ACS polymers Au最新文献

{"title":"Noninvasive Monitoring of Polycarbonate Mechanochemical Properties under Broad-Band Photodegradation","authors":"Irene Bargagli,&nbsp;Sara Mattana,&nbsp;Martina Alunni Cardinali,&nbsp;Laura Cartechini,&nbsp;Brenda Doherty,&nbsp;Aldo Romani,&nbsp;Lucia Comez,&nbsp;Marisa Pamplona,&nbsp;Marco Paolantoni,&nbsp;Daniele Fioretto,&nbsp;Rafaela Trevisan,&nbsp;Alessandra Vannini,&nbsp;Massimo Lazzari,&nbsp;Costanza Miliani,&nbsp;Paola Sassi,&nbsp;Francesca Rosi","doi":"10.1021/acspolymersau.5c00198","DOIUrl":"https://doi.org/10.1021/acspolymersau.5c00198","url":null,"abstract":"<p>A noninvasive vibrationalspectroscopy approach is proposed tomonitor the conservation state of historical polycarbonate (PC) designand heritage objects, with the aim of identifying early signs of degradationessential for effective preservation. Systematic investigations onreference PC samples, artificially aged under indoor and outdoor lightingconditions, using IR external reflection spectroscopy, enabled thenoninvasive tracking of both photo-Fries rearrangement and photo-oxidation,the two well-known degradation pathways of PC. Since mechanical lossis a key issue in plastics, the correlation between chemical and mechanicalproperties was further investigated by combining IR spectroscopy withBrillouin light scattering (BLS). This correlative analysis provideda novel noninvasive analytical tool for monitoring the mechanochemicalchanges underlying yellowing and embrittlement, linking PC moleculardegradation to its altered viscoelastic behavior. Although originallydesigned for use in cultural heritage studies, the proposed approachestablishes a framework for evaluating and monitoring a wide rangeof polymeric materials across diverse industrial applications. Bybridging the gap between fundamental preventive conservation and polymerscience, it supports strategies aimed at safeguarding both culturalheritage and modern technological materials.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 5","pages":"1241–1253"},"PeriodicalIF":6.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173318","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":"Upcycling Recycled PET into High-Performance Polyurethane Coating and Engineering Materials: Effect of NCO Index on Mechanical, Stability, and Surface Properties","authors":"Panachai Thusanaphoom,&nbsp;Jureeporn Yuennan,&nbsp;Wichain Chailad,&nbsp;Sineenard Songsri,&nbsp;Vanchai Laemlaksakul,&nbsp;Jennifer Rodon-Fores,&nbsp;Yutthana Wongnongwa,&nbsp;Nathapong Sukhawipat","doi":"10.1021/acspolymersau.6c00147","DOIUrl":"https://doi.org/10.1021/acspolymersau.6c00147","url":null,"abstract":"<p>Upcycling of polyethylene terephthalate (PET) waste intohigh-valuepolymeric materials offers a promising pathway toward circular andsustainable polymer engineering. In this work, polyurethane (PU) filmswere synthesized from recycled PET (rPET)-based polyols, and the influenceof the isocyanate index (NCO index: 100–200) on the networkstructure and functional properties of the resulting materials wasinvestigated. FT-IR results supported the formation of urethane linkagesbetween the rPET-based polyol and polymeric methylene diphenyl diisocyanate(PMDI), indicating successful network formation. Increasing the NCOindex significantly enhanced cross-link density, reflected by an increasein gel content from 54.97 to 93.46% and a decrease in swelling ratiofrom 254.58% to 133.30%. This structural evolution led to improvedmechanical performance, with tensile strength and Young’s modulusreaching 7.26 and 5.29 N/mm², respectively. Thermal analysisfurther revealed an increase in glass transition temperature (−32.05–0.93°C) and enhanced thermal stability with higher char yields (17.57–24.71%).Surface analyses demonstrated smoother, denser, and more hydrophobicmorphologies at elevated NCO indices. An optimal balance of mechanical,thermal, and surface properties was achieved at NCO indices of 150–175,highlighting the potential of rPET-based PU films as sustainable coatingand engineering materials for advanced applications.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 5","pages":"1468–1487"},"PeriodicalIF":6.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173343","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":"From Byproduct to Platform: Can Kraft Lignin Outcompete Lignosulfonates?","authors":"Jéssica S. Rodrigues,&nbsp;Amanda de S. M. de Freitas,&nbsp;Kumar D. Dutta,&nbsp;Mallika Saha,&nbsp;Leonardo F. Fraceto","doi":"10.1021/acspolymersau.6c00111","DOIUrl":"https://doi.org/10.1021/acspolymersau.6c00111","url":null,"abstract":"<p>Lignosulfonates (LS)have long set the standard of dispersantsfor construction, agrochemical, oilfield, and animal feed industries,due to their amphiphilic structure─aromatic domains linkedwith sulfonated functionalities, which result in efficient and cost-effectivecolloidal stabilization. Nevertheless, LS production is intrinsicallylimited by the falloff in sulfite pulping, which is today only a minorpercentage of the world’s pulp manufacturing. On the otherhand, kraft lignin (KL) is produced at multimillion-tonne levels annuallyand is now being acknowledged as a renewable aromatic polymer of strategicimportance. Recent studies indicate that fractionation and controlledfunctionalization of KL can produce dispersants that match or outperformLS in selected systems, providing quantitative evidence that its chemicaltunability can translate into competitive dispersant performance underdefined application conditions. But these benefits come with problemsof heterogeneity, process complexity, scalability, and cost. ThisPerspective argues that, owing to its chemical tunability, industrialavailability, and potential for process innovation, KL should be regardednot as a universal replacement for LS, but as a platform capable ofcompeting in next-generation dispersant systems where tailored performancejustifies additional processing. By combining chemistry, technologylimitations, and economics, lignin-based materials have proven tobe important enablers of circular and low-carbon industrial technologies.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 5","pages":"1234–1240"},"PeriodicalIF":6.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173479","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":"Aqueous-Phase Polyelectrolyte Behavior of Hydroxypropyl Chitosan","authors":"Julia B. Chatterjee,&nbsp;Emily Krucker-Velasquez,&nbsp;Hiroaki Sai,&nbsp;Kyle J. Gray,&nbsp;Yonggang Liu,&nbsp;Will Skyrud,&nbsp;Eleanor C. Grosvenor,&nbsp;Sara E. Branovsky,&nbsp;Samuel I. Stupp,&nbsp;Jeffrey J. Richards,&nbsp;Monica Olvera de la Cruz,&nbsp;Cécile A. C. Chazot","doi":"10.1021/acspolymersau.6c00071","DOIUrl":"https://doi.org/10.1021/acspolymersau.6c00071","url":null,"abstract":"<p>Hydroxypropyl chitosan(HPCS) is a water-soluble, cationic derivativeof chitosan whose combination of hydrophilic substituents and residualcharged and hydrophobic groups creates a unique landscape of interactionsin aqueous media. Despite growing interest in chitosan-based materials,the fundamental solution behavior of HPCS, and the way its weak polyelectrolytecharacter couples with hydrophilic substitution, has remained largelyunderexplored. Here, we present a comprehensive, multiscale characterizationof HPCS structure and dynamics across ionic strengths ranging fromsalt-free to excess-salt conditions, integrating synchrotron small-angleX-ray scattering (SAXS) with dynamic light scattering (DLS) and complementarymodel-based analyses to resolve structural transitions across lengthscales. In salt-free semidilute conditions, HPCS behaves as a semirigid,hydrophilic polyelectrolyte, exhibiting a pronounced polyelectrolytepeak and rodlike chain conformations in SAXS. The scaling of the correlationlength with polymer concentration confirms that long-range electrostaticinteractions contribute toward chain organization despite the weakenedcharge density imposed by high degrees of hydroxypropyl group substitution.With the addition of monovalent salt, the correlated mesh dissolves,and DLS reveals fast hydrodynamic modes associated with screened chains,along with slow modes corresponding to large supramolecular aggregates.At higher salt concentrations (<em>c</em>_<em>s</em> ≳ 0.25 M), salting-out is not observed, and the structuralresponse becomes nonmonotonic, revealing underscreening-like behaviorand salt-driven aggregation mechanisms captured through a phenomenologicalRandom Phase Approximation (RPA) analysis. Together, these resultsestablish how ionic environment dictates distinct HPCS structuralregimes, from electrostatically repulsed networks to screened coilsand salt-modulated supramolecular assemblies, providing foundationalinsight for tailoring hierarchical organization and self-assemblyin HPCS-based solutions.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 5","pages":"1301–1314"},"PeriodicalIF":6.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173514","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 Intramolecular Compactness in Water-Soluble Single-Chain Nanoparticles for Optimized Platinum Delivery","authors":"Miriam B. Lossa,&nbsp;Thorsten Hofe,&nbsp;Martina H. Stenzel","doi":"10.1021/acspolymersau.6c00083","DOIUrl":"https://doi.org/10.1021/acspolymersau.6c00083","url":null,"abstract":"<p>Single-chain nanoparticles(SCNPs) have been extensively studiedfor various applications, including catalysis, drug delivery, antimicrobialagents, rheology modifiers, and in nanocomposites. For catalytic applications,the collapsed polymer chain was often cross-linked using a metal complex,which also served as the active catalytic site. Inspired by the successfulformation of a metal complex containing SCNPs, we have adopted thissystem for the delivery of the anticancer drug cisplatin. However,to deliver cisplatin into cells across the cell membrane, an understandingof the detailed structure and compactness of SCNPs is essential. Inthis work, we synthesized a series of statistical copolymers basedon polyethylene glycol methyl ether acrylate (PEGMEA) as water-solublemonomer, 2-carboxy ethyl acrylate (CEA) as the ligand for platinumdrug conjugation, and a hydrophobic monomer (methyl acrylate (MA),butyl acrylate (BA), and benzyl acrylate (BzA)) to enhance the compactnessof the SCNP. The library of polymers was conjugated with cisplatin,and the resulting SCNPs were characterized predominantly by size-exclusionchromatography (SEC) with viscosity detection and small-angle X-rayscattering (SAXS), as dynamic light scattering alone is insufficientto provide information about the SCNP formation. Increasing the amountof CEA and, therefore, the amount of cisplatin reduced viscosity andthe radius of gyration (<em>R</em>_g), thus increasingcompaction. The same was achieved by incorporating hydrophobic comonomerswith BA polymers showing the strongest collapse. The toxicity of thesedrug-loaded SCNPs was tested in the ovarian cancer cell line A2780,healthy lung cells MRC-5, and cisplatin-resistant ovarian cancer cellsA2780cis, showing that greater SCNP collapse correlates with highertoxicity, but only in the absence of hydrophobic comonomers.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 5","pages":"1339–1353"},"PeriodicalIF":6.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173520","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":"Mechanically Robust and Recyclable Diels–Alder Networks from a Degradable Cellulose-Based Matrix","authors":"Yazhou Su,&nbsp;Akihide Sugawara,&nbsp;Hiroshi Uyama","doi":"10.1021/acspolymersau.6c00135","DOIUrl":"https://doi.org/10.1021/acspolymersau.6c00135","url":null,"abstract":"<p>Designing sustainablepolymer materials that combinemechanicalrobustness with recyclability remains a significant challenge. Here,we report a cellulose-based Diels–Alder (DA) cross-linked networkthat integrates structural strength, thermoreversible recyclability,and tunable biodegradability. Cellulose was functionalized with furfurylaminevia carbamate formation to introduce furan moieties while minimizingperturbation of its π-electron system, yielding furfuryl carbamatecellulose (FC). By controlling the degree of substitution, FC wasdesigned to enable efficient cross-linking through DA reactions whilepreserving the inherent biodegradability of cellulose. The DA cross-linkednetworks were prepared by reacting FC with 1,6-bis(maleimido)hexane(BMI) via solvent casting. The resulting films exhibited tunable mechanicalproperties with increasing BMI content, with Young’s modulusranging from 0.4 to 3.1 GPa and maximum stress ranging from 20 to56 MPa, while maintaining relatively high toughness. Chemical recyclingwas enabled through thermally induced retro-DA reactions in solution,followed by reformation from solution. Enzymatic degradation testsusing cellulase showed that uncross-linked FC degraded rapidly, whereascross-linked networks exhibited suppressed yet persistent degradation.This demonstrates that degradation behavior can be systematicallycontrolled by cross-linking density. This work provides a moleculardesign strategy for constructing cellulose-based polymer networksthat balance mechanical performance, recyclability, and controlledend-of-life behavior.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 5","pages":"1455–1467"},"PeriodicalIF":6.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173452","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":"Building Up Debondable Adhesion with Commercial Adhesives through Surface Modification of Substrate with Vitrimers","authors":"Nien-Hsun Wu,&nbsp;Ying-Ling Liu","doi":"10.1021/acspolymersau.6c00122","DOIUrl":"https://doi.org/10.1021/acspolymersau.6c00122","url":null,"abstract":"<p>ABSTRACT Debondableadhesion is highly attractive in the developmentof high-performance adhesives, particularly for sustainability initiativesrequiring material recycling and reuse. Vitrimers, which possess dynamicfeatures under specific conditions─typically at elevated temperatures─havebeen widely studied for the development of debondable adhesives. Thiswork demonstrates an alternative approach to achieving debondableadhesion by establishing thin vitrimer layers on substrate surfacesvia chemical modification. Poly(ethylene terephthalate) (PET) films,surface-modified with diketoenamine (DKA)-based vitrimers, were preparedto demonstrate the proposed strategy. When a commercial epoxy AB gluewas utilized as the adhesive, pristine PET films did not exhibit debondablebehavior. In contrast, the vitrimer-modified PET films demonstrateddebonding capabilities at 50 °C, evidenced by a reduction inlap shear strength from 8.2 ± 0.9 MPa to 3.3 ± 0.9 MPa.Furthermore, acid-catalyzed hydrolysis of the DKA layers in the adheredsamples resulted in a reduction in lap shear strength from 4.9 ±0.5 MPa to 1.8 ± 0.5 MPa. This study demonstrates a highly effectiveapproach for engineering debondable interfaces that is readily applicableto commercial adhesive systems.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 5","pages":"1414–1421"},"PeriodicalIF":6.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173484","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":"Free Polymers Skew Polyplex Solution Properties and Confound the Interpretation of Structure–Function Relationships","authors":"Jessica L. Lawson,&nbsp;Kaitlin C. Lesco,&nbsp;Ram Prasad Sekar,&nbsp;Grant Wheeler,&nbsp;S. Kim Ratanathanawongs Williams,&nbsp;Ramya Kumar","doi":"10.1021/acspolymersau.6c00080","DOIUrl":"https://doi.org/10.1021/acspolymersau.6c00080","url":null,"abstract":"<p>Structure–function relationships for polymericgene carriersare derived from crude, heterogeneous mixtures of free polymers andpolymer–pDNA complexes (polyplexes). Recognizing that our currentunderstanding of polyplex solution properties may be erroneous, weseparated free polymers from crude polyplexes to gain important, previouslyinaccessible perspectives into polymer-mediated pDNA delivery. Freepolymers, the numerically dominant species in crude polyplexes, imposecharacterization and quality control challenges similar to empty viralcapsids and lipid nanoparticles. Polyplexes are frequently formedat large stoichiometric excesses of cationic groups in polymers relativeto phosphates in pDNA resulting in nitrogen-to-phosphorus ratios between5–100. Most polymers exist as “free polymers”in dynamic equilibrium with pDNA-bound polymers. For the first time,we quantified the contributions of free polymers to polyplex solutionproperties and biological performance. We separated free polymersfrom polyplexes by applying asymmetrical flow field-flow fractionation(AF4), which removes free polymers under gentle laminar flow, minimizingshear stress and keeping polyplexes intact. While batch light-scatteringanalysis of unfractionated crude polyplexes severely underestimatespolyplex size and pDNA loading by 2–4×, AF4-aided removalof free polymers sharpened measurements by eliminating backgroundlight-scattering contributions. Polyplexes with 78% free polymersaggravated inflammatory responses in macrophages by 2–20×compared to polyplexes devoid of free polymers. Removing free polymersdepressed transfection efficiency by 50% while improving cell viabilityby 30%; reintroducing free polymers abrogated these contrasts. Byseparating and quantifying free polymers using AF4, we corrected systematicbiases in structure–function trends gleaned from crude polyplexes.For instance, microstructure-dependent trends in pDNA loading reportedin our earlier work originated from differences in free polymer contentrather than the polymer microstructure itself. Our study establishesthat free polymers skew measurements of polyplex properties and biologicalperformance and offers design guidance to navigate trade-offs betweentransfection efficiency, immunogenicity, and toxicity.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 5","pages":"1329–1338"},"PeriodicalIF":6.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173285","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":"High-Performance Triboelectric Nanogenerators Based on Triazine-Based Covalent Organic Framework/PVDF-HFP Composite Nanofibrous Membranes for Wearable Electronics","authors":"Ying-Hao Pan,&nbsp;Hsin-Jung Kan,&nbsp;Pei-Cih Hu,&nbsp;Hongta Yang,&nbsp;Rong-Ho Lee","doi":"10.1021/acspolymersau.6c00106","DOIUrl":"https://doi.org/10.1021/acspolymersau.6c00106","url":null,"abstract":"<p>In this study, triazine-based covalent organic framework(COF)/poly(vinylidenefluoride-<em>co</em>-hexafluoropropylene) (COF/PVDF-HFP) nanofibrousmembranes were fabricated via electrospinning and utilized as thenegative triboelectric layer in a triboelectric nanogenerator (TENG).The large electronegativity difference between PVDF-HFP and the COFgives rise to an interfacial p–n heterostructure. The polaritydisparity at the interface intensifies charge transfer during frictionalinteractions, leading to increased charge generation. The TPTP-COF-and TPBT-COF-based TENGs generated higher open-circuit voltages (<em>V</em>_OC) and short-circuit current densities (I_SC) values compared to the TPDA-COF- and TPBTz-COF-based devices,owing to their larger specific surface areas, higher dielectric constants,and more efficient surface charge generation. The optimized TPBT-COF/PVDF-HFPmembrane-based TPBT-1.5 TENG achieved maximum <em>V</em>_OC, I_SC, and transferred charge of 338.2 V, 74.0μA, and 127.1 nC, respectively. A maximum output power densityof 16.76 W m^–2 was achieved at an external loadresistance of 50 MΩ. Under operating conditions of 60 N appliedforce at 5 Hz, the COF/PVDF-HFP-based TENG successfully powered LEDswhile maintaining stable Voc performance over 20,000 contact–separationcycles. Furthermore, four TPBT-1.5 TENGs connected in series wereattached to a custom-made insole and placed inside a shoe. A researcherwore the shoe and performed jogging to generate electrical energy,which was stored in a connected capacitor and subsequently used topower an LED. The developed COF/PVDF-HFP TENG can function as a walk-inducedenergy-harvesting device, serving as a practical power source forwearable electronic devices.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 5","pages":"1389–1402"},"PeriodicalIF":6.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173300","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":"Benefits of Pyrenemethanol as an Initiator for the ROP of Morpholine-2,5-Diones: Fluorescence Probing of Nanoparticle Degradation and Cellular Uptake","authors":"Johanna Schreiber,&nbsp;Lea C. Klepsch,&nbsp;Jana Ismail,&nbsp;David Pretzel,&nbsp;Antje Vollrath,&nbsp;Christine Weber,&nbsp;Ulrich S. Schubert","doi":"10.1021/acspolymersau.6c00097","DOIUrl":"https://doi.org/10.1021/acspolymersau.6c00097","url":null,"abstract":"<p>1-Pyrenemethanolwas used as an initiator for the ring-openingpolymerization (ROP) of three morpholine-2,5-diones, which are basedon the naturally occurring amino acids <span>l</span>-phenylalanine, <span>l</span>-isoleucine, and <span>l</span>-valine. A catalytic system consistingof 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1-(3,5-bis(trifluoromethyl)phenyl)-3-cyclohexylthiourea(TU) was applied for the polymerizations at room temperature. Kineticstudies demonstrated controlled reaction conditions and the absenceof transesterification under the selected parameters. By means of ¹H NMR spectroscopy and size exclusion chromatography (SEC),monomer conversion values of about 90% were observed during the consideredreaction times of up to 1 h, whereby the dispersity remained below1.15. The covalent attachment of the pyrene α-end group to therespective poly(morpholine-2,5-dione)s (PEAs) was proven by ¹H NMR spectroscopy, SEC using a diode array detector, matrix-assistedlaser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS), and fluorescence spectroscopy. The PEAs formed spherical nanoparticleswith uniform size distribution via nanoprecipitation, which were subjectedto degradation studies using proteinase K. Due to the characteristicchange in the vibronic fine structure of the fluorescence spectrumof pyrene with the changing molecular environment, this process couldbe observed by fluorescence spectroscopy. The received data were validatedby dynamic light scattering (DLS) measurements. Furthermore, the pyreneend group served as a fluorescent label for cellular uptake studiesin L929 cells monitored by confocal laser scanning microscopy (CLSM).This report demonstrates the added value of the introduction of thefluorescence-active pyrene into the polymer structure, enabling accessto additional information about the polymer and its nanoparticleswithout additional synthesis effort.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"6 5","pages":"1363–1375"},"PeriodicalIF":6.7,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173364","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}