ACS Macro Letters最新文献_第5页

Solvent-Gated Reaction Pathway Selection for Thiol-Maleimide Polymer Networks Programming 巯基-马来酰亚胺聚合物网络规划的溶剂门控反应路径选择

IF 4.9

ACS Macro Letters Pub Date : 2026-09-15 Epub Date: 2026-09-02 DOI: 10.1021/acsmacrolett.6c00333

Yihan Ke, Yanghao Wu, Dong Wang, Fei Xie, Xiaodong Lu, Binjie Jin, Saihua Jiang

{"title":"Solvent-Gated Reaction Pathway Selection for Thiol-Maleimide Polymer Networks Programming","authors":"Yihan Ke, Yanghao Wu, Dong Wang, Fei Xie, Xiaodong Lu, Binjie Jin, Saihua Jiang","doi":"10.1021/acsmacrolett.6c00333","DOIUrl":"10.1021/acsmacrolett.6c00333","url":null,"abstract":"Thiol-maleimide click chemistry is widely employed acrossdiversefields for its rapid kinetics and mild reaction conditions, whosereversible bond exchange feature additionally imparts reprocessabilityand recyclability to polymer networks. Despite its widespread use,the influence of the reaction environment on the resulting networkarchitecture has remained largely unexplored. Here, we demonstratethat solvent choice gates competing reaction pathways during thiol-maleimidenetwork formation. From an identical precursor formation, protic solventsdirect network formation predominantly through thiol-maleimide Michaeladdition, whereas aprotic solvents enable a dual pathway in whichmaleimide homopolymerization proceeds alongside thiol addition. Thissolvent-controlled pathway selection alters the effective cross-linkingdensity and thereby modulates the mechanical and thermal propertiesof the resultant thiol-maleimide polymer networks, as well as thenetwork dynamic ability, as revealed by the distinct stress relaxationkinetics and recycling efficiency. These results indicate that thestoichiometry of thiol and maleimide alone does not define the finalnetwork, whereas the reaction environment determines whether maleimidefunctions exclusively as a Michael acceptor or additionally as a chaingrowth monomer. By converting maleimide homopolymerization from aside reaction into a programmable structural handle, this work establishessolvent-gated pathway selection as a simple, formulation-invariantstrategy for designing tunable thiol-maleimide polymer networks.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1298–1304"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148885142","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

Stretching Mucins: Exploring the Complex Rheology of a Natural Glycoprotein Network 拉伸粘蛋白：探索天然糖蛋白网络的复杂流变学。

IF 4.9

ACS Macro Letters Pub Date : 2026-09-15 Epub Date: 2026-08-21 DOI: 10.1021/acsmacrolett.6c00270

Bianca Hazt, George D. Degen, Lucas Warwaruk, Daniel J. Read, Adam O’Connell, Oliver G. Harlen, Gareth H. McKinley, Anwesha Sarkar

{"title":"Stretching Mucins: Exploring the Complex Rheology of a Natural Glycoprotein Network","authors":"Bianca Hazt, George D. Degen, Lucas Warwaruk, Daniel J. Read, Adam O’Connell, Oliver G. Harlen, Gareth H. McKinley, Anwesha Sarkar","doi":"10.1021/acsmacrolett.6c00270","DOIUrl":"10.1021/acsmacrolett.6c00270","url":null,"abstract":"Flow and extensionaldeformation of mucin networks are fundamentalin mucus biophysics, governing how mucus functions as a protective,lubricating, and transport-facilitating layer. While the shear andoscillatory rheology of mucin solutions have been characterized inconsiderable detail, their behavior under extensional deformationremains comparatively understudied. Here, we report a concentration-dependenttransition in the extensional flow response of mucin solutions usinga bespoke dripping-onto-substrate extensional rheometer. We show thatmucin solutions at the lower concentrations undergo linear filamentthinning, whereas semidilute mucin solutions form highly extensiblefilaments, with radius decaying exponentially in time, consistentwith the elastocapillary thinning observed in solutions of high molecularweight synthetic polymers. Remarkably, at higher mucin concentrationsinterchain mucin associations produce a sudden reduction in the apparentelastocapillary relaxation time. We demonstrate how increasing macromolecularconcentration redistributes the balance between viscous and elasticstresses during capillary thinning in a biopolymer network and reveala concentration-driven reduction in mucin filament extensibility.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1215–1221"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148785402","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

Water-Developable Ionic Liquid Polymer Enables Humidity-Sensing and Microscale Patterning 水显影离子液体聚合物实现湿度传感和微尺度图案

IF 4.9

ACS Macro Letters Pub Date : 2026-09-15 Epub Date: 2026-08-12 DOI: 10.1021/acsmacrolett.6c00360

Tokio Mimura, Liam Warlick, Alexandra Zele, Harrison Landfield, Louise Kuehster, Nathaniel A. Lynd, Rachel A. Segalman

{"title":"Water-Developable Ionic Liquid Polymer Enables Humidity-Sensing and Microscale Patterning","authors":"Tokio Mimura, Liam Warlick, Alexandra Zele, Harrison Landfield, Louise Kuehster, Nathaniel A. Lynd, Rachel A. Segalman","doi":"10.1021/acsmacrolett.6c00360","DOIUrl":"10.1021/acsmacrolett.6c00360","url":null,"abstract":"Polymeric ionic liquids (i.e., PILs) have diverse sensingcapabilitiesdue to their potentially high ionic conductivity and tunable chemicalresponse. However, integrating them into miniaturized sensor componentsoften requires harsh nonaqueous developers, limiting eco-friendlymicrofabrication. To overcome this challenge, we designed a systemthat utilizes a UV-active thiol–ene click reaction to cross-linka photopatternable PIL, PAGE-TFSI–EMIm+, that enables device patterning under 365 nm exposure. This specificdesign leverages the material’s ionic nature to enable fullyaqueous development, bridging the gap between precise microfabricationand processing with a lower environmental footprint in the developmentstage. The resulting films were successfully patterned with 12.8 μmresolution. As an independent proof-of-concept for the functionalapplication of these materials, an impedance-type humidity sensorwas fabricated by integrating interdigitated electrodes with patterned3 mm-diameter PAGE-TFSI–EMIm+ films.The sensor demonstrated excellent sensitivity with low hysteresis(2.5% relative humidity (RH)) across a broad humidity range of 0–78%RH. Equivalent circuit fitting of electrochemical impedance spectroscopy(EIS) results suggest that the sensing mechanism is primarily governedby the variable ionic conductivity with humidity within the film.This approach underscores the potential of photopatterned PILs foradvanced sensor architectures.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1340–1347"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148718040","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

Upcycling of PET Waste by Incorporating a Malic Acid-Based Monomer for High Performance and Chemically Recyclable Copolyesters 用苹果酸基单体制备高性能化学可回收共聚聚酯的PET废弃物升级利用研究

IF 4.9

ACS Macro Letters Pub Date : 2026-09-15 Epub Date: 2026-08-19 DOI: 10.1021/acsmacrolett.6c00302

Jialong Li, Hongsen Liu, Yahang Dong, Haiyue Zhao, Xinyu Meng, Luhan Fang, Chengcai Pang

{"title":"Upcycling of PET Waste by Incorporating a Malic Acid-Based Monomer for High Performance and Chemically Recyclable Copolyesters","authors":"Jialong Li, Hongsen Liu, Yahang Dong, Haiyue Zhao, Xinyu Meng, Luhan Fang, Chengcai Pang","doi":"10.1021/acsmacrolett.6c00302","DOIUrl":"10.1021/acsmacrolett.6c00302","url":null,"abstract":"Herein, a highly rigid monomer, 2-(2-hydroxyethyl)-1,3-dioxoisoindoline-5-carboxylicacid (HTI), was readily prepared from biosourced malic acid. A seriesof PET copolyesters were fabricated through an in situ chemical upcyclingstrategy, in which HTI units were inserted into the backbones of thePET waste via a depolymerization-repolycondensation process. The resultingcopolyesters demonstrated outstanding thermal stability (T5% > 400 °C) and excellent optical transparency,with transmittance at 700 nm ranging from 86.8% to 90.6%. Incorporationof HTI units significantly improved the glass transition temperatureand mechanical property of PET; notably, the copolyester containing41 mol % HTI exhibited a tensile strength of 62.8 MPa and a Young’smodulus of 1.66 GPa. Furthermore, these PET copolyesters underwentcomplete methanolysis at 160 °C, enabling closed-loop recyclingof the initial monomers in high yields. This work provides a new strategyfor upcycling PET waste using biobased monomers, which incentivizeboth improved thermal-resistance, mechanical properties, and plasticsreclamation.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1233–1241"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148760343","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

Termination of Acetoxyethyl Radicals Generated by Br-Atom Abstraction from 1-Bromoethyl Acetate: Implications for the Spontaneous and Catalyzed Termination of Poly(vinyl acetate) Radicals 1-溴乙酸乙酯br原子萃取生成的乙酰氧乙基自由基的终止：对聚醋酸乙烯基自发和催化终止的启示

IF 4.9

ACS Macro Letters Pub Date : 2026-09-15 Epub Date: 2026-08-10 DOI: 10.1021/acsmacrolett.6c00339

Laurianne Forget, Christophe Fliedel, Krzysztof Matyjaszewski, Rinaldo Poli

{"title":"Termination of Acetoxyethyl Radicals Generated by Br-Atom Abstraction from 1-Bromoethyl Acetate: Implications for the Spontaneous and Catalyzed Termination of Poly(vinyl acetate) Radicals","authors":"Laurianne Forget, Christophe Fliedel, Krzysztof Matyjaszewski, Rinaldo Poli","doi":"10.1021/acsmacrolett.6c00339","DOIUrl":"10.1021/acsmacrolett.6c00339","url":null,"abstract":"The present contributionexplores the termination modes of acetoxyethylradicals – unimer models of poly(vinyl acetate) radicals –generated by Br-atom abstraction from 1-bromoethyl acetate (BEA).Using [(Me6TREN)Cu(BF4)] alone, with or withoutUV light irradiation, results in a ca. 50:50 distribution of combination(Comb) and disproportionation (Disp). Using Sn2Me6 or Pb2Ph6 alone with UV light irradiationyields greater Comb fractions (67% and 88%, respectively). This trendis due to the simultaneous presence of conventional Comb-dominatedbimolecular termination and a Disp-selective in-cage hydrogen-atomtransfer (HAT) to the Me3Sn•/Ph3Pb• radical, which decreases in the order Me3Sn• > Ph3Pb•. By extrapolation, poly(vinyl acetate) growing radical chains aresuggested to terminate predominantly by Comb (>88%). On the otherhand, the simultaneous use of Sn2Me6 or Pb2Ph6 and [(Me6TREN)Cu(BF4)],with UV light irradiation, leads to 100% Disp. These results revealthat Catalyzed Radical Termination (CRT) completely overrides theintrinsic termination behavior of acetoxyethyl radicals, switchingthe product distribution from predominant combination to exclusivedisproportionation. More generally, they suggest that CRT may representan overlooked limitation in the Atom Transfer Radical Polymerization(ATRP) of less-activated monomers by highly active copper catalysts.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1292–1297"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148717886","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

Role of Amorphous Chains in Nanoplastic Formation from Semicrystalline Polymers 非晶链在半晶聚合物形成纳米塑料中的作用

IF 4.9

ACS Macro Letters Pub Date : 2026-09-15 Epub Date: 2026-08-20 DOI: 10.1021/acsmacrolett.6c00299

Michele Valsecchi, Sameer Rajendra Kalghatgi, Nicholas F. Mendez, Clarissa Lincoln, Nicholas A. Rorrer, Sanat K. Kumar

{"title":"Role of Amorphous Chains in Nanoplastic Formation from Semicrystalline Polymers","authors":"Michele Valsecchi, Sameer Rajendra Kalghatgi, Nicholas F. Mendez, Clarissa Lincoln, Nicholas A. Rorrer, Sanat K. Kumar","doi":"10.1021/acsmacrolett.6c00299","DOIUrl":"10.1021/acsmacrolett.6c00299","url":null,"abstract":"Semicrystalline polymers,e.g., polyethylene terephthalate(PET),release micro- (100 nm to 1 mm) and nanoplastics (up to 100 nm) [MNPL]when they are degraded under quiescent conditions. However, the exactmolecular mechanisms leading to material fragmentation into MNPL areunknown. Here, we monitor the evolution of chain molecular weightand the MNPL production kinetics during hydrolysis of PET pellets.We find that only ≈0.6% of the amorphous phase ester bondsare hydrolyzed at the onset of MNPL release. Then, by combining arandom scission model with measured amorphous spacings, we estimatethat only ≈15% of the stress transmitters in the amorphousphase, namely, bridges and entangled loops, have failed by this point.Thus, spontaneous fragmentation of the semicrystalline nanostructureoccurs despite significant intercrystalline connectivity. We resolvethis apparent contradiction by proposing that fragmentation can onlyoccur when progressive tie-chain scission causes the material to undergothe ductile/brittle transition. Mechanistically, we speculate thatthe internal stresses responsible for material fragmentation are causedby processing (i.e., residual stresses) and/or sample densificationinduced by chemi-crystallization. We discuss additional factors thatmay affect our analysis and thus require further investigation, suchas skin-core effects, preferential degradation of stress transmittersand/or recrystallization processes.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1228–1232"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148805799","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

Competing Substrate and Free-Surface Effects on Ion Transport in Ultrathin Polymer Electrolyte Films 竞争衬底和自由表面对超薄聚合物电解质薄膜中离子传输的影响

IF 4.9

ACS Macro Letters Pub Date : 2026-09-15 Epub Date: 2026-08-21 DOI: 10.1021/acsmacrolett.6c00250

Shannon Zhang, Ohad Bouni, Daniel Sharon, Michael A. Webb

{"title":"Competing Substrate and Free-Surface Effects on Ion Transport in Ultrathin Polymer Electrolyte Films","authors":"Shannon Zhang, Ohad Bouni, Daniel Sharon, Michael A. Webb","doi":"10.1021/acsmacrolett.6c00250","DOIUrl":"10.1021/acsmacrolett.6c00250","url":null,"abstract":"Ceramic nanoparticles incorporated into solid polymerelectrolyteshave been reported to both enhance and suppress ionic conductivity,but the origins of these effects remain unclear due to difficultiesin isolating interfacial phenomena in disordered bulk systems. Here,we characterize ion transport in ultrathin films of poly(ethyleneoxide)–lithium bis(trifluoromethanesulfonyl)imide on silicaand employ analytical modeling to elucidate how interfaces might controlthickness-dependent behavior. Ionic conductivity is suppressed forthe thinnest films at all salt concentrations and temperatures, thoughmodest enhancement appears in some films at low salt concentration.The extent of modulation, however, varies with concentration alone.A modified Vogel–Fulcher–Tammann model incorporatingboth substrate and free-interface effects on polymer dynamics bestcaptures the observed behavior, outperforming models based on nonconductinglayers, interfacial salt partitioning, or substrate-only interfaceeffects. This indicates that both inorganic surfaces and free interfacescan substantially influence polymer mobility and conductivity, suggestingthat strategies to optimize composite polymer electrolytes shouldaddress the coupled behavior of interfacial polymer dynamics.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1208–1214"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148805797","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

Tunable Relaxation in Polyborosiloxane Networks via Hydrosilylation with Dual-Functional Cross-Linkers 双功能交联剂通过硅氢化反应在聚硼硅氧烷网络中的可调弛豫

IF 4.9

ACS Macro Letters Pub Date : 2026-09-15 Epub Date: 2026-08-22 DOI: 10.1021/acsmacrolett.6c00334

Patrick T. Getty, Young Bum Lee, Taejun Eom, Colton A. D’Ambra, Craig J. Hawker, Christopher M. Bates

{"title":"Tunable Relaxation in Polyborosiloxane Networks via Hydrosilylation with Dual-Functional Cross-Linkers","authors":"Patrick T. Getty, Young Bum Lee, Taejun Eom, Colton A. D’Ambra, Craig J. Hawker, Christopher M. Bates","doi":"10.1021/acsmacrolett.6c00334","DOIUrl":"10.1021/acsmacrolett.6c00334","url":null,"abstract":"Polyborosiloxane networks are a versatile class of polymericmaterialsvalued for their unique viscoelastic properties, dynamic bonding behavior,and thermal stability. However, precisely tuning their relaxationdynamics without relying on reinforcing fillers remains a key challenge.In this work, we report the design and synthesis of a new generationof dynamic borosiloxane cross-linkers that enable tunable viscoelasticperformance in filler-free polyborosiloxane networks. These cross-linkerswere synthesized cleanly without byproducts in one step from a broadrange of commercially available boronic acids, yielding functionalboronate esters that are compatible with hydrosilylation-based networkformation. By tuning the alkyl or aryl substituent attached to boron,the cross-linkers control the rate of stress relaxation in polyborosiloxanenetworks spanning several orders of magnitude, and combining cross-linkerswith mismatched kinetics within a single network enables independentlytunable, dual-mode relaxation behavior. In summary, this strategyoffers a modular and efficient approach to tailor network dynamics,advancing the rational design of adaptive silicon-based materials.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1279–1285"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148805801","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

Too Much of a Good Thing? Thermodynamic Limits of Supramolecular Polymer Compatibilizers 好事太多？超分子聚合物相容剂的热力学极限

IF 4.9

ACS Macro Letters Pub Date : 2026-09-15 Epub Date: 2026-08-26 DOI: 10.1021/acsmacrolett.6c00355

Christopher Balzer, Dan Sun, Glenn H. Fredrickson

{"title":"Too Much of a Good Thing? Thermodynamic Limits of Supramolecular Polymer Compatibilizers","authors":"Christopher Balzer, Dan Sun, Glenn H. Fredrickson","doi":"10.1021/acsmacrolett.6c00355","DOIUrl":"10.1021/acsmacrolett.6c00355","url":null,"abstract":"Recycling mixed plastic waste remainsan unsolved challengeinmaterials science, largely because the constituent polymers are chemicallyincompatible and resist blending into useful materials. Compatibilizersaddress this by localizing at polymer–polymer interfaces tolower interfacial tension, but conventional designs based on blockor graft copolymers require the tailored synthesis for each polymerpair. Here, we develop a theoretical description of supramolecular compatibilizers, which are homopolymers bearing complementaryassociative groups that reversibly bond at polymer–polymerinterfaces. We show that the dilute addition of these compatibilizerslowers the interfacial tension, often outperforming conventional blockcopolymers; however, this benefit has a limiting behavior, terminatingonce the compatibilizer macrophase separates into a bond-rich third phase that wets the interface. The number of associativesites per chain, M, governs the existence and characterof this wetting transition and, in part, determines the effectivenessof supramolecular compatibilizers. Specifically, the tendency fornetwork formation at the interface in M > 2 compatibilizersstrongly limits the thermodynamic reduction in interfacial tension.These results frame supramolecular compatibilization as a competitionbetween interfacial association and bulk phase separation, establishinga thermodynamic limit on additive efficacy.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1320–1325"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148821777","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

Experimental Realization of Unequal-Coordination Hexagonal Cylinder Packing in ABCBA Pentablock Terpolymers ABCBA五嵌段三元共聚物不等配位六方柱填充的实验实现

IF 4.9

ACS Macro Letters Pub Date : 2026-09-15 Epub Date: 2026-08-27 DOI: 10.1021/acsmacrolett.6c00303

Ruohan Zhang, Lei Guo, Junting Xu, Binyang Du

{"title":"Experimental Realization of Unequal-Coordination Hexagonal Cylinder Packing in ABCBA Pentablock Terpolymers","authors":"Ruohan Zhang, Lei Guo, Junting Xu, Binyang Du","doi":"10.1021/acsmacrolett.6c00303","DOIUrl":"10.1021/acsmacrolett.6c00303","url":null,"abstract":"A series of poly(4-vinylpyridine)-b-polystyrene-b-polydimethylsiloxane-b-polystyrene-b-poly(4-vinylpyridine) (P4VP-b-PS-b-PDMS-b-PS-b-P4VP, denotedas VxS104D69S104Vx) pentablock terpolymers withdifferent length x (31, 46, 99, 145) of P4VP blockswere synthesized via two-step reversible addition–fragmentationchain transfer (RAFT) polymerization. Their bulk self-assembly behaviorwas investigated by small-angle X-ray scattering (SAXS) and transmissionelectron microscopy (TEM). With increasing P4VP block length, theequilibrium morphology evolved successively from tetragonally packedalternating P4VP/PDMS cylinders in the PS matrix (TETVD) to hexagonally packed alternating P4VP/PDMS cylinders with unequalcoordination numbers (HEXVD), then to lamellae containingdiscontinuous PDMS subdomains (LAM), and finally to coexisting LAMand PDMS/PS core–shell hexagonally packed cylinders (CSHSD). Notably, the HEXVD phase represents, to ourknowledge, the first experimental realization of a hexagonal cylinderphase with unequal coordination numbers in an ABCBA pentablock terpolymersystem. The TETVD to HEXVD transition is governedby the compositional asymmetry and the topological constraint imposedby the doubly tethered middle PDMS block. These results demonstratethat tuning the terminal-block length in ABCBA pentablock terpolymersprovides an effective route to unconventional three-phase nanostructures.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1242–1249"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148821778","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