ACS Macro Letters最新文献

{"title":"Room-Temperature Synthesis of a Fluorine-Functionalized Nanoporous Organic Polymer for Highly Efficient SF6 Adsorption and Separation","authors":"Sihan Tong, Lu Yao, Qilin Wang, Jiangli Zhu, Zefeng Wang, Jun Yan","doi":"10.1021/acsmacrolett.4c00559","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00559","url":null,"abstract":"Sulfur hexafluoride (SF₆) is widely used in the power industry and significantly contributes to the greenhouse effect, necessitating the development of efficient materials for SF₆ capture, particularly fluorine-containing materials. However, existing fluorine-containing materials often require complex monomers and high synthesis temperatures. Herein, we report the synthesis of a fluorine-functionalized carbazole-based nanoporous organic polymer (CNOP-7) at room temperature, using commercially available 4,4′-bis(9<i>H</i>-carbazole-9-yl)-1,1′-biphenyl and 1,1,1-trifluoroacetone. CNOP-7 contains 14.7% fluorine atoms and exhibits a high specific surface area of 1270 m²·g^–1, demonstrating excellent SF₆ adsorption and separation performance. The SF₆/N₂ selectivity of CNOP-7 reaches 107 at 273 K and 73 at 298 K. Furthermore, dynamic breakthrough experiments confirm that CNOP-7 can efficiently and repeatedly separate SF₆ from SF₆/N₂ mixtures. Molecular simulations reveal the mechanism behind its efficient separation. This work offers fresh perspectives on the development and fabrication of adsorbents for efficient SF₆ sequestration.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452351","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}

{"title":"Effects of a Mechanically Interlocked Structure on Ionic Conductivity in Polyrotaxane-Based Polymer Electrolytes","authors":"Bitgaram Kim, Eunji Lee, Ji-Hun Seo","doi":"10.1021/acsmacrolett.4c00480","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00480","url":null,"abstract":"Polyrotaxane (PR) is a mechanically interlocked polymer (MIP) utilized as an electrolyte because of its distinctive property of dynamic molecular mobility. While numerous studies have concentrated on modifying external properties to decrease high crystallinity, few have explored the control of intrinsic properties. This study examines the crystalline properties and molecular mobility of PR-based electrolytes, along with their effects on ionic conductivity, by manipulating intrinsic properties. By systematically varying the inclusion ratio, we demonstrate that lower inclusion ratios lead to reduced crystallinity, enhancing molecular mobility. Consequently, 100PRE exhibits decreased crystallinity due to lower aggregation probabilities of α-cyclodextrins (α-CDs), longer <i>T</i>₂ relaxation times (0.215 s), and higher ionic conductivity (3.4 × 10^–3 S cm^–1 at 25 °C).","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142440654","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}

{"title":"Alkyl-Substituted Polycaprolactone Poly(urethane-urea)s as Mechanically Competitive and Chemically Recyclable Materials","authors":"Derek C. Batiste, Michaela R. Pfau-Cloud, Hee Joong Kim, Christopher J. Ellison, Marc A. Hillmyer","doi":"10.1021/acsmacrolett.4c00474","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00474","url":null,"abstract":"We report the mechanical performance and chemical recycling advantages of implementing alkyl-substituted poly(ε-caprolactones) (PCLs) as soft segments in thermoplastic poly(urethane-urea) (TPUU) materials. Poly(4-methylcaprolactone) (P4MCL) and poly(4-propylcaprolactone) (P4PrCL) were prepared, reacted with isophorone diisocyanate, and chain-extended with water to form TPUUs. The resulting materials’ tensile properties were similar or superior to a commercially available polyester thermoplastic poly(urethane) and had superior elastic recovery properties compared to a PCL analogue due to the noncrystalline nature of P4MCL and P4PrCL. Additionally, monomers were recovered from the TPUU materials in high yields via ring-closing depolymerization using a reactive distillation approach at an elevated temperature and a reduced pressure (240–260 °C, 25–140 mTorr) with zinc chloride (ZnCl₂) as the catalyst. The thermodynamics of polymerization were estimated using Van’t Hoff analyses for 4MCL and 4PrCL; these results indicated that the propyl group in 4PrCL results in a lower practical ceiling temperature (<i>T</i>_c) for P4PrCL.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142436333","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}

{"title":"Controlled Fabrication of Distinct Nanostructures from Discrete Oligourethanes via Thermal Annealing","authors":"Qiangqiang Shi, Yong Yu, Lingxiao Guo, Jialin Zhang, Jiajia Tan, Jin Zhang, Jinming Hu, Shiyong Liu","doi":"10.1021/acsmacrolett.4c00615","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00615","url":null,"abstract":"The self-assembly of sequence-defined polymers (SDPs) enables the formation of a diverse array of nanostructures; however, the construction of complex hierarchical structures via thermal annealing from SDPs remains relatively unexplored. In this study, two series of oligourethanes, 2Cit-<i>p</i>B_<i>n</i>-OH and 2Cit-<i>m</i>B_<i>n</i>-OH, were synthesized to investigate their thermal annealing behaviors. Nanorod clusters were generated from 2Cit-<i>p</i>B₆-OH in a mixture of 1,4-dioxane and toluene, whereas 2Cit-<i>p</i>B₈-OH formed nanosheets after thermal annealing. Upon modifying the structure of the repeating units, 2Cit-<i>m</i>B₆-OH self-assembled into ultrathin nanosheets, transitioning from nanospheres after thermal annealing in a mixture of isopropanol and cyclohexane, while “flower” micelles were produced from 2Cit-<i>m</i>B₈-OH. Interestingly, when isopropanol was replaced with a mixture of isopropanol and tetrahydrofuran (THF), uniform nanotubes were generated by 2Cit-<i>m</i>B₆-OH under the same thermal annealing conditions. Additionally, a discrete amphiphile (2Cit-<i>m</i>B₄-(<i>S</i>)DPEG) was synthesized, leading to the formation of uniform nanosheets in aqueous solution after thermal annealing. This work highlights the significant effects of sequence and repeating unit structure of SDPs on their self-assembly behaviors and presents a novel strategy for the controlled fabrication of unique nanostructures from SDPs.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142436338","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}

{"title":"Highly Alternating Copolymer of [1.1.1]Propellane and Perfluoro Vinyl Ether: Forming a Hydrophobic and Oleophobic Surface with <50% Fluorine Monomer Content.","authors":"Mizuki Okuda, Midori Akiyama, Kosuke Funahashi, Junki Masuda, Ai Kohata, Shintaro Nakagawa, Kimiaki Kashiwagi, Norihide Sugiyama, Takashi Okazoe, Daisuke Kawaguchi","doi":"10.1021/acsmacrolett.4c00558","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00558","url":null,"abstract":"<p><p>Utilizing the unique properties of fluorine substitution is an effective strategy for constructing highly functional materials. Here, we synthesized a novel copolymer composed of [1.1.1]propellane and perfluoro(propyl vinyl ether) (PPVE), rich in alternating sequences. The spin-coated copolymer film was amorphous, and its surface exhibited an extremely low surface free energy (γ). The γ value was lower than that of polytetrafluoroethylene despite containing only 40 mol % PPVE units. This can be attributed to the cancellation of the C-F dipole moments by the entirely random orientation of the fluorine units.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.1,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398650","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}

{"title":"Functionalization and Repurposing of Polypropylene to a Thermoset Polyurethane","authors":"Ronard Herrera Monegro, Ramanan Krishnamoorti, Megan L. Robertson","doi":"10.1021/acsmacrolett.4c00505","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00505","url":null,"abstract":"Developing effective recycling pathways for polyolefin waste, enabling a move to a circular economy, is an imperative that must be met. Postuse modification has shown promising results in upcycling polyolefins, removing the limitation of inertness, and improving the final physical properties of the recycled material while extending its useful lifetime. Grafting of maleic anhydride groups to polypropylene is an established industrial process that enhances its reactivity and provides a convenient route to further functionalization and upcycling. In this work, maleic anhydride grafted polypropylene was hydroxylated and subsequently cured with a diisocyanate to form a thermoset polyurethane (PU). The crystal structure (unit cell and lamellar structure) of the polypropylene (PP) was preserved in the PU. At room temperature, the PU showed a high modulus due to the crystallization behavior of the PP; upon increasing the temperature above the melting temperature, the modulus decreased to a rubbery plateau, consistent with formation of a network. The resulting PU showed a higher glass transition temperature and lower degree of crystallinity than its PP predecessor due to the crosslinked nature of the polymer. The mechanical integrity of the PU was maintained through several reprocessing cycles due to the melt processability enabled by the presence of a urethane exchange catalyst. This functionalization and upcycling route thus offers a promising alternative to repurposing PP waste in which the creation of melt-processable thermoset polymers expands applications for the materials.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142397810","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}

{"title":"Multifunctional Polymer Synthesis via Sequential Postpolymerization Modification Using a Single Aldehyde Repeat Unit: Allylation and Orthogonal Esterification and Thiol–ene Reaction","authors":"Hyo Won Lee, Jeung Gon Kim","doi":"10.1021/acsmacrolett.4c00618","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00618","url":null,"abstract":"Herein, we present a highly efficient method for synthesizing multifunctional polymers. This method involves the sequential postpolymerization modification (PPM) of a highly reactive aldehyde polymer. We introduce an allylic alcohol functionality into the polymer backbone via Barbier-type allylation, a process facilitated by easy-to-handle indium(0) powder. This step enables the formation of orthogonal pendants, secondary alcohol, and terminal alkene, which can be further functionalized through esterification and thiol–ene click reactions. All of these processes are carried out under mild conditions, ensuring high efficiency and a wide range of functional groups. Our study underscores PPM’s operational simplicity and versatility in developing advanced polymer materials and expanding the scope of multifunctional polymer design.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142385181","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}

{"title":"Preparation of Disulfide/Trisulfide Core-Cross-Linked Polycarbonate Nanocarriers for Intracellular Reduction-Triggered Drug Release","authors":"Jiye Zhao, Dongdong Wang, Xi Zhang, Yaodong Di, Shuai Yang, Lesan Yan","doi":"10.1021/acsmacrolett.4c00443","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00443","url":null,"abstract":"Polymeric nanocarriers have attracted significant attention in the field of anticancer drug delivery due to their unique advantages. However, designing nanocarriers that can maintain stability in the bloodstream while achieving specific drug release within tumor cells remains a major challenge. To address this issue, constructing reversible cross-linked polymeric nanocarriers that are sensitive to the intracellular reducible glutathione (GSH) characteristic of the tumor microenvironment is a promising strategy. Based on this, we designed and synthesized two novel six-membered bicyclic carbonate monomers containing disulfide (DSBC) and trisulfide (TSBC) bonds. Through a one-step ring-opening polymerization, a series of reduction-sensitive polycarbonate copolymers (i.e., PEG–PDSBC and PEG–PTSBC) were prepared, and doxorubicin (DOX)-loaded nanoparticles were fabricated using a nanoprecipitation method. The <i>in vitro</i> drug release behaviors of these nanoparticles were systematically investigated. The results showed that these polymers, due to the cross-linked structure formed by the ring-opening polymerization of their bicyclic monomers, could self-assemble into stable nanoparticles. Under different concentrations of glutathione, DOX-loaded PEG–PTSBC nanoparticles demonstrated faster drug release, indicating more optimized intracellular drug release properties. Further cytotoxicity experiments revealed that both types of blank nanoparticles exhibited good biocompatibility with the 4T1 and NIH-3T3 cells. Fluorescence microscopy and flow cytometry results further indicated that DOX-loaded PEG–PTSBC nanoparticles released more drugs in 4T1 cells, significantly inhibiting tumor cell growth compared with DOX-loaded PEG–PDSBC nanoparticles, with no noticeable difference in NIH-3T3 normal cells. In conclusion, this study suggests that trisulfide cross-linked polycarbonate-based nanocarriers hold promise as an anticancer drug delivery system that combines stability in the bloodstream with specific intracellular drug release, offering new insights for the development of novel, efficient, and safe anticancer nanomedicines.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142385932","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}

{"title":"Fast, Regioselective Aminolysis of Tetrasubstituted Cyclic Carbonates and Application to Recyclable Thermoplastics and Thermosets","authors":"Thomas Habets, Raphaël Méreau, Fabiana Siragusa, Bruno Grignard, Christophe Detrembleur","doi":"10.1021/acsmacrolett.4c00570","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00570","url":null,"abstract":"Herein, the long-standing challenge of the ring-opening aminolysis of CO₂-derived tetrasubstituted cyclic carbonates at room temperature (r.T) is overcome under catalyst-free conditions. Molecular design of the cyclic carbonate by substitution of an alkyl group by a thioether unlocks quantitative conversion at r.T and ensures total regioselectivity toward highly substituted oxazolidone scaffolds. An in-depth rationalization of the high reactivity of these cyclic carbonate structures and of the aminolysis reaction mechanism is provided by a computational study supporting experimental observations. The high efficiency of the reaction is then translated to the deconstruction of high-performance thermoplastics containing tetrasubstituted cyclic carbonate linkages to deliver building blocks that are reused for designing recyclable thermosets bearing dynamic <i>N</i>,<i>S</i>-acetal linkages.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142385911","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}

{"title":"Helical Star-Shaped Bottlebrush Polymers: From Controlled Synthesis to Tunable Photoluminescence and Circularly Polarized Luminescence","authors":"Shi-Yi Li, Bing-Hui Duan, Na Liu, Jing Luo, Zheng Chen, Zong-Quan Wu","doi":"10.1021/acsmacrolett.4c00508","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00508","url":null,"abstract":"The controlled synthesis of star-shaped bottlebrush polymers with tunable topologies is a challenge. However, such materials may exhibit distinct photoluminescence properties. Bottlebrush polymers have polymerization-induced emission (PIE) properties due to their aggregated side chains, and aggregation-induced emission (AIE) is also a unique luminescent property. In this work, we prepared a variety of highly active alkyne Pd catalysts and polymerized poly(L/D-lactic acid) macromonomers containing polymerizable phenylisocyanide groups as end groups to obtain a variety of topologically structured bottlebrush polymers with controllable molecular weights and narrow molecular weight distributions. Bottlebrush polymers with tetraphenyl ethylene (TPE) units as the core exhibit tunable photoluminescence and circularly polarized luminescence properties. We propose that such properties are due to the unique AIE characteristics of the TPE unit combined with the PIE characteristics of the bottlebrush polymer.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142384470","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}