ACS Macro LettersPub Date : 2026-09-15Epub Date: 2026-09-03DOI: 10.1021/acsmacrolett.6c00379
Gautam V. Khare, Kristi S. Anseth, Kelly M. Schultz
{"title":"Reformulating Time-Cure Superposition to Describe the Phase Transition in Rearranging Gel Networks","authors":"Gautam V. Khare, Kristi S. Anseth, Kelly M. Schultz","doi":"10.1021/acsmacrolett.6c00379","DOIUrl":"10.1021/acsmacrolett.6c00379","url":null,"abstract":"<p>Rearranging hydrogels are used for applications thatrequire tailoredcontrol of solid- and liquid-like properties. These applications necessitatepinpointing the phase transition, where a sample-spanning structureis formed or broken. To characterize the mechanical properties atthe phase transition, we use time-cure superposition (TCS), whichsuperimposes rheological properties as a function of increasing extentsof gelation or degradation, <em>p</em>. We generally use reactiontime to estimate <em>p</em>. However, dynamic materials undergonetwork rearrangements, which invalidates this assumption. In thiswork, we characterize the rheology of a rearranging hydrogel duringdegradation using multiple particle tracking microrheology (MPT).The logarithmic slope of the particle mean-squared displacements,α, is used to estimate <em>p</em> instead of time, becauseα is directly related to the cross-link density, ρ, andis independent of time. This reformulation identifies the phase transitionunambiguously and more precisely, expanding the scope of the techniqueto quantify phase transitions in these types of hydrogels.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1348–1354"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148885539","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}
ACS Macro LettersPub Date : 2026-09-15Epub Date: 2026-05-20DOI: 10.1021/acsmacrolett.6c00160
Yinghao Li, Bei Qiu, Liang Yao, Jiahao Liu, Zishan Li, Xinhui Wang, Jing Lyu, Wenxin Wang
{"title":"An Overlooked Formulation Variable: Solvent Reshapes DNA Delivery","authors":"Yinghao Li, Bei Qiu, Liang Yao, Jiahao Liu, Zishan Li, Xinhui Wang, Jing Lyu, Wenxin Wang","doi":"10.1021/acsmacrolett.6c00160","DOIUrl":"10.1021/acsmacrolett.6c00160","url":null,"abstract":"<p>Nonviral polymeric vectors offer a tunable platform fornucleicacid delivery, yet formulation variables beyond polymer structureremain underexplored. Here, we systematically investigate the roleof stock solvent in shaping gene delivery performance using end-cappedhighly branched poly(amino ester) (HPAE) vectors. By combining a structuredexperimental design with an interpretable machine learning framework,we reveal that transfection efficiency is primarily governed by polymerfeatures, while solvent properties modulate performance through strongpolymer–solvent interactions. Descriptor-level analysis identifieskey molecular features associated with high-performing formulations,highlighting the importance of polymer size, charge density, and hydrophobic–polarbalance. Selected polymer–solvent combinations enable efficientCFTR protein restoration in cystic fibrosis disease cells and achieverobust <em>in vivo</em> transgene expression following systemicadministration in mice. Overall, this work establishes stock solventas a critical and tunable formulation parameter and provides a data-drivenframework for optimizing polymeric gene delivery systems.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1199–1207"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147968520","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":"Achieving In Situ Photoisomerization of Fluorene-Based Polymers on the Surface of s-SWCNTs for Bare s-SWCNTs Release","authors":"Yuchi Wan, Jun-Hao Wang, Yu Li, Yu Cao, Xuelei Liang, Gaoyi Han, Ying Zhang","doi":"10.1021/acsmacrolett.6c00361","DOIUrl":"10.1021/acsmacrolett.6c00361","url":null,"abstract":"<p>Theefficient release of semiconducting single-walledcarbon nanotubes(s-SWCNTs) from conjugated polymer wrappers via photoisomerizationunder light stimuli is attractive but has not been achieved yet andremains challenging. Herein, we report a photoisomerization polymerof PFDD-CS, by incorporating a cyano-styrene linker featuring a twistedconjugate structure. It can undergo only the desired <em>trans</em>-to-<em>cis</em> photoisomerization, but not the normal photocyclizationnor photoaddition for cyano-styrene derivatives. Particularly, itcan even occur in situ successfully on the nanotube surface underlight stimuli, facilitating the release of bare s-SWCNTs. Experimentalresults revealed that the twisted conjugate structure of the initial <em>trans</em>-form contributes to the mobility on the surface ofs-SWCNTs, while the significant conformational differences betweenthe <em>trans</em>- and <em>cis</em>-isomers facilitatepolymer detachment and bare s-SWCNT release. This work provides amild, light-triggered strategy for obtaining pure nanotubes and advancesthe development of stimuli-responsive polymers for nanomaterials processing.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1333–1339"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148717890","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}
ACS Macro LettersPub Date : 2026-09-15Epub Date: 2026-08-31DOI: 10.1021/acsmacrolett.6c00383
Jin Qian, Tianli Ren, Peiran Wei, Wisdom Kemakolam, Zhe Qiang
{"title":"Targeted Chemical Functionalization of the Amorphous Phase in Polyolefins via Controlled Solvent Swelling","authors":"Jin Qian, Tianli Ren, Peiran Wei, Wisdom Kemakolam, Zhe Qiang","doi":"10.1021/acsmacrolett.6c00383","DOIUrl":"10.1021/acsmacrolett.6c00383","url":null,"abstract":"<p>Postpolymerization modification of polyolefins enablesdirect introductionof functionality into high-volume, low-cost commodity materials, affordingaccess to functional materials that are otherwise challenging to synthesizedirectly from monomers. However, traditional postpolymerization modificationstrategies result in randomly distributed functionalization alongthe polyolefin backbone, which can disrupt crystallinity and degradethe thermomechanical properties of the derived polymers. Crystallite-templatedpostpolymerization functionalization has recently emerged as a promisingstrategy to overcome these limitations, yet existing approaches oftenrequire specially prepared semicrystalline gels. Here, we report aswelling-assisted postpolymerization functionalization strategy thatdirectly leverages the semicrystalline morphology of melt-processedpolyolefins. In this process, the chemical reagents are selectivelyintroduced to the amorphous phase of polymers for a targeted functionalizationreaction at elevated temperatures. The resulting functionalized polyolefinslargely retain the melting temperature and crystallinity of theirunmodified counterparts across multiple grafting monomers, highlightinga practical and versatile platform for producing functional polyolefinswith a preserved semicrystalline microstructure and bulk propertiesdirectly from commercial feedstocks.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1355–1361"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148858350","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}
ACS Macro LettersPub Date : 2026-09-15Epub Date: 2026-09-02DOI: 10.1021/acsmacrolett.6c00421
Yuqing Geng, Dongxu Wang, Yingbo Zhao, Tao Li
{"title":"Framework-Imprint Synthesis of Linear Porous Organic Polymers","authors":"Yuqing Geng, Dongxu Wang, Yingbo Zhao, Tao Li","doi":"10.1021/acsmacrolett.6c00421","DOIUrl":"10.1021/acsmacrolett.6c00421","url":null,"abstract":"<p>Linearporous organic polymers (L-POPs) are rare specieswithinthe broad family of POPs due to the complexity of molecular designfor preserving intrinsic free volume. With the absence of rigid structuralunit, relaxed polymer chains undergo aggregation and dense packing,severely limiting the specific surface area. As a result, the preparationof L-POPs remains a formidable challenge. Herein, we overcome theabove limitation by introducing a framework-imprint synthesis (FIS)strategy that exploits a sacrificial crystalline metal–organicframework (MOF) as a pore template. Specifically, triazolate L-POPswith flexible monomers are constructed via azide–alkyne clickreaction within the confined nanochannels of the MOF host. The as-synthesizedL-POP nanoparticles retain the octahedral morphology upon removalof the MOF scaffold. This process yields abundant hierarchical porositycomprising both micropores and mesopores, driven by the spatiallyorganizing of polymer chains, which are impossible through solvothermalpolymerization.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 9","pages":"1376–1381"},"PeriodicalIF":4.9,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148885143","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}
ACS Macro LettersPub Date : 2026-08-18Epub Date: 2026-07-23DOI: 10.1021/acsmacrolett.6c00295
Katherine M. Gunter, Richard A. Register
{"title":"Stiffness Tuning and Ductility Enhancement of Semicrystalline Polymers by Incorporating Miscible Noncrystallizable Blocks","authors":"Katherine M. Gunter, Richard A. Register","doi":"10.1021/acsmacrolett.6c00295","DOIUrl":"10.1021/acsmacrolett.6c00295","url":null,"abstract":"<p>The mechanical behaviorof hydrogenated poly(norbornene-<em>b</em>-substituted norbornene)diblock copolymers was investigated,where the substituted norbornene blocks are intimately mixed withinthe amorphous layer between hydrogenated polynorbornene (N) crystallites.In particular, hydrogenated poly(norbornene-<em>b</em>-norbornylnorbornene) diblock copolymers were studied; hydrogenated poly(norbornylnorbornene) homopolymers are glassy at room temperature. Enhancementof both yield stress and Young’s modulus was found at an enrichmentof just 20 wt % glassy (G) block in the amorphous layer. Surprisingly,these N-G diblocks exhibit improved toughness over N homopolymers,with a nearly 4× decrease in minimum tie molecule fraction forductility compared to quenched N homopolymers. Enhanced ductilityis observed whether the substituted norbornene block is glassy orrubbery, as was demonstrated with a hydrogenated poly(norbornene-<em>b</em>-hexylnorbornene) diblock copolymer (N-R). These materials’strain-hardening moduli reveal that the amorphous block promotes ductilityby reducing disentanglement of tie molecules during drawing.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 8","pages":"1129–1134"},"PeriodicalIF":4.9,"publicationDate":"2026-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148552382","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}
ACS Macro LettersPub Date : 2026-08-18Epub Date: 2026-07-23DOI: 10.1021/acsmacrolett.6c00284
Stephen Wong, Ankush Kumar Mishra, Baskar Ganapathysubramanian, Enrique D. Gomez
{"title":"Machine Learning Driven Analysis Yields Insight into the Processing Robustness of Organic Photovoltaics","authors":"Stephen Wong, Ankush Kumar Mishra, Baskar Ganapathysubramanian, Enrique D. Gomez","doi":"10.1021/acsmacrolett.6c00284","DOIUrl":"10.1021/acsmacrolett.6c00284","url":null,"abstract":"<p>Optimizing the processing window for organic photovoltaics(OPVs)can deliver high efficiency and yield. In practice, small drifts insolution concentration, additive fraction, drying rate, or ambienthumidity readily perturb the evolving morphology, making championdevices hard to reproduce. We combine a complementary Taguchi andspace-filling design-of-experiments strategy with machine-learningsurrogates to map processing robustness in PM6:Y6 films using acetoneand 1-chloronaphthalene as the processing additives. Robustness isquantified via parameter-space fraction (share of conditions exceedinga power conversion efficiency threshold), persistence curves (howthat share contracts as the threshold tightens), and fill fraction(compactness of high-performing regions). The parameter space landscapewhen using acetone as a solvent additive exhibits a broad, robustregime, with around 73% of the explored space exceeding 9% PCE; thisis consistent with our hypothesis that faster evaporation yields morphologytolerant to routine variability. This ML-enabled framework disentanglesmanufacturing-relevant robustness from peak PCE and offers a general,data-efficient way to compare processing-window robustness with reducedexperimental effort. Such tools integrate naturally with self-drivinglaboratories and can identify new processing opportunities for OPVs.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 8","pages":"1117–1122"},"PeriodicalIF":4.9,"publicationDate":"2026-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148552383","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}
ACS Macro LettersPub Date : 2026-08-18Epub Date: 2026-07-27DOI: 10.1021/acsmacrolett.6c00246
Richard B. Huang, Patrick S. Doyle
{"title":"Modeling Bending and Kinking of DNA Minicircles in Elongational Flow","authors":"Richard B. Huang, Patrick S. Doyle","doi":"10.1021/acsmacrolett.6c00246","DOIUrl":"10.1021/acsmacrolett.6c00246","url":null,"abstract":"<p>DNA minicircles are a model system for DNA bending mechanics,andtheir response to nonuniform forcing, such as flow, provides insightinto the deformation of broader DNA nanostructures in applicationenvironments. In this work we use molecular dynamics simulations toinvestigate DNA minicircles undergoing deformation and structuraltransitions in strong elongational flow. We derive an analytical modelbased on the worm-like chain and the extensional flow potential thatpredicts the extent of deformation without additional fitting parameters,and show that the data collapse across chain lengths when expressedin terms of the elasto-viscous number. Under uniaxial extensionalflow, minicircles adopt a “racetrack” shape, concentratingbending energy toward the extrema of the minicircle along the extensionalaxis. At large flow strengths, the localized bending disrupts thedouble helix, resulting in a kink that is predicted by a dimensionlesskinking number. DNA minicircles are relevant in biological processessuch as gene expression, plasmids, and histone wrapping and, moregenerally, as building blocks for DNA nanostructures at similar lengthscales. These results provide a framework for understanding DNA deformationunder nonuniform forcing in environments such as nanopores and microfluidicdevices.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 8","pages":"1086–1092"},"PeriodicalIF":4.9,"publicationDate":"2026-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148589286","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}
ACS Macro LettersPub Date : 2026-08-18Epub Date: 2026-07-27DOI: 10.1021/acsmacrolett.6c00307
Roman Shrestha, Derrick Nguyen, Victoria Oh, Zhibin Guan
{"title":"Dynamic Diels–Alder Block Copolymers for Compatibilization of Multicomponent Polymer Blends","authors":"Roman Shrestha, Derrick Nguyen, Victoria Oh, Zhibin Guan","doi":"10.1021/acsmacrolett.6c00307","DOIUrl":"10.1021/acsmacrolett.6c00307","url":null,"abstract":"<p>Mechanical recycling of mixed plastic waste is limitedby the inherentimmiscibility of different polymers, which causes phase separationand degraded mechanical properties. Preformed block copolymers cancompatibilize immiscible blends, but this strategy becomes syntheticallyimpractical for multicomponent mixtures because each pairwise polymerinterface typically requires a distinct compatibilizer. Here, we introducea dynamic compatibilization strategy in which Diels–Alder (DA)homopolymers undergo thermally induced exchange to generate blockcopolymers <em>in situ</em>. Using a difunctional RAFT initiatorbearing a dicyclopentadiene (DCPD) motif, we synthesized well-definedDA-functionalized homopolymers by photoiniferter RAFT polymerizationunder 365 nm irradiation. After confirming the dynamic exchange ofthe DA homopolymers, the resulting equilibrated block copolymers wereused directly to compatibilize binary, ternary, and quaternary polymerblends, leading to substantial domain-size reductions observed byAFM and SEM. In melt-processed blends, the morphology <strong>i</strong>mprovement produced substantial enhancements in mechanical performance,with toughness increase of up to 550%. This proof-of-concept studyestablishes dynamic DA homopolymers as an adaptable platform thatgenerates block copolymers <em>in situ</em> for compatibilizingcomplex polymer mixtures relevant to mixed-plastic waste recycling.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 8","pages":"1149–1156"},"PeriodicalIF":4.9,"publicationDate":"2026-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148595875","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}
ACS Macro LettersPub Date : 2026-08-18Epub Date: 2026-08-06DOI: 10.1021/acsmacrolett.6c00316
Beomsu Kim, Thi Oanh Oanh Nguyen, Roopa Hirachand Patil, Basavaraj Rudragouda Patil, Ngoc Duy Le, Thang Nguyen Quoc, Huy Xuan Luong, Jeonghwan Kim, Jong Oh Kim
{"title":"Rational Design of Pyrrole-Based Ionizable Lipids for mRNA Delivery","authors":"Beomsu Kim, Thi Oanh Oanh Nguyen, Roopa Hirachand Patil, Basavaraj Rudragouda Patil, Ngoc Duy Le, Thang Nguyen Quoc, Huy Xuan Luong, Jeonghwan Kim, Jong Oh Kim","doi":"10.1021/acsmacrolett.6c00316","DOIUrl":"10.1021/acsmacrolett.6c00316","url":null,"abstract":"<p>Ionizable lipids are key components of lipid nanoparticlesformRNA delivery. Inspired by the DLin-KC2-DMA ionizable lipid, we developeda series of pyrrole-based ionizable lipids to evaluate the feasibilityof incorporating a rigid heterocyclic scaffold into ionizable lipiddesign. Systematic variation of headgroup architecture revealed thatpositioning the tertiary amine outside the pyrrole core substantiallyimproved RNA encapsulation and transfection activity and identifiedlipid <strong>6</strong> as the lead structure within this series. Lipidnanoparticles formulated with lipid <strong>6</strong>, administered viaintramuscular injection, outperformed other pyrrole analogs and achievedlymph node transfection comparable to structural reference DLin-KC2-DMA.Mechanistic studies combining Förster resonance energy transferassays and multiscale molecular dynamics simulations suggested thatthe improved delivery was associated with enhanced lipid–RNAelectrostatic interactions and favorable membrane fusion behavior.Overall, this work establishes pyrrole as a feasible scaffold forionizable lipid development and expands the chemical design spaceof mRNA delivery materials.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 8","pages":"1163–1168"},"PeriodicalIF":4.9,"publicationDate":"2026-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148692137","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}