ACS Macro Letters最新文献

Bioinspired Adhesives with Debonding-on-Demand Capability

IF 5.8

ACS Macro Letters Pub Date : 2025-03-18 DOI: 10.1021/acsmacrolett.5c00035

Athanasios Skandalis, Mathieu A. Ayer, Christoph Weder

{"title":"Bioinspired Adhesives with Debonding-on-Demand Capability","authors":"Athanasios Skandalis, Mathieu A. Ayer, Christoph Weder","doi":"10.1021/acsmacrolett.5c00035","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00035","url":null,"abstract":"Adhesives with debonding-on-demand (DoD) capability can simplify and improve manufacturing processes, extend the life cycle of products, and facilitate recycling, thus attracting fast-growing interest for use in different sectors. A general design approach for DoD adhesives is based on supramolecular polymers, which can be disassembled by an external stimulus, allowing the modification of the physical properties of these materials. However, the adhesive strength of supramolecular adhesives is generally limited to a few megapascals, and their synthesis is often quite involved. Here, we report that these problems can be overcome by a family of adhesives that were inspired by the structure and function of the natural resin shellac. These adhesives are based on linear oligomers of bisphenol A diglycidyl ether and secondary diamines and have, despite the widespread use of cross-linked epoxy thermosets, remained unexplored thus far. We show that if the molecular weight is limited, highly soluble and melt-processable adhesives can be produced. Adhesion tests performed on lap joints made with stainless steel substrates reveal a shear strength of 3.5–16 MPa, and the upper limit of this range exceeds the bond strength of the shellac blueprint and many previous supramolecular adhesives. We demonstrate that debonding upon heating above the glass transition temperature is readily possible and that broken joints can easily rebond without any loss in adhesive strength.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"40 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640361","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

High Radiation-Resistant Elastomer via Constructing Radiation-Stable Macromolecular Network

IF 5.8

ACS Macro Letters Pub Date : 2025-03-17 DOI: 10.1021/acsmacrolett.5c00006

Jiading Wang, Yang Pan, Shaoyun Guo, Xianlong Zhang

{"title":"High Radiation-Resistant Elastomer via Constructing Radiation-Stable Macromolecular Network","authors":"Jiading Wang, Yang Pan, Shaoyun Guo, Xianlong Zhang","doi":"10.1021/acsmacrolett.5c00006","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00006","url":null,"abstract":"The high-energy radiation in nuclear energy, space missions, and other radiation-related fields would accelerate the deterioration of polymers, greatly reducing their service life and reliability. Here, a new concept of radiation resistance has been proposed, which is to reduce the effect of radiation degradation on polymer properties by constructing a radiation-stable macromolecular network. Concretely, this strategy was achieved by introducing a stable coordination interaction between macromolecules, and radiation-resistant elastomers (PG-Zn) were prepared. In radiated PG-Zn, the intermolecular coordination interaction could maintain the chain network well, even though its main chain has undergone a chain-breaking reaction. Therefore, after 300 kGy irradiation, PG-Zn still maintained nearly 18 MPa strength and 650% elongation at break, and its tensile deformation hysteresis rate was almost unchanged. The PG-Zn could be further modified, and the modified elastomer retains more than 80% of its mechanical properties after 300 kGy radiation, which is the most radiation-resistant elastomer reported to date. In addition, the design has good scalability and could be used to prepare radiation-resistant sensors, showing more than three times the service life of the ordinary group under irradiation. This radiation-resistant design presented a novel and promising approach for solving the radiation-aging problem of polymers.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"69 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635399","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

Impact of Coiled-Coil Domains on the Phase Behavior of Biomolecular Condensates

IF 5.8

ACS Macro Letters Pub Date : 2025-03-17 DOI: 10.1021/acsmacrolett.4c00821

Zhouyi He, Jens-Uwe Sommer, Tyler S. Harmon

引用次数: 0

Polymer Chain Modification via HAT Chemistry and Its Application in Graft Copolymer Synthesis

IF 5.8

ACS Macro Letters Pub Date : 2025-03-15 DOI: 10.1021/acsmacrolett.5c00068

Manish Kumar, Maxime Michelas, Cyrille Boyer

{"title":"Polymer Chain Modification via HAT Chemistry and Its Application in Graft Copolymer Synthesis","authors":"Manish Kumar, Maxime Michelas, Cyrille Boyer","doi":"10.1021/acsmacrolett.5c00068","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00068","url":null,"abstract":"Hydrogen atom transfer (HAT) chemistry has emerged as a powerful tool for selective molecular functionalization, with significant applications in the pharmaceutical and agricultural industries. More recently, HAT has been explored in polymer chemistry as a versatile strategy for introducing targeted functional groups onto polymer chains, enabling precise control over properties such as solubility and mechanical strength. This study investigates the use of HAT to synthesize reversible addition–fragmentation chain transfer (RAFT) agents (or chain transfer agents, CTAs) by modifying various substrates, including toluene, ethyl acetate, and dioxane, in the presence of bis(dodecylsulfanylthiocarbonyl) disulfide or bis(3,5-dimethyl-1H-pyrazol-1-ylthiocarbonyl) disulfide. The resulting CTAs were evaluated in both thermal and photoinduced electron transfer (PET)-RAFT polymerization for controlled polymerization of various monomers. This approach was then extended to functionalize polycaprolactone (PCL) and polyvinyl acetate (PVAc), enabling the synthesis of graft copolymers with various vinyl monomers. To promote HAT, a range of photocatalysts, including iron(III) chloride (FeCl3), were investigated, offering advantages over conventional thermal HAT systems. Photocatalysis enables mild and efficient radical generation under light irradiation, providing a cost-effective and environmentally friendly alternative to expensive or toxic metal catalysts.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"216 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143627481","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

Quantized Fusion Kinetics in Block Copolymer Micelles

IF 5.8

ACS Macro Letters Pub Date : 2025-03-12 DOI: 10.1021/acsmacrolett.5c00134

Ali Sattari, Sanghee Yang, Timothy P. Lodge

{"title":"Quantized Fusion Kinetics in Block Copolymer Micelles","authors":"Ali Sattari, Sanghee Yang, Timothy P. Lodge","doi":"10.1021/acsmacrolett.5c00134","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00134","url":null,"abstract":"The fusion kinetics of block copolymer micelles in dilute solutions have been investigated. As a model system, 1,2-polybutadiene-block-poly(ethylene oxide) micelles in the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate have been studied. The ionic liquid is a selective solvent for poly(ethylene oxide), promoting the self-assembly of the block copolymer into spherical micelles. Furthermore, the quality of the solvent for the corona block is near-theta, thereby reducing the large steric barrier to fusion. Small, kinetically trapped micelles were prepared using a cosolvent, and the kinetics of fusion were subsequently monitored via dynamic light scattering at elevated temperatures. Small-angle X-ray scattering and cryo-transmission electron microscopy quantified significant increases in the mean aggregation number after thermal annealing and confirmed the formation of well-defined, larger spherical micelles. For higher annealing temperatures, the process occurs in two steps, with the relaxation time of the second step being at least an order of magnitude longer than the first. Interestingly, the steady-state micelles after the first step had approximately twice the starting aggregation number, and those after the second step had four times the original value. This result strongly suggests a quantization effect, where the rate of fusion is much slower for larger micelles, presumably due to enhanced corona crowding. The relaxation rate is also an increasing function of concentration, consistent with fusion being the dominant mechanism.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"86 1 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143599139","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

Reëntanglement Dynamics in Polymer Melts Can Be Explained by Fast Dangling End Retraction without Resorting to Nonuniversality

IF 5.8

ACS Macro Letters Pub Date : 2025-03-10 DOI: 10.1021/acsmacrolett.4c00809

Andrés Córdoba, Diego Becerra, Jay D. Schieber

{"title":"Reëntanglement Dynamics in Polymer Melts Can Be Explained by Fast Dangling End Retraction without Resorting to Nonuniversality","authors":"Andrés Córdoba, Diego Becerra, Jay D. Schieber","doi":"10.1021/acsmacrolett.4c00809","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00809","url":null,"abstract":"Recent molecular dynamics simulations of entangled polymer melts suggest that chains reëntangle on the (Rouse) time scale of chain retraction, rather than on the longest, disengagement relaxation time, upon cessation of flow [O’Connor\u0000et al. <cite>Macromolecules</cite> 2019, 52, 8540−8550]. Inspired by these results, it has been suggested by using a tube model that reëntanglement kinetics are chemistry specific [Dolata et al. <cite>ACS Macro Lett.</cite> 2024, 13, 896−902]. Here we argue that their conclusions arise from interpreting simulations with a model that does not have a sufficiently detailed level of description. We employ the discrete-slip-link model, which is more detailed and so contains important fluctuations. We show that this universal level of description can describe the results without resorting to chemistry specificity. Our results suggest that a significant amount of reëntanglement happens on the Rouse time, which obscures the fact that it finishes only on the disengagement time, resolving the apparent paradox.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"68 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143583003","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

Reëntanglement Dynamics in Polymer Melts Can Be Explained by Fast Dangling End Retraction without Resorting to Nonuniversality

IF 5.1

ACS Macro Letters Pub Date : 2025-03-10 DOI: 10.1021/acsmacrolett.4c0080910.1021/acsmacrolett.4c00809

Andrés Córdoba*, Diego Becerra* and Jay D. Schieber*,

{"title":"Reëntanglement Dynamics in Polymer Melts Can Be Explained by Fast Dangling End Retraction without Resorting to Nonuniversality","authors":"Andrés Córdoba*, Diego Becerra* and Jay D. Schieber*, ","doi":"10.1021/acsmacrolett.4c0080910.1021/acsmacrolett.4c00809","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00809https://doi.org/10.1021/acsmacrolett.4c00809","url":null,"abstract":"Recent molecular dynamics simulations of entangled polymer melts suggest that chains reëntangle on the (Rouse) time scale of chain retraction, rather than on the longest, disengagement relaxation time, upon cessation of flow [O’Connoret al. <cite>Macromolecules</cite> 2019, 52, 8540−8550]. Inspired by these results, it has been suggested by using a tube model that reëntanglement kinetics are chemistry specific [Dolata et al. <cite>ACS Macro Lett.</cite> 2024, 13, 896−902]. Here we argue that their conclusions arise from interpreting simulations with a model that does not have a sufficiently detailed level of description. We employ the discrete-slip-link model, which is more detailed and so contains important fluctuations. We show that this universal level of description can describe the results without resorting to chemistry specificity. Our results suggest that a significant amount of reëntanglement happens on the Rouse time, which obscures the fact that it finishes only on the disengagement time, resolving the apparent paradox.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"14 3","pages":"385–390 385–390"},"PeriodicalIF":5.1,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143636164","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

Recycling Polyester and Polycarbonate Plastics with Carbocation Lewis Acidic Organocatalysts

IF 5.1

ACS Macro Letters Pub Date : 2025-03-08 DOI: 10.1021/acsmacrolett.5c0005410.1021/acsmacrolett.5c00054

Nan Wang, Qiao Zhang*, Zhiqiang Sun, Han Zhang, Chenyang Hu, Hai Sun, Xuan Pang* and Xuesi Chen,

引用次数: 0

Recycling Polyester and Polycarbonate Plastics with Carbocation Lewis Acidic Organocatalysts 使用碳位路易斯酸有机催化剂回收聚酯和聚碳酸酯塑料

IF 5.8

ACS Macro Letters Pub Date : 2025-03-08 DOI: 10.1021/acsmacrolett.5c00054

Nan Wang, Qiao Zhang, Zhiqiang Sun, Han Zhang, Chenyang Hu, Hai Sun, Xuan Pang, Xuesi Chen

引用次数: 0

Polystyrene–Br End-Group Modification via Electrolysis: Adjusting Hydrogenation vs Coupling Selectivity

IF 5.8

ACS Macro Letters Pub Date : 2025-03-07 DOI: 10.1021/acsmacrolett.5c00053

Alessandro Zampieri, Felix Schnaubelt, Khidong Kim, Giovanni Lissandrini, Marco Fantin, Krzysztof Matyjaszewski, Christian Durante, Abdirisak A. Isse

{"title":"Polystyrene–Br End-Group Modification via Electrolysis: Adjusting Hydrogenation vs Coupling Selectivity","authors":"Alessandro Zampieri, Felix Schnaubelt, Khidong Kim, Giovanni Lissandrini, Marco Fantin, Krzysztof Matyjaszewski, Christian Durante, Abdirisak A. Isse","doi":"10.1021/acsmacrolett.5c00053","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00053","url":null,"abstract":"Atom transfer radical polymerization (ATRP) enables the precise synthesis of polymers with well-defined architectures, controlled molecular weights, and low dispersity. However, the halogen end-groups inherent to ATRP polymers can pose challenges due to their chemical reactivity and thermal instability. To address these issues, various strategies, including chemical and photochemical methods, have been developed for chain-end modification. This study introduces an electrochemical approach to selectively reduce halogen end-groups in ATRP polymers. Using glassy carbon (GC) and silver electrodes, the reductive cleavage of C–Br in bromine-capped polystyrene was investigated. Cyclic voltammetry revealed that polystyrene-bromide undergoes electron transfer accompanied by the concerted removal of the C–Br functionality. The Ag electrode facilitated electrocatalysis with enhanced activity. Controlled-potential electrolysis demonstrated that reaction conditions, particularly the choice of proton donors, significantly influence product distribution, enabling selective hydrogenation or dimerization of polystyrene-bromide chain ends. This work advances the understanding of electrochemical strategies for tailoring polymer end-group functionality.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"17 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143570100","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