ACS Macro Letters最新文献

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Highly Branched Poly[dimethylaminoethyl methacrylate-co-bis(2-acryloyloxy) ethyl disulfide] for Efficient Intracellular Protein Delivery 高效细胞内蛋白质递送的高支化聚[二甲氨基乙基甲基丙烯酸酯-co-双(2-丙烯氧基)乙基二硫]。
IF 5.2
ACS Macro Letters Pub Date : 2025-07-07 DOI: 10.1021/acsmacrolett.5c00220
Xiaojia Wang, Wei Sun, Rui Guo, Zhili Li, Chenfei Wang, Zhedong Ma, Siyi Cai* and Dezhong Zhou*, 
{"title":"Highly Branched Poly[dimethylaminoethyl methacrylate-co-bis(2-acryloyloxy) ethyl disulfide] for Efficient Intracellular Protein Delivery","authors":"Xiaojia Wang,&nbsp;Wei Sun,&nbsp;Rui Guo,&nbsp;Zhili Li,&nbsp;Chenfei Wang,&nbsp;Zhedong Ma,&nbsp;Siyi Cai* and Dezhong Zhou*,&nbsp;","doi":"10.1021/acsmacrolett.5c00220","DOIUrl":"10.1021/acsmacrolett.5c00220","url":null,"abstract":"<p >Intracellular protein delivery holds great potential for the prevention and treatment of various diseases but remains challenging. Cationic polymers are promising candidates for protein delivery because of their highly tailorable chemical composition, topological structure, and terminal functionalities and thus are capable of navigating multiple extracellular and intracellular barriers. Here phenylboric acid (PBA)-functionalized, biodegradable, highly branched poly[dimethylaminoethyl methacrylate-<i>co</i>-bis(2-acryloyloxy) ethyl disulfide] [P(DM-<i>co</i>-DS)-E] were developed for efficient cytoplasmic protein delivery. The electrostatic interactions, nitrogen–boronate (N–B) coordination, and cation−π interactions between the DMAEMA units, PBA moieties, and protein facilitate protein packaging, leading to formation of nanosized, nearly neutral nanoparticles, while the disulfide bonds in the branching junctions impart biodegradability to promote protein release in the cytoplasm. In human chondrosarcoma (SW1353) cells, the optimal P(DM<sub>10</sub>-<i>co</i>-DS<sub>1</sub>)-E1 achieved up to 20-fold higher delivery efficiency compared to commercial PULSin, while maintaining high cell viability.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"14 7","pages":"1026–1031"},"PeriodicalIF":5.2,"publicationDate":"2025-07-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144568548","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 Cross-Link Density on Polybutadiene Permanent and Vitrimer Networks 交联密度对聚丁二烯永久网络和玻璃体网络的影响。
IF 5.2
ACS Macro Letters Pub Date : 2025-07-04 DOI: 10.1021/acsmacrolett.5c00267
Dana Ezzeddine, Daniel C. Barzycki and Ralm G. Ricarte*, 
{"title":"Impact of Cross-Link Density on Polybutadiene Permanent and Vitrimer Networks","authors":"Dana Ezzeddine,&nbsp;Daniel C. Barzycki and Ralm G. Ricarte*,&nbsp;","doi":"10.1021/acsmacrolett.5c00267","DOIUrl":"10.1021/acsmacrolett.5c00267","url":null,"abstract":"<p >Vitrimers are polymer networks that undergo structural rearrangement through dynamic associative bond exchange without compromising the overall topological connectivity. In this study, we investigate the impact of cross-link density on the structural, viscoelastic, and glass transition properties of both vitrimer and permanent networks. We synthesized polybutadiene (PB) networks using a photoinitiated thiol–ene click reaction to incorporate either dynamic dioxaborolane or permanent 1,4-benzenedimethanethiol cross-links, with the number of cross-links per chain ranging from 2 to 15. To quantify the actual cross-link density, we developed a network disassembly procedure in which an excess of 1,2-octanediol de-cross-links the PB vitrimer, after which the resulting fragments are analyzed using <sup>1</sup>H nuclear magnetic resonance spectroscopy. Although both networks exhibit identical gel fractions, small-amplitude oscillatory shear measurements combined with phantom network theory analysis reveal that vitrimers have a higher effective cross-link density than do their permanent counterparts. Vapor swelling experiments further indicated that PB vitrimers have fewer defects than permanently cross-linked networks. Differential scanning calorimetry demonstrated that vitrimers and permanent networks exhibit distinct relationships between the glass transition temperature and cross-link density. Overall, our findings underscore the significant influence of dynamic associative cross-links on the behavior and performance of elastomeric materials.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"14 7","pages":"1011–1018"},"PeriodicalIF":5.2,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144564148","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
Nitroarene Photoactivation Promotes Oxidative Deconstruction of Olefinic Polymers 硝基芳烃光活化促进烯烃聚合物的氧化解构。
IF 5.2
ACS Macro Letters Pub Date : 2025-07-01 DOI: 10.1021/acsmacrolett.5c00329
Thi H. Le, Kamal Bhatt, Sylwia Dworakowska, Kevin A. Stewart, Parker T. Boeck, Adam S. Veige, Daniel Seidel* and Brent S. Sumerlin*, 
{"title":"Nitroarene Photoactivation Promotes Oxidative Deconstruction of Olefinic Polymers","authors":"Thi H. Le,&nbsp;Kamal Bhatt,&nbsp;Sylwia Dworakowska,&nbsp;Kevin A. Stewart,&nbsp;Parker T. Boeck,&nbsp;Adam S. Veige,&nbsp;Daniel Seidel* and Brent S. Sumerlin*,&nbsp;","doi":"10.1021/acsmacrolett.5c00329","DOIUrl":"10.1021/acsmacrolett.5c00329","url":null,"abstract":"<p >Photoactivation of nitroarenes has been recently reported to induce the transformation of alkenyl bonds into carbonyl functionalities. Capitalizing on this unique photochemical mechanism, this study explores the use of nitroarenes to achieve oxidative cleavage of olefinic polymers under visible light irradiation. The degradation of various olefinic polymers, including commercially available polybutadiene, polynorbornene, both linear and cyclic poly(phenylacetylene), as well as backbone-modified polyacrylates with alkenyl functionality was investigated. To elucidate the efficacy of this methodology, a series of nitroarene derivatives bearing variable substituents were screened for their degradative efficiency on polybutadiene. Varying nitroarene stoichiometry, reaction temperature, and pos-treaction workup conditions were investigated to optimize degradation conditions. The results demonstrated that photoexcited nitroarenes enable efficient oxidative degradation of olefinic polymers in a safe and sustainable manner, providing a novel strategy for mild macromolecular deconstruction.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"14 7","pages":"1004–1010"},"PeriodicalIF":5.2,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533432","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
Cosolvent Control of Lower and Upper Critical Solution Behavior in Polyelectrolyte Complexes 多电解质配合物中上下临界溶液行为的共溶剂控制。
IF 5.2
ACS Macro Letters Pub Date : 2025-07-01 DOI: 10.1021/acsmacrolett.5c00315
Yuanchi Ma*,  and , Vivek M. Prabhu*, 
{"title":"Cosolvent Control of Lower and Upper Critical Solution Behavior in Polyelectrolyte Complexes","authors":"Yuanchi Ma*,&nbsp; and ,&nbsp;Vivek M. Prabhu*,&nbsp;","doi":"10.1021/acsmacrolett.5c00315","DOIUrl":"10.1021/acsmacrolett.5c00315","url":null,"abstract":"<p >We report that polar cosolvent–water mixtures offer a unique approach to controlling the liquid–liquid phase separation (LLPS) of polyelectrolyte complex solutions formed from degree of polymerization-matched mixtures of strong and weak polyelectrolytes─respectively, quaternary poly(<i>N,N</i>-dimethylaminoethyl methacrylate chloride) (qPDMAEMA) and sodium poly(acrylate) (PA). As observed in prior work, associative LLPS in water exhibits an upper-critical salt concentration with stoichiometric complexes and lower-critical solution temperature (LCST) behavior, where electrostatic correlations are believed to drive phase behavior. However, upon addition of a miscible cosolvent prior to mixing the individual polyelectrolytes at room temperature, we observe a shift in the LCST and the appearance of an upper-critical solution temperature (UCST). This new UCST feature corresponds to a segregative LLPS, whereby the polycation partitions out of the polyanion-rich dense phase and into the supernatant. This behavior arises with cosolvents that decrease (e.g., ethylene glycol) or increase (e.g., <i>N</i>-methyl formamide) the average solvent dielectric constant, suggesting that electrostatic correlations may not primarily control the phase behavior for cosolvated coacervate systems. A conceptual 3D phase surface summarizing these observations for the cosolvated system suggests that two distinct surfaces with critical lines appear on the polymer–salt–temperature phase diagram.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"14 7","pages":"962–968"},"PeriodicalIF":5.2,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsmacrolett.5c00315","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533368","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Combining Metal-Free and Metal-Mediated Ring-Opening Metathesis Polymerization for Efficient Synthesis of Bottlebrush Polymers 无金属与金属介导开环复聚相结合高效合成瓶刷聚合物。
IF 5.2
ACS Macro Letters Pub Date : 2025-06-30 DOI: 10.1021/acsmacrolett.5c00300
Margaret E. Tetzloff,  and , Andrew J. Boydston*, 
{"title":"Combining Metal-Free and Metal-Mediated Ring-Opening Metathesis Polymerization for Efficient Synthesis of Bottlebrush Polymers","authors":"Margaret E. Tetzloff,&nbsp; and ,&nbsp;Andrew J. Boydston*,&nbsp;","doi":"10.1021/acsmacrolett.5c00300","DOIUrl":"10.1021/acsmacrolett.5c00300","url":null,"abstract":"<p >Metal-mediated ring-opening metathesis polymerization (ROMP) is a common tool used to synthesize the backbone of bottlebrush polymers by a graft-through approach. However, examples of ROMP oligomers or polymers as macromolecular side chains are limited due in part to the challenges associated with preparing a macromonomer via the same polymerization mechanism as the one used to create the main chain. Accordingly, installation of polymerizable units onto macromonomers produced via ROMP has been achieved in a multistep fashion. In such cases, one metal initiator is used in the preparation of each macromonomer, thus constituting an overall usage of the metal complex that is 1:1 with repeat units in the final bottlebrush polymer product. By leveraging the modularity of organic initiators in metal-free ROMP (MF-ROMP), as well as the differences in monomer selectivities between metal-mediated ROMP and MF-ROMP, we demonstrate a uniquely efficient and low-metal-use route to bottlebrush polymers. Specifically, we found that norbornene imide-functionalized vinyl ether initiators were successful in MF-ROMP to produce macromonomers from tetracyclododecene without compromising the norbornene imide unit. Subsequent metal-mediated graft-through ROMP of the norbornene imide chain end using Grubbs’ third-generation catalyst then produced high-molecular-weight bottlebrush copolymers. We report the synthetic methods for this sequential ROMP–ROMP approach, comparative analyses for <i>endo</i>- and <i>exo</i>-isomers of the macromonomers, and thermal characterization of the bottlebrush polymers.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"14 7","pages":"983–988"},"PeriodicalIF":5.2,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144521080","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
Sequence-Dependent Effects of Folded Glycopolymer Structures on Their Biomolecular Recognition 折叠糖共聚物结构对其生物分子识别的序列依赖效应
IF 5.2
ACS Macro Letters Pub Date : 2025-06-30 DOI: 10.1021/acsmacrolett.5c00377
Masanori Nagao*, Daichi Yoshimatsu, Hikaru Matsumoto and Yoshiko Miura*, 
{"title":"Sequence-Dependent Effects of Folded Glycopolymer Structures on Their Biomolecular Recognition","authors":"Masanori Nagao*,&nbsp;Daichi Yoshimatsu,&nbsp;Hikaru Matsumoto and Yoshiko Miura*,&nbsp;","doi":"10.1021/acsmacrolett.5c00377","DOIUrl":"10.1021/acsmacrolett.5c00377","url":null,"abstract":"<p >We demonstrate that folded polymer structures have distinct effects on their binding affinity to target biomolecules depending on the polymer sequence pattern. We synthesized random and triblock glycopolymers with either folded or non-folded structures in water. These glycopolymers contained mannose units as a biofunctional group, while di(phenylalanine) units were incorporated into the folded glycopolymers as hydrophobic segments to promote self-folding of the polymer chains in aqueous solution. We then evaluated the interactions of these glycopolymers with a model protein, concanavalin A (ConA), using isothermal titration calorimetry. The folded random glycopolymer exhibited a higher binding constant than its non-folded counterpart, whereas the opposite trend was observed in the triblock glycopolymer series. In both sequence patterns, further compaction of the polymer structures led to a decrease in binding affinity to ConA. These findings highlight the importance of the spatial arrangement of functional groups and polymer-chain flexibility in the design of functional polymers inspired by protein behavior.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"14 7","pages":"989–995"},"PeriodicalIF":5.2,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144520992","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
Healable Glassy Metallosupramolecular Polymers 可愈合玻璃金属超分子聚合物。
IF 5.2
ACS Macro Letters Pub Date : 2025-06-30 DOI: 10.1021/acsmacrolett.5c00317
Chaninya Mak-iad, Luca Bertossi, Georges J. M. Formon* and Christoph Weder*, 
{"title":"Healable Glassy Metallosupramolecular Polymers","authors":"Chaninya Mak-iad,&nbsp;Luca Bertossi,&nbsp;Georges J. M. Formon* and Christoph Weder*,&nbsp;","doi":"10.1021/acsmacrolett.5c00317","DOIUrl":"10.1021/acsmacrolett.5c00317","url":null,"abstract":"<p >Metallosupramolecular polymers (MSPs), formed through ligand–metal coordination, feature dynamic bonds that enable damage repair <i>via</i> reversible dissociation. Here, we report the synthesis of healable MSPs by modifying commercially available glycol-modified polyethylene terephthalate (PETG), an amorphous commodity polyester known for its durability, chemical resistance, and formability. The new materials were accessed through the Zn-catalyzed transesterification of PETG with ethylene glycol, end-functionalization of the resulting homobifunctional oligomers with the 2,6-bis(1′-methylbenzimidazolyl)pyridine (Mebip) ligand, and subsequent assembly of these macromonomers into MSPs <i>via</i> Zn<sup>2+</sup> complexation. One of the MSPs made offers an attractive combination of high tensile strength (31 MPa), high Young’s Modulus (1 GPa), and excellent healability (94% in 2.5 min).</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"14 7","pages":"996–1003"},"PeriodicalIF":5.2,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12269065/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144525310","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Electrostatic Compatibilization of Amorphous and Semicrystalline Immiscible Polymer Blends 非晶和半晶非混相聚合物共混物的静电增容。
IF 5.2
ACS Macro Letters Pub Date : 2025-06-27 DOI: 10.1021/acsmacrolett.5c00294
Haley K. Beech, Kseniia M. Karnaukh, Madeleine E. Miyamoto, KeRay Chen, Jerrick Edmund, Javier Read de Alaniz*, Craig J. Hawker* and Rachel A. Segalman*, 
{"title":"Electrostatic Compatibilization of Amorphous and Semicrystalline Immiscible Polymer Blends","authors":"Haley K. Beech,&nbsp;Kseniia M. Karnaukh,&nbsp;Madeleine E. Miyamoto,&nbsp;KeRay Chen,&nbsp;Jerrick Edmund,&nbsp;Javier Read de Alaniz*,&nbsp;Craig J. Hawker* and Rachel A. Segalman*,&nbsp;","doi":"10.1021/acsmacrolett.5c00294","DOIUrl":"10.1021/acsmacrolett.5c00294","url":null,"abstract":"<p >The rapid accumulation of plastic waste underscores the urgent need for effective recycling strategies, yet conventional approaches are hindered by the immiscibility of chemically dissimilar polymers, which phase-separate upon blending and yield poor material properties. This study demonstrates a versatile strategy for electrostatic compatibilization, utilizing acid–base proton transfer between minimally functionalized polymers. Waste-derived polystyrene (PS) was successfully modified with &lt;4 mol % acid groups, while amorphous polybutadiene (PBD) was functionalized with &lt;6 mol % diethylamino base groups and subsequently hydrogenated to yield semicrystalline polyethylene (PE) with the same functionalization level as the PBD. In both cases, blending with functionalized PS produced optically transparent, mechanically robust films. Notably, increasing charge density from 1.0 to 3.5 mol % significantly reduced domain sizes, indicating enhanced compatibilization, while increasing PS molecular weight from 28 to 470 kDa led to a three-order-of-magnitude increase in toughness. In PE/PS blends, the preservation of crystallinity during melt reprocessing was achieved by maintaining low functionalization levels, demonstrating compatibility without sacrificing critical material properties. These findings establish electrostatic compatibilization as a powerful, scalable platform for creating high-performance materials from chemically diverse and mixed plastic waste streams.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"14 7","pages":"969–975"},"PeriodicalIF":5.2,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144504118","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
Temperature-Responsive Rheology Modifiers from Cellulose to Enable Acoustic Additive Manufacturing of Hydrogels 纤维素的温度响应流变改性剂使水凝胶的声学增材制造成为可能。
IF 5.2
ACS Macro Letters Pub Date : 2025-06-27 DOI: 10.1021/acsmacrolett.5c00244
Lillian E. Mortensen, Fernando Enriquez Barrero, Talaial B. Alina, Jennifer N. Cha and Andrew P. Goodwin*, 
{"title":"Temperature-Responsive Rheology Modifiers from Cellulose to Enable Acoustic Additive Manufacturing of Hydrogels","authors":"Lillian E. Mortensen,&nbsp;Fernando Enriquez Barrero,&nbsp;Talaial B. Alina,&nbsp;Jennifer N. Cha and Andrew P. Goodwin*,&nbsp;","doi":"10.1021/acsmacrolett.5c00244","DOIUrl":"10.1021/acsmacrolett.5c00244","url":null,"abstract":"<p >While photopolymerization is a widely adopted method for additive manufacturing, its versatility is limited by high attenuation by the polymerization medium, which leads to anisotropic parts and slow printing times. Ultrasound bypasses these depth limitations, but challenges of acoustic streaming and heat localization remain. Here, we investigated a single-phase system that integrates temperature-responsive rheology modifiers to enhance ultrasound-based additive manufacturing. We employed cellulose derivatives with lower critical solution temperatures (LCST) to restrict acoustic streaming and localize heat within the focal zone. Our findings show that these rheology modifiers effectively contain heat, minimizing bulk polymerization and enhancing printing precision. Hydroxypropyl cellulose (HPC)-based sono-inks enable rapid printing speeds of up to 60 mm/min with sub-5 mm resolution. Furthermore, HPC inks demonstrated the capability to print at a distance and through optically opaque tissues. Conversely, methylcellulose (MC) formulations improved printing resolution but reduced speed, likely because the LCST could not be reached during the printing process. The developed sono-ink holds promise for future applications such as <i>in vivo</i> 3D printing, volumetric fabrication, and composite material synthesis.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"14 7","pages":"976–982"},"PeriodicalIF":5.2,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144511249","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
Polar Perturbations of Dipolar Interactions in Azole-Based Poly(ionic liquids) 偶极相互作用的极性摄动
IF 5.2
ACS Macro Letters Pub Date : 2025-06-20 DOI: 10.1021/acsmacrolett.5c00309
Jiahui Liu, Md. Walli Ullah and Marek W. Urban*, 
{"title":"Polar Perturbations of Dipolar Interactions in Azole-Based Poly(ionic liquids)","authors":"Jiahui Liu,&nbsp;Md. Walli Ullah and Marek W. Urban*,&nbsp;","doi":"10.1021/acsmacrolett.5c00309","DOIUrl":"10.1021/acsmacrolett.5c00309","url":null,"abstract":"<p >Azole-based polymeric ionic liquids (PILs) containing imidazolium (Im) p(Im-TFSI) and triazolium (Tr) p(Tr-TFSI) ring cations naturalized by bis(trifluoromethane sulfonyl)imide (TFSI) anions were synthesized to elucidate the origin of dipolar–ionic interactions and their role in conductivity and mechanical properties. Spectroscopic analysis of p(Im-TFSI) and p(Tr-TFSI) PILs revealed that the presence of polar H<sub>2</sub>O alters ionic and dipolar interactions, resulting in distinct ring-dependent hydration effects. In p(Tr-TFSI), more stable cation–anion–H<sub>2</sub>O entities result from stronger electrostatic surface potentials (∼2 kcal/mol), where distinct separation of positive and negative electrostatic potentials in Tr-TFSI cation–anion pairs facilitates the formation of localized clusters inducing dipole–dipole interactions. In the presence of H<sub>2</sub>O, ionic mobility is enhanced by solvating cation–anion pairs at the expense of weaker van der Waals interactions. The content of H<sub>2</sub>O near Tr rings is higher, but there is restricted ionic mobility due to stronger polar forces that are formed at the expense of diminished induced dipole–dipole interactions. In contrast, in Im-based polymers, H<sub>2</sub>O molecule associations with cation–anion pairs are weaker, and enhanced ionic mobility is reflected in increased conductivity values by a factor of 2. Both Im and Tr rings also facilitate distinct parallel resistor–capacitor (RC) responses with constant phase element (CPE) combinations; upon exposure to H<sub>2</sub>O, the parallel RC circuits undergo configuration by an additional in-series connected R-CPE element.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"14 7","pages":"948–954"},"PeriodicalIF":5.2,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144335004","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
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