ACS Macro Letters最新文献

Polypropylene Covalent Adaptable Networks with Full Cross-Link Density Recovery after Reprocessing: Development by Free-Radical Reactive Processing with Resonance-Stabilized, Aromatic Disulfide Cross-Linkers

IF 5.8

ACS Macro Letters Pub Date : 2025-03-05 DOI: 10.1021/acsmacrolett.5c00061

Yen-Wen Huang, Mathew J. Suazo, Stephanie M. Barbon, Hayley A. Brown, Evelyn Auyeung, Colin Li Pi Shan, John M. Torkelson

{"title":"Polypropylene Covalent Adaptable Networks with Full Cross-Link Density Recovery after Reprocessing: Development by Free-Radical Reactive Processing with Resonance-Stabilized, Aromatic Disulfide Cross-Linkers","authors":"Yen-Wen Huang, Mathew J. Suazo, Stephanie M. Barbon, Hayley A. Brown, Evelyn Auyeung, Colin Li Pi Shan, John M. Torkelson","doi":"10.1021/acsmacrolett.5c00061","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00061","url":null,"abstract":"A single-step method that produces percolated, dynamic covalent cross-links integrated into the PP homopolymer has not been previously demonstrated. Here, we synthesized covalent adaptable networks (CANs) from polypropylene (PP) homopolymers using 180 °C, radical-based, reactive processing with a free-radical initiator, dicumyl peroxide (DCP), and resonance-stabilized, aromatic disulfide cross-linkers, one methacrylate-based and another phenyl acrylate-based. Both cross-linkers yielded networks when reactively processed at 4 wt % with relatively high molecular weight (MW) PP (melt flow index (MFI) = 12) and 4 wt % DCP. The phenyl acrylate-based cross-linker also yielded PP networks at other studied DCP/cross-linker concentrations and with relatively low MW PP (MFI = 35). Notably, our highest cross-link density PP CAN exhibited full recovery of cross-link density after three reprocessing steps by compression molding; that PP CAN also exhibited full cross-link density recovery within experimental uncertainty after reprocessing by melt extrusion.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"11 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547037","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

cis-/trans-Specific Synthesis of Functionalized Bottlebrush Ring Opening Metathesis Polymerization Polymers Containing Terthiophene and Pyrene That Exhibit Unique Thermal and Emission Properties

IF 5.8

ACS Macro Letters Pub Date : 2025-03-05 DOI: 10.1021/acsmacrolett.4c00845

Kanticha Jaiyen, Sirilak Mekcham, Daisuke Shimoyama, Akihiro Ohira, Kotohiro Nomura

引用次数: 0

Topological Transition in One-Dimensional π-Conjugated Polymers via Strain Engineering

IF 5.8

ACS Macro Letters Pub Date : 2025-02-25 DOI: 10.1021/acsmacrolett.5c00047

Yifan Li, Kai Zhang, Haifeng Lv, Xiaojun Wu

{"title":"Topological Transition in One-Dimensional π-Conjugated Polymers via Strain Engineering","authors":"Yifan Li, Kai Zhang, Haifeng Lv, Xiaojun Wu","doi":"10.1021/acsmacrolett.5c00047","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00047","url":null,"abstract":"Topological trivial and nontrivial phases can be readily realized in low-dimensional organic polymers via bottom-up synthesis. However, to effectively harness these topological phases in practical devices, it is crucial to develop strategies for achieving a controllable topological transition. Inspired by topology and π-electron pairing, we propose a method to induce topological transitions through orbital crossover driven by continuous external strain in 10 one-dimensional (1D) π-conjugated polymers (CPs), categorized into aromatic and quinonoid forms. Our results reveal that quinonoid polymers exhibit edge states, indicative of nontrivial topological phases (Zak invariant, Z2 = 1), while aromatic polymers correspond to trivial topological phases (Z2 = 0). Notably, the poly(thiophene dioxide) (TDO) quinonoid polymer undergoes a reversible topological transition under a tensile strain of 3.6%, demonstrating a strain-dependent topological phase. This phenomenon is attributed to the gap closure resulting from the orbital crossover between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). This work uncovers the topological phases in 1D organic polymers and highlights the topological transitions induced by strain engineering.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"22 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486545","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

One-Step Soaking Approach for the Development of High-Strength, Tough Silicone Hydrogels with Elevated Polysiloxane Content

IF 5.8

ACS Macro Letters Pub Date : 2025-02-24 DOI: 10.1021/acsmacrolett.4c00769

Hao Zhang, Fanghao Wang, Yunqian Ma, Ruifang Guan, Teng Long, Xiao Cheng, Chuanjian Zhou

{"title":"One-Step Soaking Approach for the Development of High-Strength, Tough Silicone Hydrogels with Elevated Polysiloxane Content","authors":"Hao Zhang, Fanghao Wang, Yunqian Ma, Ruifang Guan, Teng Long, Xiao Cheng, Chuanjian Zhou","doi":"10.1021/acsmacrolett.4c00769","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00769","url":null,"abstract":"Silicone hydrogels (SiHys) present a variety of promising applications. However, their intrinsic mechanical limitations and low silicone content often restrict their practical use. In this study, we propose a simple and versatile one-step soaking strategy to produce double-network SiHys with high silicone content and enhanced mechanical strength and toughness. Hydrophobic amino-modified polydimethylsiloxane (APDMS) becomes hydrophilic through a “salt-forming” reaction with acetic acid (HAc), enabling substantial incorporation within a poly(vinyl alcohol) (PVA) network. This is followed by a one-step soaking in a polyhydric-acid salt aqueous solution, facilitating the in situ formation of a physically cross-linked APDMS network via acid exchange. By controlling the feed concentration of APDMS and the types of polyhydric-acid salts employed, we can fine-tune the hydrogel’s aggregated structural characteristics and the strength of intermolecular electrostatic interactions, thereby enabling a wide range of tunability in the mechanical properties of the SiHys. This study innovatively establishes a simple and universal technique for preparing silicon-based hydrogels with high mechanical performance and silicone content, advancing the development of silicon-based hydrogels.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"22 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486546","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

Tuning Room-Temperature Injectability of Gelatin-Based Hydrogels via Introduction of Competitive Hydrogen Bonds

IF 5.8

ACS Macro Letters Pub Date : 2025-02-24 DOI: 10.1021/acsmacrolett.5c00018

Donglin Xie, Jiang Bian, Chao Ni, Pei Zhao, Zuo Pu, Jun Yue

引用次数: 0

Synthesis of Star Polymers with Ultrahigh Molecular Weights and Tunable Dispersities via Photoiniferter Polymerization

IF 5.8

ACS Macro Letters Pub Date : 2025-02-21 DOI: 10.1021/acsmacrolett.5c00023

Meng Zhang, Steven P. Armes, Zesheng An

{"title":"Synthesis of Star Polymers with Ultrahigh Molecular Weights and Tunable Dispersities via Photoiniferter Polymerization","authors":"Meng Zhang, Steven P. Armes, Zesheng An","doi":"10.1021/acsmacrolett.5c00023","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00023","url":null,"abstract":"Simultaneous control over macromolecular chain topology, molecular weight, and dispersity is an important synthetic goal in polymer chemistry. The synthesis of well-defined poly(methyl acrylate) star polymers with ultrahigh molecular weights (>106 g mol–1) and tunable dispersities is realized for the first time via blue light-controlled photoiniferter polymerization using a tetrafunctional switchable RAFT agent (SRA4). The spectroscopic properties and polymerization activity of SRA4 can be reversibly tuned by addition of acid/base. For example, protonation of SRA4 with 4-toluenesulfonic acid (TsOH) leads to enhanced UV–visible light absorption, a faster polymerization rate, and a lower dispersity for the resulting star polymer. Star polymers were prepared with predicted molecular weights (Mn ≈ 80–1550 kg mol–1) and tunable dispersities (Đ ≈ 1.8–1.2) when targeting degrees of polymerization in the range of 1000–20000 in the presence of varying amounts of TsOH. High end-group fidelity for such star polymers was confirmed by one-pot chain extension experiments, which afforded a series of pseudoblock copolymers with controlled dispersities. Finally, rotational rheology was used to examine the effect of molecular weight, dispersity, and chain topology (whether linear or star-shaped) on solution viscosity.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"65 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462307","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

Strong Bioadhesives from Helical Polypeptides

IF 5.8

ACS Macro Letters Pub Date : 2025-02-21 DOI: 10.1021/acsmacrolett.5c00021

Jiangyan Shi, Liufen Kong, Ning Wang, Zhimin Li, Chuanzhuang Zhao, Chongyi Chen

{"title":"Strong Bioadhesives from Helical Polypeptides","authors":"Jiangyan Shi, Liufen Kong, Ning Wang, Zhimin Li, Chuanzhuang Zhao, Chongyi Chen","doi":"10.1021/acsmacrolett.5c00021","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00021","url":null,"abstract":"Bioadhesives have emerged as versatile and powerful tools for tissue repair and integration with biomedical devices, offering a wide range of applications that have captured significant clinical and scientific interest. Synthetic polypeptide adhesives are particularly promising candidates for bioadhesives, but often face limitations in adhesive strength. In this study, inspired by marine adhesive proteins, the secondary structure and hydrophobic–hydrophilic balance of polypeptides were precisely regulated to transform the polyelectrolyte to a strong adhesive. The resulting polypeptide adhesive demonstrated an adhesive strength exceeding 1.0 MPa, more than 10× higher than that of the previously reported synthetic polypeptide adhesive. The cohesion and adhesion of polypeptide adhesive can be optimized by adjusting the content of the secondary structure and hydrophobic residue ratios. More helices in polypeptides enhance the interactions between the polypeptide backbone and side chains as well as the interactions between polypeptides and substrates. In addition, these polypeptide adhesives exhibit excellent tolerance to strong acids or alkalis, remarkable adhesion to variable materials and tissues, and an impressive sealing performance.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"16 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462297","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

Strengthening the Self-Assembly of Supramolecular Polymeric Nanotubes in Water via the Introduction of Hydrophobic Moieties

IF 5.8

ACS Macro Letters Pub Date : 2025-02-20 DOI: 10.1021/acsmacrolett.4c00759

Zihe Cheng, Stephen C. L. Hall, Qiao Song, Sébastien Perrier

引用次数: 0

Enzymatically Covalent and Noncovalent Weaving toward Highly Efficient Synthesis of 2D Monolayered Molecular Fabrics.

IF 5.1

ACS Macro Letters Pub Date : 2025-02-18 Epub Date: 2025-02-03 DOI: 10.1021/acsmacrolett.5c00017

Zhenzhu Wang, Yunpeng Ge, Wencan Li, Chenyang Zhang, Zeyuan Dong

{"title":"Enzymatically Covalent and Noncovalent Weaving toward Highly Efficient Synthesis of 2D Monolayered Molecular Fabrics.","authors":"Zhenzhu Wang, Yunpeng Ge, Wencan Li, Chenyang Zhang, Zeyuan Dong","doi":"10.1021/acsmacrolett.5c00017","DOIUrl":"10.1021/acsmacrolett.5c00017","url":null,"abstract":"Molecular fabrics with fascinating physical characteristics, such as structural flexibility and single-layered thinness, have attracted much attention. Chemists worldwide have been working on building unique molecularly woven structures in two dimensions. However, the synthesis of two-dimensional molecular weaving remains a challenging task, especially in water. Herein, we propose a straightforward and practical method to construct 2D molecular fabrics by enzymatically covalent and noncovalent syntheses in water. In particular, aromatic helical pentamers with two-terminal tyrosine residues (Penta-Tyr) can spontaneously dimerize via π-π interactions into double-helical interlocking structure, and the two-terminal tyrosine moieties of Penta-Tyr can undergo oxidative polymerization catalyzed by horseradish peroxidase (HRP) and hydrogen peroxide (H2O2) for effective covalent cross-linking. The 2D monolayered molecular fabrics can be readily prepared by the catalysis of HRP and H2O2 under mild conditions, which exhibit concentration-dependent weaving behavior. This work not only demonstrates an enzyme-catalyzed approach for the highly efficient synthesis of 2D monolayered molecular fabrics for the first time but also will promote the controllable preparation and application of water-soluble 2D molecular fabrics.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":" ","pages":"201-206"},"PeriodicalIF":5.1,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143077862","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

Kinetically Controlled Approach for One-Pot Synthesis of Poly(peptide-b-peptoid) Exhibiting Well-Defined Secondary Structure and Thermal Stability. 单锅合成具有明确二级结构和热稳定性的聚（肽-b-肽）的动力学控制方法

IF 5.1

ACS Macro Letters Pub Date : 2025-02-18 Epub Date: 2025-01-31 DOI: 10.1021/acsmacrolett.4c00823

Prabir Maity, Arjun Singh Bisht, Deepak, Raj Kumar Roy

{"title":"Kinetically Controlled Approach for One-Pot Synthesis of Poly(peptide-b-peptoid) Exhibiting Well-Defined Secondary Structure and Thermal Stability.","authors":"Prabir Maity, Arjun Singh Bisht, Deepak, Raj Kumar Roy","doi":"10.1021/acsmacrolett.4c00823","DOIUrl":"10.1021/acsmacrolett.4c00823","url":null,"abstract":"Sequence-controlled polymerization aims to bridge the gap between biopolymers and synthetic macromolecules. In a kinetically controlled approach, the inherent reactivity differences among monomers determine the primary structure or sequence of the monomers linked within the resulting copolymer chains. This report outlines a one-pot synthesis of polypeptide-b-polypeptoid by choosing a suitable pair of N-carboxy anhydride (NCA) monomers with significant reactivity differences. We have demonstrated the preparation of well-defined block copolymers, including polyproline-b-polysarcosine (PLP-b-PSar) and poly(propargyl proline)-b-polysarcosine (PLPP-b-PSar) in a single step. 1H NMR kinetic studies confirmed the sequence-controlled primary structures of these block copolymers. The NMR analysis indicated a striking reactivity ratio difference (rPLP = 925 and rPSar = 0.0014; rPLPP = 860 and rPSar = 0.0015) between the selected monomer pairs, which was crucial for a one-pot block copolymer synthesis. Notably, these sequence-controlled copolymers' secondary structures and stability were remarkably similar to those of block copolymers synthesized through conventional sequential addition methods. This further underscores the practicality of this kinetically controlled approach.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":" ","pages":"188-194"},"PeriodicalIF":5.1,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143070722","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