ACS Macro Letters最新文献

{"title":"Rational Design of Self-Reporting Polymersomes for the Controlled Release of Sulfur Dioxide","authors":"Zhezhe Li,&nbsp;Yue Zhang,&nbsp;Suzhen Wang,&nbsp;Yihan Wu and Hailong Che*,&nbsp;","doi":"10.1021/acsmacrolett.4c0068710.1021/acsmacrolett.4c00687","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00687https://doi.org/10.1021/acsmacrolett.4c00687","url":null,"abstract":"<p >As a new member of the gaseous regulators, sulfur dioxide (SO₂) plays a crucial role in many biological activities. Recent studies have shown that SO₂ is capable of inducing cancer cell apoptosis by regulating intracellular reactive oxygen species (ROS), allowing SO₂ to serve as an efficient therapeutic agent. Although various polymer-based platforms have presented great potential for the controlled release of SO₂, most of the systems are incapable of monitoring the intracellular generation of SO₂. In this work we present the rational design of SO₂-releasing biodegradable polymersomes, accompanied by a self-reporting property. The polymersome consists of a hydrophilic block of poly(ethylene glycol) (PEG) and a hydrophobic segment of poly(trimethylene carbonate) (PTMC)-based SO₂ donors. The polymersomes not only exhibit good SO₂-releasing performance upon treatment with glutathione (GSH), but can also regulate the fluorescence change of the system, offering a good platform for real-time monitoring of the intracellular production of SO₂. Significantly, the <i>in vitro</i> and <i>in vivo</i> studies indicate the potential for exploitation of these polymersomes as antitumor agents. We expect that incorporating both the SO₂-releasing capacity and self-reporting feature within a polymersome system will provide a unique opportunity for the development of intelligent gas nanovehicles.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"13 12","pages":"1691–1697 1691–1697"},"PeriodicalIF":5.1,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850626","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":"Rational Design of Self-Reporting Polymersomes for the Controlled Release of Sulfur Dioxide","authors":"Zhezhe Li, Yue Zhang, Suzhen Wang, Yihan Wu, Hailong Che","doi":"10.1021/acsmacrolett.4c00687","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00687","url":null,"abstract":"As a new member of the gaseous regulators, sulfur dioxide (SO₂) plays a crucial role in many biological activities. Recent studies have shown that SO₂ is capable of inducing cancer cell apoptosis by regulating intracellular reactive oxygen species (ROS), allowing SO₂ to serve as an efficient therapeutic agent. Although various polymer-based platforms have presented great potential for the controlled release of SO₂, most of the systems are incapable of monitoring the intracellular generation of SO₂. In this work we present the rational design of SO₂-releasing biodegradable polymersomes, accompanied by a self-reporting property. The polymersome consists of a hydrophilic block of poly(ethylene glycol) (PEG) and a hydrophobic segment of poly(trimethylene carbonate) (PTMC)-based SO₂ donors. The polymersomes not only exhibit good SO₂-releasing performance upon treatment with glutathione (GSH), but can also regulate the fluorescence change of the system, offering a good platform for real-time monitoring of the intracellular production of SO₂. Significantly, the <i>in vitro</i> and <i>in vivo</i> studies indicate the potential for exploitation of these polymersomes as antitumor agents. We expect that incorporating both the SO₂-releasing capacity and self-reporting feature within a polymersome system will provide a unique opportunity for the development of intelligent gas nanovehicles.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"258 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142718897","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":"A Macrocycle-Mediated Protein Cage","authors":"Ronan J. Flood,&nbsp;Aurélien Thureau and Peter B. Crowley*,&nbsp;","doi":"10.1021/acsmacrolett.4c0065610.1021/acsmacrolett.4c00656","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00656https://doi.org/10.1021/acsmacrolett.4c00656","url":null,"abstract":"<p >Engineered protein cages are of great interest considering their diverse applications in delivery and catalysis. Here, we describe macrocycle-triggered icosahedral cage assembly of a designed β-propeller. Cage assembly was evidenced by small-angle X-ray scattering and X-ray crystallography.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"13 12","pages":"1686–1690 1686–1690"},"PeriodicalIF":5.1,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmacrolett.4c00656","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850828","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}

{"title":"A Macrocycle-Mediated Protein Cage","authors":"Ronan J. Flood, Aurélien Thureau, Peter B. Crowley","doi":"10.1021/acsmacrolett.4c00656","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00656","url":null,"abstract":"Engineered protein cages are of great interest considering their diverse applications in delivery and catalysis. Here, we describe macrocycle-triggered icosahedral cage assembly of a designed β-propeller. Cage assembly was evidenced by small-angle X-ray scattering and X-ray crystallography.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"20 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142718888","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":"Enhancing Mechanophore Activation through Polymer Crystallization","authors":"Qinxin Sheng, Rui Tan, Xiaohua Zhang, Hang Shen, Zhengbiao Zhang","doi":"10.1021/acsmacrolett.4c00709","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00709","url":null,"abstract":"In the field of polymer mechanochemistry, the activation of mechanophores within linear polymers in the bulk state is often limited by low activation rates. Herein, we demonstrate that the crystallization of polymers can significantly enhance the activation of mechanophores. Employing rhodamine-containing poly(lactic acid) (PLA) and polycaprolactone (PCL) as representative examples, our study reveals that the micromechanical force generated by crystallization is more effective in activating mechanophores than the macroscopic mechanical force induced by compression and ultrasonication, which is particularly pronounced for polymers with low molecular weights. Furthermore, the activation of the mechanophore is found to be positively correlated with the degree of crystallinity and polymer molecular weight, whereas the chirality of polymers does not influence the activation. This study offers new insights into mechanochemical reactions induced by polymer crystallization and provides a novel approach to enhancing mechanochemical reactivity.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"253 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678678","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":"Influence of Solvent Dielectric Constant on the Complex Coacervation Phase Behavior of Polymerized Ionic Liquids","authors":"Jowon Shin,&nbsp;Heewoon Shin,&nbsp;Sang-Ho Lee,&nbsp;Jong Dae Jang and Hyeong Jun Kim*,&nbsp;","doi":"10.1021/acsmacrolett.4c0066310.1021/acsmacrolett.4c00663","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00663https://doi.org/10.1021/acsmacrolett.4c00663","url":null,"abstract":"<p >Complex coacervation is an associative phase separation process of oppositely charged polyelectrolyte solutions, resulting in a coacervate phase enriched with charged polymers and a polymer-lean phase. To date, studies on the phase behavior of complex coacervation have been largely restricted to aqueous systems with relatively high dielectric constants due to the limited solubility of most polyelectrolytes, hindering the exploration of the effects of electrostatic interactions from differences in solvent permittivity. Herein, we prepare two symmetric but oppositely charged polymerized ionic liquids (PILs), consisting of poly[1-[2-acryloyloxyethyl]-3-butylimidazolium bis(trifluoromethane)sulfonimide] (PAT) and poly[1-ethyl-3-methylimidazolium 3-[[[(trifluoromethyl)sulfonyl]amino]sulfonyl]propyl acrylate] (PEA). Due to the delocalized ionic charges and their chemical structure similarity, both PAT and PEA are soluble in various organic solvents with a wide range of dielectric constants, ranging from 16.7 (hexafluoro-2-propanol (HFIP)) to 66.1 (propylene carbonate (PC)). Notably, no significant correlation is observed between the solvent dielectric constant and the phase diagram of the complex coacervation of PILs. Most organic solvents lead to similar phase diagrams and salt resistances regardless of their dielectric constants, except two protic solvents (HFIP and 2,2,2-trifluoroethanol (TFE)) showing significantly low salt resistances compared to the others. The low salt resistance in these protic solvents primarily arises from strong hydrogen bonding between PILs and solvents as evidenced by ¹H NMR and small-angle neutron scattering (SANS) experiments. Our finding suggests that for the coacervation of PILs, particularly those with delocalized and weak charge interactions, entropy from the counterion release and polymer–solvent interaction χ parameter play a more important role than the electrostatic interactions of charged molecules, rendered by the dielectric constant of the solvent medium.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"13 12","pages":"1678–1685 1678–1685"},"PeriodicalIF":5.1,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843305","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":"Enhancing Mechanophore Activation through Polymer Crystallization","authors":"Qinxin Sheng,&nbsp;Rui Tan,&nbsp;Xiaohua Zhang,&nbsp;Hang Shen* and Zhengbiao Zhang*,&nbsp;","doi":"10.1021/acsmacrolett.4c0070910.1021/acsmacrolett.4c00709","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00709https://doi.org/10.1021/acsmacrolett.4c00709","url":null,"abstract":"<p >In the field of polymer mechanochemistry, the activation of mechanophores within linear polymers in the bulk state is often limited by low activation rates. Herein, we demonstrate that the crystallization of polymers can significantly enhance the activation of mechanophores. Employing rhodamine-containing poly(lactic acid) (PLA) and polycaprolactone (PCL) as representative examples, our study reveals that the micromechanical force generated by crystallization is more effective in activating mechanophores than the macroscopic mechanical force induced by compression and ultrasonication, which is particularly pronounced for polymers with low molecular weights. Furthermore, the activation of the mechanophore is found to be positively correlated with the degree of crystallinity and polymer molecular weight, whereas the chirality of polymers does not influence the activation. This study offers new insights into mechanochemical reactions induced by polymer crystallization and provides a novel approach to enhancing mechanochemical reactivity.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"13 12","pages":"1670–1677 1670–1677"},"PeriodicalIF":5.1,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850971","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":"Semiaromatic Polyester-Ethers with Tunable Degradation Profiles.","authors":"Nicola G Judge, Maddison I Segal, Robert O Silzer, Courtney S Dziewior, Yin Mei Chan, Sawyer J Grovogel, Matthew L Becker","doi":"10.1021/acsmacrolett.4c00617","DOIUrl":"10.1021/acsmacrolett.4c00617","url":null,"abstract":"<p><p>Poly(ε-caprolactone) (PCL) is a widely utilized polymer within the biomedical field; however, one of its limitations is the multi-year long degradation profile. Herein, we report a semiaromatic polyester-ether (SAEE) PCL copolymer using a salicylic acid-based monomer which can disrupt the semicrystalline nature of the bulk material. The molar percentage of incorporation correlated to a linear decrease in melting and crystallization temperature, until a totally amorphous solid was seen at 37 mol %. Alongside this, mechanical analysis elucidated a softer, more extensible material with <i>E</i>' decreasing from 292 to 222 to 43.8 MPa for PCL to 10 to 22 mol % SAEE, respectively. Accelerated basic degradation studies (2 M NaOH) exhibited total mass loss after 16 weeks for 6 mol % compared to only 38% mass loss for PCL over the same period. Overall, by varying the SAEE mol %, we show the ability to finely tune the thermal, mechanical, and degradation profiles of PCL copolymers while maintaining an advantageous biological profile.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":" ","pages":"1531-1538"},"PeriodicalIF":5.1,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142520302","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":"Eutectic Strategy for the Solvent-Free Synthesis of Hydrophobic Cellulosic Cross-Linked Networks with Broad Multifunctional Applications.","authors":"Huanhuan Wu, Kaili Zhang, Hanyu Jiang, Ren'ai Li","doi":"10.1021/acsmacrolett.4c00573","DOIUrl":"10.1021/acsmacrolett.4c00573","url":null,"abstract":"<p><p>Cellulose-based functional materials play a crucial role in sustainable social development. However, during the material synthesis process, there is typically significant reliance on various solvent systems for macroscopic- or molecular-scale functionalization modifications. In this study, an innovative hydrophobic eutectic solvent (HES) was developed using ethyl cellulose (EC) and thymol (Thy) without any external solvents. Utilizing this homogeneous system, it is convenient to chemically modify the components without any catalyst. Furthermore, a hydrophobic cellulosic cross-linked network (HCCN) can be successfully prepared through in situ photopolymerization. The HCCN film exhibits high transparency, excellent mechanical properties, chemical stability, and durability. The EC/Thy prepolymer system also demonstrates favorable processability for the preparation of various polymeric materials. Additionally, the applicability of other biomasses and derivatives based on the eutectic strategy has been verified. The methodology proposed in this study offers novel insights into the green and solvent-free preparation of biomass functional materials.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":" ","pages":"1558-1564"},"PeriodicalIF":5.1,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556533","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":"Aqueous Photoiniferter Polymerization of Acrylonitrile","authors":"Evan K. Stacy,&nbsp;Mac L. McCormick,&nbsp;Kaden C. Stevens,&nbsp;Penelope E. Jankoski,&nbsp;Jeff Aguinaga,&nbsp;Derek L. Patton,&nbsp;Brent S. Sumerlin and Tristan D. Clemons*,&nbsp;","doi":"10.1021/acsmacrolett.4c0064210.1021/acsmacrolett.4c00642","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00642https://doi.org/10.1021/acsmacrolett.4c00642","url":null,"abstract":"<p >Polyacrylonitrile (PAN) is a key industrial polymer for the production of carbon fiber for high-strength, lightweight composite material applications, with an estimated 90% of the carbon fiber market relying on PAN-based polymers. Traditionally, PAN synthesis is achieved by conventional radical polymerization, resulting in broad molecular weight distributions and the use of toxic organic solvents or surfactants during the synthesis. Additionally, attempts to improve polymer and processing properties by controlled radical polymerization methods suffer from low monomer conversions and struggle to achieve molecular weights suitable for producing high-performance carbon fiber. In this study, we present an aqueous photoiniferter (aqPI) polymerization of acrylonitrile, achieving high monomer conversion and high PAN molecular weights with significantly faster kinetics and dispersity control when compared to traditional methods. This approach allows for the unprecedented control of polymer properties that are integral for downstream processing for enhanced carbon fiber production.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"13 12","pages":"1662–1669 1662–1669"},"PeriodicalIF":5.1,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmacrolett.4c00642","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142842940","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}