ACS polymers Au最新文献

{"title":"Understanding the Swelling Behavior of Polysaccharide-Based Hydrogels through a Kinetic Modeling","authors":"Vinicius Duarte Machado,&nbsp;Michele Karoline Lima-Tenório,&nbsp;Ernandes Taveira Tenório-Neto","doi":"10.1021/acspolymersau.5c00208","DOIUrl":"10.1021/acspolymersau.5c00208","url":null,"abstract":"<p>Hydrogels are versatile polymeric materials widely usedin variousapplications, including drug delivery, agriculture, and environmentaltechnologies. Their performance and applicability are mainly governedby the swelling behavior. As a result, an accurate description ofswelling kinetics is crucial for understanding the transport mechanismsthat guide the hydrogel design. However, the power-law model failsto describe the full swelling profile and transient phenomena, suchas, nonmonotonic swelling. In this work, we propose a physical modelbased on a kinetic interpretation, which is capable of describingthe entire swelling profile of hydrogels. The model is derived fromfundamental transport concepts, and incorporates both Fickian diffusionand macromolecular relaxation within a unified framework. Importantly,several classical swelling equations<span></span>including the power law,first-order kinetic, Peppas–Sahlin, and Higuchi models<span></span>areshown to emerge as particular cases of the proposed formulation. Themodel was validated using experimental swelling data of chemicallycross-linked polysaccharide-based hydrogels with different compositions.The proposed equation accurately fitted the swelling curves, includingthe overshooting behavior, with high correlation coefficients. Themodel quantified the contribution of Fickian diffusion and macromolecularrelaxation in the swelling mechanism. The proposed model offers asimple and comprehensive tool for analyzing hydrogel swelling kinetics.By describing the full swelling process with only three physical parameters,it enables improved mechanistic interpretation, providing valuableguidance for the rational design of hydrogels with tailored swellingand absorption properties.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 2","pages":"634–644"},"PeriodicalIF":6.7,"publicationDate":"2026-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147679206","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":"How to Characterize Supramolecular Polymers: A User Guide","authors":"Yuhang Sheng,&nbsp;Menglan Ma,&nbsp;Shijun Li,&nbsp;Li Shao,&nbsp;Bin Hua,&nbsp;Feihe Huang,&nbsp;Zibin Zhang","doi":"10.1021/acspolymersau.5c00153","DOIUrl":"10.1021/acspolymersau.5c00153","url":null,"abstract":"<p>Unlike traditional macromolecules, supramolecular polymersareassemblies composed of individual monomeric units that are connectednot by covalent bonds but through reversible, noncovalent interactions.This fundamental distinction from conventional polymers endows themwith a wide range of novel and tunable properties, such as intrinsicdynamic reversibility, responsiveness to external stimuli (e.g., temperature,pH, light, and chemical environment), self-healing capability, andthe ability to undergo controllable disassembly and reassembly. However,standardized or universally applicable techniques for the comprehensivecharacterization of supramolecular polymers have not been fully establishedyet. To address this gap, this review provides a detailed and systematicsummary of various methodologies currently employed to characterizesupramolecular polymers, including nuclear magnetic resonance spectroscopies(VC-NMR, VT-NMR, COSY, NOESY, ROESY, DOSY NMRs), mass spectrometries(ESI, MALDI, APCI), photo spectroscopies (UV–vis, FL, CD, IR,et al.), light scattering methods (DLS, SLS), X-ray techniques (SC-XRD,SAXS, WAXS, et al.), microscopies (AFM, SEM, TEM, CLSM, et al.) andmethods used in traditional polymers (SEC, VPO, TGA, DSC, et al.).Due to the complexity and multifaceted nature of supramolecular systems,no single technique is capable of providing a complete and unambiguousdescription. Therefore, a combination of complementary techniquesis typically required to achieve a thorough insight into their thermodynamics,kinetics, morphology, and responsiveness.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 1","pages":"117–156"},"PeriodicalIF":6.7,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146203903","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":"Tailored Plasticization of Bio- and Fossil-Based Polymers Using a Versatile Bioplasticizer Derived from Phenylacetic Acid and Glycerol","authors":"Laura Martellosio,&nbsp;Martina Ferri,&nbsp;Luca Lenzi,&nbsp;Arianna Tauro,&nbsp;Andrea Dorigato,&nbsp;Micaela Degli Esposti,&nbsp;Davide Morselli,&nbsp;Paola Fabbri","doi":"10.1021/acspolymersau.5c00149","DOIUrl":"10.1021/acspolymersau.5c00149","url":null,"abstract":"<p>For acceleratingthe shift from fossil-derived plastics towardbiopolymers, there is an urgent need to develop efficient and versatilebiobased plasticizers to improve biopolymer performance without compromisingbiodegradability and/or safety. This study explores the versatilityof the emerging triphenylacetic glyceroate (TPAG) bioplasticizer byincorporating it into a range of biobased and conventional polymers.An increasing content of TPAG, from 5 to 20 parts per hundred of resin(phr), has been compounded with polyhydroxybutyrate (PHB), polyhydroxybutyrate-<em>co</em>-valerate (PHBV), polyvinyl chloride (PVC), and polybutylenesuccinate (PBS), which present complicated processability and/or limitedmechanical properties as bare polymers. Differential scanning calorimetryreveals a clear reduction in glass-transition temperatures (<em>T</em>_g) for PHB, PHBV, and PVC, with the most significantdrop observed for PVC (Δ<em>T</em>_g = −25°C at 20 phr TPAG), confirming the significant plasticizing efficiencyof TPAG. A melting temperature decrease is also noted for PHB andPBS, with PHB exhibiting β-crystalline phase formation at highTPAG contents, which is attributed to enhanced chain mobility. Mechanicaltests demonstrate that only 10 phr TPAG reduces Young’s modulusacross all polymers, importantly enhancing their flexibility. Furthermore,20 phr of TPAG increases the elongation at break of PVC and PHBV upto 349% and 22%, respectively. Volatility and migration studies demonstrateminimal plasticizer loss with values remaining well below safety limits.Moreover, TPAG addition also tailors both water contact angle andUV-blocking activity of the tested polymers, clearly indicating theversatility and multifunctionality of TPAG as a potentially suitableadditive for consumer-facing applications.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 1","pages":"353–365"},"PeriodicalIF":6.7,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146203928","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":"Sustainable Thermoplastic Elastomers from Commercial Cyclic Esters: One-Pot Synthesis of Poly(l‑lactide)‑b‑(δ-hexalactone-stat-ε-caprolactone)‑b‑(l‑lactide) and Its Chemical Recycling to the Monomers","authors":"Giuseppe Gravina,&nbsp;Joseph N. A. Tagoe,&nbsp;Rocco Di Girolamo,&nbsp;Maria Gentile,&nbsp;Luciano Di Maio,&nbsp;Claudio Pellecchia","doi":"10.1021/acspolymersau.5c00172","DOIUrl":"10.1021/acspolymersau.5c00172","url":null,"abstract":"<p>We report the <em>one-pot</em> synthesis of ABA triblockcopolymers composed of poly­(<span>l</span>-lactide) (PLA) as hard segmentsand δ-hexalactone/ε-caprolactone (HL/CL) copolymers assoft midblock. Use of an environmentally benign and highly activeand living Fe­(II)-based catalyst enabled precise molecular designand control over copolymer architecture, providing low-<em>T</em>_g, amorphous statistical HL/CL dihydroxy-terminated copolymers,which could be chain extended with <span>l</span>-lactide in the samereactor, resulting in poly­(<span>l</span>-lactide)-<em>b</em>-(δ-hexalactone-<em>stat</em>-ε-caprolactone)-<em>b</em>-(<span>l</span>-lactide) triblock copolymers. The <em>one-pot</em> syntheticroute enabled control of block composition and length, resulting inmaterial property profiles ranging from silicone-like soft elastomersto SBS-like rubbers, and to toughened PLA. Finally, efficient chemicalrecycling to the pristine monomers with &gt;90% recovery was achievedby catalytic thermal depolymerization under mild conditions.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 1","pages":"468–479"},"PeriodicalIF":6.7,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146203930","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":"Solvent-Tuned Aggregation and Its Limited Functional Impact in a Rigid-Rod Indacenodithiophene-Benzothiadiazole Copolymer","authors":"Lorenzo Guio,&nbsp;Parker Sommerville,&nbsp;Lilo D. Pozzo,&nbsp;Christine K. Luscombe","doi":"10.1021/acspolymersau.5c00155","DOIUrl":"10.1021/acspolymersau.5c00155","url":null,"abstract":"<p>We investigate the influence of solvent quality on solution-stateaggregation and solid-state morphology in a rigid indacenodithiophene-baseddonor–acceptor copolymer, PIDTC16-BT. Using UV–vis spectroscopyand temperature-dependent small-angle X-ray scattering (SAXS), wecharacterize aggregation behavior across three solvents of varyingsegmental compatibility. Anisole promotes rapid, cooperative aggregationwith lamellar ordering, while toluene and tetrahydrofuran (THF) supportmore gradual or dispersed clustering. Grazing-incidence small-angleX-ray scattering (GISAXS) reveals that these solution-state differencespartially translate into solid-state packing, with anisole-cast filmsexhibiting enhanced lamellar coherence and backbone alignment. Despitethese structural variations, organic field-effect transistor (OFET)measurements show comparable hole mobilities across all solvents.These results suggest that backbone rigidity and kinetic trappingduring casting suppress the functional impact of solvent-driven aggregation.Segment-specific solubility analysis using Hansen parameters providesa framework for understanding aggregation pathways in rigid D–Asystems. Our findings highlight the morphological robustness of PIDTC16-BTand underscore the need for multiscale characterization when linkingprocessing to performance in conjugated polymer devices.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 1","pages":"388–398"},"PeriodicalIF":6.7,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146203918","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":"Predicting Properties from Near-Infrared Spectra with Machine Learning for Improved Polyolefin Differentiation","authors":"Shuaijun Li,&nbsp;Robert J. S. Ivancic,&nbsp;Bradley P. Sutliff,&nbsp;Derek Huang,&nbsp;Enrique Blázquez-Blázquez,&nbsp;Tyler B. Martin,&nbsp;Kalman B. Migler,&nbsp;Debra J. Audus,&nbsp;Sara V. Orski","doi":"10.1021/acspolymersau.5c00131","DOIUrl":"10.1021/acspolymersau.5c00131","url":null,"abstract":"<p>As the scale andvariety of plastics produced continueto grow,plastics recycling will require innovative solutions. The industrialstate-of-the-art sorting technology, near-infrared (NIR) spectroscopy,as currently used, cannot effectively differentiate polyolefins, thesingle largest class of polymers by volume. Chemical similarity combinedwith architectural diversity in polyolefins stymies subclass delineation,such as differentiating low-density polyethylene from high-densitypolyethylene, due to their spectral similarity and chemical overlap.To address this challenge, we use machine learning (ML) to directlypredict density, crystallinity, and short-chain branching from NIRspectra, enabling property-based sorting for more effective recycling.After testing a variety of ML models, we find that partial least squaresregression provides high prediction accuracy with model simplicity.Since the resulting model leverages the correlated intensities, wedevelop a method to enhance interpretability by identifying the mostimportant wavenumbers for property prediction, which we then relateto known polyolefin CH₃ NIR vibrational absorption bands.This approach provides a linkage between ML model predictions andthe underlying polyolefin chemistry and confirms that our models effectivelycapture spectrum–structure–property relationships inpolyolefins, reinforcing the fundamental role of polymer chain structurein determining properties. These findings significantly contributeto the understanding of polyolefin differentiation using NIR spectroscopy,which could inform future advancements in property-based sorting strategiesfor plastic recycling efficiency.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 1","pages":"246–255"},"PeriodicalIF":6.7,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146203992","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":"Understanding Interlayer Adhesion in Lamellar Polymer Composite Materials via Computation","authors":"Ahmed H. Ibrahim,&nbsp;Mark DelloStritto,&nbsp;Subhajit Acharya,&nbsp;Fei Ren,&nbsp;Dmitriy A. Dikin,&nbsp;Simona Percec,&nbsp;Michael L. Klein","doi":"10.1021/acspolymersau.5c00134","DOIUrl":"10.1021/acspolymersau.5c00134","url":null,"abstract":"<p>Personal body armor applications often rely on high-performancepolymers, such as <em>poly</em>(p-phenylene terephthalamide)(PPTA) and ultrahigh-molecular-weight polyethylene (UHMWPE). Whilethese materials have seen success, improvements can be made by utilizingcomposites, thereby combining desirable properties from several differentpolymers into layered materials with variable thickness, weight, andrigidity. Herein, we use fully atomistic molecular dynamics (MD) simulations,as a complement to peel test and imaging experiments, to explore strategiesfor modifying the PPTA/UHMWPE interface with an aim to improve adhesionand ballistic performance. Specifically, we investigate how the adhesionbetween PPTA and UHMWPE is impacted by plasma treatment and/or bycoating with polypyrrole (PPy) in the form of either nanoclustersor nanodomains. Our MD simulations, coupled with peel test experiments,demonstrate that while plasma-treatment of UHMWPE results in strongeradhesion to PPTA, it is not as effective as coating with PPy. Insightfrom density functional theory (DFT) electronic structure calculationsshows that pyrrole and benzene moieties have a relatively high bindingenergy due to the polar nature of pyrrole. However, H-bond interactionsare even stronger. Thus, the interfacial adhesion appears to dependon both the specific interactions between different polymer monomersand the accessible surface area at each polymer–polymer interface.This finding is also evidenced by the poor performance of PPy nanodomainsversus nanofibers, demonstrated in our peeling experiments. Therefore,achieving an optimal balance between the interaction strength andthe density of interaction sites is crucial for improving adhesionbetween these polymer interfaces.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 1","pages":"267–277"},"PeriodicalIF":6.7,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146203956","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":"Blended and Microparticle Composite Hyaluronan Hydrogels with Programmable Degradation through Selective Oxidation","authors":"Melanie Grimm,&nbsp;Fiona Ye Rojo Acero,&nbsp;Fatemeh Safari,&nbsp;Desiré Venegas-Bustos,&nbsp;Andreas Wagner,&nbsp;Clara Presciutti,&nbsp;Wen Chen,&nbsp;Matteo D’Este,&nbsp;Jacek K. Wychowaniec","doi":"10.1021/acspolymersau.5c00129","DOIUrl":"10.1021/acspolymersau.5c00129","url":null,"abstract":"<p>The design spaceof hydrogels for biomedical applicationsembracesa wide variety of parameters that can be tuned through chemical modification.Among them, tissue adhesion and viscoelastic properties contributeto the integration of tissue-engineered constructs with native tissues,while the degradation profile determines their temporal evolutionand cell invasion. Selective 1,2-diol oxidation is a versatile toolto control all of these properties in polysaccharide-based hydrogelsby generating aldehyde groups. A key challenge in implementing thistool is that although aldehyde groups improved adhesion, they alsopromoted chain fragmentation, demanding a trade-off. To address this,we devised a strategy that leverages the adhesiveness of oxidizedbiopolymers together with the mechanical stability of their nonoxidizedcounterparts. Here, we synthesized tyramine-modified hyaluronan (THA)and its oxidized form (oTHA) and evaluated their degradation and adhesionin various combinations and formats, including <em>blended hydrogels</em> and <em>hydrogel microparticle composite</em> networks.As the degree of oxidation increased in oTHA, its molecular weightdecreased, the storage modulus of the resulting hydrogels slightlydeclined, brittleness increased, and physical degradation accelerated.These opposing properties were finely offset in two-component blendedhydrogels; increasing the oTHA content proportionally acceleratedthe degradation rate in both bulk and hydrogel microparticle compositeformats while maintaining consistent viscoelastic properties and networktopology at a fixed total polymer concentration. By adjusting theoTHA-to-THA ratio, we generated composite hydrogels with two distinctdegradation behaviors: (i) <em>collapse-type mode</em>, where <em>blended hydrogels</em> gradually softened and spread withoutfragmenting; and (ii) <em>fragmentation-type mode</em>, where <em>hydrogel microparticle composites</em> abruptly broke into discretepieces over degradation time. This tunability enables the design ofa new class of composite soft biomaterials with programmable degradation.Such materials show potential for tunable tissue engineering strategies,which could be implemented for controlling cell invasion, migration,and proliferation in biological applications.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 1","pages":"226–245"},"PeriodicalIF":6.7,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146203700","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":"Engineering Functional PVA: A Comprehensive Review of Chemical Modifications and Prospective Developments","authors":"Nhu Q. Vu,&nbsp;Thai M. Le,&nbsp;An N. B. Ngo,&nbsp;Minh H. T. Nguyen,&nbsp;Ying-Chih Liao,&nbsp;Thuy T. Tran","doi":"10.1021/acspolymersau.5c00133","DOIUrl":"10.1021/acspolymersau.5c00133","url":null,"abstract":"<p>In response to the growing demand for biocompatible andmechanicallyresilient materials, poly­(vinyl alcohol) (PVA)-based systems havegained considerable attention for their versatility in biomedical,industrial, and environmental uses. While PVA exhibits excellent film-formingand hydrogel-forming capabilities, as well as great biocompatibility,emerging applications require enhancements in thermal and mechanicalperformance, along with eco-friendly processing. This work identifieskey strategies to augment PVA with desirable qualities, namely, cross-linking,grafting, and functionalization. For each approach, the underlyingreaction mechanisms, critical processing parameters, and post-treatmenteffects are discussed in detail. The functional outcomes of thesemodifications are evaluated in the context of real-world applications,demonstrating PVA’s adaptability and performance potential.Finally, obstacles impeding the development of PVA materials are addressed,along with noteworthy breakthroughs found in the recent literature.Future directions in research are also proposed to both leverage thesenewfound advancements and overcome the current hardships to furtherremarkable developments in practical utilizations.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 1","pages":"33–60"},"PeriodicalIF":6.7,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146203923","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":"Topology-Dependent Polymer Stretching and Scission in Solution at Extreme Shear Rates","authors":"Bas G. P. van Ravensteijn,&nbsp;Patrick T. Corona,&nbsp;Anukta Datta,&nbsp;Kexin Dai,&nbsp;Raghida Bou Zerdan,&nbsp;Katie M. Weigandt,&nbsp;Ryan P. Murphy,&nbsp;Craig J. Hawker,&nbsp;Matthew E. Helgeson","doi":"10.1021/acspolymersau.5c00105","DOIUrl":"10.1021/acspolymersau.5c00105","url":null,"abstract":"<p>There has been significant interest in the engineeringof polymertopology to control rheology and mechanical stability in dilute solutionsfor applications involving extreme shear rate flows. However, methodsto experimentally probe properties at relevant shear rates (≈10⁴–10⁶ s^–1) have remained <em>ex situ</em>, obscuring access to measures of polymer deformationand rheology that would otherwise provide mechanistic insight intothe topology-dependent properties that control their behavior in extremeshear flows. In this study, we used novel <em>in situ</em> small angle neutron scattering measurements in a capillary rheometer(capillary rheo-SANS) to simultaneously measure solution viscositiesand polymer deformations in high shear on a series of chemically homologoustopology-defined polymers including linear, randomly branched, andstar-shaped molecules. We demonstrate that differences in the onsetof chain stretching and shear thinning of these polymers in dilutesolution are controlled primarily by differences in their molecularrelaxation time. These differences correlate with differences in chainscission inferred from <em>ex situ</em> measurements at moreextreme shear rates. Together, the results demonstrate a direct couplingbetween chain deformation and scission, and suggest that the dominanteffect of branching as a means to impart resilience against mechanicaldegradation is through differences in relaxation dynamics due to branching.We anticipate that these results will provide key insights to engineertopology-controlled polymers for rheological modification, mechanicalstability, and controlled mechano-chemistry.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 1","pages":"194–202"},"PeriodicalIF":6.7,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146203960","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}