ACS Macro Letters最新文献_第3页

Light- and Temperature-Programmed Block Copolymer Capsules with Tunable Shell Nanostructures 具有可调壳纳米结构的光和温度编程嵌段共聚物胶囊

IF 4.9

ACS Macro Letters Pub Date : 2026-10-20 Epub Date: 2026-09-06 DOI: 10.1021/acsmacrolett.6c00395

Zhengping Tan, Jinwoo Kim, Younghyeon Ahn, Jaeyoung Choi, Dong-Po Song, Yuesheng Li, Kang Hee Ku, Bumjoon J. Kim

{"title":"Light- and Temperature-Programmed Block Copolymer Capsules with Tunable Shell Nanostructures","authors":"Zhengping Tan, Jinwoo Kim, Younghyeon Ahn, Jaeyoung Choi, Dong-Po Song, Yuesheng Li, Kang Hee Ku, Bumjoon J. Kim","doi":"10.1021/acsmacrolett.6c00395","DOIUrl":"10.1021/acsmacrolett.6c00395","url":null,"abstract":"Polymercapsules capable of adopting distinct shell nanostructuresin response to external stimuli are attractive microcompartments forencapsulation, separation, and triggered release. Realizing such capsulesrequires orthogonal control, in which distinct stimuli independentlydefine the structural outcome. Here, we report a light- and temperature-programmedassembly strategy for hollow polystyrene-block-poly(4-vinylpyridine)(PS-b-P4VP) block copolymer (BCP) capsules with tunableshell nanostructures. The key to this dual responsiveness is a photocleavablethermoresponsive additive, in which an amide-based thermoresponsivebackbone sets the transition temperature and a photocleavable comonomerencodes the light response. During emulsion-confined assembly, photocleavageshifts the lower critical solution temperature of the additive andredistributes it between the aqueous and organic phases, selectingeither concentric lamellar or cylindrical shells at a given temperature.Replacing the poly(N-isopropylacrylamide) backbonewith poly(N-isopropylmethacrylamide) raises the operatingtemperature from 27 to 50 °C, whereas replacing the o-nitrobenzyl group with a coumarin unit shifts photoactivation from365 to 410 nm and reverses the direction of the light-driven morphologyselection. This modular design offers a versatile strategy for programmingBCP capsule shell morphologies under user-defined thermal and opticalconditions.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 10","pages":"1483–1490"},"PeriodicalIF":4.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148896031","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

Light-Programmed Reversible Valence Reconfiguration of Polymeric Colloidal Molecules 高分子胶体分子的光控可逆价态重构

IF 4.9

ACS Macro Letters Pub Date : 2026-10-20 Epub Date: 2026-09-11 DOI: 10.1021/acsmacrolett.6c00426

Hongzhu Lai, Yuying Huang, Li Jiang, Daoyong Chen

{"title":"Light-Programmed Reversible Valence Reconfiguration of Polymeric Colloidal Molecules","authors":"Hongzhu Lai, Yuying Huang, Li Jiang, Daoyong Chen","doi":"10.1021/acsmacrolett.6c00426","DOIUrl":"10.1021/acsmacrolett.6c00426","url":null,"abstract":"Polymericcolloidal molecules (CMs) with light-switchable compartmentalarchitectures and valences are attractive building blocks for reconfigurablecolloidal materials. Here, we report the stepwise and reversible light-inducedvalence reconfiguration of preformed AB2-type CMs. TheCMs were prepared by associating an amine-functionalized trans-azobenzene (t-AZO) with the PAA corona of poly(acrylicacid)-block-poly(vinylnaphthalene) (PAA-b-PVN) micelles, producing a PVN core (A) and two t-AZO-rich PAA corona compartments (B). Upon 365 nm UV irradiation,the AB2 CMs evolved successively into AB3- andAB4-rich states, whereas 470 nm visible-light irradiationdrove the reverse AB4/AB3/AB2 evolutionover repeated cycles. The reversible reconfiguration is attributedprimarily to photoisomerization-induced changes in AZO packing withinthe PAA corona, which regulate B compartment formation and number.The light-selected valence states further directed secondary assemblyinto linear chains, branched assemblies, and interconnected networks.Light therefore enables dynamic reprogramming of both the valenceof preformed CMs and the topology of their subsequent higher-orderassemblies.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 10","pages":"1544–1549"},"PeriodicalIF":4.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148933574","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

Modular Control of Glass Transition and Transparency in ROMP-Derived Oxanorbornene Polymers romp衍生的氧化冰片烯聚合物玻璃化转变和透明度的模块化控制

IF 4.9

ACS Macro Letters Pub Date : 2026-10-20 Epub Date: 2026-09-18 DOI: 10.1021/acsmacrolett.6c00446

Huigyung Kim, Sang-Ho Lee, Hyeonuk Yeo

引用次数: 0

Dynamic Covalent Lewis Pair Grafting Enables Spontaneous Linear-to-Bottlebrush Polymer Assembly and Adaptive Elastomers 动态共价路易斯对接枝实现了自发的线性到瓶刷聚合物组装和自适应弹性体

IF 4.9

ACS Macro Letters Pub Date : 2026-10-20 Epub Date: 2026-10-02 DOI: 10.1021/acsmacrolett.6c00433

Edip Ajvazi, Verena Schinegger, Milan Kracalik, Oliver Brüggemann, Ingrid Graz, Uwe Monkowius, Ian Teasdale

{"title":"Dynamic Covalent Lewis Pair Grafting Enables Spontaneous Linear-to-Bottlebrush Polymer Assembly and Adaptive Elastomers","authors":"Edip Ajvazi, Verena Schinegger, Milan Kracalik, Oliver Brüggemann, Ingrid Graz, Uwe Monkowius, Ian Teasdale","doi":"10.1021/acsmacrolett.6c00433","DOIUrl":"10.1021/acsmacrolett.6c00433","url":null,"abstract":"Bottlebrush and comb-graft polymers, macromolecules withdenselygrafted side chains along a central backbone, exhibit distinctiveconformational, rheological, and self-assembly behaviors. Althoughthese architectures are widely used to tune mechanical responses,most reported systems rely on stable covalent carbon frameworks, orfragile supramolecular assemblies, while dynamic covalent chemistriesremain largely unexplored. Herein, we harness Lewis acid–basepairs whose directional coordinate bonds drive the spontaneous assemblyof graft architectures by simply mixing Lewis acid-terminated polydimethylsiloxane(PDMS) oligomers with the polymeric Lewis base poly(4-vinylpyridine)(P4VP). The PDMS-oligomers efficiently graft to the P4VP backbone. 11B and 1H NMR studies revealing a dynamic-covalentequilibrium, with rapid kinetics. Upon addition of a difunctionalboronate cross-linker, the dynamically grafted polymers form stretchableelastomeric networks that can be thermally reprocessed and undergoautonomous self-healing. This Lewis-pair strategy expands bottlebrushpolymer chemistry beyond static covalent and fragile supramoleculardesigns, with a simple, tunable route to recyclable covalent adaptablenetworks of soft and elastic materials.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 10","pages":"1565–1571"},"PeriodicalIF":4.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091708","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

Hydrogen Atom Transfer-Triggered Chemical Recycling of Commercial Poly(methyl methacrylate) Utilizing Continuous Monomer Removal 利用连续单体去除的氢原子转移触发商业聚甲基丙烯酸甲酯化学回收

IF 4.9

ACS Macro Letters Pub Date : 2026-10-20 Epub Date: 2026-09-29 DOI: 10.1021/acsmacrolett.6c00454

Matylda Szewczyk-Łagodzińska, Ferdinando De Luca Bossa, Yanzhe Fang, Jakub Józiewicz, Halil Ibrahim Coskun, Krzysztof Matyjaszewski

{"title":"Hydrogen Atom Transfer-Triggered Chemical Recycling of Commercial Poly(methyl methacrylate) Utilizing Continuous Monomer Removal","authors":"Matylda Szewczyk-Łagodzińska, Ferdinando De Luca Bossa, Yanzhe Fang, Jakub Józiewicz, Halil Ibrahim Coskun, Krzysztof Matyjaszewski","doi":"10.1021/acsmacrolett.6c00454","DOIUrl":"10.1021/acsmacrolett.6c00454","url":null,"abstract":"We report a thermal hydrogen atom transfer (HAT) depolymerizationstrategy for the efficient chemical recycling of unmodified commercialpoly(methyl methacrylate) (PMMA). A reaction engineering approachcombining controlled radical concentration with continuous monomerremoval enables efficient depolymerization under practical conditionswithout light, chlorinated solvents, or high dilution. A semibatchprotocol employing multiple small additions of cumene hydroperoxide(CHP) and continuous removal of methyl methacrylate (MMA) suppressedradical side reactions and shifted the equilibrium toward monomerformation. At a repeating-unit concentration of 1.83 M and a totalCHP loading of 3 mol %, depolymerization reached 90% with only 2%monomer consumption. The method remained effective at 3.00 M, scaledto 20 g of polymer (79% depolymerization, 4.5 mol % CHP loading),and was effective for commercial Plexiglas containing stabilizingadditives. Recovered MMA was successfully repolymerized, demonstratingits circularity. These results establish radical concentration controland continuous monomer removal as the key design principles for hydroperoxide-assistedthermal HAT depolymerization.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 10","pages":"1587–1593"},"PeriodicalIF":4.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092757","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

Regulating Radical Flux in Frontal Polymerization 正面聚合中自由基通量的调节。

IF 4.9

ACS Macro Letters Pub Date : 2026-10-20 Epub Date: 2026-04-29 DOI: 10.1021/acsmacrolett.6c00114

Darya A. Ivannikava, Audrey N. McMullin, Kevin A. Stewart, Jacob J. Lessard

引用次数: 0

Barbier Polymerization-Induced Emission toward Organophosphorus-Containing Clusteroluminescent Polymer with Aggregation-Induced Emission and Photochromic Characteristics 具有聚集致发光和光致变色特性的含有机磷簇发光聚合物的Barbier聚合致发光研究

IF 4.9

ACS Macro Letters Pub Date : 2026-10-20 Epub Date: 2026-10-01 DOI: 10.1021/acsmacrolett.6c00424

Hong-Min Du, Xi-Yao Gu, Wen-Ming Wan, Xiao-Li Sun

引用次数: 0

Designing an Emulsion-Templated Pentablock Copolymer for Hierarchical Porosity 设计一种乳液模板五嵌段共聚物

IF 4.9

ACS Macro Letters Pub Date : 2026-10-20 Epub Date: 2026-10-10 DOI: 10.1021/acsmacrolett.6c00399

Shani Admoni, Shira Haber, Krzysztof Matyjaszewski, Michael S. Silverstein

{"title":"Designing an Emulsion-Templated Pentablock Copolymer for Hierarchical Porosity","authors":"Shani Admoni, Shira Haber, Krzysztof Matyjaszewski, Michael S. Silverstein","doi":"10.1021/acsmacrolett.6c00399","DOIUrl":"10.1021/acsmacrolett.6c00399","url":null,"abstract":"Hierarchically porouspolymers integrate macro-, meso-,and microporesto enhance mass transport, diffusion, and specific surface area, makingthem attractive for applications in filtration, separation, and storage.Here, an innovative pentablock copolymer (PBC), synthesized usingsequential atom transfer radical polymerizations (ATRPs), was designedso that each block would contribute a distinct level of porosity toa hierarchically porous monolith. First, a triblock copolymer withhyper-cross-linkable polystyrene (PS) end-blocks was synthesized froma macroinitiator based on a degradable polycaprolactone (PCL) diol.The PBC was then synthesized by adding cross-linkable poly(glycidylmethacrylate) (PGMA) end-blocks to the PS-b-PCL-b-PS. The PBC was used to form the external phase of anoil-in-oil medium internal phase emulsion and then cross-linked viathe PGMA’s epoxide groups to generate a macroporous monolith.Selectively etching the sacrificial PCL midblocks in the emulsion-templatedmonolith generated mesopores. Hyper-cross-linking the PS blocks generatedmicropores and etched some of the PCL, generating mesopores. Thismultiblock pore-generation strategy enabled control over the hierarchicalnature of the porous structure, providing a rational approach to designingrobust, tunable porous monoliths for advanced applications.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 10","pages":"1498–1505"},"PeriodicalIF":4.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151448","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

Two-Step Self-Assembly Mechanisms and Crystal–Quasicrystal Transition Kinetics in DNA Dodecagonal Quasicrystals DNA十二方准晶的两步自组装机制和晶体-准晶转变动力学

IF 4.9

ACS Macro Letters Pub Date : 2026-10-20 Epub Date: 2026-09-07 DOI: 10.1021/acsmacrolett.6c00286

Yu-Wei Sun, Xiao-Ya Xia, Zhan-Wei Li

{"title":"Two-Step Self-Assembly Mechanisms and Crystal–Quasicrystal Transition Kinetics in DNA Dodecagonal Quasicrystals","authors":"Yu-Wei Sun, Xiao-Ya Xia, Zhan-Wei Li","doi":"10.1021/acsmacrolett.6c00286","DOIUrl":"10.1021/acsmacrolett.6c00286","url":null,"abstract":"Quasicrystals are materials that exhibit long-range bond-orientationalorder without translational periodicity. Although various crystalsand quasicrystals have been assembled from DNA nanomotifs, the self-assemblymechanisms of quasicrystals and the transition kinetics between crystalsand quasicrystals remain poorly understood. Here, we introduce a coarse-grainedpatchy-particle-chain model for branched DNA nanomotifs to revealthe formation and transition kinetics of two-dimensional dodecagonalquasicrystals. The simulations capture the self-assembly of bridged5- and 6-point-star DNA motifs into dodecagonal quasicrystals at appropriatestoichiometric ratios, consistent with experiments. The formationproceeds via a non-classical two-step self-assembly pathway, involvingnetwork-like intermediates, followed by nucleation and assimilationgrowth into ordered quasicrystals. By tuning DNA motif rigidity, thetransition from hexagonal crystals to dodecagonal quasicrystals occursthrough nucleation and growth at defect sites, whereas the reversetransition preferentially proceeds via destabilization of square-likearrangements, with both transitions driven by binding-energy differences.Rational design of 3- and 4-point-star DNA motifs further enablesthe assembly of decagonal quasicrystal approximants. These findingsclarify the formation mechanisms of quasicrystals and crystal–quasicrystaltransition kinetics, providing insights into symmetry breaking andstructural reorganization in complex self-assembly systems.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 10","pages":"1428–1437"},"PeriodicalIF":4.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973157","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

Penetrant-Triggered Responsiveness in Carboxylate Polymer of Intrinsic Microporosity 固有微孔隙度羧酸聚合物的渗透触发响应性

IF 4.9

ACS Macro Letters Pub Date : 2026-10-20 Epub Date: 2026-10-08 DOI: 10.1021/acsmacrolett.6c00475

Maria S. Tavera-Villamizar, Durga Acharya, Cara M. Doherty, Anita J. Hill, Michele Galizia

{"title":"Penetrant-Triggered Responsiveness in Carboxylate Polymer of Intrinsic Microporosity","authors":"Maria S. Tavera-Villamizar, Durga Acharya, Cara M. Doherty, Anita J. Hill, Michele Galizia","doi":"10.1021/acsmacrolett.6c00475","DOIUrl":"10.1021/acsmacrolett.6c00475","url":null,"abstract":"While complex mixturefractionation has become a primary focusin membrane science, the mechanisms behind penetrant-penetrant andpenetrant-polymer interactions governing molecular separations requiredeeper investigation. Of equal importance, how the external environmentdictates these interactions remains poorly understood. To addressthis knowledge gap, we elucidate the molecular mechanisms that controlhow microporous polymers structurally adapt to their external environment.Resolving previous speculations, we show that upon reaction with carboxylicacid groups in carboxylate polymer of intrinsic microporosity (cPIM),ammonia forms ammonium carboxylate adducts. This chemical modificationalters small-molecule sorption, local chain organization, free volumedistribution, and, ultimately, penetrant diffusion. Notably, ammonia-modifiedcPIM rapidly reacts with carbon dioxide, causing in situ polymer ionic cross-linking. Using a suite of advanced experimentalmethods, including transport measurements, FTIR, PALS, and NMR, weuncover the mechanisms behind the observed responsiveness and itstime-evolution. Ultimately, we demonstrate that accounting for coupledinteractions is crucial for accurate performance prediction and optimaldesign of responsive membranes.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 10","pages":"1610–1616"},"PeriodicalIF":4.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151451","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