ACS Macro Letters最新文献

Degradable and Chain Extendable Segmented Hyperbranched Copolymers by Wavelength-Selective Photoiniferter Polymerization Using a Trithiocarbonate-Derived Dimethacrylate

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

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

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

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

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

Polyelectrolyte–Carbon Dot Complex Coacervation

IF 5.8

ACS Macro Letters Pub Date : 2024-12-19 DOI: 10.1021/acsmacrolett.4c00745

Pankaj Kumar Pandey, Arvind Sathyavageeswaran, Nickolas Holmlund, Sarah L. Perry

引用次数: 0

Bicontinuous Nanoparticles from Spontaneous Self-Assembly of Block Copolymer Prodrug in Aqueous Medium for Potential Cancer Therapy

IF 5.8

ACS Macro Letters Pub Date : 2024-12-18 DOI: 10.1021/acsmacrolett.4c00590

Juthi Pal, Pousali Samanta, Afruja Khan, Rishabh Maity, Amirul Islam Mallick, Dibakar Dhara

{"title":"Bicontinuous Nanoparticles from Spontaneous Self-Assembly of Block Copolymer Prodrug in Aqueous Medium for Potential Cancer Therapy","authors":"Juthi Pal, Pousali Samanta, Afruja Khan, Rishabh Maity, Amirul Islam Mallick, Dibakar Dhara","doi":"10.1021/acsmacrolett.4c00590","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00590","url":null,"abstract":"Despite having several advantages, bicontinuously structured polymeric nanoparticles (BSPNPs) are far less explored in the field of controlled drug delivery owing to the requirement of complex precursor copolymers and the associated multistep synthetic procedures. In this work, we report the synthesis of a redox-sensitive diblock copolymer (P1), which was subsequently utilized to prepare doxorubicin (DOX) containing a pH-labile prodrug (P2). P1 and P2 spontaneously self-assembled in aqueous media above their critical aggregation concentration, forming micellar nanoparticles with rare bicontinuous morphology that promotes loading of both hydrophobic and hydrophilic cargoes in different compartments. To the best of our knowledge, the formation of BSPNPs through direct self-assembly in aqueous media has not yet been reported. In vitro cellular studies asserted the higher safety profile of the nanoparticles against noncancerous cells (HEK293T) than free DOX, whereas they displayed higher drug-induced cytotoxicity against cancer cells (MCF-7) in comparison to free DOX, establishing them as promising cancer drug delivery systems.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"89 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142840901","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 Solvent Dielectric Constant on the Complex Coacervation Phase Behavior of Polymerized Ionic Liquids. 溶剂介电常数对聚合离子液体复合物共存相行为的影响

IF 5.1

ACS Macro Letters Pub Date : 2024-12-17 Epub Date: 2024-11-21 DOI: 10.1021/acsmacrolett.4c00663

Jowon Shin, Heewoon Shin, Sang-Ho Lee, Jong Dae Jang, Hyeong Jun Kim

{"title":"Influence of Solvent Dielectric Constant on the Complex Coacervation Phase Behavior of Polymerized Ionic Liquids.","authors":"Jowon Shin, Heewoon Shin, Sang-Ho Lee, Jong Dae Jang, Hyeong Jun Kim","doi":"10.1021/acsmacrolett.4c00663","DOIUrl":"10.1021/acsmacrolett.4c00663","url":null,"abstract":"Complex coacervation is an associative phase separation process of oppositely charged polyelectrolyte solutions, resulting in a coacervate phase enriched with charged polymers and a polymer-lean phase. To date, studies on the phase behavior of complex coacervation have been largely restricted to aqueous systems with relatively high dielectric constants due to the limited solubility of most polyelectrolytes, hindering the exploration of the effects of electrostatic interactions from differences in solvent permittivity. Herein, we prepare two symmetric but oppositely charged polymerized ionic liquids (PILs), consisting of poly[1-[2-acryloyloxyethyl]-3-butylimidazolium bis(trifluoromethane)sulfonimide] (PAT) and poly[1-ethyl-3-methylimidazolium 3-[[[(trifluoromethyl)sulfonyl]amino]sulfonyl]propyl acrylate] (PEA). Due to the delocalized ionic charges and their chemical structure similarity, both PAT and PEA are soluble in various organic solvents with a wide range of dielectric constants, ranging from 16.7 (hexafluoro-2-propanol (HFIP)) to 66.1 (propylene carbonate (PC)). Notably, no significant correlation is observed between the solvent dielectric constant and the phase diagram of the complex coacervation of PILs. Most organic solvents lead to similar phase diagrams and salt resistances regardless of their dielectric constants, except two protic solvents (HFIP and 2,2,2-trifluoroethanol (TFE)) showing significantly low salt resistances compared to the others. The low salt resistance in these protic solvents primarily arises from strong hydrogen bonding between PILs and solvents as evidenced by 1H NMR and small-angle neutron scattering (SANS) experiments. Our finding suggests that for the coacervation of PILs, particularly those with delocalized and weak charge interactions, entropy from the counterion release and polymer-solvent interaction χ parameter play a more important role than the electrostatic interactions of charged molecules, rendered by the dielectric constant of the solvent medium.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":" ","pages":"1678-1685"},"PeriodicalIF":5.1,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142685397","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

Aqueous Photoiniferter Polymerization of Acrylonitrile. 丙烯腈的水性光增塑聚合。

IF 5.1

ACS Macro Letters Pub Date : 2024-12-17 Epub Date: 2024-11-19 DOI: 10.1021/acsmacrolett.4c00642

Evan K Stacy, Mac L McCormick, Kaden C Stevens, Penelope E Jankoski, Jeff Aguinaga, Derek L Patton, Brent S Sumerlin, Tristan D Clemons

引用次数: 0

Circular Cross-Linked Polyethylene Enabled by In-Chain Ketones. 链内酮促成环状交联聚乙烯。

IF 5.1

ACS Macro Letters Pub Date : 2024-12-17 Epub Date: 2024-11-15 DOI: 10.1021/acsmacrolett.4c00660

Tobias O Morgen, Stefan Mecking

引用次数: 0