ACS Macro Letters最新文献

Microphase Separation Controls the Dynamics of Associative Vitrimers 微相分离控制结合体的动力学

IF 5.8

ACS Macro Letters Pub Date : 2025-10-01 DOI: 10.1021/acsmacrolett.5c00544

Rahul Karmakar, Abhishek S. Chankapure, Srikanth Sastry, Sanat K. Kumar, Tarak K. Patra

引用次数: 0

Diiron Disulfide Methacrylate Metallopolymers as Sustainable Electrocatalysts for Water-Splitting and Molecular Hydrogen Production. 甲基丙烯酸二硫化二铁金属聚合物作为水裂解和分子制氢的可持续电催化剂。

IF 5.8

ACS Macro Letters Pub Date : 2025-10-01 DOI: 10.1021/acsmacrolett.5c00567

Arthur C Gibson,Richard S Glass,Dennis L Lichtenberger,Jeffrey Pyun

{"title":"Diiron Disulfide Methacrylate Metallopolymers as Sustainable Electrocatalysts for Water-Splitting and Molecular Hydrogen Production.","authors":"Arthur C Gibson,Richard S Glass,Dennis L Lichtenberger,Jeffrey Pyun","doi":"10.1021/acsmacrolett.5c00567","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00567","url":null,"abstract":"We review in this Viewpoint recent progress on the development of a new sustainable electrocatalytic system for water-splitting and molecular hydrogen generation using [diiron-disulfur] ([2Fe-2S]) active site methacrylate metallopolymers. To date, noble metal catalysts (e.g, platinum) remain the best electrocatalysts for molecular hydrogen generation using water as the chemical feedstock and proton donor. However, there remains a need for the synthesis of efficient electrocatalytic systems using low cost, earth abundant materials for sustainable H2 generation. We focus on our recent work in this area using well-defined single site [2Fe-2S]-metallopolymer catalysts. Thus, far, these systems have demonstrated rates of hydrogen production >25 times faster than [FeFe]-hydrogenase enzymes and match the current densities of platinum with only 0.2 V higher potential when operating in water at neutral pH with tris(hydroxymethyl)aminoethane (TRIS) buffer (Faradaic yields 100 ± 3%). The molecular design and synthesis of [2Fe-2S]-metallopolymers are reviewed along with mechanistic studies unraveling the causality of efficient H2 production from this catalytic system. The overall current output and overpotential are improved by the reversible electrostatic adsorption of the metallopolymer on the carbon electrode surface that enhances the proton and electron transfer rates and the use of protic buffer electrolytes (PBEs) that enhance the availability of protons. The schemes summarized here to improve the performance of [2Fe-2S] catalysts by incorporation into metallopolymers may be used to enhance the performance of other molecular electrocatalysts at the electrode surface.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"580 1","pages":"1504-1517"},"PeriodicalIF":5.8,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203677","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Regiochemical Control of Shape Morphing in Diels-Alder Covalent Adaptable Networks. Diels-Alder共价自适应网络形态变形的区域化学控制。

IF 5.8

ACS Macro Letters Pub Date : 2025-10-01 DOI: 10.1021/acsmacrolett.5c00465

Yilei Zhao,Junho Moon,Svetlana A Sukhishvili

{"title":"Regiochemical Control of Shape Morphing in Diels-Alder Covalent Adaptable Networks.","authors":"Yilei Zhao,Junho Moon,Svetlana A Sukhishvili","doi":"10.1021/acsmacrolett.5c00465","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00465","url":null,"abstract":"We demonstrate that regioisomerism in Diels-Alder (DA) reactions offers a subtle yet powerful way to tune the thermomechanical and shape morphing behavior of dynamic polymer networks. Here, we directly compare DA polymer (DAP) networks built from linear polymers with identical backbones but containing either 2- or 3-substituted furan pendant groups. For a wide range of cross-linking degrees, the 3-substituted DAP (3-DAP) networks exhibited higher thermal stability, with retro-DA dissociation temperatures (TrDA) of ∼150 °C versus 120 °C for the 2-substituted counterparts, higher elastic moduli and significantly slower temperature-dependent stress relaxation rates. The difference in the stress relaxation rates of 2- and 3-DAP elastomers was leveraged to demonstrate controlled bending in a bilayer structure via selective network plasticization. Moreover, due to the higher TrDA values, the use of 3-DAP elastomers in the single-material constructs opened a wider and a higher-temperature window (i.e., between 80 and 140 °C) for shape morphing, which is more practical compared to the traditionally employed DA-based networks such as 2-DAP elastomers which could be morphed only between 60 and 90 °C. These findings establish regioisomerism in the furan ring as a powerful parameter for designing DA-based shape morphing materials.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"102 1","pages":"1497-1503"},"PeriodicalIF":5.8,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194637","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Unidirectional Chain Transfer of Enol Ethers Yields Heterotelechelic Degradable Poly(Enol Ether). 烯醇醚单向链转移制备杂远螺旋可降解聚烯醇醚。

IF 5.8

ACS Macro Letters Pub Date : 2025-10-01 DOI: 10.1021/acsmacrolett.5c00524

Moritz E Hansen,Yan Xia

{"title":"Unidirectional Chain Transfer of Enol Ethers Yields Heterotelechelic Degradable Poly(Enol Ether).","authors":"Moritz E Hansen,Yan Xia","doi":"10.1021/acsmacrolett.5c00524","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00524","url":null,"abstract":"In ring opening metathesis polymerization (ROMP), vinyl and enol ethers have been predominantly used to terminate the polymerization. However, contrary to convention, we have previously reported ROMP of a cyclic enol ether, 2,3-dihydrofuran, to give an acid degradable poly(enol ether). Herein, we describe the use of linear, hetero bifunctional enol ethers as chain transfer agents to synthesize heterotelechelic poly(enol ether). Unidirectional chain transfer was achieved by leveraging regioselective addition of enol ethers to the Grubbs complexes. Excellent regioselectivity in producing the desired heterotelechelic polymers was confirmed by high-resolution mass spectroscopy and NMR spectroscopy. We demonstrate various tranformations of the end group functionalities without causing unwanted degradation of the poly(enol ether) backbone. The end group functionalities were also used to synthesize fully degradable block copolymers, where each block can be degraded under orthogonal conditions. The unique unidirectional chain transfer allows for the installation of functionalities at one or both chain ends, facilitating further applications of readily synthesized poly(enol ether) as a sustainable polymer.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"28 1","pages":"1492-1496"},"PeriodicalIF":5.8,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194926","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Cyclic Macromolecular Chains Visualized by Cryo-EM and AFM Reveal a Ring Expansion Polymerization Mechanism in a Classical Synthetic Pathway to Polyphosphazenes. 低温电镜和原子力显微镜观察到的环状大分子链揭示了聚磷腈经典合成途径中的扩环聚合机制。

IF 5.8

ACS Macro Letters Pub Date : 2025-09-29 DOI: 10.1021/acsmacrolett.5c00529

Raman Hlushko,Vivek M Prabhu,Alexander K Andrianov

引用次数: 0

Theory of Condensate Size Control by Molecular Charge Asymmetry. 分子电荷不对称控制凝结物大小的理论。

IF 5.8

ACS Macro Letters Pub Date : 2025-09-29 DOI: 10.1021/acsmacrolett.5c00342

Chengjie Luo,Nathaniel Hess,Dilimulati Aierken,Yicheng Qiang,Jerelle A Joseph,David Zwicker

{"title":"Theory of Condensate Size Control by Molecular Charge Asymmetry.","authors":"Chengjie Luo,Nathaniel Hess,Dilimulati Aierken,Yicheng Qiang,Jerelle A Joseph,David Zwicker","doi":"10.1021/acsmacrolett.5c00342","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00342","url":null,"abstract":"Biomolecular condensates are complex droplets comprising diverse molecules that interact by various mechanisms. Condensation is often driven by short-range attraction, but net charges can also mediate long-range repulsion. Using molecular dynamics simulations and an equilibrium field theory, we show that such opposing interactions can suppress coarsening, so many droplets of equal size coexist at equilibrium. This size control depends strongly on the charge asymmetry between molecular constituents, while the strength of the short-range attractions has a weak influence. The mechanism relies on droplets expelling ions; therefore, they cannot screen electrostatics effectively, implying that droplets acquire a net charge and cannot grow indefinitely. Our simulations indicate that this effect is likely less prevalent in biomolecular condensates within cells, although we still observe stable small clusters in this case. Taken together, our work reveals that electrostatic effects through molecular charge asymmetries can control droplet size, which contributes to our understanding of biomolecular condensates and the creation of synthetic patterns in chemical engineering.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"2 1","pages":"1484-1491"},"PeriodicalIF":5.8,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189412","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Non-Newtonian Behavior of Spherical Coacervate Micelle Dispersions in Aqueous Media. 水介质中球形凝聚胶束分散体的非牛顿行为。

IF 5.8

ACS Macro Letters Pub Date : 2025-09-26 DOI: 10.1021/acsmacrolett.5c00499

Bookun Kim,Tae-Young Heo,Ju Min Kim,Soo-Hyung Choi

{"title":"Non-Newtonian Behavior of Spherical Coacervate Micelle Dispersions in Aqueous Media.","authors":"Bookun Kim,Tae-Young Heo,Ju Min Kim,Soo-Hyung Choi","doi":"10.1021/acsmacrolett.5c00499","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00499","url":null,"abstract":"Non-Newtonian viscoelastic behavior of disordered spherical micelle dispersions composed of complex coacervate core micelles (C3Ms) in aqueous media is investigated by combining rotational rheometry and microfluidic particle focusing measurements. C3Ms were prepared by mixing oppositely charged block copolymers, resulting in spherical micelles with electrostatically neutral coacervate cores surrounded by hydrophilic coronas. Despite the spherical morphology and dispersion in low-viscosity solvents, lateral migration of micrometer-sized particles in microfluidic flow revealed measurable elasticity. The relaxation time (λ), quantified from particle focusing behavior, increased with micelle concentration and scaled with the short-time Brownian diffusion time scale. This suggests that viscoelasticity in C3M solutions originates from diffusive colloidal dynamics consistent with hard-sphere-like interactions. Upon salt addition, micelle dimension and λ decreased significantly, while solution viscosity remained nearly constant. These results demonstrate that λ can be a quantitative indicator of capturing micellar structural changes under external stimuli. This study highlights the use of centerline particle migration as a sensitive probe for weak viscoelasticity in micellar systems and establishes a quantitative link between micellar structure and relaxation dynamics.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"87 1","pages":"1459-1464"},"PeriodicalIF":5.8,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140096","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

PMSE Centennial: Celebration of Success and New Frontiers in Polymer Materials Science and Engineering. PMSE百年纪念：庆祝高分子材料科学与工程的成功和新领域。

IF 5.8

ACS Macro Letters Pub Date : 2025-09-26 DOI: 10.1021/acsmacrolett.5c00626

Melissa A Grunlan,LaShanda T J Korley,Qinghuang Lin,Christopher L Soles,Rigoberto Advincula,Arthi Jayaraman,Elizabeth Cosgriff-Hernandez,Elsa Reichmanis,Jodie L Lutkenhaus,Rodney D Priestley,Brigitte Voit,Thomas H Epps

{"title":"PMSE Centennial: Celebration of Success and New Frontiers in Polymer Materials Science and Engineering.","authors":"Melissa A Grunlan,LaShanda T J Korley,Qinghuang Lin,Christopher L Soles,Rigoberto Advincula,Arthi Jayaraman,Elizabeth Cosgriff-Hernandez,Elsa Reichmanis,Jodie L Lutkenhaus,Rodney D Priestley,Brigitte Voit,Thomas H Epps","doi":"10.1021/acsmacrolett.5c00626","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00626","url":null,"abstract":"In 2024, the American Chemical Society (ACS), Division of Polymeric Materials: Science and Engineering (PMSE), celebrated its centennial. This historic occasion was marked at the 2024 Spring ACS Meeting in New Orleans with a Centennial Symposium entitled \"PMSE Centennial: Celebration of Success and New Frontiers in Polymeric Materials Science and Engineering\". The symposium reflected on past scientific breakthroughs, technological advancements, and new frontiers in the field of polymeric materials science and engineering. Eight thematic areas comprised the symposium: Advanced Manufacturing, AI and Materials Discovery, Biomaterials, Electronic Materials, Energy, Entrepreneurship, Smart Materials, and Sustainability. The 31 distinguished speakers, representing academia, industry, and national laboratories, shared their unique perspectives. Within this Viewpoint, distinguished speakers have expanded on the symposium's themes, summarizing key takeaways, identifying critical challenges, and exploring opportunities for continued advancements in polymer science.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"37 1","pages":"1465-1475"},"PeriodicalIF":5.8,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140502","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Sustainable Long-Spaced Polycondensates toward Polyethylene-Like Materials. 面向类聚乙烯材料的可持续长间距聚聚物。

IF 5.8

ACS Macro Letters Pub Date : 2025-09-24 DOI: 10.1021/acsmacrolett.5c00503

Shanshan Xu,Ying Zheng,Pengju Pan

{"title":"Sustainable Long-Spaced Polycondensates toward Polyethylene-Like Materials.","authors":"Shanshan Xu,Ying Zheng,Pengju Pan","doi":"10.1021/acsmacrolett.5c00503","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00503","url":null,"abstract":"Long-spaced polycondensates generally refer to the synthetic polymers containing long methylene segments in repeating units, which are separated by functional groups such as ester, amide, and carbonate groups. Such polymers usually show the polyethylene-like crystallization behavior, mechanical property, processability, and also good chemical recyclability. Since most of the long-spaced polycondensates are highly crystalline, understanding the relationships between their chain structure, crystallization, and macroscopic properties is of fundamental importance for developing novel sustainable polymer materials. This Viewpoint focuses on discussing the crystallization and its relations to the chain structure, macroscopic performances (e.g., thermal, mechanical, barrier properties) through the case studies on long-spaced polyesters and polyamides, followed by a brief review on other long-spaced polymer families. Then, chemical recycling of long-spaced polycondensates is also commented. Finally, a conclusion of the Viewpoint and an outlook for future directions are shared. We hope that this Viewpoint can provide inspiration for future studies on advanced sustainable polymers.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"2 1","pages":"1448-1458"},"PeriodicalIF":5.8,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127392","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Visible Light-induced Living Cationic Polymerization Using Boranil Complex as a Robust Photocatalyst. 以硼腈配合物为强光催化剂的可见光诱导活性阳离子聚合。

IF 5.8

ACS Macro Letters Pub Date : 2025-09-22 DOI: 10.1021/acsmacrolett.5c00536

Yun Liao,Shuai Zhou,Xue Yang,Ziwei Yang,Wenya Liu,Zhaohui Li,Saihu Liao

引用次数: 0