Macromolecules最新文献

{"title":"Binary Macromolecular Mesocrystals via Designed Block Copolymer Blends","authors":"Jiayu Xie, Junyin Zhang, Feiyan Wu, Yiwang Chen, An-Chang Shi","doi":"10.1021/acs.macromol.5c01801","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01801","url":null,"abstract":"The theoretical prediction that various binary macromolecular mesocrystals composed of A and C spheres could be formed by B₁AB₂CB₃ pentablock terpolymers ( <cite><i>JACS</i></cite> <span>2014</span>, <em>136</em>, 2974–2977) offers a promising route to fabricate these intricately structured nanomaterials. However, experimental realization of this strategy has been impeded by the requirement of synthesizing precisely designed pentablock terpolymers. Here, we propose a conceptually new and technically simpler route to engineer binary macromolecular mesocrystals by using BA′/ABC/C′B ternary block copolymer blends that are designed to replicate the phase behavior of B₁AB₂CB₃ pentablock terpolymers. Using self-consistent field theory, we show that the ternary blends exhibit similar self-assembly behaviors as the pentablock copolymers, forming various mesocrystals with controllable coordination numbers. This study offers a simpler alternative to fabricating novel macromolecular mesocrystals and introduces a general design principle for emulating multiblock copolymers by block copolymer blends.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"3 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145078428","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":"Crowders-Induced Compaction of Multi-kbp Long DNA Molecules Followed by TPM","authors":"Manoel Manghi, Philippe Rousseau, Quentin Bédel, Sylvain Vicente, Kenza Boubekeur, Erwan Le Floch, Nicolas Destainville, Catherine Tardin","doi":"10.1021/acs.macromol.5c00631","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00631","url":null,"abstract":"DNA organization in bacteria contributes to their environmental adaptation and survival. This includes the DNA compaction induced by a wide variety of nucleoproteins binding to DNA, especially the nucleoid associated proteins, as well as the presence of high concentrations of nonbinding crowders. Weak multivalent interactions and depletion effects, which are central to this process of DNA compaction, can be affected by the experimental constraints. Here, we combine experiments and polymer physics theory to quantitatively determine to what extent the Tethered Particle Motion can faithfully monitor the conformational changes of DNA molecules up to 15 kbp in length, resulting from their immersion in a medium crowded with synthetic and biological molecules, namely, PEG and BSA. By developing a theoretical model that includes monomer–monomer interactions modified by the depletion interaction due to the presence of crowders as well as the ones due to the substrate and the TPM particle, we show that the reversible coil–globule transition induced by crowders can be safely observed by TPM with only a slight effect of the presence of the substrate and the particle. The experimental results are consistent with previous bulk experiments and well-fitted by our detailed theoretical model, which also shows that the transition crowder concentration decreases with the length of the DNA molecule and proportionally to the size of the crowders. DNA compaction can therefore be studied by TPM in the near future with nucleoid associated proteins.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"53 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145084084","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":"Understanding the Interfacial Exchange Reaction Kinetics and Rheological Behavior of Multiphase Vitrimers","authors":"Huawei Qiao, Tianxing Huang, Shuangjian Yu, Siwu Wu, Zhenghai Tang, Liqun Zhang, Baochun Guo","doi":"10.1021/acs.macromol.5c01535","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01535","url":null,"abstract":"Next-generation thermoplastic vulcanizates (TPVs) employ a multiphase architecture constructed from vitrimeric networks with distinct cross-linking densities, where accelerated interfacial network relaxation confers unique advantages during high-throughput reprocessing (e.g., extrusion). Nevertheless, the influences of disparity in cross-linking density between the original networks and of interphase broadening on the viscoelastic and interfacial relaxation behaviors of multiphase vitrimers remain poorly understood. Here, a model multiphase vitrimer system consisting of monodioxaborolane-grafted and bis-dioxaborolane-cross-linked styrene–butadiene rubber (SBR) was developed to systematically evaluate the effects of grafting density and cross-linking density on interfacial exchange kinetics. The investigation reveals that stress overshoot and interfacial relaxation are both governed by interphase broadening and cross-linking density contrast. When the contrast between the two original networks is significant, interfacial relaxation persists over long time scales of interfacial broadening, whereas the contrast is insignificant, and interfacial relaxation is limited to short time scale of interfacial broadening. Moreover, increasing interfacial exchange extent and dispersed phase cross-linking density both exacerbate irreversible structural damage during cyclic reprocessing. These findings imply that multiphase vitrimers designed to exploit interfacial relaxation for efficient extrusion reprocessing require judicious control of the component structure and processing/annealing time windows, providing theoretical guidance and design criteria for their optimization and applications.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"9 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145078429","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":"Efficient Access to Functionalized Mesoporous Materials with Bicontinuous Morphologies via a Kinetic Approach","authors":"Jun Yuan, Xiang Liu, Yingying Wang, Tao Wen","doi":"10.1021/acs.macromol.5c02200","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02200","url":null,"abstract":"In this work, we report a versatile strategy enabling simultaneous regulation of both morphology and pore-surface chemistry in mesoporous materials. By introducing diols as ‘noncovalent cross-linking agents’, microphase separation of polystyrene-<i>b</i>-poly(4-vinylpyridine)-<i>b</i>-polylactide triblock terpolymers can be tuned, inducing the formation of a metastable phase with disordered bicontinuous morphology. After selective etching to remove the polylactide end-block, mesoporous structures are obtained with poly(4-vinylpyridine) midblocks retained on the inner pore walls. We demonstrate that the resulting mesoporous materials exhibit efficient adsorption performance for both organic dyes and metal ions, leveraging the functional P4VP segments and interconnected bicontinuous channels. This work offers a facile approach to fabricating functionalized mesoporous materials and provides new mechanistic insights into the design of nanostructured materials with tailored morphology and surface chemistry.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"56 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145078448","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":"Topologicity-Dependent Spinning and Phase Separation toward High-Performance Polyetherketoneketone Fibers","authors":"Yanbo Li, Xin Wang, Kunpeng Li, Xia Yin, Jianyong Yu, Bin Ding, Xiaohua Zhang","doi":"10.1021/acs.macromol.5c00322","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00322","url":null,"abstract":"High-performance thermoplastic fibers are very important in widespread applications owing to their excellent mechanical and thermal properties. However, for advanced engineering thermoplastics, melt processing meets severe problems of high melting point and high melt viscosity, and there is a lack of efficient wet spinning due to high indissolubility. Here, we report a novel topologicity-dependent processing for poly(ether ketone ketone) (PEKK), including dissolution, spinning, phase separation, and structural stability. With the randomly appearing para- and meta-positioned ketone groups and high chain rigidity as well, PEKK shows a strong entanglement, namely, molecular locking even after dissolution. Such locking is the real source of spin flexibility, especially for low-concentration solutions. It also causes a special phase separation from which highly porous fibers are spun. By reducing the phase separation rate to realize the overall condensation and a consequent hot stretching, solid fibers with high strength (516 MPa) and stiffness (6.13 GPa) are prepared. PEKK fibers do not show evident viscoelasticity and are mechanically stable within a temperature range of – 196–300 °C, as the topological locking hinders the reconstruction of chain condensation. The locking also retards flame by avoiding chain disassembling. This work provides a new strategy to process thermoplastics by introducing topological structure into polymer chains.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"38 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145078430","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":"Multiscale Control of Ultrahigh-Molecular-Weight Isotactic Poly(4-methyl-pentene-1) with Nascent Single-Crystal-like Morphology: From Molecular Synthesis to Macroscopic Properties","authors":"Maryah Mamdouh Almaghrabi, Ameur Louhichi, Jiayi Zhao, Sumesh Raman, Sanjay Rastogi","doi":"10.1021/acs.macromol.5c01848","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01848","url":null,"abstract":"Isotactic poly(4-methyl-1-pentene) (<i>i</i>P4MP1) is a unique material known for its high transparency and gas permeability. <i>i</i>P4MP1 possesses high thermal and chemical stabilities, making it suitable for a wide variety of applications. We investigate the influence of polymerization medium on the resulting polymorphs and mechanical properties. By employing an aryl pyridylamido hafnium catalyst in a mixture of <i>n</i>-heptane and toluene, ultrahigh-molecular-weight UHMW-<i>i</i>P4MP1 having a unimodal distribution is achieved. The use of <i>n</i>-heptane as the polymerization solvent, where <i>i</i>P4MP1 chains are poorly miscible, resulted in the formation of metastable monoclinic Form II crystals, which below melting transform into the stable tetragonal Form I. The study demonstrates that crystallization kinetics during polymerization can be tailored to synthesize single-crystal-like <i>i</i>P4MP1. The low-entangled single-crystal-like <i>i</i>P4MP1 enables uniaxial deformation below the melting temperature, facilitating chain alignment. Consistent with the stereospecific nature of <i>i</i>P4MP, rheological analysis suggests high molecular weight between entanglements (<i>M</i>_e ≈ 26,000 g/mol). Mechanical properties of the synthesized polymers, including tensile strength, elongation at break, and toughness, increase with the molecular weight, highlighting the potential for achieving uniform mechanical properties required for advanced applications.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"72 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145078447","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":"Bottlebrush Block Copolymer Thin Films","authors":"Zhan Chen, Xuchen Gan, Xindi Li, Mingqiu Hu, Yashodha Kahandawaarachchi, Hong-Gyu Seong, Todd Emrick, William T. Heller, Javid Rzayev, Thomas P. Russell","doi":"10.1021/acs.macromol.5c01420","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01420","url":null,"abstract":"The self-assembly of block copolymers (BCPs) in thin films is governed by interfacial interactions (enthalpy) between the blocks and interfaces (at both the substrate and the surface). Advantage can also be taken of entropy to control the polymer orientation. Here, we synthesized a series of bottlebrush block copolymers (BBCPs), with deuterated polystyrene (DPS) as the core block and poly(solketal acrylate) (PSA) as the corona block, where the backbone length (<i>N</i>_BB) and grafting densities (GDs) were varied. The hydrophobic PSA block was converted to a hydrophilic poly(glyceryl acrylate) (PGA) block by solid-state hydrolysis, bringing the BBCP from a disordered state into an ordered state with a lamellar microdomain morphology. The orientation of the morphology as a function of distance from the interfaces was systematically investigated by atomic force microscopy (AFM), interference microscopy, grazing-incidence small-angle X-ray scattering (GISAXS), and grazing-incidence small angle neutron scattering (GISANS). For <i>N</i>_BB = 1 (diblock BCP), a mixed lamellar orientation was found. For <i>N</i>_BB = 5 (star-like BBCP), a vertical orientation of the lamellar microdomains was found dominantly at the interfaces that propagated into the bulk of the film due to the entropic penalty associated with constraints on the junction points. Increasing the <i>N</i>_BB to 50 (rod-like BBCP) and 100 (worm-like BBCP) yielded a random orientation, as the side chains became overcrowded when aligned in the same direction. By reducing the grafting density (GD) of a <i>N</i>_BB = 50 BBCP from 100% to 75% and 50% by the incorporation of spacers into the backbone, the steric hindrance of side chains is reduced markedly, facilitating a vertical orientation of the lamellar microdomains. However, the vertical orientation becomes more random within the bulk of the thin film for different BBCP architectures. By modifying the substrate with a layer of PS, the preferential interactions between the core block of the BBCP and the interfaces induce a reconfiguration of the BBCP, drawing the core block out to contact substrate directly driven by enthalpy. Under these conditions, <i>N</i>_BB = 5 showed a predominantly parallel orientation of the lamellar microdomains with the corona block minimizing contact with the substrate. Higher <i>N</i>_BB values of 50 and 100 showed a more random orientation of the lamellar microdomains at different depths on the PS-modified substrate. Overall, thin-film morphology was regulated by tuning the configuration of the BBCP, varying the entropic contribution to the microdomain orientation.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"22 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145078446","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":"Colloidal Helical Inverse-Phase Assemblies Constructed by Liquid Crystal Block Copolymer with Tunable Chiral Amino Acid Spacers","authors":"Juanjuan Gao, Yangge Ren, Tiantian Cai, Yujia Guo, Yuanxiang He, Yue Lu, Lin Jia","doi":"10.1021/acs.macromol.5c01304","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01304","url":null,"abstract":"Inverse-phase micelles have been extensively studied due to their high porosity, large specific surface area, and structural versatility. However, the construction of inverse-phase assemblies from anisotropic polymers driven by complex synergistic interactions has largely been underexplored. Here, we report a class of cholesterol-based block copolymers (BCPs), POEGMA_<i>m</i>-<i>b</i>-P(R)Chol_<i>n</i> (R = Ala, Leu, Phe), featuring chiral amino acid moieties as side-chain spacers and liquid crystalline (LC) cholesterol as mesogenic units. The integration of chirality and liquid crystallinity imparts unique anisotropic properties to these BCPs, enabling synergetic interactions between hydrogen bonding, LC ordering, and hydrophobic aggregation during self-assembly. Notably, the chirality of the amino acid spacers is preserved within the micellar structure and effectively transmitted during the self-assembly process, resulting in the formation of inverse-phase micelles with pronounced helicity. These findings highlight a versatile strategy for constructing inverse-phase nanostructures with helicity and complexity by leveraging the synergistic effects of chirality and LC order within block copolymer frameworks.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"28 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145078431","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":"Folding-Unfolding Transition of Active Polymer on the Reconfiguration of Bidirectional Tangential Active Force","authors":"Arindam Panda, Sunil P. Singh","doi":"10.1021/acs.macromol.5c01098","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01098","url":null,"abstract":"The role of active stress on the conformational dynamics of a polymer has drawn significant interest due to its potential applications in understanding the energy landscape of protein structures, buckling of biopolymers, genomic spatial organization and their large-scale coherent dynamics. We present a model of bidirectional active force that acts along the polymer’s tangent, with its direction stochastically reversing between head-to-tail and tail-to-head orientations. The active polymer shows a structural transition from a random coil-like state to a compressed state with variations in the active force, directional (polarity) reversal rate, and their fraction. Furthermore, the polymer reswells and stretches more than its passive limit for a large active force. The polymer’s radius of gyration follows the ideal chain-like scaling relation, R<sub arrange=\"stack\">g</sub><sup arrange=\"stack\">2</sup>∼N<sub arrange=\"stack\">m</sub><sup arrange=\"stack\">2ν</sup> with an exponent ν ≈ 1/2, in both the compressed and swelled states. The bidirectional active force drives dynamical transitions, where the effective diffusivity abruptly shifts from a linear to quadratic increase. Similarly, in the regime of large activity, the linear decrease of the longest relaxation time of the polymer changes behavior to a power-law behavior Pe^–4/3 with Péclet number. We have shown that the active polymer’s conformational, relaxation, and diffusive behaviors display a transition from an active polar linear polymer model (APLP) to an active Brownian particle (ABP) polymer model with the increase in the fraction of the opposite polarity and their reconfiguration time.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"72 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145068531","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":"Characterizing the Structural Conformation of Highly Charged Star-Linear Polyelectrolyte Mixtures in Solution","authors":"Utku Gürel, Ilija A. Gjerapic, Wouter J. H. Arends, Roshan Akdar Mohamed Yunus, Aleksander Guzik, Patrizio Raffa, Daniele Parisi, Andrea Giuntoli","doi":"10.1021/acs.macromol.5c01180","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01180","url":null,"abstract":"Long-range electrostatic interactions provide unique opportunities to tune the conformation and phase behavior of polymeric micelles and soft colloids in solution, but their effects remain understudied due to the higher synthesis, characterization, and simulation complexity. We recently showed that micelles with long, charged polymer arms exhibit unique softness and glassy behavior at varying concentrations due to long-range electrostatic interactions, and developed a molecular dynamics model to validate the experimental results. Here we further explore our new system, and we investigate mixtures of highly charged star polyelectrolytes (SPEs, mimicking spherical micelles) and oppositely charged linear polyelectrolytes (LPEs) using molecular dynamics simulations and rheological validation. SPE size and conformation are strongly affected by LPE addition, which introduces charge neutralization within the SPEs’ bounding spheres, leading to shrinkage or expansion depending on the LPE length and concentration. Long LPEs form bridges between multiple SPEs, inducing clustering and promoting liquid–liquid phase separation at high charge ratios, triggering a glass-to-coacervate transition. Experimental rheology confirms that increasing the LPE initially decreases, then drastically increases viscosity, together with visual phase separation of the system, validating the simulation results. These findings highlight the interplay between electrostatic interactions, chain entropy, and packing effects, offering insights into how polyelectrolyte mixtures can be tuned for controlled complexation and phase behavior in soft materials design.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"19 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145068528","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}