Macromolecules最新文献

{"title":"Deuteration Effects on the Physical and Optoelectronic Properties of Donor–Acceptor Conjugated Polymers","authors":"Kundu Thapa, Madison Mooney, Guorong Ma, Zhiqiang Cao, Gage T. Mason, Naresh Eduguorala, Surabhi Jha, Derek L. Patton, Jason D. Azoulay, Simon Rondeau-Gagné, Xiaodan Gu","doi":"10.1021/acs.macromol.4c02778","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02778","url":null,"abstract":"The significant differences in scattering cross sections between deuterium and protium are unique to neutron scattering techniques and have been a long-standing area of interest within the neutron scattering community. Researchers have explored selective deuteration to manipulate scattering contrast in soft matter systems, leading to the widespread use of deuterium labeling in materials development. As deuteration changes the atomic mass, it alters physical properties such as molecular volume, polarizability, and polarity, which in turn may affect noncovalent interactions and crystal ordering. Despite previous studies, there remains a limited understanding of how deuteration impacts donor–acceptor (DA) conjugated polymers. To address this, we synthesized deuterated DPP polymers and systematically investigated the effects of side-chain deuteration on their thermal stability, crystal packing, morphology, and optoelectronic properties. We found that deuteration increased the melting and crystallization temperatures of DPP polymers, although it did not significantly alter their morphology, molecular packing, or charge mobility. These properties were assessed by using atomic force microscopy (AFM), X-ray scattering, and thin-film transistor device measurements, respectively, for DPP polymers. Our work shows that deuterium labeling could be a powerful method for controlling scattering length density, enabling neutrons to study the structure and dynamics of conjugated polymers without impacting their electronic performance.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"40 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143884950","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":"Elastin-Based Janus Hydrogel Tape with Adhesive, Stretchable, and Conductive Properties for Soft Bioelectronic Applications","authors":"Zhongwei Guo, Yilin Guo, Shiqiang Zhang, Wenlong Yu, Qiulei Gao, Jiyu Chen, Yahui Xiong, Lei Chen, Jingjiang Qiu, Ronghan Wei","doi":"10.1021/acs.macromol.5c00150","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00150","url":null,"abstract":"Achieving robust adhesion and optimal conductivity simultaneously is highly important and challenging for soft bioelectronics. Although numerous adhesive hydrogels have been investigated, they are designed for double-sided adhesion and lack optimal sensing performance. Therefore, we developed a two-step casting strategy to fabricate Janus hydrogel tape (J-Tape) for soft bioelectronics. The J-Tape was composed of an adhesive poly(acrylic acid)-<i>N</i>-hydroxysuccinimide/elastin-methacrylate (PAAc-NHS/ElaMA) bottom layer and a nonadhesive poly(acrylic acid)/gelatin-methacrylate (PAAc/GelMA) top layer and exhibited multiple functions, such as sufficient bioadhesion, high stretchability, optimal sensitivity, and good biocompatibility. Benefiting from the NHS ester group, the bottom layer can rapidly and robustly adhere to biological tissues. In addition, the top layer was supplemented with PEDOT:PSS (poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)) to enhance its conductive performance. The application of this J-Tape for tissue adhesion and wound sealing <i>in vitro</i> was successfully demonstrated. When exploited as a strain sensor to monitor diverse physiological signals, the hydrogel showed excellent sensitivity and reliability. Furthermore, J-Tape was integrated with a machine learning algorithm and developed into a wireless wearable electronic sensing system that can recognize diverse gestures with up to 98.87% accuracy. Overall, this work may provide new insights for the design and fabrication of functional bioelectronics.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"9 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143889858","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":"Time-Dependent Information Encryption Using a Supramolecular Polymer Gel Based on a Pillararene","authors":"Yujie Cheng, Bicong Liang, Xuehong Wei, Sidian Li, Pi Wang, Danyu Xia","doi":"10.1021/acs.macromol.5c00290","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00290","url":null,"abstract":"With the rapid development of information technology, information security has become a hot topic of global concern. Many efforts have been devoted to developing intelligent materials for safeguarding information. Time-dependent information encryption based on supramolecular polymer gel (SPG) materials has many advantages including intrinsic stimuli responsiveness, good processability, excellent self-healing property, and so on. Herein, we report a time-dependent information encryption material constructed by a SPG with tunable fluorescence emission based on a pillararene. A bipyridine derivative-containing fluorescent polymer <b>P1</b> and a pillararene-containing polymer <b>P2</b> were prepared. <b>P1</b> underwent a fluorescence emission decrease with a red shift from blue to blue-green after adding the acid due to the protonation of its bipyridine group. The protonated form of <b>P1</b> was denoted as <b>P1H</b>. When <b>P1H</b> was mixed with <b>P2</b>, a SPG formed, accompanied by quenching of the blue-green fluorescence due to the host–guest interactions between a pillararene and the protonated bipyridine derivative guest. Intriguingly, adjusting the concentration of the acid added to the SPG can control the rate of fluorescence color change, enabling dynamic information encryption that can vary over different time scales. Due to the reversible property of this supramolecular system under external stimuli, the decrypted information could be encrypted again by treating with base or waiting for a period of time without any treatment, avoiding the leakage of the stored information and upgrading the information security.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"18 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143885452","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":"Controlling the Morphology of Conjugated Polyfluorene through Physical Stretching and Solvent Variation","authors":"Yang Xu, Zifei Chen, Lili Sun, Jamie S. Laird, Bin Liu, Salvy P. Russo, Jinyi Lin, Kenneth P. Ghiggino, Trevor A. Smith","doi":"10.1021/acs.macromol.4c03164","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c03164","url":null,"abstract":"In this paper, the intentional control of morphology and photophysical properties of a conjugated polydiarylfluorene, PODPF, in thin films is achieved through various systematic approaches including physical stretching when hosted in a highly elastic polymer, poly(vinyl butyral) (PVB) at various weight-to-weight ratios, and by varying the solvent. Microspectroscopic techniques were employed to monitor the resulting variations. Significant differences in the excitation and emission spectra are observed as functions of the concentration of PODPF mixed in the PVB film. This indicates the formation of different types of aggregates in these films through the coupling between dipoles with different relative orientations. Fluorescence anisotropy images show dramatic differences as a function of the extent of physical stretching of the film and as a function of PODPF concentration. Shifts in the emission spectra of the films as a function of the concentration in films cast from different solvents illustrate that the morphology of the films is highly dependent on the properties of the solvent from which the film is cast. The results highlight effective approaches for influencing the morphology and properties of conjugated polymers in thin films, with particular emphasis on the crucial role of solvent selection. Theoretical modeling is also employed to provide insight into the underlying principles governing these observed phenomena.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"7 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143878041","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":"Living Anionic Polymerization of 2-Isopropenylthiophene Derivatives","authors":"Yuki Kurishiba, Daisuke Yamamoto, Chihiro Homma, Raita Goseki, Takashi Ishizone","doi":"10.1021/acs.macromol.4c02845","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02845","url":null,"abstract":"The anionic polymerization of 2-isopropenylthiophene (<b>1</b>), 2-(1-adamantyl)-5-isopropenylthiophene (<b>2</b>), 5-phenyl-2-isopropenylthiophene (<b>3</b>), and 2-cyano-5-isopropenylthiophene (<b>4</b>) was performed in tetrahydrofuran (THF) with various initiators including <i>sec</i>-BuLi, oligo(α-methylstyryl)lithium, potassium naphthalenide, and diphenylmethylpotassium at −78 °C. The anionic polymerization of <b>2</b>–<b>4</b> proceeded quantitatively to provide novel polymers with the predicted molecular weights and narrow molecular weight distributions (<i>M</i>_w/<i>M</i>_n &lt; 1.2), whereas the polymerization of <b>1</b> often suffered from side reactions, probably due to proton abstraction on the thiophene ring. After the complete polymerization at −78 °C, the propagating carbanion of the resulting polymers of <b>2</b>–<b>4</b> can be depolymerized to give the starting monomer by elevating the temperature to 0 °C. In particular, <b>3</b> showed a reversible equilibrium polymerizability similar to that of α-methylstyrene by varying the temperature of the polymerization system. From the plot of logarithm of equilibrium monomer concentration, ln[M]_e, against reciprocal temperature, the thermodynamic parameters, Δ<i>H</i> and Δ<i>S</i>, and the ceiling temperature (<i>T</i>_c) of the anionic polymerization of <b>3</b> in THF were estimated to be −8.09 ± 0.22 kcal mol^–1, −27.3 ± 0.9 cal mol^–1 K^–1, and 24 °C, respectively.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"101 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143876236","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":"Red Sea Star-Inspired, Rapid Underwater Self-Healing Polyurethane Based on Dual Hydrophobic Units and Tandem Dynamic Bonds","authors":"Fenglong Li, Haofeng Qiu, Chao Chen, Xiaolin Wang, Minghui Cui, Shijie Qiu, Kyung Jin Lee, Jing Chen, Wu Bin Ying, Jin Zhu","doi":"10.1021/acs.macromol.4c03007","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c03007","url":null,"abstract":"Red sea stars exhibit an extraordinary underwater self-healing capability driven by fibrinolytic enzyme secretion, enabling survival in challenging marine environments. Inspired by this biological mechanism, we developed a polyurethane (DSFPU-3) capable of rapid underwater self-healing. By integrating dual hydrophobic units (alkyl side chains and fluorine groups) with tandem dynamic bonds (disulfide and imine bonds), DSFPU-3 achieved a water contact angle of 99.3° and maintained stable microphase structures and micromorphology even after 4-day water soaking. The synergistic effect of hydrophobic units and dynamic bonds enabled self-healing at a speed exceeding 33.33 μm/h, achieving 98% efficiency and allowing the material to endure significant mechanical stress post-healing. Small-molecule modeling experiments and rheological analyses validated the bond exchange mechanisms of the tandem dynamic bonds, underscoring their critical role in accelerating the self-healing process. This study presents a novel strategy for fabricating rapid underwater self-healing polyurethanes, representing a significant advancement in their application under aquatic conditions.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"74 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143876283","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":"Crystallization and Melting Behaviors of Discrete Butyolactone–Caprolactone Alternative Co-Oligomer: The Effect of End Groups","authors":"Huijun Xu, Ao Feng, Zhihao Huang, Rui Tan, Zefan Wang, Xiaohua Zhang, Zhengbiao Zhang","doi":"10.1021/acs.macromol.5c00593","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00593","url":null,"abstract":"Discrete oligomers are ideal candidates for the investigation of the crystallization behaviors of polymers since the molecular weight distribution and the precision of molecular structures play a crucial role in the crystallization behaviors of polymers. We precisely synthesize discrete alternative co-oligomers (<i>o</i>(γ-BL-<i>alt</i>-ε-CL)s) with different end groups based on ε-caprolactone (ε-CL) and γ-butyrolactone (γ-BL) as monomers using an iterative exponential growth (IEG) strategy and systematically study the crystallization and melting behaviors of the <i>o</i>(γ-BL-<i>alt</i>-ε-CL)s with precise monomer sequence. The roles that the end group plays in the crystallization and melting of co-oligomers are highlighted. The <i>o</i>(γ-BL-<i>alt</i>-ε-CL)s with different end groups (<i>tert</i>-butyldiphenylsilyl, benzoyl, acetyl) crystallize in an extended-chain conformation. Observation on the decrease of the crystallization rate of co-oligomers with the increase of the size of the end groups is associated with the slow dynamics or slow relaxation of co-oligomer chains with the large end group. The melting–recrystallization during the heating process for the <i>o</i>(γ-BL-<i>alt</i>-ε-CL)s with small end group is attributed primarily to the reduced steric hindrance effect. For the <i>o</i>(γ-BL-<i>alt</i>-ε-CL)s with large end groups, the rearrangement of co-oligomer chains is substantially hindered by steric effects, which lead to a significant suppression of the melting–recrystallization.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"35 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867096","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":"Influence of Network Design Parameters on the Morphology Evolution in Diels–Alder Blends via Thermodynamics and Kinetics Control","authors":"Fatemeh Sahraeeazartamar, Nirmayi Sadanand Joshi, Roos Peeters, Bram Vanderborght, Guy Van Assche, Joost Brancart","doi":"10.1021/acs.macromol.4c02936","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02936","url":null,"abstract":"Reversible polymer network blends leverage the advantageous properties of immiscible polymer backbones. Previous work showed that the phase morphology of blends of a hydrophilic poly(propylene oxide) (PPO) and hydrophobic polydimethylsiloxane (PDMS) cured by the reversible Diels–Alder reaction depends on the mass ratio of the two polymers and the maleimide-to-furan ratio used for the reversible network polymerization. This work studies the competition between the reversible Diels–Alder reaction and the phase separation kinetics and thermodynamics to control the phase formation. A furan-functionalized PPO with a molar mass of 4546 g mol^–1 was blended with furan-functionalized PDMS with different molar masses, mass ratios of the polymers, and stoichiometric ratios. At the highest molar mass of 4961 g mol^–1, the PDMS and PPO separated quickly into separate layers, creating a barrier against both water and oxygen, respectively. The thickness, morphology, and composition of the layers depend on the composition of the blend. At a lower molar mass of the PDMS, the chemistry of the furan end groups becomes more pronounced, which increases the compatibility of the two polymers, reducing the thermodynamic driving force for phase separation. In addition, the increased concentration of furan and maleimide groups increases the Diels–Alder reaction rates and leads to more cross-linked network blends. Mastering the interplay between the thermodynamics of the blends and the kinetics of the network formation and phase separation by judicious combinations of the network design parameters leads to final blend morphologies ranging from kinetically trapped uniform microstructures to almost completely phase-segregated morphologies. Finally, the solvent extraction time was used as a process parameter of the wet blending process. Slow evaporation of the solvent over the course of 1 week resulted in a near-equilibrium separation of the two immiscible polymers into separate layers with perfect interfacial bonding by the same Diels–Alder chemistry. Manipulation of these factors enables the development of Diels–Alder network blends with a wide range of properties that are suitable for a wide variety of applications. The fastest and most efficient autonomous healing is achieved at higher PPO contents and for the highest PDMS molar masses, while the best barriers against water and oxygen are obtained at the highest cross-link densities.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"7 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867083","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 Evolution of Chain Orientation and Crystal Structure under the Dual Action of Temperature and Stress","authors":"Chengyao Liang, Weilei Huang, Senlong Yu, Qianqian Wang, Zexu Hu, Hengxue Xiang, Meifang Zhu","doi":"10.1021/acs.macromol.5c00686","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00686","url":null,"abstract":"A comprehensive understanding of the multiscale structural evolution that governs fiber properties during polyamide formation is essential for the theoretical development of high-strength fibers. This study systematically investigates the hierarchical structural transformations in high-strength polyamide 66 fibers (H-PA66F) at key stages during high-speed spinning, with a focus on molecular chain conformations, hydrogen bonding networks, crystalline organization, orientation dynamics, and long-period structural features. By constructing a three-phase structural model, the study elucidates the progressive structural-property relationships during fiber processing. The mechanical enhancement observed throughout the formation process is attributed to synchronized structural optimizations: hot drawing enhances fiber strength through crystal perfection and increases the alignment of rigid segments, while subsequent heat setting stabilizes the structure by reducing defects. These findings establish a robust structure-performance framework, providing theoretical insights for the targeted multiscale structural engineering of high-performance polyamide fibers.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"7 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867085","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":"Facile Synthesis of High-Molecular-Weight Biobased Polythioethers with Outstanding Mechanical Properties and Intrinsic Antiultraviolet Performance","authors":"Qiubo Wang, Xinyu Hu, Min Yan, Xingyu Luo, Xiaojuan Liao, Meiran Xie","doi":"10.1021/acs.macromol.5c00389","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00389","url":null,"abstract":"Common methods, including adding inorganic and organic ultraviolet (UV) absorbers, for preparing anti-UV polymers inevitably have the disadvantages of poor stability, low transparency, and coloration of samples. To overcome these shortcomings, high-molecular-weight polythioethers with excellent intrinsic anti-UV performance were prepared by anion ring-opening polymerization of episulfides derived from the biobased epoxides containing a substituted phenyl group. The mechanical properties, reprocessability, and anti-UV performance of polythioethers were significantly improved through copolymerization and cross-linking modification. A cross-linked copolythioether displayed a UV protection factor value of 91.8 and a light transmittance of over 68% in the visible range and moreover exhibited outstanding mechanical properties with a tensile strength of 17.9 MPa and an elongation at break of 534%. The mechanical properties and anti-UV performance of copolythioether decreased significantly after prolonged exposure to UV light, while the cross-linked copolythioether maintained good stability. This work provided a feasible method for preparing colorless, transparent, and high-performance intrinsic anti-UV polythioethers, which can be used in the manufacture of lenses and can effectively prevent UV-light damage to the eyes.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"36 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867141","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}