ACS Macro Letters最新文献_第5页

Commodity Polymer Functionalization by a Combination of Hydrogen Atom Transfer Reversible Addition-Fragmentation Chain Transfer Polymerization and Pentafluorophenyl-Ester-Ligation Chemistry. 氢原子转移、可逆加成-破碎链转移聚合和五氟苯基酯-连接化学相结合的商品聚合物功能化研究。

IF 5.8

ACS Macro Letters Pub Date : 2025-07-09 DOI: 10.1021/acsmacrolett.5c00368

Guanwen Huang,Zhuohan Wu,Yichen Liu,Lingjie Chang,Zhongming Wang,Xinghao Du,Binbin Xu,Zhongfan Jia,Chun Feng

{"title":"Commodity Polymer Functionalization by a Combination of Hydrogen Atom Transfer Reversible Addition-Fragmentation Chain Transfer Polymerization and Pentafluorophenyl-Ester-Ligation Chemistry.","authors":"Guanwen Huang,Zhuohan Wu,Yichen Liu,Lingjie Chang,Zhongming Wang,Xinghao Du,Binbin Xu,Zhongfan Jia,Chun Feng","doi":"10.1021/acsmacrolett.5c00368","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00368","url":null,"abstract":"Development of highly efficient and versatile strategies for functionalization of commodity polymers direct from carbon-hydrogen (C-H) bonds has attracted growing interest due to the ubiquity of C-H bonds in various commodity polymers and the great desire for upcycle of commodity polymers. However, the efficiency of C-H activation is usually low (<20%) and only one (potential) functional unit was introduced into each activated C-H bond. The low content of introduced functional units could be one great hindrance to the improvement of performance of resulting polymers. Herein we report a photocatalytic hydrogen atom transfer reversible addition-fragmentation chain transfer (HAT-RAFT) grafting polymerization strategy to introduce polymeric side chains of activated pentafluorophenyl esters (PFEs) into commodity polymers of poly(ethylene glycol), poly(propylene oxide), polybutylene, polypropylene, and poly(vinylpyrrolidone) by using the C-H bonds of commodity polymers as the initiating sites. The grafting polymerization of pentafluorophenyl acrylate (PFA) exhibits living/controlled features and temporal controllability. With the amplification effect of grafting polymerization, each activated C-H bond allows to the introduction of tens of PFEs, leading to a high content of PFE groups. Owing to the high reactivity of PFEs toward amino- and hydroxyl-containing molecules under mild conditions with excellent efficiency and group tolerance, the introduced PFEs of PPFA chains enable quantitative transesterification and amidation for efficient functionalization of commodity polymers via PFE-ligation chemistry.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"21 1","pages":"1038-1047"},"PeriodicalIF":5.8,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144586709","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 Performance, Reprocessable, and Degradable Biobased Polyhydroxyurethane Vitrimers from an Imine-Containing Vanillin Dicyclocarbonate. 高性能，可再加工，可降解的生物基聚羟基聚氨酯聚合物，从含亚胺的香草醛二环碳酸盐。

IF 5.8

ACS Macro Letters Pub Date : 2025-07-09 DOI: 10.1021/acsmacrolett.5c00308

Yuanmeng Wang,Min Fan,Jingbo Zhao

引用次数: 0

Nanoparticle Percolation Improves the Mechanical Properties of Polymer Nanocomposite Films. 纳米颗粒的渗透改善了聚合物纳米复合膜的力学性能。

IF 5.8

ACS Macro Letters Pub Date : 2025-07-08 DOI: 10.1021/acsmacrolett.5c00258

Aria C Zhang,Kohji Ohno,Russell J Composto

{"title":"Nanoparticle Percolation Improves the Mechanical Properties of Polymer Nanocomposite Films.","authors":"Aria C Zhang,Kohji Ohno,Russell J Composto","doi":"10.1021/acsmacrolett.5c00258","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00258","url":null,"abstract":"Nanoparticle (NP) percolation governs the mechanical reinforcement of polymer nanocomposite (PNC) films. In this study, we demonstrate that both internal network morphology and near-surface morphology of NPs influence the mechanical properties of PNC films composed of poly(methyl methacrylate)-grafted silica nanoparticles (PMMA-NPs) in a poly(styrene-ran-acrylonitrile) (SAN) matrix. By systematically varying film thickness and annealing conditions, we achieve distinct NP morphologies, including continuous pillars, discrete pillars, clusters, and interconnected networks, each exhibiting different levels of NP percolation. Atomic force microscopy nanoindentation reveals that films with interconnected networks exhibit the highest reduced modulus (7.6 GPa), nearly quadrupling that of as-cast films with uniform NP dispersion (1.8 GPa), along with a substantial increase in hardness (624 MPa compared to 298 MPa). Notably, surface NP structures formed during annealing contribute to an enhanced modulus at low loads. These findings establish a direct structure-property relationship, providing insights into designing mechanically robust PNCs for applications in coatings, electronics, and energy storage.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"10 1","pages":"1032-1037"},"PeriodicalIF":5.8,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144586281","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

Tough Hydrogels Designed for a Stretch-Induced Decrease in Electrical Resistance Using Tandem Host-Guest and Ionic Cross-Linking. 使用串联主-客体和离子交联设计用于拉伸诱导电阻降低的坚韧水凝胶。

IF 5.8

ACS Macro Letters Pub Date : 2025-07-07 DOI: 10.1021/acsmacrolett.5c00347

May Myat Noe,Akihide Sugawara,Yoshinori Takashima,Hiroshi Uyama

{"title":"Tough Hydrogels Designed for a Stretch-Induced Decrease in Electrical Resistance Using Tandem Host-Guest and Ionic Cross-Linking.","authors":"May Myat Noe,Akihide Sugawara,Yoshinori Takashima,Hiroshi Uyama","doi":"10.1021/acsmacrolett.5c00347","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00347","url":null,"abstract":"Developing hydrogels that simultaneously exhibit mechanical toughness, interfacial adhesion, and a stretch-induced decline in electrical resistance remains a key challenge for soft and stretchable devices. Here, we present a supramolecular hydrogel system based on a tandem cross-linking strategy, formed through host-guest complexation between β-cyclodextrin (β-CD) and hydrophobic anions (TFSI- or NFO-), followed by sequential ionic interactions between anions and imidazolium polycations. The supramolecular hydrogels formed stable networks with enhanced mechanical strength, moderate swelling, and tunable adhesion, governed by the alkyl chain length of polycations, counteranions, and matrix polymers. Under tensile strain, the tandem cross-linked hydrogels exhibited a distinctive reduction in resistance, attributed to the sacrificial dissociation of dynamic cross-links that increase the anion mobility and facilitate ion transport. This supramolecular approach provides a versatile platform for designing robust, multifunctional hydrogels suited for mechanically demanding and stimuli-responsive applications with strong potential in flexible and wearable electronics.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"26 1","pages":"1019-1025"},"PeriodicalIF":5.8,"publicationDate":"2025-07-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144568551","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

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 5.8

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,Dezhong Zhou

{"title":"Highly Branched Poly[dimethylaminoethyl methacrylate-co-bis(2-acryloyloxy) ethyl disulfide] for Efficient Intracellular Protein Delivery.","authors":"Xiaojia Wang,Wei Sun,Rui Guo,Zhili Li,Chenfei Wang,Zhedong Ma,Siyi Cai,Dezhong Zhou","doi":"10.1021/acsmacrolett.5c00220","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00220","url":null,"abstract":"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-co-bis(2-acryloyloxy) ethyl disulfide] [P(DM-co-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(DM10-co-DS1)-E1 achieved up to 20-fold higher delivery efficiency compared to commercial PULSin, while maintaining high cell viability.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"20 1","pages":"1026-1031"},"PeriodicalIF":5.8,"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

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 5.8

ACS Macro Letters Pub Date : 2025-07-01 DOI: 10.1021/acsmacrolett.5c00315

Yuanchi Ma,Vivek M Prabhu

{"title":"Cosolvent Control of Lower and Upper Critical Solution Behavior in Polyelectrolyte Complexes.","authors":"Yuanchi Ma,Vivek M Prabhu","doi":"10.1021/acsmacrolett.5c00315","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00315","url":null,"abstract":"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(N,N-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., N-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.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"11 1","pages":"962-968"},"PeriodicalIF":5.8,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533368","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 5.8

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,Brent S Sumerlin

{"title":"Nitroarene Photoactivation Promotes Oxidative Deconstruction of Olefinic Polymers.","authors":"Thi H Le,Kamal Bhatt,Sylwia Dworakowska,Kevin A Stewart,Parker T Boeck,Adam S Veige,Daniel Seidel,Brent S Sumerlin","doi":"10.1021/acsmacrolett.5c00329","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00329","url":null,"abstract":"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.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"19 1","pages":"1004-1010"},"PeriodicalIF":5.8,"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

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 5.8

ACS Macro Letters Pub Date : 2025-06-30 DOI: 10.1021/acsmacrolett.5c00300

Margaret E Tetzloff,Andrew J Boydston

{"title":"Combining Metal-Free and Metal-Mediated Ring-Opening Metathesis Polymerization for Efficient Synthesis of Bottlebrush Polymers.","authors":"Margaret E Tetzloff,Andrew J Boydston","doi":"10.1021/acsmacrolett.5c00300","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00300","url":null,"abstract":"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 endo- and exo-isomers of the macromonomers, and thermal characterization of the bottlebrush polymers.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"36 1","pages":"983-988"},"PeriodicalIF":5.8,"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 5.8

ACS Macro Letters Pub Date : 2025-06-30 DOI: 10.1021/acsmacrolett.5c00377

Masanori Nagao, Daichi Yoshimatsu, Hikaru Matsumoto, Yoshiko Miura

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 5.8

ACS Macro Letters Pub Date : 2025-06-20 DOI: 10.1021/acsmacrolett.5c00309

Jiahui Liu, Md. Walli Ullah, Marek W. Urban

{"title":"Polar Perturbations of Dipolar Interactions in Azole-Based Poly(ionic liquids)","authors":"Jiahui Liu, Md. Walli Ullah, Marek W. Urban","doi":"10.1021/acsmacrolett.5c00309","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00309","url":null,"abstract":"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 H2O alters ionic and dipolar interactions, resulting in distinct ring-dependent hydration effects. In p(Tr-TFSI), more stable cation–anion–H2O 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 H2O, ionic mobility is enhanced by solvating cation–anion pairs at the expense of weaker van der Waals interactions. The content of H2O 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, H2O 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 H2O, the parallel RC circuits undergo configuration by an additional in-series connected R-CPE element.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"15 1","pages":""},"PeriodicalIF":5.8,"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