Macromolecules最新文献_第2页

Cyclization Boosted Long-Lived Polymeric Phosphorescence under Ambient Conditions

IF 5.5 1区化学

Macromolecules Pub Date : 2025-03-04 DOI: 10.1021/acs.macromol.4c02450

Xiaojuan Wang, Bangmin Liu, Lunjun Qu, Qian Zhou, Jiayue Huang, Shunnan Jiang, Fengling Guo, Hui Hou, Meiyi He, Qiankun Li, Liyan Liang, Chaolong Yang

{"title":"Cyclization Boosted Long-Lived Polymeric Phosphorescence under Ambient Conditions","authors":"Xiaojuan Wang, Bangmin Liu, Lunjun Qu, Qian Zhou, Jiayue Huang, Shunnan Jiang, Fengling Guo, Hui Hou, Meiyi He, Qiankun Li, Liyan Liang, Chaolong Yang","doi":"10.1021/acs.macromol.4c02450","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02450","url":null,"abstract":"Room-temperature phosphorescence (RTP) is a fascinating optical phenomenon, and a variety of methods have been developed to achieve and improve the desirable phosphorescent performance on demand. Cyclization of the molecular structure is an efficient strategy to promote phosphorescence at 77 K by boosting intersystem crossing (ISC). However, cyclization-triggered phosphorescence at room temperature has not yet been reported, especially for polymer systems. Herein, we proposed and demonstrated a concise yet efficient strategy to obtain ultralong phosphorescence under room temperature by the cyclization of the polymer chain, in which the carboxyl and cyano groups are rearranged and isomerized to generate an imide ring at high temperatures. In this work, the phosphorescent performance of materials is greatly advanced. Interestingly, cyclized phosphorescence lifetime and phosphorescence quantum yield have been increased by 17 times (51.4–914.0 ms) and 9 times (1.5–14.0%), respectively, compared to linear polymers. The reason for promoting phosphorescence was that the cyclization of the polymer chain dramatically increased the ISC channel, which was accompanied by the rigid structure of the system, leading to satisfactory phosphorescence efficiency at room temperature. This strategy may provide a new idea for the preparation of ultralong RTP materials by enhancing ISC and rigidification.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"10 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143538927","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}

引用次数: 0

Direct Observation of the “End-Capping Effect” of a PEG@α-CD Polypseudorotaxane in Aqueous Media

IF 5.5 1区化学

Macromolecules Pub Date : 2025-03-04 DOI: 10.1021/acs.macromol.4c02491

Ryoga Hori, Ken-ichi Shinohara

{"title":"Direct Observation of the “End-Capping Effect” of a PEG@α-CD Polypseudorotaxane in Aqueous Media","authors":"Ryoga Hori, Ken-ichi Shinohara","doi":"10.1021/acs.macromol.4c02491","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02491","url":null,"abstract":"This study demonstrates that the shuttling of α-cyclodextrin (α-CD) rings in a poly(ethylene glycol) (PEG) polypseudorotaxane drives the shrinkage and extension of the molecule and that a strong end-capping effect stabilizes the structure at the solid–liquid interface. We performed single-molecule imaging of PEG100k@α-CD polypseudorotaxane under aqueous solution using fast-scanning atomic force microscopy. The polypseudorotaxane displayed shrinking and extending motions driven by the α-CD rings shuttling along the polymer chain. These motions mainly occurred in exposed, self-shrinking PEG segments, where repeated expansion and reshrinking were observed as α-CD moved. All-atom molecular dynamics simulations corroborated these findings, confirming dynamic structural changes linked to α-CD shuttling. Additionally, globules formed at both ends of the PEG chain caused a strong end-capping effect that stabilized the structure in solution. These insights into the localized structural changes in PEG@α-CD polypseudorotaxane improve our understanding of supramolecular functionality and could inform the design of advanced materials.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"85 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547034","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}

引用次数: 0

A Multi-State Comparative Coarse-Grained Modeling of Semi-Crystalline Poly(vinyl alcohol)

IF 5.5 1区化学

Macromolecules Pub Date : 2025-03-04 DOI: 10.1021/acs.macromol.4c03146

Chunhua Zhu, Senbo Xiao, Yu Ding, Zhiliang Zhang, Jianying He, Junhua Zhao

{"title":"A Multi-State Comparative Coarse-Grained Modeling of Semi-Crystalline Poly(vinyl alcohol)","authors":"Chunhua Zhu, Senbo Xiao, Yu Ding, Zhiliang Zhang, Jianying He, Junhua Zhao","doi":"10.1021/acs.macromol.4c03146","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c03146","url":null,"abstract":"Poly(vinyl alcohol) (PVA) is a promising material with exceptional mechanical properties, adhesion, and abrasion resistance. To accurately predict its mesoscopic properties, such as crystal size and morphology, while improving computational efficiency, novel coarse-grained (CG) potentials are developed using iterative Boltzmann inversion (IBI) coupled with density correction. These CG potentials are derived from various thermodynamic states based on two different mapping schemes to overcome the limitations of traditional CG potentials in predicting the glass transition, crystallization, and melting temperatures. By comparing the simulation results obtained from these CG potentials with atomistic molecular dynamics (MD) simulations and experimental data, we identify the most suitable CG model of semicrystalline PVA that effectively reproduces both atomistic structures and thermodynamic properties. In particular, X-ray diffraction (XRD) experiments are used to further validate the accuracy of the CG potentials. This multistate comparative CG strategy provides efficient and accurate CG models for deeper investigations of PVA and other semicrystalline polymers. Our study paves the way for establishing a systematic and comprehensive database of CG potentials, serving as a valuable resource for future research on semicrystalline polymers.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"1 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547035","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}

引用次数: 0

Correction to “Synthesis, Morphology, and Particle Size Control of Acidic Aqueous Polyurethane Dispersions”

IF 5.5 1区化学

Macromolecules Pub Date : 2025-03-03 DOI: 10.1021/acs.macromol.5c00418

Ellen J. Quane, Niels Elders, Anna S. Newman, Sophia van Mourik, Neal S. J. Williams, Keimpe J. van den Berg, Anthony J. Ryan, Oleksandr O. Mykhaylyk

{"title":"Correction to “Synthesis, Morphology, and Particle Size Control of Acidic Aqueous Polyurethane Dispersions”","authors":"Ellen J. Quane, Niels Elders, Anna S. Newman, Sophia van Mourik, Neal S. J. Williams, Keimpe J. van den Berg, Anthony J. Ryan, Oleksandr O. Mykhaylyk","doi":"10.1021/acs.macromol.5c00418","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00418","url":null,"abstract":"The originally published Table 2 is incorrect. The sample names were entered in the wrong order such that they matched up with the incorrect corresponding parameters. This mistake has been resolved in the corrected Table 2 below: R is the geometric mean particle radius with multiplicative standard deviation σ*. The proportion of PU distributed as supramolecular structures is quantified by ϕ2/ϕtot. Rg gives the radius of gyration of these structures, and ν is a structural parameter that indicates solubilization of these polymer-like structures. The caption to the originally published Figure 7 refers to the tables incorrectly. The first reference should be made to Table 1 and not to Table S1. The second reference should be made to Table 2 and not to Table 1. The value ϕ2/ϕtot is given in Table 2, as specified in the corrected caption below: Corrected Figure 7 caption: Relationship between the acid (COOH) content in the original PU formulation (Table 1) and the fraction of PU in supramolecular structures formed by (H12MDI)n+1DMPAn molecules, measured by SAXS (Table 2, ϕ2/ϕtot) for PUD samples synthesized with polyether (soft segment) of Mn = 650 g mol–1 (blue circles), 1000 g mol–1 (green squares), and 2000 g mol–1 (red triangles). This article has not yet been cited by other publications.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"15 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143538930","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}

引用次数: 0

Ferric Salt-Mediated Tough Zwitterionic Hydrogel

IF 5.5 1区化学

Macromolecules Pub Date : 2025-03-03 DOI: 10.1021/acs.macromol.4c02688

Yuming Deng, Jiahui Zhou, Mengjie Si, Gaopeng Wang, Yueman Tang, Zi Rong Zhang, Jiayu Hu, Yan-jie Wang, Jintao Yang, Si Yu Zheng

{"title":"Ferric Salt-Mediated Tough Zwitterionic Hydrogel","authors":"Yuming Deng, Jiahui Zhou, Mengjie Si, Gaopeng Wang, Yueman Tang, Zi Rong Zhang, Jiayu Hu, Yan-jie Wang, Jintao Yang, Si Yu Zheng","doi":"10.1021/acs.macromol.4c02688","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02688","url":null,"abstract":"Polyzwitterionic gels possess a high density of ionic groups and present great potential in ionotronics. However, zwitterionic chains are easy to be highly hydrated, leading to weak interchain interactions and a poor mechanical performance. Although metal ions like Fe3+ show great effectiveness in toughening hydrogels, they usually weaken the zwitterionic gel inversely due to the anti-polyelectrolyte effect. Herein, a special co-ion effect of Fe(ClO4)3 is found, which is adopted to toughen the zwitterionic hydrogel. In contrast to the weak effect of Fe(NO3)3, FeBr3, and FeCl3 salts on gel toughness, Fe(ClO4)3 can toughen the imidazolium-based polyzwitterion (pVBIPS) effectively. The Fe(ClO4)3-treated pVBIPS gel exhibits a high ultimate tensile stress of 1.34 MPa, a Young’s modulus of 1.2 MPa, and tensile work of 2.29 MJ/m3, surpassing many existing pure zwitterionic hydrogels. It is found that the ClO4– ions can effectively bind to the imidazolium moiety of pVBIPS and promote the formation of SO3––Fe3+ interactions; the trivalent Fe3+ ions can then bridge multiple sulfonate groups to impart the strength. This work should offer a new strategy for developing tough zwitterionic hydrogels.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"2 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143538929","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}

引用次数: 0

Drive to Asymmetric Lamellar Order by Polymerization-Induced Microphase Separation from the Janus Bottlebrush Architecture

IF 5.5 1区化学

Macromolecules Pub Date : 2025-03-02 DOI: 10.1021/acs.macromol.4c02426

Changsu Yoo, Myungeun Seo

{"title":"Drive to Asymmetric Lamellar Order by Polymerization-Induced Microphase Separation from the Janus Bottlebrush Architecture","authors":"Changsu Yoo, Myungeun Seo","doi":"10.1021/acs.macromol.4c02426","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02426","url":null,"abstract":"We report growing a polymer chain from the backbone of a bottlebrush polymer in the neat polymerization condition produces nanostructured polymer monoliths with ordered morphologies based on the Janus bottlebrush architecture. We installed a norbornene unit at the end of the polylactide macro-chain transfer agent (PLA-CTA) by single unit monomer insertion. We polymerized the resulting macromonomer via ring-opening metathesis polymerization to produce the PLA bottlebrush polymer, where a trithiocarbonate moiety remains on the backbone per every repeating unit. Neat polymerization of styrene in the presence of the PLA bottlebrush polymer proceeded in a grafting-from manner following the reversible addition–fragmentation chain transfer mechanism, resulting in a monolithic solid containing the doubly grafted PLA and polystyrene (PS) side chains. Polymerization-induced microphase separation (PIMS) spontaneously occurred, driven by the incompatibility between PLA and the growing PS segment. In contrast to the significant disordered fraction in PLA-b-PS produced with the linear PLA-CTA, the PLA/PS Janus bottlebrush polymer showed improved order across the investigated composition range. Formation of the asymmetric lamellae up to >80 vol % of PS indicated a strong preference for the lamellar symmetry of the Janus architecture. The in situ structured monoliths even exhibited narrower scattering peak widths compared to the solution-cast and annealed sample, suggesting the utility of the Janus PIMS process for facile preparation of ordered nanostructured materials with uniform domain size.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"39 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532729","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}

引用次数: 0

Quantitative Insights into Pressure-Responsive Phase Behavior in Diblock Copolymers

IF 5.5 1区化学

Macromolecules Pub Date : 2025-03-02 DOI: 10.1021/acs.macromol.4c02253

Hiroki Degaki, Ikuo Taniguchi, Shigeru Deguchi, Tsuyoshi Koga

引用次数: 0

Fluorene Oligomers Featuring a Central 2,1,3-Benzothiadiazole Unit with High Photoluminescence Quantum Yield and Amplified Spontaneous Emission

IF 5.5 1区化学

Macromolecules Pub Date : 2025-03-02 DOI: 10.1021/acs.macromol.4c03110

Philipp J. Welscher, Ulrich Ziener, Alexander J. C. Kuehne

{"title":"Fluorene Oligomers Featuring a Central 2,1,3-Benzothiadiazole Unit with High Photoluminescence Quantum Yield and Amplified Spontaneous Emission","authors":"Philipp J. Welscher, Ulrich Ziener, Alexander J. C. Kuehne","doi":"10.1021/acs.macromol.4c03110","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c03110","url":null,"abstract":"Fluorene-based conjugated materials are pivotal to optoelectronic applications due to their tunable optical properties and high photoluminescence quantum yields. While conjugated polymers like poly(fluorene-co-benzothiadiazole) have been extensively studied, their performance is often limited by product inhomogeneity and morphological constraints. Oligofluorenes, with their well-defined structures and controlled morphologies, offer a promising alternative but have been underexplored in substoichiometric fluorene-benzothiadiazole systems. Here, we report the synthesis and characterization of a novel series of substoichiometric fluorene-BT oligomers featuring a central BT unit flanked by dioctylfluorene arms of varying repeat lengths, ranging from trimers to heptamers. These oligomers exhibit superior optical properties compared to conventional F8BT polymers, including enhanced quantum yields and amplified spontaneous emission thresholds of down to 1.5 μJ cm–2. The optical performance is analyzed in relation to oligomer length and fluorene-to-BT ratio, providing insights into the relationship between molecular design and photophysical behavior. Our findings highlight the potential of these defect-free, tunable green-emitting oligomers for next-generation light-emitting diodes and low-threshold lasers, paving the way for further advancements in photonic and optoelectronic materials.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"34 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532599","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}

引用次数: 0

Effects of Block Copolymer Compatibilizers and Interfacial Entanglements on Strengthening Immiscible Glassy Polymer Blends

IF 5.5 1区化学

Macromolecules Pub Date : 2025-03-02 DOI: 10.1021/acs.macromol.4c02848

Yunjia Zhang, Wenlin Zhang

{"title":"Effects of Block Copolymer Compatibilizers and Interfacial Entanglements on Strengthening Immiscible Glassy Polymer Blends","authors":"Yunjia Zhang, Wenlin Zhang","doi":"10.1021/acs.macromol.4c02848","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02848","url":null,"abstract":"We employ molecular dynamics (MD) simulations to investigate the mechanical behaviors of immiscible polymer interfaces enhanced by block copolymer compatibilizers. We show that the entanglement density at the interface, governed by the Flory–Huggins parameter χ, is critical for mechanical performance. Increasing immiscibility leads to sharper interfaces with reduced interfacial entanglements, resulting in easy chain pullout during tensile deformation and weaker interfacial strength. Adding block copolymer compatibilizers to the blends can switch the failure mechanism from interfacial chain pullout to bulk-phase crazing, substantially enhancing mechanical performance. Although long diblock and tetrablock copolymers only mildly increase the interfacial entanglement density, they can act as stress transmitters across the interface by entangling with chains in the bulk domains. Tetrablock copolymers are particularly effective for strengthening polymer blends by forming loops at the interface, making chain pullout topologically more difficult and promoting energy dissipation through crazing in the bulk regions. Our findings reveal the roles of both entanglement at interfaces and block copolymer architecture in the mechanical properties of immiscible polymer interfaces, which may guide the design of better compatibilizers for enhancing inhomogeneous polymer samples.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"66 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532600","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}

引用次数: 0

Influence of Topological Segment Length on the Mechanical Properties of Semicrystalline Polyethylene: A Bias-Controlled Monte Carlo Approach

IF 5.5 1区化学

Macromolecules Pub Date : 2025-03-01 DOI: 10.1021/acs.macromol.4c02643

Jianlan Ye, Minghao Liu, Jing Hu, Jay Oswald

引用次数: 0