ACS Macro Letters最新文献_第6页

Copolymer Self-Assembly Triggered by Cis–Trans Polyproline Isomerization 顺-反式聚脯氨酸异构化引发共聚物自组装

IF 4.9

ACS Macro Letters Pub Date : 2026-09-15 Epub Date: 2026-09-03 DOI: 10.1021/acsmacrolett.6c00340

Ernesto Tinajero-Díaz, Antxon Martínez de Ilarduya

{"title":"Copolymer Self-Assembly Triggered by Cis–Trans Polyproline Isomerization","authors":"Ernesto Tinajero-Díaz, Antxon Martínez de Ilarduya","doi":"10.1021/acsmacrolett.6c00340","DOIUrl":"10.1021/acsmacrolett.6c00340","url":null,"abstract":"Polyproline existsin two forms, the all-cis right-handedpolyproline helix (type I) and the all-trans left-handedpolyproline helix (type II). While the former is favored in commonorganic solvents, the latter is favored in aqueous solutions. Takingadvantage of the hydrophilicity of type II polyproline, we preparedpeptide-based nanostructures from a series of block copolymers ofε-caprolactone and l-proline. Copolymers were synthesizedvia N-carboxyanhydride polymerization in DMF usingamino-ended polycaprolactone as initiator and covering a broad rangeof polyproline compositions. By simple stirring in water, the cis–trans isomerization of polyproline triggeredtheir solubilization, leading to the spontaneous self-assembly ofthe copolymers into colloidally stable nanoparticles. Optical rotationmeasurements demonstrated the mutarotation of prolyl residues andcircular dichroism spectroscopy shed light on the preferential typeII secondary structure of polyproline that stabilizes nanostructures.Nanodevices encapsulated doxorubicin hydrochloride, highlighting theirpotential as drug delivery systems.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1305–1310"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148885200","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

Counterion-Modulated Microphase Separation of a Solvent-Free Block Polyampholyte 一种无溶剂嵌段多两性聚合物的反离子调制微相分离

IF 4.9

ACS Macro Letters Pub Date : 2026-09-15 Epub Date: 2026-08-11 DOI: 10.1021/acsmacrolett.6c00323

Seulki Kang, Christopher Balzer, Glenn H. Fredrickson, Ryan C. Hayward

{"title":"Counterion-Modulated Microphase Separation of a Solvent-Free Block Polyampholyte","authors":"Seulki Kang, Christopher Balzer, Glenn H. Fredrickson, Ryan C. Hayward","doi":"10.1021/acsmacrolett.6c00323","DOIUrl":"10.1021/acsmacrolett.6c00323","url":null,"abstract":"Interfacesbetween oppositely charged polymers presentstrong localgradients in the electrical environment, enabling applications inelectrochemical devices, ionic diodes, and low-voltage electroadhesives.As these responses are often highly dependent on the area of contactbetween the polymers, many efforts have been made to prepare structureswith a high interfacial area to enhance performance. However, tailoringthe miscibility of polycations and polyanions to realize targetednanoscale structures remains an outstanding challenge. In this study,we present a novel approach to achieving microphase separation insolvent-free block polyampholytes by manipulating counterion chemistry.Using a block polyampholyte composed of a positively charged imidazoliumblock and a negatively charged sulfonylimide block, we demonstratethat the phase behavior can be modulated by the chemistry of the addedionic liquid salts. Specifically, immiscibility between a fixed alkyl-imidazoliumand a bulky alkyl-phosphonium counterion drives microphase separationof the block polyampholyte. Theoretical predictions of microphasebehavior support the experimental observation that the chemical incompatibilitybetween like-charged species increases the propensity for microphaseseparation. This work highlights a facile route to realizing nanoscalestructures of block polyampholytes using chemically incompatible ionicliquids.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1258–1264"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148717891","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

Accessible One-Pot Approach to Syndiotactic Non-Conjugated Pendant Electroactive Polymers via Sequential Radical Photopolymerization in Water and Post-Polymerization Functionalization 通过在水中的顺序自由基光聚合和聚合后官能化的可接近的一锅方法来研究共规非共轭垂坠型电活性聚合物

IF 4.9

ACS Macro Letters Pub Date : 2026-09-15 Epub Date: 2026-08-26 DOI: 10.1021/acsmacrolett.6c00389

Dhairya Patel, Barry C. Thompson

{"title":"Accessible One-Pot Approach to Syndiotactic Non-Conjugated Pendant Electroactive Polymers via Sequential Radical Photopolymerization in Water and Post-Polymerization Functionalization","authors":"Dhairya Patel, Barry C. Thompson","doi":"10.1021/acsmacrolett.6c00389","DOIUrl":"10.1021/acsmacrolett.6c00389","url":null,"abstract":"Stereoregular non-conjugated pendant electroactive polymers(NCPEPs)show promising hole mobilities (μh) as measured byspace charge limited current (SCLC) but have required rigorous anionicpolymerization techniques to obtain higher stereoregularity. SyndiotacticNCPEPs in particular are the subject of only one literature reportdue to synthetic challenges despite the exceptional reported μh. Here, a facile one-pot sequential synthetic strategy involvingthe accessible radical photopolymerization of methacrylate salt inwater, followed by guanidine mediated post-polymerization modification(PPM) with alkyl bromide-functional pendant carbazole has been developedfor synthesizing syndiotactic poly(alkyl methacrylates). This routeis not only accessible but also reduces polymer loss through the sequentialone-pot nature of the polymerization and functionalization. A poly(N-carbazolylhexyl methacrylate) thus synthesized has 87%triad syndiotacticity (rr), an Mn of 370.5 kg mol–1 and shows μh of 1.36 × 10–3 cm2 V–1 s–1. This approach thus demonstratesa significant improvement in the synthesis of syndiotactic polymethacrylate-basedNCPEPs.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1362–1367"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148821776","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

Solid-State Chemical Recycling of Anhydride-Based Polymers: From Linear Copolyesters to Cross-Linked Epoxy Networks 酸酐基聚合物的固态化学回收：从线性共聚酯到交联环氧树脂网络

IF 4.9

ACS Macro Letters Pub Date : 2026-09-15 Epub Date: 2026-09-02 DOI: 10.1021/acsmacrolett.6c00401

Guo-Xu Wang, Xiang Li, Yu-Hao Zhang, Hao-Yun Liu, Ze-Hua Liu, Bai-Hao Ren, Qing Liu, Qiu-Yu Zhang, Jie Li

{"title":"Solid-State Chemical Recycling of Anhydride-Based Polymers: From Linear Copolyesters to Cross-Linked Epoxy Networks","authors":"Guo-Xu Wang, Xiang Li, Yu-Hao Zhang, Hao-Yun Liu, Ze-Hua Liu, Bai-Hao Ren, Qing Liu, Qiu-Yu Zhang, Jie Li","doi":"10.1021/acsmacrolett.6c00401","DOIUrl":"10.1021/acsmacrolett.6c00401","url":null,"abstract":"Chemicalrecycling of polymers to the parent monomers (CRM) representsa cornerstone strategy for establishing a sustainable circular plasticeconomy. Polyesters prepared by ring-opening copolymerization of epoxideswith cyclic anhydrides feature highly tunable properties and representpromising alternatives to petroleum-derived polymers. Nevertheless,direct and selective chemical recycling of such copolyesters intopristine monomers continues to pose a substantial challenge. Herein,we report a versatile and highly efficient strategy for the solid-statedepolymerization of both linear copolyesters and cross-linked epoxynetworks derived from diphenylmaleic anhydride (DPMA) and epoxides.The depolymerization process is catalyzed by ZnCl2 viaa random chain-scission mechanism, delivering exceptional DPMA selectivity(>99%) and high recovery yield (≥85%). Combined mechanisticinvestigations and density functional theory (DFT) calculations elucidatea stepwise depolymerization route involving spirolactone intermediatesas critical species. Notably, DPMA-based epoxy resins exhibit attractivethermomechanical performance, with glass transition temperatures spanning101–136 °C and a tensile strength at break of ∼74.7MPa, while retaining efficient closed-loop chemical recyclability.This work thus establishes a reliable platform for the rational designof high-performance polymer materials that integrate robust mechanicalproperties with fully reversible chemical recycling.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1368–1375"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148885141","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

Sterically Exposed Bromothiophene C–Br Bonds as Structural Warning Signs for Hidden Homocoupling in Migita–Stille-Derived DPP–DTE Polymers 立体暴露的溴噻吩C-Br键是migata - stille衍生的DPP-DTE聚合物中隐藏均偶联的结构警告信号

IF 4.9

ACS Macro Letters Pub Date : 2026-09-15 Epub Date: 2026-08-17 DOI: 10.1021/acsmacrolett.6c00327

Masayuki Wakioka, Takeru Hirukawa, Risa Ishizuka, Hinatsu Ito, Hitoshi Hanamura, Akira Shinohara, Takuya Akiyama

{"title":"Sterically Exposed Bromothiophene C–Br Bonds as Structural Warning Signs for Hidden Homocoupling in Migita–Stille-Derived DPP–DTE Polymers","authors":"Masayuki Wakioka, Takeru Hirukawa, Risa Ishizuka, Hinatsu Ito, Hitoshi Hanamura, Akira Shinohara, Takuya Akiyama","doi":"10.1021/acsmacrolett.6c00327","DOIUrl":"10.1021/acsmacrolett.6c00327","url":null,"abstract":"Here, we identify sterically exposed bromothiophene C–Brbonds in diketopyrrolopyrrole (DPP) monomers as monomer-level structuralwarning signs for hidden homocoupling defects in Migita–Stille-derivedDPP–dithienylethene (DTE) polymers. High-temperature 1H NMR analysis revealed 11% DPP–DPP and 10% DTE–DTElinkages in a Stille-derived polymer represented by an alternatingDPP–DTE repeat unit, whereas a locally hexyl-substituted structuralcomparator contained <1% and approximately 1%, respectively. Matchedsmall-molecule Stille reactions reproduced the same substrate-dependentordering in every catalyst system directly compared. Under Pd/P(o-tolyl)3 conditions, lowering the temperaturedecreased cross-coupling selectivity for the exposed substrate, butnot the locally substituted analogue, thereby highlighting the elevatedhomocoupling susceptibility of exposed C–Br sites. Comparisonof the homocoupling-rich Stille-derived polymer with a low-homocouplingSuzuki–Miyaura reference revealed distinct optical/electronicproperties, thin-film organization, and transistor characteristics.These findings underscore the need to verify polymer linkage sequencesexperimentally rather than infer them from formally drawn repeat unitsor general expectations regarding coupling selectivity.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1265–1271"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148760351","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

Dynamic Decoupling in Polymerized Ionic Liquids, Supercooled Melts, and Glasses 聚合离子液体、过冷熔体和玻璃的动态解耦

IF 4.9

ACS Macro Letters Pub Date : 2026-09-15 Epub Date: 2026-08-26 DOI: 10.1021/acsmacrolett.6c00337

Ankita Das, Harmandeep Singh, Shinian Cheng, Michelle Lehmann, Catalin Gainaru, Alexei P. Sokolov, Kenneth S. Schweizer

引用次数: 0

Crystalline Isotactic Polyterpenoid from Citronellal: A Viscous Bottlebrush Polymer with Order–Disorder Transitions 香茅醛结晶等规聚萜：具有有序-无序过渡的粘性瓶刷聚合物

IF 4.9

ACS Macro Letters Pub Date : 2026-09-15 Epub Date: 2026-08-21 DOI: 10.1021/acsmacrolett.6c00329

Xinru Zhang, Jian Hu, Wenpeng Zhao, Heng Liu, Kohji Tashiro

引用次数: 0

Interfacial Penetration Drives Anomalous Domain Spacing in Strongly Segregated Linear-Bottlebrush Copolymers 强分离线性瓶刷共聚物的界面穿透驱动异常畴间距

IF 4.9

ACS Macro Letters Pub Date : 2026-09-15 Epub Date: 2026-08-20 DOI: 10.1021/acsmacrolett.6c00296

Baiqiang Huang, Haobo Wang, Patryk Wąsik, Eliot Gann, Li-Heng Cai

引用次数: 0

Copolymerization Attenuates Membrane Perturbation in Cationic Antibacterial Polymers 共聚减少阳离子抗菌聚合物中的膜摄动

IF 4.9

ACS Macro Letters Pub Date : 2026-09-15 Epub Date: 2026-08-12 DOI: 10.1021/acsmacrolett.6c00358

Meiyu Fang, Keyu Chen, Yongjin Hu, Zhiyuan Zhu, Kang Liang, Jingyi Rao

{"title":"Copolymerization Attenuates Membrane Perturbation in Cationic Antibacterial Polymers","authors":"Meiyu Fang, Keyu Chen, Yongjin Hu, Zhiyuan Zhu, Kang Liang, Jingyi Rao","doi":"10.1021/acsmacrolett.6c00358","DOIUrl":"10.1021/acsmacrolett.6c00358","url":null,"abstract":"Copolymerizationis widely used to combine functional moietiesin antimicrobial polymers, assuming their activities are retainedafter covalent integration. Here, we show that covalent integrationcan instead attenuate antibacterial membrane-perturbation activityin cationic polymethacrylates. Using quaternary ammonium- and sulfonium-containingpolymers as model systems, we compared homopolymers, physical mixtures,and random and block copolymers. Rifampicin potentiation against Escherichia coli was used as a functional readout. Althoughthe quaternary ammonium homopolymer enhanced rifampicin activity by1024-fold, this effect was largely lost after copolymerization, withboth random and block copolymers exhibiting only 2–4-fold potentiationdespite identical compositions. In contrast, physical mixtures retainedthe activity of the highly potent component. Mechanistically, copolymerarchitectures preserved membrane binding but restricted postadsorptioninterfacial organization, thereby reducing interfacial dissipationand membrane depolarization. These findings demonstrate that identicalcomposition does not guarantee preservation of functional output aftercopolymerization, highlighting the importance of intrachain organizationin antimicrobial polymer design.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1326–1332"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148717893","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

Mussel-Inspired Catechol-Based Curing Agent for Ultra-Strong Underwater Adhesion of Epoxy Resin via Multiple Synergistic Mechanisms 以贻贝为灵感的儿茶酚基固化剂通过多种协同机制用于环氧树脂的超强水下附着力

IF 4.9

ACS Macro Letters Pub Date : 2026-09-15 Epub Date: 2026-08-21 DOI: 10.1021/acsmacrolett.6c00306

Xin Zhang, Ting Zheng, Jingxue Zhou, Xiaotian Bian, Si Shen, Guoxing Sun, Lili Zhang, Chengying Bai, Xiaohong Zhang, Yingjie Qiao, Xiaodong Wang

{"title":"Mussel-Inspired Catechol-Based Curing Agent for Ultra-Strong Underwater Adhesion of Epoxy Resin via Multiple Synergistic Mechanisms","authors":"Xin Zhang, Ting Zheng, Jingxue Zhou, Xiaotian Bian, Si Shen, Guoxing Sun, Lili Zhang, Chengying Bai, Xiaohong Zhang, Yingjie Qiao, Xiaodong Wang","doi":"10.1021/acsmacrolett.6c00306","DOIUrl":"10.1021/acsmacrolett.6c00306","url":null,"abstract":"Underwater adhesives are critical for marine engineeringand biomedicalapplications, but face challenges in their bonding strength and processingcomplexity. Inspired by mussel foot proteins, catechol-based curingagents (D-A and D-C) were successfully synthesized via a one-stepcondensation reaction, while monophenol-based curing agents (D-L andD-P) were prepared as the control groups. The D-C curing system exhibitedsuperior performance, demonstrating an exceptionally low curing activationenergy of 38.29 kJ/mol (27.70% lower than that of D-P), an ultrahighunderwater adhesion strength exceeding 15 MPa on stainless steel substrates(125.89% improvement over D-P), and an antidispersion behavior withcomplete flow cessation within 30 min of underwater application. Byintegrating multiscale characterization techniques (SFG spectroscopy,DFT calculations, AIMD simulations, and XPS), we systematically elucidatedthe multisynergistic adhesion mechanism of the D-C system. The resultsreveal a highly cooperative water displacement, interfacial bonding,and bulk network locking mechanism that collectively governs the superiorunderwater adhesion performance.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1250–1257"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148805800","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