Zhang, Jianbo Tan","doi":"10.1021/acsmacrolett.4c00771","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00771","url":null,"abstract":"In this study, segmented hyperbranched copolymers with degradable and chain extendable cross-linker branch points were synthesized via green light-activated photoiniferter copolymerization of poly(ethylene glycol) methyl ether methacrylate (PEGMA) and a trithiocarbonate-derived dimethacrylate. A series of segmented hyperbranched copolymers with different degrees of branching were synthesized by changing the feed ratio of PEGMA to cross-linker to chain transfer agent. The segmented hyperbranched copolymers could be degraded into linear polymer chains by removing the trithocarbonate groups, which provides fundamental insights into the growth of primary chains during photoiniferter copolymerization. Switching to blue light irradiation allowed for the chain extension of poly(N,N-dimethylacrylamide) (PDMA) both at the branch points and at the chain ends. Finally, the formed segmented hyperbranched copolymers were explored as macromolecular chain transfer agents to prepare segmented hyperbranched block copolymer nanoparticles via polymerization-induced self-assembly. This study not only leads to new examples of degradable and chain extendable segmented hyperbranched polymers but also provides important insights into the formation of branched polymers via copolymerization of multivinyl monomers.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"12 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880072","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

Influence of Water Sorption on Ionic Conductivity in Polyether Electrolytes at Low Hydration 低水化条件下吸水对聚醚电解质离子电导率的影响

IF 5.8

ACS Macro Letters Pub Date : 2024-12-23 DOI: 10.1021/acsmacrolett.4c00707

Rahul Sujanani, Phong H. Nguyen, Leo W. Gordon, James T. Bamford, Alexandra Zele, Benjamin J. Pedretti, Nathaniel A. Lynd, Raphaële J. Clément, Rachel A. Segalman

{"title":"Influence of Water Sorption on Ionic Conductivity in Polyether Electrolytes at Low Hydration","authors":"Rahul Sujanani, Phong H. Nguyen, Leo W. Gordon, James T. Bamford, Alexandra Zele, Benjamin J. Pedretti, Nathaniel A. Lynd, Raphaële J. Clément, Rachel A. Segalman","doi":"10.1021/acsmacrolett.4c00707","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00707","url":null,"abstract":"Ion-containing polymers are subject to a wide range of hydration conditions across electrochemical and water treatment applications. Significant work on dry polymer electrolytes for batteries and highly swollen membranes for water purification has informed our understanding of ion transport under extreme conditions. However, knowledge of intermediate conditions (i.e., low hydration) is essential to emerging applications (e.g., electrolyzers, fuel cells, and lithium extraction). Ion transport under low levels of hydration is distinct from the extreme conditions typically investigated, and the relevant physics cannot be extrapolated from existing knowledge, stifling materials design. In this study, we conducted ion transport measurements in LiTFSI-doped polyethers that were systematically hydrated from dry conditions. A semiautomated apparatus that performs parallel measurements of water uptake and ionic conductivity in thin-film polymers under controlled humidity was developed. For the materials and swelling range considered in this study (i.e., <0.07 g water/g dry polymer electrolyte), ionic conductivity depends nonlinearly on water uptake, with the initial sorbed water weakly affecting conductivity. With additional increases in swelling, more significant increases in conductivity were observed. Remarkably, changes in conductivity induced by water sorption were correlated with the number of water molecules per lithium ion, with the normalized molar conductivity of different samples effectively collapsing onto one another until this unit of hydration exceeded the solvation number of lithium ions under aqueous conditions. These results provide important knowledge regarding the effects of trace water contamination on conductivity measurements in polymer electrolytes and demonstrate that the lithium-ion solvation number marks a key transition point regarding the influence of water on ion transport in ion-containing polymers.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"24 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874102","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

Syndioselective Ring-Opening Polymerization of β-Lactones Enabled by Dimethylbiphenyl-Salen Yttrium Complexes 二甲联苯- salen钇配合物诱导β-内酯的共二选择开环聚合

IF 5.8

ACS Macro Letters Pub Date : 2024-12-22 DOI: 10.1021/acsmacrolett.4c00757

Min Xie, Hao-Yi Huang, Yu-Ting Huang, Yun-Cong Ye, Zhongzheng Cai, Jian-Bo Zhu

{"title":"Syndioselective Ring-Opening Polymerization of β-Lactones Enabled by Dimethylbiphenyl-Salen Yttrium Complexes","authors":"Min Xie, Hao-Yi Huang, Yu-Ting Huang, Yun-Cong Ye, Zhongzheng Cai, Jian-Bo Zhu","doi":"10.1021/acsmacrolett.4c00757","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00757","url":null,"abstract":"Polyhydroxyalkanoates (PHAs) have served as promising alternatives to traditional petroleum-based plastics. Chemical synthesis of stereoregular PHAs via stereocontrolled ring-opening polymerization (ROP) of racemic β-lactones was a desired strategy with a formidable challenge. Herein, we developed a class of DiMeBiPh-salen yttrium complexes that adopted a cis-α configuration for stereoselective ROP of rac-β-butyrolactones (rac-BBL) and rac-β-valerolactone (rac-BVL). Notably, catalyst Y5 promoted robust polymerization with TOF up to 104 h–1 and furnished syndiotactic P3HB, P3HV, and P(3HB)-co-P(3HV) copolymers with Pr values of up to 0.95. Varying the compositions in P(3HB)-co-P(3HV) copolymers offered an intriguing opportunity to fine tune the thermal properties. Our kinetic study supported a polymeryl exchange mechanism. This work demonstrated that the DiMeBiPh-salen system could serve as a new catalytic framework for the stereoselective ROP of β-lactones, which leverages the catalyst design for stereoselective polymerization.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"2 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874101","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

Constructing Strategy for Realizing White-Light-Emitting of Organic Aggregates Based on Self-Assembling Conjugated Polymer Nanobowls 基于自组装共轭聚合物纳米碗实现有机聚集体白光的构建策略

IF 5.8

ACS Macro Letters Pub Date : 2024-12-21 DOI: 10.1021/acsmacrolett.4c00714

Weijie Yuan, Lan Shu, Jing Xu, Chenhao Hua, Jin Huang

{"title":"Constructing Strategy for Realizing White-Light-Emitting of Organic Aggregates Based on Self-Assembling Conjugated Polymer Nanobowls","authors":"Weijie Yuan, Lan Shu, Jing Xu, Chenhao Hua, Jin Huang","doi":"10.1021/acsmacrolett.4c00714","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00714","url":null,"abstract":"The construction of single-component, white-light-emitting, conjugated polymers always utilizes fluorescence resonance energy transfer (FRET) for efficient emission. However, the main challenges in developing such materials primarily come from the effects of aggregation states during solution processing and the precise structural control required for the synthesis of compounds. Both aspects can affect the FRET between different lumophores in white-light-emitting materials. A novel supermolecular assembly strategy using new conjugated polymers (CPs) to fabricate single-component white-light-emitting CPs nanobowls (CPNBs) was developed to overcome the two difficulties. Specifically, through molecular structure engineering, side chains have been modified with a uracil group capable of hydrogen bonding, which stabilized the nanobowl structure during the supramolecular assembly process. Furthermore, by blending two kinds of CPs emitting different colors during the supramolecular assembly, single-component, white-light-emitting CPNBs have been achieved. The supramolecular strategy has resulted in stable and high-brightness, white-light emission, whether in aqueous solutions of different concentrations or in solid-state, polymer-based, composite materials. It also offers a more straightforward and environmentally friendly synthesis process for white-light-emitting organic materials.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"12 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2024-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142867184","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

Biodegradable Nanobowls with Controlled Dents 具有可控凹痕的可生物降解纳米碗

IF 5.8

ACS Macro Letters Pub Date : 2024-12-19 DOI: 10.1021/acsmacrolett.4c00671

Jinhui Jiang, Min Sun, Qianxi Gu, Shangning Liu, Hui Sun, Zhen Fan, Yunqing Zhu, Jianzhong Du

引用次数: 0