ACS polymers Au最新文献

{"title":"Chemically Fueled Functionalization-Induced Self-Assembly of Block Copolymers for Transient Assemblies in Water","authors":"Zehou You,&nbsp;Andrew J. D. Magenau","doi":"10.1021/acspolymersau.6c00089","DOIUrl":"https://doi.org/10.1021/acspolymersau.6c00089","url":null,"abstract":"<p>Chemically fueled dissipative self-assembly offers apowerful routeto transient structures and biomimetic materials, yet a limited rangeof chemistries have been demonstrated with block copolymers to formdiscrete self-assembled structures. Here, we report a chemically fueledtransient functionalization-induced self-assembly (ct-FISA) systemin water using poly(dimethylacrylamide-<em>block</em>-acrylicacid), p(DMA-<em>b</em>-AA), and dimethyl sulfate (DMS) asboth a functionalization reagent and chemical fuel. The water-solublep(DMA-<em>b</em>-AA) copolymer was synthesized by sequentialreversible addition–fragmentation chain-transfer (RAFT) polymerizationsand <em>tert</em>-butyl ester deprotection. Upon additionof DMS to a solution of p(DMA-<em>b</em>-AA) in water, thecarboxylate groups in the acrylic acid block were transiently methylatedto form hydrophobic methyl acrylate repeat units, converting the solubleunimers into self-assembled particles. Dynamic light scattering revealeda rapid increase in particle diameter from unimers to assemblies,as large as ∼700 nm, followed by spontaneous disassembly backto unimers within approximately 70 min. Nuclear magnetic resonanceconfirmed transient methyl ester formation, and microscopy supportedthe formation of spherical particles. The particle lifetime was tunablethrough the initial pH, buffer concentration, and DMS loading, reflectinga balance between fuel-driven alkylation and competing fuel decompositionand ester hydrolysis. Repeated assembly–disassembly cycleswere also achieved following pH readjustment. This ct-FISA platformexpands the chemical toolbox for powering transient block copolymerself-assembly into discrete macromolecular assemblies in water.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 5","pages":"1354–1362"},"PeriodicalIF":6.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173516","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}

{"title":"Monomer Structure and Discharge Power Influence the Multiscale Architecture of Plasma-Polymerized Hydrocarbon Nanoparticles","authors":"Andrei Choukourov,&nbsp;Marco Tosca,&nbsp;Ján Šomvársky,&nbsp;Daniil Nikitin,&nbsp;Mariia Protsak,&nbsp;Iqra Wahid,&nbsp;Jan Hanuš,&nbsp;Veronika Červenková,&nbsp;Ronaldo Katuta,&nbsp;Krzysztof Tadyszak,&nbsp;Jiří Pánek,&nbsp;Eduardo Pitthan,&nbsp;Dmitrii Moldarev,&nbsp;Daniel Primetzhofer,&nbsp;Jakub Čížek,&nbsp;Eric Hirschmann,&nbsp;Maciej Oskar Liedke,&nbsp;Andreas Wagner,&nbsp;Maik Butterling,&nbsp;Hynek Biederman","doi":"10.1021/acspolymersau.6c00072","DOIUrl":"https://doi.org/10.1021/acspolymersau.6c00072","url":null,"abstract":"<p>Plasma polymer nanoparticles (pp-NPs) have emerged aslinker-freenanocarriers for bioactive cargo and as nanofuels for laser-drivennuclear fusion, yet the structural factors governing their functionalityremain poorly understood. Here, pp-NPs were synthesized via plasmapolymerization of hexane, cyclohexane, and benzene to determine howmonomer structure and specific energy input control radical concentration,hydrogen content, and hierarchical topology. Electron spin resonanceand variable-energy positron annihilation lifetime spectroscopy establishthat unquenched radical concentrations (10¹⁴–10¹⁶ spins mg^–1) and free-volume size (0.5–0.6nm) increase from aliphatic to aromatic monomers, whereas free-volumeconcentration decreases inversely. These trends arise from biradicalformation in benzene plasma, steric constraints of aromatic rings,and denser packing caused by reduced hydrogen content, as confirmedby elastic recoil detection analysis. Higher discharge power unexpectedlyreduces cross-link density in pp-NPs; statistical network reconstructionreveals that unsaturated carbon bonds reduce the concentration ofelastically active network chains more strongly than dehydrogenationincreases it. Atomic force microscopy demonstrates that aliphaticmonomers yield smoother overall NP surfaces but with a more locallyroughened profile (roughness exponent α = 0.68), whereas pp-benzeneNPs exhibit higher global roughness yet smoother local morphology(α = 0.75). Upon deposition, pp-NPs assemble into porous coatingswith interparticle voids tunable via NP size (65–560 nm). Together,these findings elucidate how plasma chemistry governs the hierarchicalarchitecture of pp-NPs from subnanometer free volumes to nanoscalesurface morphology and mesoscopic interparticle voids, establishingdesign principles for tailoring radical concentration, hydrogen content,and multiscale porosity for advanced applications.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 5","pages":"1315–1328"},"PeriodicalIF":6.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173286","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}

{"title":"Reprocessable Covalent Adaptable Networks Enabled by Transamidation and Imine Metathesis Exchanges","authors":"Tommaso Telatin,&nbsp;Thijs Van Casteren,&nbsp;Silvia De La Flor,&nbsp;Àngels Serra,&nbsp;Xavier Montané","doi":"10.1021/acspolymersau.6c00150","DOIUrl":"https://doi.org/10.1021/acspolymersau.6c00150","url":null,"abstract":"<p>Here, we report thepreparation of a series of dynamiccovalentpoly(amide-imine) materials synthesized from a biobased triester monomer:methyl tricarballylate (TM), commercial di- and triamines (tris(2-aminoethyl)amine,Jeffamine D230, and hexamethylene diamine), and a synthesized imine-containingdiamine (IDA). These high-<em>T</em>_g materials(&gt;79 °C) feature dynamic amide and imine groups that contributeindependently to material dynamicity while exhibiting a synergisticeffect through transimination reactions promoted by primary aminesreleased during amide dissociation. The coexistence of these two dynamicmoieties enhances stress relaxation; however, the relaxation kineticsresult from a delicate balance between dynamic chemistry rates andnetwork architecture. We demonstrated that modulating the proportionof the imine-containing monomer, the flow behavior of the preparedmaterials can be controlled, shifting from a purely dissociative toa mainly associative viscous profile. This acquires great technologicalrelevance considering the critical importance of material flowabilityin several manufacturing processes and industrial applications. Adhesivetesting revealed a strong correlation between adhesive strength andhigh-temperature viscosity, along with facile debondability underextremely low loads. These findings demonstrate that amide exchangeand imine metathesis/transimination are promising dynamic partnersfor unlocking rheological properties unattainable with conventionalthermosets, thereby expanding applications in high-performance fields.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 5","pages":"1488–1498"},"PeriodicalIF":6.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173383","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}

{"title":"Donor–Acceptor Pyridine-Based Conjugated Microporous Polymers for Visible-Light-Driven Reactive Oxygen Species Generation and Photocatalytic Dye Degradation","authors":"Shimaa Abdelnaser,&nbsp;M. Rashad,&nbsp;Wei-Lung Tseng,&nbsp;Shiao-Wei Kuo,&nbsp;Ahmed F. M. EL-Mahdy","doi":"10.1021/acspolymersau.6c00054","DOIUrl":"https://doi.org/10.1021/acspolymersau.6c00054","url":null,"abstract":"<p>Conjugated microporous polymers (CMPs) are attractiveorganic photocatalystsbecause their porosity, extended π conjugation, and tunabledonor–acceptor (D–A) architectures can promote lightharvesting, charge separation, and substrate transport. Herein wereport two pyridine-based donor–acceptor CMPs, BTPP-TPA andBTPP-TPT, synthesized through Suzuki coupling of a tetrabrominatedpyridine-containing building block (BTPP) with triphenylamine (TPA)-or triphenyltriazine (TPT)-based boronate monomers. Both CMPs exhibithigh thermal stability, permanent porosity, broad visible-light absorption,and favorable electronic structures for photocatalytic applications.Notably, the more planar and nitrogen-rich BTPP-TPT framework showsenhanced interfacial charge transport, stronger dye–frameworkinteractions, and superior photocatalytic activity relative to BTPP-TPA.BTPP-TPT delivered adsorption efficiencies of 98.29% for rhodamineB (RhB) and 98.24% for methylene blue (MB) within 90 min and achievedvisible-light-driven photodegradation rate constants of 2.6 ×10^–2 min^–1 for RhB and 1.7 ×10^–2 min^–1 for MB. Spectroscopicand electrochemical studies, together with molecular orbital calculations,indicate that D–A polarization and linker planarity governcharge separation and reactive oxygen species generation in theseframeworks. This work highlights how molecular-level engineering ofpyridine-based CMPs can regulate porosity, electronic structure, andphotocatalytic function, providing an effective strategy for metal-freepolymer photocatalysts for wastewater remediation.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 5","pages":"1286–1300"},"PeriodicalIF":6.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173283","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}

{"title":"Development of a Property-Guided HS-SPME-GC-MS Method for Broad-Range Qualitative Screening of Potentially Hazardous VOCs in Recycled Polypropylene","authors":"Wei Jiang,&nbsp;Huijun Yi,&nbsp;Caleb Chatfield,&nbsp;Chloe Higdon,&nbsp;Nathan Mancos,&nbsp;Shaoyang Liu","doi":"10.1021/acspolymersau.6c00124","DOIUrl":"https://doi.org/10.1021/acspolymersau.6c00124","url":null,"abstract":"<p>The increasing use of recycled plastics has raised concernsregardingthe potential emission of hazardous volatile organic compounds (VOCs)during recycling and in subsequent applications. However, systematicanalytical methods for VOC analysis in real recycled plastic materialsremain limited due to the complex and diverse composition of emittedVOCs. In this study, a qualitative analytical method based on headspacesolid-phase microextraction coupled with gas chromatography–massspectrometry (HS-SPME-GC-MS) was developed for characterizing potentiallyhazardous VOCs in recycled polypropylene (rPP). A total of 622 candidatecontaminants associated with recycled plastics were compiled. Afterscreening by NFPA health hazard rating and volatility, 274 potentiallyhazardous VOCs were retained, and 27 representative compounds wereselected to cover broad vapor-pressure and polarity ranges. Five SPMEfiber coatings were evaluated, among which DVB/C-WR/PDMS providedthe broadest detection coverage, detecting 24 of the 27 representativecompounds. Response surface methodology based on rotatable centralcomposite designs was then used to optimize SPME temperature, incubationtime, and extraction time. SPME temperature was the dominant factoraffecting extraction efficiency, and that vapor pressure was the primaryphysicochemical determinant of extraction behavior. High- and medium-vapor-pressureVOCs were most efficiently extracted under relatively moderate-temperatureconditions, with an optimized SPME temperature of 68.7 °C, incubationtime of 5.5 min, and extraction time of 10.4 min. In contrast, low-vapor-pressureVOCs required higher temperatures to promote transfer from the polymermatrix to the headspace, and 110 °C was identified as a practicalcompromise. Using the optimized method, aliphatic hydrocarbons, aromatichydrocarbons, oxygenated compounds, and lindane were detected in industrialrPP samples, indicating multiple potential contamination sources inrecycled plastic streams. This study provides a systematic HS-SPME-GC-MSstrategy for broad qualitative screening of potentially hazardousVOCs in rPP and may support quality control, emission assessment,and process optimization in plastic recycling.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 5","pages":"1422–1434"},"PeriodicalIF":6.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173453","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}

{"title":"Quantitative Epoxidation of High-Vinyl and Dimethylamino-Functionalized Polybutadiene Synthesized via LAP","authors":"Kun Liu,&nbsp;Yao Long,&nbsp;Jiahao Zhou,&nbsp;Haoyun Tan,&nbsp;Xupeng Han,&nbsp;Xihao Gao,&nbsp;Shana Wei,&nbsp;Zhifang Chen,&nbsp;Tingxuan Shang,&nbsp;Jiaping Tan,&nbsp;Meilin Liu,&nbsp;Wenjun Yi,&nbsp;Xiaoxing Gu,&nbsp;Lijun Li","doi":"10.1021/acspolymersau.6c00125","DOIUrl":"https://doi.org/10.1021/acspolymersau.6c00125","url":null,"abstract":"<p>High vinyl polybutadiene (HVPB) liquid rubber has extensiveapplicationsin multiple fields, such as rubber, coatings, and adhesives. Quantitativefunctionalization modification of polybutadiene will further expandits application scope. In this paper, a classic living anionic polymerization(LAP) method was adopted, using 1,2-bis(4-ethylpiperazin-1-yl)ethane(BEPE) as a novel modifier, <em>n</em>-butyllithium as aninitiator, and N,N-dimethylvinylbenzylamine as a functional monomer.Through an in situ copolymerization mode, the quantitative and chain-middle/endpositioning introduction of tertiary amine functional groups was achieved,and a series of highly vinyl-functionalized polybutadiene (<em>f</em>-HVPB) liquid rubbers with controlled molecular weightsand narrow molecular weight distributions were prepared. On the otherhand, <em>m</em>-chloroperbenzoic acid was used as an epoxidizingagent to quantitatively epoxidize liquid high-vinyl polybutadieneand functionalized polybutadiene to prepare side-chain highly epoxy/tertiaryamine bifunctional polybutadiene (<em>bf</em>-HVPB) products.The effects of different reaction systems, including different solvents,different epoxidizing agent ratios, different temperatures, differentmolecular weights, and amine modification, on the epoxidation of HVPBand <em>f</em>-HVPB were mainly investigated. The fine structuresof the polymerization products were systematically analyzed by ¹H NMR, FTIR, DSC, and GPC.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 5","pages":"1444–1454"},"PeriodicalIF":6.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173381","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}

{"title":"Photoresponsive Reversible Assembly of Helical Poly(isocyanide)s","authors":"Jingyang Wang,&nbsp;Federica Kauffmann,&nbsp;Chengyuan Wang,&nbsp;Matthew D. Hannigan,&nbsp;Marcus Weck","doi":"10.1021/acspolymersau.6c00119","DOIUrl":"https://doi.org/10.1021/acspolymersau.6c00119","url":null,"abstract":"<p>We report the synthesis of helical poly(isocyanide)s(PICs) functionalizedwith azobenzene-ureidopyrimidinone (Azo-Upy) motifs, designed to providephotoswitchable control over quadruple hydrogen-bonding interactions.The PICs were accessed via nickel-catalyzed polymerization with controlledmolecular weights and low dispersities. With the photoisomerizationof the <em>E</em>-Azo-Upy motif to form the (<em>Z</em>-Azo-Upy)₂ dimer, the resulting polymers undergo reversiblehydrogen bonding triggered by UV/blue light irradiation. The assemblycan be tuned between intrachain collapse and interchain cross-linkingby varying concentration or solvent. Circular dichroism (CD) spectroscopyconfirms that the helical integrity of the PIC backbone is retainedduring the photoswitching process. Furthermore, an azide-functionalizedAzo-Upy motif exhibits efficient photoresponsiveness to facilitatepostpolymerization modification using click chemistry. The presentedsystem establishes a robust platform for realizing controllable assemblyof helical polymers to achieve higher-order structural hierarchiesthrough photoresponsive hydrogen bonding.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 5","pages":"1403–1413"},"PeriodicalIF":6.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173276","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}

{"title":"Isosteric Polymer Design as an Approach to Recapitulate the Properties of Plasticized Commercial Polymers","authors":"Yonghwan Kwon,&nbsp;Caleb T. Kozuszek,&nbsp;Mason C. Chapman,&nbsp;Nicholas G. Taylor,&nbsp;Aleksandr V. Zhukhovitskiy,&nbsp;Frank A. Leibfarth","doi":"10.1021/acspolymersau.6c00123","DOIUrl":"https://doi.org/10.1021/acspolymersau.6c00123","url":null,"abstract":"<p>Plasticizers aresmall molecule additives compounded with polymersto tune their physical properties and facilitate processing, but plasticizersoften leach from plastics, where they potentially have negative environmentaland ecological consequences. Synthetic design can obviate the needfor plasticizers by identifying a polymer with the required propertiesfor an application without the need for external additives. In particular,designing isosteric analogues to commercial polymers that preservekey functionality while expanding the range of accessible thermaland mechanical properties would provide benefits beyond conventionalcopolymerization or side-chain modification strategies. Here, we demonstratethat a simple and efficient postpolymerization modification procedureprovides access to poly(vinyl ether-<em>co</em>-vinyl alcohol)copolymers which are isosteric analogues of poly(vinyl butyral) (PVB).These copolymers exhibit thermal and rheological properties that arecomplementary to plasticized PVB and existing PVB-like polymers. Theability to tune both density of hydroxyl groups and vinyl ether sidechain provided a library of copolymers with glass transition temperaturesranging from −54 to 18 °C. Rheological characterizationconfirmed that these materials behaved as entangled polymer meltsat room temperature, with moduli and relaxation dynamics that dependedon both hydroxyl content and side chain identity. Overall, this studydemonstrates the value of creating isosteric analogues to commercialpolymers that diversify their properties, with the potential for reducingthe use of leachable small molecule additives.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 5","pages":"1435–1443"},"PeriodicalIF":6.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173382","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}

{"title":"Quinoline-based Photoinitiators for Vat Photopolymerization: Synthesis and Formulation Design for 3D Printing","authors":"Ilana S. Rosário,&nbsp;Caroline Gaglieri,&nbsp;Vinicius H. de Carvalho,&nbsp;Emily B. de Barros,&nbsp;João A. R. Bassetto,&nbsp;Gabriela Cremasco,&nbsp;Gilbert Bannach,&nbsp;Luiz C. da Silva-Filho","doi":"10.1021/acspolymersau.6c00101","DOIUrl":"https://doi.org/10.1021/acspolymersau.6c00101","url":null,"abstract":"<p>Quinoline derivatives (<strong>Q-OMe</strong> and <strong>Q-SMe</strong>) were synthesized via a green one-pot multicomponent reaction andevaluated as photoinitiators for urethane dimethacrylate (UDMA) photopolymerization.Their performance was investigated under UV (370 nm) and blue (456nm) irradiation, in the presence and absence of ethyl <em>p</em>-dimethylaminobenzoate (EDB). Blue light led to significantly higherconversions (up to 73%) compared to UV irradiation (&lt;5%). Statisticalanalysis confirmed that both the photoinitiating system and photoinitiatorconcentration significantly affected the final monomer conversion,with the Q-SMe/EDB system consistently exhibiting the highest conversionvalues. UV–vis and mass spectrometry provided evidence forthe formation of a sulfoxide intermediate during Q-SMe photoactivation,supporting the proposal that this derivative can operate through bothtype I and type II photoinitiation pathways, whereas the photochemicalbehavior of Q-OMe is consistent with a predominantly type II mechanism.The optimized Q-SMe/EDB formulation (0.3 wt % Q-SMe/0.5 wt % EDB)was subsequently applied to UDMA/TEGDMA resins for vat photopolymerization,where increasing the TEGDMA content increased the penetration depth(138–172 μm) while reducing the monomer conversion. Underidentical printing conditions, the optimized Q-SMe/EDB formulationproduced well-defined 3D structures without overcuring, unlike theconventional CQ/EDB system. These results demonstrate the potentialof quinoline-based photoinitiating systems for visible-light vat photopolymerizationof methacrylate resins and highlight the importance of exploring newquinoline derivatives for the development of efficient photoinitiatingsystems.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 5","pages":"1376–1388"},"PeriodicalIF":6.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173273","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}

{"title":"Full (Electro-)Chemical Control over the Aggregation State of Diblock Copolymer Mixtures Including Nonequilibrium Micelles","authors":"Vincent Schildknecht,&nbsp;Annika Lehmann,&nbsp;Richard Neubert,&nbsp;Quirin Prasser,&nbsp;Anja Voigt,&nbsp;Gilbert Chahine,&nbsp;Isabelle Morfin,&nbsp;Erica Brendler,&nbsp;Sabine Rosenfeldt,&nbsp;Ulrich Mansfeld,&nbsp;Felix A. Plamper","doi":"10.1021/acspolymersau.6c00044","DOIUrl":"https://doi.org/10.1021/acspolymersau.6c00044","url":null,"abstract":"<p>Stimuli-responsive polymers have endowed soft matterresearch withnumerous applications. Moving beyond classical stimuli like temperatureor pH, we introduce an electrochemical approach to control block copolymeraggregation by shifting between bishydrophilic and amphiphilic states.The aqueous solutions of the nonionic-cationic block copolymers poly[<em>N</em>-(3-aminopropyl)methacrylamide]₃₀-<em>b</em>-poly(<em>N</em>,<em>N</em>-dimethylacrylamide)₁₂₀ (PAPMA₃₀-<em>b</em>-PDMAA₁₂₀), synthesized via RAFT polymerization, and poly(ethylene oxide)₁₁₄-<em>b</em>-poly{[2-(methacryloyloxy)ethyl]diisopropylmethylammoniumchloride}₁₇₁ (i.e., PEO₁₁₄-<em>b</em>-PDPAEMA₁₇₁ with a quaternized poly(diisopropylaminoethylmethacrylate) block, abbreviated as qPDPAEMA), were investigated formicellization via Dynamic Light Scattering (DLS), Small Angle X-rayScattering (SAXS), and Cryogenic Transmission Electron Microscopy(cryo-TEM). Both polymers exhibit selective aggregation with hexacyanoferratespecies: PAPMA-<em>b</em>-PDMAA forms aggregates specificallyin the presence of ferrocyanide ions ([Fe(CN)₆]^4–), while PEO-<em>b</em>-qPDPAEMA forms micelles with ferricyanideions ([Fe(CN)₆]^3–). These polymer systemsdemonstrate both chemical and electrochemical reversibility, withthe combined polymer system allowing selective control over the typeof polymer that aggregates by modulating the ferricyanide/ferrocyanideratio. Furthermore, the pH sensitivity of PAPMA-<em>b</em>-PDMAA allows the disintegration of the micellar state by increasingthe pH (electro-)chemically. In total, these results demonstrate fullcontrol over the assembly state of complex polymer mixtures by electrochemicalmeans. In addition, it is shown for PEO-<em>b</em>-qPDPAEMAthat electrochemical switching as a soft trigger leads to the thermodynamicallypreferred micelle morphology, while rapid chemical redox leads tokinetically trapped, nonequilibrium micelles. Here, electrochemistrycan act as a trigger to transform the trapped micelles toward thethermodynamically stable ones, which can be recycled back to the nonequilibriummicelles. The principle of this electrochemically triggered micellizationcould represent a significant step toward developing stimuli-sensitivematerials for autonomous drug delivery, sensing, or even smart materialswithin a systems chemistry approach.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 5","pages":"1267–1285"},"PeriodicalIF":6.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173282","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}