Macromolecules最新文献

{"title":"Frustrated Lewis Pair-Mediated Catalyst Efficiency in ROMP: Mechanistic Insights from Boronic Ester-Functionalized Monomers","authors":"Sitong Feng, Xin Zhang, Yuanzhi Li, Feng Yu, Zhen Dong, Zhiqiang Sun, Zhong-Ren Chen","doi":"10.1021/acs.macromol.5c01553","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01553","url":null,"abstract":"The ring-opening metathesis polymerization (ROMP) of boronic ester-functionalized monomers remains underexplored compared with other polymerization strategies, despite the unique physical and chemical properties offered by boronic esters. Herein, we report an unrecognized mechanistic insight into which boronic ester-functionalized monomers modulate ROMP kinetics via frustrated Lewis pair (FLP) interactions. In situ nuclear magnetic resonance (NMR) spectroscopy and density functional theory (DFT) calculations reveal that the boron atoms in norbornylboronic acid pinacol ester (NB-Bpin) and norbornylboronic acid dibutyl ester (NB-B(OBu)₂ ) can associate with tricyclohexylphosphine (PCy₃) ligands of Grubbs’ catalyst, forming FLPs that shift the ligand-catalyst binding equilibrium toward active ruthenium species. This FLP-mediated mechanism increases the polymerization rate proportionally to monomer concentration, with NB-B(OBu)₂ (flexible butoxy groups) exhibiting a 3.75-fold enhancement compared with a 1.26-fold increase for NB-Bpin (rigid five-membered pinacol boronate). In contrast, methylnorbornylboronic acid pinacol ester (MNB-Bpin), designed with a methyl group adjacent to the boron atom to suppress FLP formation, shows no enhancement in the polymerization rate. Crucially, the weak interaction nature of FLP allows PCy₃ to dissociate completely from the polymer product, preserving the material’s intrinsic properties. The resulting boronic ester-functionalized polymer exhibits high thermal stability, optical transparency (>91% ), and dynamic covalent cross-linking characteristics. By elucidating the monomer-ligand interactions in ROMP, this study demonstrates the potential of these FLPs in modulating the catalyst efficiency, and offers broad implications for diverse reaction systems.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"118 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183036","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Identifying Memory Effects in Short-Time Dynamics of Polymer Systems by Machine Learning","authors":"Kaihua Zhang, Yongzhi Ren, Shuanhu Qi, Ying Jiang","doi":"10.1021/acs.macromol.5c01522","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01522","url":null,"abstract":"Memory effects are intrinsic properties of flexible macromolecular systems emerging originally from their hierarchical microstructures and multiscale dynamic behaviors of polymer chains during nonequilibrium processes. The nonlocal temporal dependence of transport coefficients (e.g., the Onsager coefficient), a fundamental manifestation of memory effects that govern the dynamic evolution of collective observables, still poses significant challenges for analytical formulations. Herein, we propose a machine-learning-based framework to extract the history-dependent Onsager coefficient directly from the density evolution data, generated from particle-based single-chain in mean-field simulations, thereby enabling these coefficients to accurately capture underlying microscopic characteristics. This framework, termed the dynamic density functional theory-ordinary differential equation (DDFT-ODE) Net, embeds equations of DDFT into the ODE network, enhancing the physical consistency and computational efficiency of the framework. Our study of the relaxation of density fluctuations in an ideal symmetric diblock copolymer melt reveals that memory effects play a dominant role in determining density evolution processes at early times. Further analysis of the memory kernel function of the Onsager coefficient identifies two characteristic relaxation times, which are both smaller than the Rouse time, a signature suggesting that memory effects are closely related to short-time segmental motions. By defining two types of time averages and comparing their asymptotic behaviors at the long-time limit, we establish connections linking the history-dependent Onsager coefficient, the instantaneous Onsager coefficient, and the memory-free one, which provide a theoretical foundation for quantitatively evaluating the reliability of various DDFT implementations. Our data-driven framework is easily extensible to other different systems, combining different particle-based simulations and continuum field-based DDFT schemes, thereby providing a useful framework for developing structure–property correlations in complex polymer systems.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"24 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189548","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effects of Isohexide Stereochemistry on Vinylogous Urethane Covalent Adaptable Networks","authors":"Noé Fanjul-Mosteirín, Karin Odelius","doi":"10.1021/acs.macromol.5c00270","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00270","url":null,"abstract":"The starch-derived isohexides, with their unique structures of two fused tetrahydrofuran rings in a cis conformation, have been exploited to prepare covalent adaptable networks (CANs) and to tailor and understand their structure–property relationships, in pursuit of replacing oil-based thermosets. Here, dynamicity was achieved through vinylogous urethane chemistry, rigidity via the use of the starch-derived isomeric building blocks isosorbide, isomannide, and isoidide, and flexibility through the amines utilized. Similar to what is known for thermoplastics, depending on the isomer chosen, thermal stability and mechanical properties could be tailored to some extent. The distance between cross-links was ruled by the amines employed, and when this distance was long enough to allow sufficient chain mobility, stereochemical effects on mechanical performance were observed. The CAN structures all display thermoset properties, and as a consequence of the incorporated dynamic bonds, they were mechanically reprocessable. Based on the CANs structural design, i.e., isohexide isomer and amine structure, tensile strengths (σ_b) ranging from 1.57 to 19.1 MPa, glass transition temperatures (T_g) ranging from 20 to 114 °C, and thermal stabilities (T_d,5%) between 200 and 305 °C were achievable. Mechanical reprocessing was proven, and no mechanical performance decay was observed after two reprocessing cycles. This provides important information on the structure–property relationship of CANs from starch-derived building blocks, and consequently, how material properties can be tailored depending on the targeted application.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"24 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189532","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Quantitative Correlation of Single-Molecule Mechanical Behavior with the Yield Stress of Polymer Fibers","authors":"Xiaoye Zhang, Shengjie Lu, Honglin Zhang, Yu Song, Wenke Zhang","doi":"10.1021/acs.macromol.5c01683","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01683","url":null,"abstract":"A quantitative correlation between single-molecule and macroscopic mechanical properties is crucial for rationally improving the performance and designing polymer materials. However, it remains challenging due to the complexity of the material systems and the lack of suitable methods for characterizing single-molecule structures and mechanics in real materials. Here, we report a quantitative correlation between the single-molecule mechanics of the tie chains and the macroscopic mechanical properties of polycaprolactone and polyethylene (PE) fibers. The density and stress of tie chains were quantified by using atomic force microscopy-based single-molecule force spectroscopy (SMFS) to pull single polymer chains out of the fibers along the fiber axis. The SMFS-predicted maximum yield stress (σ_SMFS) was comparable to the tensile yield stress (σ_y) of fibers, with the utilization of tie chains (σ_y/σ_SMFS) in PE fiber reaching 96%. Moreover, this quantitative correlation was validated by the dependence of the density and utilization of tie chains on the stretching orientation. Finally, we illustrate a subnanometer-level length adjustment mechanism of tie chain, which explains the extremely high utilization of tie chain in PE fiber and further proves our quantitative correlation.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"99 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183037","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Robust Artificial Spider Silk via Synergistic Cross-Linking of Slide-Ring and Covalent Bonds","authors":"Guangkai Mei, Zihao Su, Ning Liu, Junli Qu, Xiao Liu, Dong Qian, Xiang Zhou, Zunfeng Liu","doi":"10.1021/acs.macromol.5c02101","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02101","url":null,"abstract":"Inspired by the structure of spider silk, the introduction of slide-ring molecules into covalent networks to construct double cross-linked networks (DCNs) has become an effective strategy for preparing robust polymer artificial spider silk. However, the complex interplay between the two cross-linking modes poses significant challenges for elucidating the molecular mechanisms underlying mechanical enhancement and hinders the precise design and fabrication of robust artificial silks. Here, we engineered robust artificial spider silk fibers based on DCNs and employed coarse-grained molecular dynamics (CGMD) simulations to establish quantitative models linking the network architecture to macroscopic mechanical properties. The models reveal that slide-ring-only networks suffer from ring aggregation and chain slippage under strain, which leads the multifolded axis chains to straighten and unfold, ultimately forming highly oriented structures. In contrast, DCNs utilize covalent anchors to regulate the ring mobility, stabilize multifolded chain structures, and balance energy dissipation with mechanical integrity. These molecular-level insights are supported by experiments. By tuning the slide-ring cross-linking fraction and introducing Zr⁴⁺ ions as dynamic supramolecular regulators, we achieved highly aligned nanofibers with both exceptional tensile strength (1.18 GPa) and toughness (135 MJ m^–3). The synergy between dynamic and permanent cross-links enables efficient stress redistribution and crack resistance. This work provides inspiration for the design of high-performance fiber materials.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"15 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145154059","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemical C–H Phosphonylation of Dissolved Conjugated Polymers via Direct Electron Transfer at the Electrode","authors":"Kohei Taniguchi, Kosuke Sato, Shinsuke Inagi","doi":"10.1021/acs.macromol.5c01783","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01783","url":null,"abstract":"π-Conjugated polymers (CPs) exhibit attractive optoelectronic properties conferred by an extended π-conjugation system along their main chains. CPs containing polar phosphonate groups have attracted special interest because their exceptional affinity to metal ions and electrodes can be exploited in electrochemical devices. A favorable strategy for postfunctionalizing CPs with phosphonate groups is electrochemical phosphonylation, which requires only a simple protocol under mild reaction conditions. However, this established method requires a CP film for the electrolytic process. A postfunctionalization method based on the conventional electrolysis of CPs in solution is expected to improve the versatility and scalability of electrochemical phosphonylation. Herein, we demonstrate that CPs dissolved in an electrolyte can be electrochemically phosphonylated via direct electron transfer at the anode. In particular, we show the quantitative phosphonylation of poly(9,9-dioctylfluorene) (PFO) at low current densities, despite the small diffusion coefficient of PFO. Stirring-induced convection facilitated polymer diffusion, thereby improving the efficiency of electrochemical PFO phosphonylation. Moreover, the degree of functionalization could be precisely controlled by adjusting the amount of passed charge. Interestingly, a moderate functionalization degree improved the fluorescence quantum yield to 0.82 in phosphonylated PFO and the reaction proceeded from various trialkyl phosphites. Finally, the reaction mechanism of anodic phosphonylation was determined through density functional theory calculations.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"41 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140709","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Development of Polyolefin Elastomers with Distinct Dual Long-Chain Branch Structures","authors":"Bangban Zhu, Haitao Wang, Kan Liu, Minghao Sun, Zhenjia Shi, Shuo Wang, Xingfen Huang, Shengbin Shi, Jieyuan Zheng, Xuan Yang, Pingwei Liu, Wen-Jun Wang","doi":"10.1021/acs.macromol.5c01900","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01900","url":null,"abstract":"Long-chain branched (LCB) structures significantly impact the processability and mechanical performance of polyolefin materials. Comb-branched polyolefin elastomer (CPOE) represents an emerging class of polyolefin thermoplastic elastomers composed of an amorphous ethylene/1-octene copolymer backbone and crystalline polyethylene (PE) LCBs (T-type). While CPOEs exhibit higher melting points and improved thermal stability compared to conventional polyolefin elastomers, achieving both high mechanical strength and excellent elastic recovery remains a key challenge. In this study, a second LCB structure was strategically introduced into CPOEs to develop a dual-branched polyolefin elastomer (DPOE). In addition to the existing crystalline T-type LCBs, which act as reversible physical cross-linking sites, covalently bonded H-type LCBs were generated through the incorporation of 1,7-octadiene. The resulting DPOEs possessed 0.5–0.6 T-type LCBs and 0.5–1.6 H-type LCBs per polymer chain, forming an integrated dual cross-linking network. This dual-LCB design led to a remarkable enhancement in mechanical properties and thermal performance. Compared to CPOEs, the DPOEs exhibited an increase in tensile strengths from 9.4 to 16.6 MPa, elongations at break from 975% to 1085%, toughness from 70.1 MJ/m³ to 105 MJ/m³, and elastic recoveries from 65.8% to 73.7%. Furthermore, the DPOEs maintained a storage modulus plateau of 0.2–0.3 MPa across the 150–200 °C range. Notably, the materials also showed outstanding reprocessability, retaining up to 96% of their original mechanical strengths and nearly unchanged elongations at break after five hot-pressing cycles. The introduction of dual LCBs offers a powerful design strategy for producing high-performance, thermally stable, and reprocessable polyolefin thermoplastic elastomers, expanding their potential for advanced industrial applications.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"15 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140712","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unlocking the Potential of Organic Semiconductors: Synergistic Alkylthio-Halogen Substitutions for Superior Photoelectrochemical Cathodic Protection","authors":"Rui Ding, Jin-ying Li, Yi-wen Zhang, Hao-han Cao, Xiao Liu, Yu-han Wang, Ming-di Lei, Yu-lin Zhang, An-lan Ji, Yu-chen Zhang, Jie Liu, Taijiang Gui, Weihua Li","doi":"10.1021/acs.macromol.5c01906","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01906","url":null,"abstract":"In this study, seven organic polymer semiconductors based on benzodithiophene and fluorinated thiophene conjugated backbones were designed and synthesized. These included the unmodified polymer, polymers singly substituted with alkoxy, alkylthio, fluorine, or chlorine, as well as polymers with synergistic substitutions of alkylthio and F (or Cl). The synergistic substitution not only optimized the geometric and electronic structures at the molecular level but also enabled high-performance photoelectrochemical cathodic protection in macroscopic devices. The synergistically substituted polymers exhibited HOMO/LUMO energy levels of −5.51/–3.54 eV (bandgap 1.97 eV) and −5.47/–3.52 eV (bandgap 1.95 eV). Intermolecular F···S and Cl···S interactions reduced the π–π stacking distance to 4.48 Å, resulting in well-defined microphase separation and an interpenetrating network in the bulk heterojunction. These polymers showed extended carrier lifetimes of up to 4.47 and 4.10 ns, prolonged exciton recombination times of 214.8 and 209.9 μs, and shortened charge transport times of only 41.7 and 31.9 μs─superior to their singly substituted and unmodified counterparts. Moreover, their double-layer capacitance was significantly enhanced, indicating a higher density of electrochemically active sites. In protecting Q235 carbon steel, the synergistically substituted polymers reduced the open-circuit potential to 0.822 and 0.831 V in the presence of a hole scavenger, maintained high photocurrent densities of 70.7 and 62.5 μA cm^–2, significantly decreased interfacial charge transfer resistance, and minimized overall impedance. Polarization tests further demonstrated the highest steady-state currents and the lowest polarization resistances, reflecting excellent polarization behavior and operational stability. Even in a 3.5 wt % NaCl environment, these polymers maintained cathodic protection capabilities due to their low HOMO levels, which facilitated oxygen evolution reactions to supply electrons. This strategy markedly improved carrier separation/transport efficiency and corrosion resistance, offering a new avenue for the development of high-performance organic photoelectrochemical cathodic protection materials.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"15 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140713","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The Emergent Dynamics of Double-Folded Randomly Branching Ring Polymers","authors":"Elham Ghobadpour, Max Kolb, Ivan Junier, Ralf Everaers","doi":"10.1021/acs.macromol.5c00697","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00697","url":null,"abstract":"The statistics of randomly branching double-folded ring polymers are relevant to the secondary structure of RNA, the large-scale branching of plectonemic DNA (and thus bacterial chromosomes), the conformations of single-ring polymers migrating through an array of obstacles, as well as to the conformational statistics of eukaryotic chromosomes and melts of crumpled, nonconcatenated ring polymers. Double-folded rings fall into different dynamical universality classes depending on whether the random tree-like graphs underlying the double-folding are quenched or annealed, and whether the trees can undergo unhindered Brownian motion in their spatial embedding. Locally, one can distinguish (i) repton-like mass transport around a fixed tree, (ii) the spontaneous creation and deletion of side branches, and (iii) displacements of tree nodes, where complementary ring segments diffuse together in space. Here we employ dynamic Monte Carlo simulations of a suitable elastic lattice polymer model of double-folded, randomly branching ring polymers to explore the mesoscopic dynamics that emerge from different combinations of the above local modes in three different systems: ideal noninteracting rings, self-avoiding rings, and rings in the melt state. We observe the expected scaling regimes for ring slithering, the dynamics of double-folded rings in an array of obstacles, and Rouse-like tree dynamics as limiting cases. Notably, the monomer mean-square displacements of <i>g</i>₁ ∼ <i>t</i>^0.4 observed for crumpled rings with ν = 1/3 are similar to the subdiffusive regime observed in bacterial chromosomes. In our analysis, we focus on the question to which extent contributions of different local dynamical modes to the emergent dynamics are simply additive. In particular, we reveal a nontrivial acceleration of the dynamics of interacting rings, when all three types of local motion are present. In the melt case, the asymptotic ring center-of-mass diffusion is dominated by the contribution from coupling of the ring-in-an-array-of-obstacles dynamics with the tree dynamics. This contribution scales inversely with the ring weight and is compatible with a scenario in which constraint release restores a Rouse-like dynamics.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"89 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140708","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Morphology Regulation and Quenching Mechanism of AIE Nanobowls by Side Chain Engineering of Azobenzene Homopolymers","authors":"Yaning Gao, Yin Wang, Hui Sun","doi":"10.1021/acs.macromol.5c01846","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01846","url":null,"abstract":"The precise regulation of the luminescent properties of fluorophores by molecular engineering strategies has evolved into a crucial method for constructing intelligent photoresponsive nanomaterials. However, the factors influencing the fluorescence quenching efficiency and the mechanism of aggregation-induced emission (AIE) nanoparticles are still unclear. In this study, a series of amphiphilic azobenzene homopolymers with different side chains containing ether, amino, and amide bonds were synthesized, and the linkage has a significant impact on the UV–vis absorption of azobenzene. When coassembled with a tetraphenylethylene (TPE)-containing homopolymer, nanobowls with controlled size and openings were formed, and the fluorescence of TPE was quenched due to the inhibitory effect of azobenzene. It was found that the opening size of the nanobowls decreased with the increase of azobenzene content, and the quenching efficiency derived from the intensity of the amide-bonded azobenzene homopolymer was 10 times higher than that of the others due to the formation of hydrogen bonds. While the quenching efficiencies of the ether- and amino-bonded azobenzene homopolymers were quite low, owing to the red-shift of the emission wavelength induced by the formation of exciplexes. Overall, a hydrogen bond-enhanced fluorescence quenching mechanism is proposed, and the formation of exciplexes in polymeric nanoparticles is also observed and verified, providing a fresh perspective for an in-depth understanding of the quenching mechanism of fluorophores by chromophores.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"63 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140711","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}