Macromolecules最新文献_第7页

Controlling Crystal Orientation in Films of Conjugated Polymers by Tuning the Surface Energy 通过调节表面能控制共轭聚合物薄膜的晶体取向

IF 5.5 1区化学

Macromolecules Pub Date : 2024-10-29 DOI: 10.1021/acs.macromol.4c01819

Oleksandr Dolynchuk, Robert T. Kahl, Florian Meichsner, Alexander J. Much, Andrii Pechevystyi, Anna Averkova, Andreas Erhardt, Mukundan Thelakkat, Thomas Thurn-Albrecht

{"title":"Controlling Crystal Orientation in Films of Conjugated Polymers by Tuning the Surface Energy","authors":"Oleksandr Dolynchuk, Robert T. Kahl, Florian Meichsner, Alexander J. Much, Andrii Pechevystyi, Anna Averkova, Andreas Erhardt, Mukundan Thelakkat, Thomas Thurn-Albrecht","doi":"10.1021/acs.macromol.4c01819","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c01819","url":null,"abstract":"It has been a long-term goal to understand the molecular orientation in films of conjugated polymers, which is crucial to their efficient exploitation. Here, we show that the surface energies determine the crystal orientation in films of model conjugated polymers, substituted polythiophenes crystallized on substrates. We systematically increase the surface energy of edge-on crystals formed at the vacuum interface by attaching polar groups to the ends of the polymer side chains. This suppresses crystallization at the vacuum interface, resulting in a uniform face-on crystal orientation induced by the graphene substrate in polythiophene films as thick as 200 nm, which is relevant for devices. Surprisingly, face-on crystal orientation is attained in the modified polythiophenes crystallized even on amorphous surfaces. Furthermore, for the samples with still competing interfacial interactions, the crystal orientation can be switched in the same sample, depending on the crystallization conditions. Thus, we report a fundamental understanding and control of the equilibrium crystal orientation in films of conjugated polymers.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"16 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142536668","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

Enhanced Entanglement Density and Its Implication on Chain Diffusion Dynamics at the Air/Polyethylene Melt Interface 增强的纠缠密度及其对空气/聚乙烯熔体界面链扩散动力学的影响

IF 5.5 1区化学

Macromolecules Pub Date : 2024-10-29 DOI: 10.1021/acs.macromol.4c01588

Natsumi Kyoda, Tatsuya Ishiyama

引用次数: 0

Influence of Crystallinity on the Mechanochemical Degradation of Poly(lactide) with Ball-Mill Grinding 结晶度对球磨法聚乳酸机械化学降解的影响

IF 5.5 1区化学

Macromolecules Pub Date : 2024-10-29 DOI: 10.1021/acs.macromol.4c02156

Somin Cha, Jeung Gon Kim, Gregory I. Peterson

引用次数: 0

Efficient Oxygen-Accelerated Near-Infrared Photoinduced Atom Transfer Radical Polymerization Mediated with S-Scheme Heterojunction Photocatalyst Composed of Lead-Free Halide Perovskite Encapsulated into Metal–Organic Framework 由封装在金属有机框架中的无铅卤化物包晶组成的 S 型异质结光催化剂介导的高效氧气加速近红外光诱导原子转移辐射聚合作用

IF 5.5 1区化学

Macromolecules Pub Date : 2024-10-29 DOI: 10.1021/acs.macromol.4c01764

Bei Liu, Zhinan Xia, Wanchao Hu, Shiyi Li, Changli Lü

{"title":"Efficient Oxygen-Accelerated Near-Infrared Photoinduced Atom Transfer Radical Polymerization Mediated with S-Scheme Heterojunction Photocatalyst Composed of Lead-Free Halide Perovskite Encapsulated into Metal–Organic Framework","authors":"Bei Liu, Zhinan Xia, Wanchao Hu, Shiyi Li, Changli Lü","doi":"10.1021/acs.macromol.4c01764","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c01764","url":null,"abstract":"All-inorganic lead-free halide perovskite Cs3Bi2I9 was encapsulated in a zirconium-porphyrin metal–organic framework (MOF-545) to create a S-scheme heterojunction photocatalyst Cs3Bi2I9@MOF-545 for efficient copper-mediated photoinduced atom transfer radical polymerization (photo-ATRP). The close interfacial contact and the disparity in the work function between MOF-545 and Cs3Bi2I9 has been demonstrated to facilitate photoinduced charge transfer at the interface and boost the efficiency of photogenerated charge separation and utilization. The distinctive advantage of S-scheme charge transfer enabled the optimized Cs3Bi2I9@MOF-545 to effectively regulate the Cu-mediated photo-ATRP of diverse monomers under 850 nm near-infrared (NIR) light with good terminal fidelity, even achieving high monomer conversion on the barriers of 5 mm PP board and 4 mm pigskin. In a large reaction volume (250 mL), the monomer conversion reached approximately 99% with a first-order kinetic behavior under 850 nm NIR light, demonstrating potential for industrial applications. High photocatalytic activity was maintained after 10 cycles of use in organic solvent (DMSO) or 6 days of water immersion. Furthermore, it is unveiled that the limited oxygen can enhance trithanolamine (TEOA) oxidation to accelerate Cu-mediated photo-ATRP in heterojunction photocatalysts for the first time. This study offers insights into designing MOF-based photocatalysts to augment Cu-mediated photo-ATRP performance under NIR-light.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"6 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541783","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

Accelerated Crystallization and Preferred Formation of a Thermally Stable Crystal Phase in Enantiomeric Blends of Long-Spaced Chiral Polyesters 长间距手性聚酯对映体混合物的加速结晶和热稳定晶相的优先形成

IF 5.5 1区化学

Macromolecules Pub Date : 2024-10-28 DOI: 10.1021/acs.macromol.4c01881

Chenxuan Sun, Xuekuan Ma, Mengru Ding, Chengtao Yu, Junfeng Liu, Guorong Shan, Yongzhong Bao, Ying Zheng, Pengju Pan

{"title":"Accelerated Crystallization and Preferred Formation of a Thermally Stable Crystal Phase in Enantiomeric Blends of Long-Spaced Chiral Polyesters","authors":"Chenxuan Sun, Xuekuan Ma, Mengru Ding, Chengtao Yu, Junfeng Liu, Guorong Shan, Yongzhong Bao, Ying Zheng, Pengju Pan","doi":"10.1021/acs.macromol.4c01881","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c01881","url":null,"abstract":"Enantiomeric blends of L- and D-type chiral polymers usually show distinct crystallization behavior and physical properties from the corresponding enantiopure polymers. However, the crystallization kinetics and crystalline structure of the enantiomeric blends of L- and D-polymers are not yet well understood, particularly concerning the chiral polymers with low chiral moiety densities. Herein, we synthesized a series of long-spaced chiral polyesters with a relatively low chiral moiety content and investigated the effects of enantiomeric blending on the crystallization kinetics and crystal polymorphism of chiral polyesters. Different from the other chiral polyesters with high chiral moiety content, the enantiomeric blends of long-spaced chiral polyesters do not crystallize into the new stereocomplex crystals but have a faster crystallization rate than the corresponding enantiopure polyesters. Compared to the enantiopure polyesters, the enantiomeric blends show the preferred formation of thermally stable form-I crystals in the cooling process and the broader temperature range for generating the form-I crystals in isothermal crystallization. The effects of enantiomeric blending on crystallization become less obvious with decreasing the chiral moiety content or increasing the methylene spacer length. We infer that the accelerated crystallization and facilitated formation of form-I crystals in enantiomeric blends are correlated with the interchain interactions between L- and D-polyesters. This study provides new insights into the crystallization of long-spaced chiral polyesters.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"10 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142519947","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

High-Selectivity CO2 Mixture Separations by a Guanylated Polymer of Intrinsic Microporosity (PIM-G) Membrane 利用官能团化聚合物固有微孔（PIM-G）膜实现高选择性二氧化碳混合物分离

IF 5.5 1区化学

Macromolecules Pub Date : 2024-10-28 DOI: 10.1021/acs.macromol.4c01434

Samuel J. Kaser, Pablo Dean, Philippe Jean-Baptiste, Simar Kaur Mattewal, Taigyu Joo, Jing Ying Yeo, Zachary P. Smith

引用次数: 0

Genetic Code Expansion History and Modern Innovations 基因密码扩展历史与现代创新

IF 51.4 1区化学

Macromolecules Pub Date : 2024-10-28 DOI: 10.1021/acs.chemrev.4c0027510.1021/acs.chemrev.4c00275

Alan Costello, Alexander A. Peterson, Pei-Hsin Chen, Rustam Bagirzadeh, David L. Lanster and Ahmed H. Badran*,

{"title":"Genetic Code Expansion History and Modern Innovations","authors":"Alan Costello, Alexander A. Peterson, Pei-Hsin Chen, Rustam Bagirzadeh, David L. Lanster and Ahmed H. Badran*, ","doi":"10.1021/acs.chemrev.4c0027510.1021/acs.chemrev.4c00275","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00275https://doi.org/10.1021/acs.chemrev.4c00275","url":null,"abstract":"The genetic code is the foundation for all life. With few exceptions, the translation of nucleic acid messages into proteins follows conserved rules, which are defined by codons that specify each of the 20 proteinogenic amino acids. For decades, leading research groups have developed a catalogue of innovative approaches to extend nature’s amino acid repertoire to include one or more noncanonical building blocks in a single protein. In this review, we summarize advances in the history of in vitro and in vivo genetic code expansion, and highlight recent innovations that increase the scope of biochemically accessible monomers and codons. We further summarize state-of-the-art knowledge in engineered cellular translation, as well as alterations to regulatory mechanisms that improve overall genetic code expansion. Finally, we distill existing limitations of these technologies into must-have improvements for the next generation of technologies, and speculate on future strategies that may be capable of overcoming current gaps in knowledge.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"124 21","pages":"11962–12005 11962–12005"},"PeriodicalIF":51.4,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609109","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

Controlling the Microstructure and Mechanical Response of Polybutadiene Elastomers Through Phosphite Inhibited Ring-Opening Metathesis Polymerization 通过亚磷酸抑制开环偏聚聚合反应控制聚丁二烯弹性体的微观结构和机械响应

IF 5.5 1区化学

Macromolecules Pub Date : 2024-10-26 DOI: 10.1021/acs.macromol.4c01497

Evan M. Lloyd, Stephen L. Craig

{"title":"Controlling the Microstructure and Mechanical Response of Polybutadiene Elastomers Through Phosphite Inhibited Ring-Opening Metathesis Polymerization","authors":"Evan M. Lloyd, Stephen L. Craig","doi":"10.1021/acs.macromol.4c01497","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c01497","url":null,"abstract":"With microstructures that typically favor crystallization at low temperatures, commercial polybutadiene elastomers often suffer from poor toughness and limited elongation when utilized in applications near room temperature. By controlling competition between primary and secondary metathesis through phosphite inhibition of ruthenium catalysts during the ring-opening metathesis polymerization of cyclooctadiene and a bis-norbornene cross-linker, we effectively tune the proportion of cis and trans alkenes and the resulting polybutadiene microstructure. With microstructural control, a wide range of room temperature mechanical responses are revealed by simply tuning the phosphite to catalyst ratio. Importantly, toughening due to the presence of crystalline domains initially or those formed in situ through strain-induced crystallization is possible at room temperature, and polybutadiene elastomers with room temperature elongation at failure greater than 600% are obtained. Further, strain-mediated crystallization allows for storage of strain energy and on-demand actuation upon application of a mild thermal stimulus. Our results suggest a scalable synthetic route to high-toughness polybutadiene elastomers with a single catalytic system and hold promise for enabling excellent toughness in polybutadiene elastomers over a broad temperature range.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"29 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142490665","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

Anion-Influenced Hydration and Layering Vastly Modulate Polyzwitterionic Brush Responses 受阴离子影响的水合作用和分层作用极大地调节了聚齐微电刷的反应

IF 5.5 1区化学

Macromolecules Pub Date : 2024-10-25 DOI: 10.1021/acs.macromol.4c01976

Evan Angelo Quimada Mondarte, Xin-Xing Zhang, Xueyu Feng, Yuchen Shi, Hanyan Xu, Tomohiro Hayashi, Jing Yu

{"title":"Anion-Influenced Hydration and Layering Vastly Modulate Polyzwitterionic Brush Responses","authors":"Evan Angelo Quimada Mondarte, Xin-Xing Zhang, Xueyu Feng, Yuchen Shi, Hanyan Xu, Tomohiro Hayashi, Jing Yu","doi":"10.1021/acs.macromol.4c01976","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c01976","url":null,"abstract":"This study investigates the influence of different anions on the hydration states and conformational changes of poly(sulfobetaine methacrylate) (PSBMA) brushes, unraveling their intricate role in modulating tribomechanical properties and antifouling performance. Through bimodal atomic force microscopy (AFM), we reveal that anion identity affects the layered structure thicknesses of PSBMA brushes in accordance with the Hofmeister series. Enhanced screening of dipole–dipole interactions and increased hydration were observed with higher concentrations of more chaotropic counterions, showcasing the anti-polyelectrolyte effect (APE), a phenomenon that was not observed in highly kosmotropic sulfate anions. Infrared spectroscopy highlighted the impact of anions on the incorporation of strongly H-bonded water clusters within the PSBMA chains. Our findings underscore the complex interplay of interfacial interactions (chain dipole–dipole, ion-chain dipole, ion–water, and water-chain dipole), leading to variations in tribomechanical behavior and antifouling performance of PSBMA brushes. Pearson correlational analysis with anion descriptors further elucidated these relationships, offering insights for tailored material design in engineering applications, thus advancing materials science and biotechnology.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"78 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142489867","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

Complex Cage, Cage-Brush, and Lantern Polymers with Topological-Enhancing Phosphorescence 具有拓扑增强磷光的复杂笼型、笼刷型和灯笼型聚合物

IF 5.5 1区化学

Macromolecules Pub Date : 2024-10-25 DOI: 10.1021/acs.macromol.4c01857

Hao Wang, Qiubo Wang, Shuyao Wang, Huijing Han, Ruyi Sun, Xiaojuan Liao, Cuihong Ma, Meiran Xie

{"title":"Complex Cage, Cage-Brush, and Lantern Polymers with Topological-Enhancing Phosphorescence","authors":"Hao Wang, Qiubo Wang, Shuyao Wang, Huijing Han, Ruyi Sun, Xiaojuan Liao, Cuihong Ma, Meiran Xie","doi":"10.1021/acs.macromol.4c01857","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c01857","url":null,"abstract":"Cage polymers, a type of special cyclic polymer with an intriguing three-dimensional topology and internal cavity, have attracted increasing attention. However, because of the complicated topological structure, precise preparation of cage polymers is a formidable challenge. Herein, an effective and versatile synthetic strategy was developed to precisely construct complex topological polymers with a well-defined structure and high molecular weight, including three-arm cage, three-arm cage-brush, bi(three-arm) cage, and six-arm cage polymers, by a ring-opening metathesis polymerization-based blocking-cyclization technique using different short polymeric ladderphanes containing multiple living ends as the initial and end-cyclizing motifs, which was the key factor in simply tuning the polymer topology. Moreover, bi- and six-arm lantern polymers were readily derived from the corresponding cage polymers. By comparison of the performance differences between these novel polymers, the dependence of the properties on the topology was revealed. Therefore, this work provided a platform for constructing complex topological polymers with unique topological-enhancing phosphorescent performance and mechanical properties.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"110 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142489898","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