ACS Macro Letters最新文献

Biobased Cyclic Polycarbonate: Synthesis and Applications via Dynamic Bis(hindered amino)disulfide Linkers 生物基环状聚碳酸酯：动态双（受阻氨基）二硫连接体的合成与应用

IF 5.8

ACS Macro Letters Pub Date : 2025-05-17 DOI: 10.1021/acsmacrolett.5c00233

Hirogi Yokochi, Takumi Abe, Shunsuke Fujimata, Daisuke Aoki, Hideyuki Otsuka

{"title":"Biobased Cyclic Polycarbonate: Synthesis and Applications via Dynamic Bis(hindered amino)disulfide Linkers","authors":"Hirogi Yokochi, Takumi Abe, Shunsuke Fujimata, Daisuke Aoki, Hideyuki Otsuka","doi":"10.1021/acsmacrolett.5c00233","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00233","url":null,"abstract":"Cyclic polymers have garnered significant interest due to their unique structure; however, their synthesis remains challenging, often hindered by low yields and limited selectivity. Considering that the cyclization step during the synthesis of cyclic polymers is presumably the most challenging, using a spontaneous and selective cyclization system is ideal. Here, we present a topology transformation from linear to cyclic, which is achieved through the error-checking ability provided by the dynamic covalent bonding between bis(2,2,6,6-tetramethylpiperidin-1-yl)disulfide (BiTEMPS) and its stable radicals with a high bond exchange rate. When applying this method to biobased poly(isosorbide carbonate) (PIC), an attractive alternative to conventional petroleum-based polycarbonates, high-molecular-weight cyclic polymers were unexpectedly obtained. Since the functionalization of PICs has been traditionally limited to copolymerization techniques, we aimed to introduce dynamic covalent bonds to establish novel functionalization methods for PICs. Interestingly, the synthesis of cyclic PICs through intramolecular cyclization using dynamic covalent bonds in a heterogeneous system proceeded via a ring-expansion polymerization-like mechanism, affording high-molecular-weight cyclic polymers consisting of a PIC backbone and BiTEMPS units as dynamic units. The resulting PIC-based cyclic polymers with BiTEMPS units were applied to bond exchange reactions, providing an effective approach for the synthesis of cyclic block polymers and end-functionalized linear block polymers with a PIC skeleton. These results demonstrate the potential of dynamic covalent chemistry in polymer synthesis.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"54 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-05-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066933","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

Mass-Produced Chemically Recyclable Aromatic Polymers with Exceptional Strength and Stability 大规模生产化学可回收芳香族聚合物具有卓越的强度和稳定性

IF 5.8

ACS Macro Letters Pub Date : 2025-05-15 DOI: 10.1021/acsmacrolett.5c00239

Peng Xie, Xingyuan Lu, Xiang Li, Xiaojuan Wen, Junqi Sun

{"title":"Mass-Produced Chemically Recyclable Aromatic Polymers with Exceptional Strength and Stability","authors":"Peng Xie, Xingyuan Lu, Xiang Li, Xiaojuan Wen, Junqi Sun","doi":"10.1021/acsmacrolett.5c00239","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00239","url":null,"abstract":"Developing chemically recyclable polymers that offer ultrahigh mechanical strength, exceptional chemical stability, mild recycling conditions, and scalability for mass production remains a significant challenge. This study presents a novel class of chemically recyclable plastics, synthesized at kilogram scale in the laboratory, by reversibly cross-linking aromatic polyamide macromonomers with boroxines, imine bonds, and hydrogen bonds. These plastics, denoted as PA-B3O3, exhibit an impressive tensile strength of 142.1 MPa, a Young’s modulus of 2.39 GPa, a glass transition temperature of ∼211.6 °C, and outstanding chemical resistance to acidic/basic aqueous solutions and organic solvents. PA-B3O3 plastics can be depolymerized in a mixed solvent of N,N-dimethylacetamide and aqueous HCl solution, allowing for efficient recovery of the original amino-terminated polyamide (PA-NH2) via precipitation in selective solvents, even when mixed with polymer waste streams. This study represents a significant advancement toward the practical application of mechanically robust, chemically resistant, and recyclable polymers.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"53 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143979977","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

Poly(siloxane)-Derived Ionosilicone Elastomers Reveal the Role of Interfacial Polymer Dynamics in Ionic Double-Layer Rectification 聚硅氧烷衍生的离子硅弹性体揭示了界面聚合物动力学在离子双层整流中的作用

IF 5.8

ACS Macro Letters Pub Date : 2025-05-15 DOI: 10.1021/acsmacrolett.5c00207

Owen A. Lee, Matthew K. McBride, Yitian Li, Ryan C. Hayward

{"title":"Poly(siloxane)-Derived Ionosilicone Elastomers Reveal the Role of Interfacial Polymer Dynamics in Ionic Double-Layer Rectification","authors":"Owen A. Lee, Matthew K. McBride, Yitian Li, Ryan C. Hayward","doi":"10.1021/acsmacrolett.5c00207","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00207","url":null,"abstract":"Poly(siloxane ionic liquid)s (PSILs) have highly flexible siloxane backbones, affording them low glass transition temperatures and therefore high solvent-free ionic conductivity at ambient temperature, offering promise for ion-mediated electronic devices. Here, cross-linked, highly conductive (>4 × 10–3 mS/cm) cationic and anionic PSILs (termed ionosilicones) were prepared. The backbone of these ionosilicone networks could be tuned by copolymerization with acrylate monomers to create ionosilicone–acrylate hybrid networks with intermediate properties. When two oppositely charged networks are brought into contact, an ionic double layer (IDL) consisting of fixed cations and anions is formed, and the heterojunction exhibits diode-like nonlinear conductance and ionic current rectification. Interestingly, we observe a trade-off between IDL polarization speed and rectification performance with increased ionosilicone content. We show that the more rapid interfacial polymer dynamics induced by increasing temperature switches the diode “on” in a similar manner as applying a forward DC bias voltage. To explain this multimodal switching behavior, we posit the formation of an interfacial complex with distinctly slower dynamics than the bulk, low-Tg ionoelastomers, limiting ion motion at low temperatures and under reverse bias. These findings provide insight into the key role of backbone flexibility of IDL-based device performance and shine new light on interfacial polymer dynamics as an important design criterion in bipolar ionotronic devices.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"40 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143980047","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

Cholesteric Contact Lenses for Diabetics-Related Noninvasive Glucose Monitoring and Eye Healthcare. 抗胆固醇隐形眼镜用于糖尿病相关的无创血糖监测和眼部保健。

IF 5.8

ACS Macro Letters Pub Date : 2025-05-15 DOI: 10.1021/acsmacrolett.5c00200

Xinxin Yan,Yungeng Qi,Weiqing Liu,Shihao Wang,Afroza Akter Liza,Xuemei Ge,Junlong Song,Long Bai,Haiming Li,Orlando J Rojas,Jiaqi Guo

{"title":"Cholesteric Contact Lenses for Diabetics-Related Noninvasive Glucose Monitoring and Eye Healthcare.","authors":"Xinxin Yan,Yungeng Qi,Weiqing Liu,Shihao Wang,Afroza Akter Liza,Xuemei Ge,Junlong Song,Long Bai,Haiming Li,Orlando J Rojas,Jiaqi Guo","doi":"10.1021/acsmacrolett.5c00200","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00200","url":null,"abstract":"Blood sugar monitoring has crucial significance for diabetes mellitus diagnosis, and noninvasive continuous detection methods are the future development trend. Among various noninvasive detection methods, glucose detection in tears has the advantages of a high level of subject compliance, minimal pollution, and accuracy. However, sensors used for detecting glucose concentration in tears usually embed noble microelectrical components into contact lenses, making the process complicated and costly, and easily cause environmental pollution and resource wastage. Here, we propose a construction strategy for contact lenses based on the cellulose nanocrystal (CNC) cholesteric structure, preparing products that change color according to the concentration of glucose. In addition, the surface of the contact lenses can be loaded with drugs for adjuvant treatment of diabetic eye complications. Contact lenses offer advantages such as a fast response speed (<240 s), high sensitivity with distinct colors at specific glucose concentrations (green at 0 mM, yellow at 5 mM, and red at 10 mM), and a reversible response process. Furthermore, they exhibit good biocompatibility (90% cell viability by CCK-8 assay) and biodegradability (complete biodegradation in soil within 120 days). CNC cholesteric contact lenses realize noninvasive, wearable continuous glucose detection, providing a new strategy for health monitoring of diabetics.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"3 1","pages":"743-749"},"PeriodicalIF":5.8,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144065662","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

Bioinspired Tough and Antiswelling Hydrogel via in Situ Self-Assembly of Amphiphilic Copolymers within a Hydrophilic Network 通过亲水性网络中两亲共聚物的原位自组装的仿生坚韧和消肿水凝胶

IF 5.8

ACS Macro Letters Pub Date : 2025-05-14 DOI: 10.1021/acsmacrolett.5c00188

Changzhi Xu, Mengyu Li, Yi Wang, Yujiao Jiang, Jiahui Yin, Wenjie Ma, Xuelan Hu, Wanqing Zeng, Yanfei Ma, Shuwang Wu, Mingyuan Gao

{"title":"Bioinspired Tough and Antiswelling Hydrogel via in Situ Self-Assembly of Amphiphilic Copolymers within a Hydrophilic Network","authors":"Changzhi Xu, Mengyu Li, Yi Wang, Yujiao Jiang, Jiahui Yin, Wenjie Ma, Xuelan Hu, Wanqing Zeng, Yanfei Ma, Shuwang Wu, Mingyuan Gao","doi":"10.1021/acsmacrolett.5c00188","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00188","url":null,"abstract":"Inspired by tropoelastin coacervation, a process in elastic fiber formation driven by hydrophobic interactions, we developed a tough, antiswelling hydrogel, PHEA-(PVA-co-PE), by incorporating amphiphilic poly(vinyl alcohol-co-ethylene) (PVA-co-PE) into a hydrophilic poly(2-hydroxyethyl acrylate) (PHEA) network. The PHEA-(PVA-co-PE) hydrogel was prepared by UV-induced polymerization of a PHEA precursor dimethyl sulfoxide (DMSO) solution containing PVA-co-PE, followed by immersion in water. During solvent exchange, PVA-co-PE self-assembled into micellar structures within the PHEA matrix, mimicking the coacervation of tropoelastin. Compared with PHEA and PVA-co-PE hydrogels, the strength of PHEA-(PVA-co-PE) increased by 83 and 7 times, while the toughness increased by 145 and 97 times. This strategy can be further extended to a variety of amphiphilic copolymers, demonstrating the universality. In vitro and in vivo tests demonstrated that the hydrogel possesses excellent biocompatibility and antiswelling capability. This study provides a simple method for developing a tough, biocompatible, and antiswelling hydrogel.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"29 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143980049","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

Revealing Mechanochemical Force Distributions with Polymechanophore Block Copolymers 揭示多机械基团嵌段共聚物的机械化学力分布

IF 5.8

ACS Macro Letters Pub Date : 2025-05-14 DOI: 10.1021/acsmacrolett.5c00197

Vittal Bhat, Yan Xia

{"title":"Revealing Mechanochemical Force Distributions with Polymechanophore Block Copolymers","authors":"Vittal Bhat, Yan Xia","doi":"10.1021/acsmacrolett.5c00197","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00197","url":null,"abstract":"Polymer mechanochemistry is most studied under ultrasonication conditions, where the force distribution along a polymer chain is typically modeled as a parabola centered at the chain midpoint. How far the forces required for mechanoactivation extend toward the chain ends remains a question of interest. Investigating the mechanochemical reactivity of mechanophores at defined locations off chain center and toward termini would provide valuable information regarding this, but preparing such polymers to study the effects of mechanophore location and chain length on mechanoactivation has been synthetically cumbersome. Using an operationally simple procedure, we synthesized a series of block copolymers containing a block of mechanophores by living ring opening metathesis polymerization of a ladderene-type mechanophore and a norbornene, with good control over block positions and lengths. We found that for polymers of initial degrees of polymerization (DP) ≈ 1000, terminal mechanophore blocks activated less than more centrally located ones. However, simply by extending the length of the mechanochemically inert block, terminal mechanophore blocks of DP ≈ 200 achieved surprisingly high degrees of mechanoactivation comparable to those of centrally located ones or mechanophore homopolymers, after an induction period. These findings revealed the broad range of high force coverage along a polymer chain under sonication conditions and the possibility to still achieve high degrees of productive mechanochemistry far away from chain centers.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"5 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143980051","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

Laves Phases Emerge in Neat AB-Type Block Copolymer as Hybrid Spherical Phases 在纯ab型嵌段共聚物中，叶状相以杂化球形相的形式出现

IF 5.8

ACS Macro Letters Pub Date : 2025-05-14 DOI: 10.1021/acsmacrolett.5c00084

Bin Zhao, Chao Wang, Weihua Li, Yicheng Qiang

{"title":"Laves Phases Emerge in Neat AB-Type Block Copolymer as Hybrid Spherical Phases","authors":"Bin Zhao, Chao Wang, Weihua Li, Yicheng Qiang","doi":"10.1021/acsmacrolett.5c00084","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00084","url":null,"abstract":"Soft spherical domains assembled from block copolymers can pack into Frank–Kasper phases, reminiscent of those found in alloys. As a special subcategory of Frank–Kasper phases, Laves phases are particularly challenging to obtain. So far, the most stable Laves phases have been realized in copolymer blends, where mixing different polymers accommodates the size discrepancy between the two types of spheres. Here, we propose an intramolecular blending strategy to stabilize Laves phases in neat AB-type block copolymer melts. By designing multiblock copolymers with two separate A blocks in different topological environments, we predict stable Laves phases within a substantial parameter window using self-consistent field theory, together with several hybrid phases. We find that Laves phases can be regarded as a hybrid structure to some extent, so they resemble the stabilization mechanism as the usual hybrid structures; that is, the two A-blocks can adapt to two different interface curvatures. Our intramolecular blending strategy provides an effective way for stabilizing novel ordered structures, especially those hybrid structures with bimodal interfacial curvatures, by rationally designing the architecture of block copolymer.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"78 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143980048","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 Solution Aggregates and Thin Film Polymorphs in Conjugated Polymers via External Electric Field for Field-Effect Transistors 场效应晶体管外电场调谐共轭聚合物中的溶液聚集体和薄膜多晶

IF 5.8

ACS Macro Letters Pub Date : 2025-05-13 DOI: 10.1021/acsmacrolett.5c00163

Yanan Guo, Hao Zheng, Yan Guan, Xuebing Luo, Juan Peng

{"title":"Tuning Solution Aggregates and Thin Film Polymorphs in Conjugated Polymers via External Electric Field for Field-Effect Transistors","authors":"Yanan Guo, Hao Zheng, Yan Guan, Xuebing Luo, Juan Peng","doi":"10.1021/acsmacrolett.5c00163","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00163","url":null,"abstract":"Tailoring polymorphic crystals of π-conjugated semiconducting polymers is crucial for elucidating the structure-optoelectronic property relationship. However, facile and generic strategies for tuning their polymorphs remain a grand challenge. Herein, we report, an effective external electric field (EEF) strategy to adjust polymorphs of poly(3-butylthiophene) (P3BT) in thin film and correlate different polymorphs strongly to their chain conformation and aggregates in solution. Specifically, P3BT without EEF displays a twisted chain conformation and aggregates weakly in solution, yielding sole polymorph II. Interestingly, the EEF induces P3BT chains to a planarized conformation and strengthens the solution aggregates, rendering an efficient polymorph II-to-I transition. The carrier transport properties correlate strongly with their various polymorphs. Such an EEF-induced polymorph transformation is easily exercised to other conjugated polymers. This work demonstrates the robustness of EEF to tailor polymorphs of conjugated polymers and their charge transport properties, contributing to a deep understanding of their crystalline behaviors for diverse optoelectronic applications.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"112 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940028","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

Rapid Interchain Charge Transfer via Intra-macromolecular Hydrogen Bond Interactions Promotes Photocatalytic Hydrogen Production 通过大分子内氢键相互作用的快速链间电荷转移促进光催化制氢

IF 5.8

ACS Macro Letters Pub Date : 2025-05-13 DOI: 10.1021/acsmacrolett.5c00120

Jiani Peng, Aodi Wang, Xin Li, Lei Wang

{"title":"Rapid Interchain Charge Transfer via Intra-macromolecular Hydrogen Bond Interactions Promotes Photocatalytic Hydrogen Production","authors":"Jiani Peng, Aodi Wang, Xin Li, Lei Wang","doi":"10.1021/acsmacrolett.5c00120","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00120","url":null,"abstract":"Efficient electron transfer between photosensitizers (PS) and catalysts is essential for improving the photocatalytic performance of multicomponent systems. In conventional homogeneous catalytic systems, electron transfer typically occurs through random collisions, which are inherently inefficient. While various strategies have been proposed to enhance this process, many are limited by their dependence on high concentrations. Here, we reported a new strategy that significantly enhanced visible-light-driven hydrogen evolution reactions (HER) under low-concentration conditions for non-noble-metal-complex-based homogeneous systems. By employing RAFT polymerization, we immobilized copper PS (Cu-PS) and cobalt catalyst (Co-Cat) units on a carbamate-linkage-containing polymer chain. The introduction of carbamate linkages in the pendant chains closes the distance between the center of Cu-PS and Co-Cat by additional H-bond interactions, enabling high photocatalytic activity at low concentrations. Comparative analysis showed that the carbamate-linkage-containing polymeric complexes demonstrate a 20-fold hydrogen production over their non-H-bond polymeric complex, while no hydrogen was produced when using their small molecular counterparts in 24 h. This work underscores the superiority of the H-bond-containing polymeric complexes in photocatalytic activities. Given the versatility of RAFT polymerization and the ease of ligand modification, this method offers broad applicability across multicomponent photocatalytic systems.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"74 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940027","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

Viscosity-Controlled Thiol-Ene Reaction and Its Impact on Mechanical Response of Dynamic Networks. 粘度控制的硫醇-烯反应及其对动态网络力学响应的影响。

IF 5.8

ACS Macro Letters Pub Date : 2025-05-12 DOI: 10.1021/acsmacrolett.5c00097

Chen Chen,Yijue Xu,Yingying Chen,Christopher M Evans,Paul V Braun

{"title":"Viscosity-Controlled Thiol-Ene Reaction and Its Impact on Mechanical Response of Dynamic Networks.","authors":"Chen Chen,Yijue Xu,Yingying Chen,Christopher M Evans,Paul V Braun","doi":"10.1021/acsmacrolett.5c00097","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00097","url":null,"abstract":"The impact of curing conditions on the final properties of thioester-thiol-based dynamic polymer networks was systematically investigated. Despite identical monomer and cross-linker compositions, networks synthesized in the absence of solvent exhibited significantly higher shear moduli and longer relaxation times compared to those cured in solvent. These differences arise from viscosity-controlled photoinitiated thiol-ene reactions, where reduced chain mobility under solvent-free conditions suppresses termination between two polymer radicals, leading to higher reaction conversion. Fourier Transform Infrared (FTIR) spectroscopy and solid-state NMR (ssNMR) spectroscopy confirmed a greater degree of \"click\" reaction completion in higher viscosity environments. Control experiments revealed that prolonged radical lifetimes and suppressed termination reactions under solvent-free curing conditions contribute to these variations. This study highlights the crucial role of processing conditions in determining cross-link density and, consequently, the dynamic mechanical behavior of polymer networks. It demonstrates that, beyond polymer chemistry, dynamic cross-linker design, and phase separation, curing conditions serve as a key design parameter for tailoring material performance to specific applications.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"8 1","pages":"687-694"},"PeriodicalIF":5.8,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143932886","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