Pub Date : 2026-02-06DOI: 10.1021/acsmacrolett.5c00829
Neil D. Dolinski, Lily Alperstein, Ran Tao, Anthony P. Kotula, Hojin Kim, Kyle J. Petersen, Elina Ghimire, Charlie A. Lindberg, Julia G. Murphy, Kexin Li, Steven J. Sibener, Aaron M. Forster, Stuart J. Rowan
The addition of hard fillers to polymeric networks allows for enhancement of mechanical properties, generally at the expense of extensibility. In the case of filled elastomers (such as tires), the hard particles cause damage to the underlying network when strained, resulting in severe mechanical hysteresis in cyclic loading experiments (the Mullins effect). As such, dynamic networks, which are able to heal damage through exchange reactions, are a promising candidate for composite matrices. This work investigates the influence of tunable dynamic bonds at the surface of silica particles in the presence of a fixed, complementary dynamic network matrix. The surface chemistry, composed of benzalcyanoacetamide Michael acceptors, undergoes room temperature, catalyst-free dynamic exchange with thiols with equilibrium constants (Keq) that can be manipulated by the electronic nature of the acceptor. Increasing the Keq of the particle surface relative to the dynamic matrix was found to promote the overall reinforcement of the composites, while also influencing the phase separation behavior of the matrix. Critically, tensile experiments reveal that ambient dynamic exchange allows for the recovery of network damage as a function of waiting time between loading cycles.
{"title":"Control of Dynamic Composites through Filler Surface Chemistry","authors":"Neil D. Dolinski, Lily Alperstein, Ran Tao, Anthony P. Kotula, Hojin Kim, Kyle J. Petersen, Elina Ghimire, Charlie A. Lindberg, Julia G. Murphy, Kexin Li, Steven J. Sibener, Aaron M. Forster, Stuart J. Rowan","doi":"10.1021/acsmacrolett.5c00829","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00829","url":null,"abstract":"The addition of hard fillers to polymeric networks allows for enhancement of mechanical properties, generally at the expense of extensibility. In the case of filled elastomers (such as tires), the hard particles cause damage to the underlying network when strained, resulting in severe mechanical hysteresis in cyclic loading experiments (the Mullins effect). As such, dynamic networks, which are able to heal damage through exchange reactions, are a promising candidate for composite matrices. This work investigates the influence of tunable dynamic bonds at the surface of silica particles in the presence of a fixed, complementary dynamic network matrix. The surface chemistry, composed of benzalcyanoacetamide Michael acceptors, undergoes room temperature, catalyst-free dynamic exchange with thiols with equilibrium constants (<i>K</i><sub>eq</sub>) that can be manipulated by the electronic nature of the acceptor. Increasing the <i>K</i><sub>eq</sub> of the particle surface relative to the dynamic matrix was found to promote the overall reinforcement of the composites, while also influencing the phase separation behavior of the matrix. Critically, tensile experiments reveal that ambient dynamic exchange allows for the recovery of network damage as a function of waiting time between loading cycles.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"83 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122088","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}
Polysarcosine (PSar) has been recognized as a promising alternative to poly(ethylene glycol) (PEG) in biomedical fields. The development of efficient methods for synthesizing PSar with complex architectures is therefore essential for creating optimal biomaterials. Herein, we propose a “one-pot” approach for synthesizing PSar molecular bottlebrush (MBB) with abundant active terminal amino groups through the combination of N-carboxyanhydride (NCA) polymerization and monomer-emulsified aqueous ring-opening metathesis polymerization (ME-ROMP). Briefly, the NCA polymerization of Sar-NCA monomer using norbornenyl amino (NB-NH2) as the initiator was first conducted to prepare norbornenyl terminal PSar (NB-PSar). Subsequently, without purification, this NB-PSar macromonomer was employed to synthesize PSar MBBs with precise architecture by ME-ROMP in the CH2Cl2/H2O (v/v = 1/10) mixtures through a grafting-through strategy. Kinetic studies indicated that the entire process could be completed within 20 min with near-quantitative conversion, and worm-like PSar MBBs with varied length and diameter could be easily synthesized by varying the feed ratios. Moreover, the terminal secondary amines of PSar side chains were retained, which could be further utilized for the surface modification of the MBBs. This work provides a one-pot approach for worm-like nanostructured PSar materials, which are expected to hold promising potential for creating advanced biomaterials.
{"title":"One-Pot Synthesis of Polysarcosine Molecular Bottlebrushes: From Monomer to Worm-Like Nanostructures","authors":"Wangmeng Hou, Xiuzhe Yin, Yingqing Zhou, Zhijia Liu, Yi Shi, Yongming Chen","doi":"10.1021/acsmacrolett.6c00013","DOIUrl":"https://doi.org/10.1021/acsmacrolett.6c00013","url":null,"abstract":"Polysarcosine (PSar) has been recognized as a promising alternative to poly(ethylene glycol) (PEG) in biomedical fields. The development of efficient methods for synthesizing PSar with complex architectures is therefore essential for creating optimal biomaterials. Herein, we propose a “one-pot” approach for synthesizing PSar molecular bottlebrush (MBB) with abundant active terminal amino groups through the combination of N-carboxyanhydride (NCA) polymerization and monomer-emulsified aqueous ring-opening metathesis polymerization (ME-ROMP). Briefly, the NCA polymerization of Sar-NCA monomer using norbornenyl amino (NB-NH<sub>2</sub>) as the initiator was first conducted to prepare norbornenyl terminal PSar (NB-PSar). Subsequently, without purification, this NB-PSar macromonomer was employed to synthesize PSar MBBs with precise architecture by ME-ROMP in the CH<sub>2</sub>Cl<sub>2</sub>/H<sub>2</sub>O (<i>v</i>/<i>v</i> = 1/10) mixtures through a grafting-through strategy. Kinetic studies indicated that the entire process could be completed within 20 min with near-quantitative conversion, and worm-like PSar MBBs with varied length and diameter could be easily synthesized by varying the feed ratios. Moreover, the terminal secondary amines of PSar side chains were retained, which could be further utilized for the surface modification of the MBBs. This work provides a one-pot approach for worm-like nanostructured PSar materials, which are expected to hold promising potential for creating advanced biomaterials.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"89 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122089","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}
Pub Date : 2026-02-06DOI: 10.1021/acsmacrolett.6c00015
Juan F. Hincapié, Dorleta Otaegui, Zhong Zeng, Bernd Reck, Nicholas Ballard, José M. Asua
Understanding the mechanism of radical entry has been a major challenge in the development of process-by-design in emulsion polymerization systems. Although many theories have been put forward across decades of experimental work, conclusive evidence of the determining factors in radical entry across the range of systems that are of industrial importance has not been forthcoming. In this work, a new technique for elucidating the root causes of radical entry is described. The technique involves the initial synthesis of a miniemulsion system in which the monomer droplets contain a hydrophobic, UV-active radical trap. This method allows the rate of entry to be followed by UV–vis spectroscopy and, furthermore, by MALDI-ToF-MS analysis of the oligomeric products present in the aqueous and organic phases; it is shown that it is possible to gain additional insights into the nature of radical entry.
{"title":"Revisiting the Mechanism of Radical Entry in Emulsion Polymerization","authors":"Juan F. Hincapié, Dorleta Otaegui, Zhong Zeng, Bernd Reck, Nicholas Ballard, José M. Asua","doi":"10.1021/acsmacrolett.6c00015","DOIUrl":"https://doi.org/10.1021/acsmacrolett.6c00015","url":null,"abstract":"Understanding the mechanism of radical entry has been a major challenge in the development of process-by-design in emulsion polymerization systems. Although many theories have been put forward across decades of experimental work, conclusive evidence of the determining factors in radical entry across the range of systems that are of industrial importance has not been forthcoming. In this work, a new technique for elucidating the root causes of radical entry is described. The technique involves the initial synthesis of a miniemulsion system in which the monomer droplets contain a hydrophobic, UV-active radical trap. This method allows the rate of entry to be followed by UV–vis spectroscopy and, furthermore, by MALDI-ToF-MS analysis of the oligomeric products present in the aqueous and organic phases; it is shown that it is possible to gain additional insights into the nature of radical entry.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"58 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122090","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}
Pub Date : 2026-02-02DOI: 10.1021/acsmacrolett.5c00820
Zijian Song, Ming Wang, Federico Caporaletti, Shuai Yang, Yingchun Li, Guoming Liu, Simone Napolitano, Dujin Wang
Physical aging in amorphous polymers reflects the slow structural relaxation toward equilibrium below the glass transition. Isoconversional analysis suggests that progressively larger activation barriers are explored during aging, approaching that of α-relaxation near equilibrium. Yet the molecular origin of the low-barrier regime that defines the onset of aging, where the recovered enthalpy is only a few percent of the total, remains poorly understood. Here, we combine calorimetry and broadband dielectric spectroscopy on bulk and nanopore-confined poly(methyl methacrylate) (PMMA) to isolate the earliest stage of aging through the identification of the induction time of the kinetics (tind). We find that tind follows a clear Arrhenius dependence with an activation energy that, for both bulk and confined PMMA, is more aligned with that of the slow Arrhenius process, rather than that of the β-relaxation mode resolved in the dielectric spectra. These findings challenge the prevailing assumption that Arrhenius-like behavior is a unique signature of the β-relaxation, suggesting that additional localized modes play key roles in the dynamics of disordered solids and calling for a reassessment of how low-barrier processes are assigned.
{"title":"Low-Barrier Onset of Physical Aging Across Bulk and Nanopore-Confined Poly(methyl methacrylate)","authors":"Zijian Song, Ming Wang, Federico Caporaletti, Shuai Yang, Yingchun Li, Guoming Liu, Simone Napolitano, Dujin Wang","doi":"10.1021/acsmacrolett.5c00820","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00820","url":null,"abstract":"Physical aging in amorphous polymers reflects the slow structural relaxation toward equilibrium below the glass transition. Isoconversional analysis suggests that progressively larger activation barriers are explored during aging, approaching that of α-relaxation near equilibrium. Yet the molecular origin of the low-barrier regime that defines the onset of aging, where the recovered enthalpy is only a few percent of the total, remains poorly understood. Here, we combine calorimetry and broadband dielectric spectroscopy on bulk and nanopore-confined poly(methyl methacrylate) (PMMA) to isolate the earliest stage of aging through the identification of the induction time of the kinetics (<i>t</i><sub>ind</sub>). We find that <i>t</i><sub>ind</sub> follows a clear Arrhenius dependence with an activation energy that, for both bulk and confined PMMA, is more aligned with that of the slow Arrhenius process, rather than that of the β-relaxation mode resolved in the dielectric spectra. These findings challenge the prevailing assumption that Arrhenius-like behavior is a unique signature of the β-relaxation, suggesting that additional localized modes play key roles in the dynamics of disordered solids and calling for a reassessment of how low-barrier processes are assigned.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"94 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101795","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}
In this study, using bio-based eugenol as the basic polymerization unit, the directional coupling of quaternary phosphonium cations and eugenol was achieved through covalent bonding, and a new type of degradable antibacterial monomer (Eu-PH) was successfully synthesized. Notably, cubic nanoparticles were obtained via the self-assembly of Eu-PH during its homopolymerization, whereas spherical nanoparticles were generated when Eu-PH was copolymerized with N-vinylpyrrolidone (NVP). This structural transformation not only induced significant changes in the material’s physicochemical properties but also markedly enhanced its antibacterial efficacy. Experimental results demonstrated that PHx–PVPy achieved inhibition rates of 100% against Escherichia coli and Staphylococcus aureus, with a relative biocompatibility of 99% toward L-929 cells. In addition, PHx–PVPy exhibited excellent degradability and fruit preservation performance. In brief, by virtue of structural regulation of bio-based eugenol and NVP, a promising new approach is proposed for the development of antibacterial materials that simultaneously possess high antibacterial activity, good biocompatibility, and satisfactory degradability.
{"title":"Structurally Adjustable Eugenyl-Based Quaternary Phosphonium Cation Degradable Antibacterial Nanomaterials via RAFT","authors":"Xiangbin Sun, Xiaobing Ma, Rongmin Wang, Yufeng He, Pengfei Song, Hailin Cong","doi":"10.1021/acsmacrolett.5c00756","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00756","url":null,"abstract":"In this study, using bio-based eugenol as the basic polymerization unit, the directional coupling of quaternary phosphonium cations and eugenol was achieved through covalent bonding, and a new type of degradable antibacterial monomer (Eu-PH) was successfully synthesized. Notably, cubic nanoparticles were obtained via the self-assembly of Eu-PH during its homopolymerization, whereas spherical nanoparticles were generated when Eu-PH was copolymerized with <i>N</i>-vinylpyrrolidone (NVP). This structural transformation not only induced significant changes in the material’s physicochemical properties but also markedly enhanced its antibacterial efficacy. Experimental results demonstrated that PH<sub><i>x</i></sub>–PVP<sub><i>y</i></sub> achieved inhibition rates of 100% against <i>Escherichia coli</i> and <i>Staphylococcus aureus</i>, with a relative biocompatibility of 99% toward L-929 cells. In addition, PH<sub><i>x</i></sub>–PVP<sub><i>y</i></sub> exhibited excellent degradability and fruit preservation performance. In brief, by virtue of structural regulation of bio-based eugenol and NVP, a promising new approach is proposed for the development of antibacterial materials that simultaneously possess high antibacterial activity, good biocompatibility, and satisfactory degradability.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"179 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070482","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}
Pub Date : 2026-01-27DOI: 10.1021/acsmacrolett.5c00779
Kwanghee Lee,Jin Sol Shin,Weijia Tang,Jeehae Shin,Sheng Li
Polyelectrolyte complex micelles (PCMs) offer a promising platform for oligonucleotide delivery; however, conventional preparation methods based on block copolymers require chemical modification of either the oligonucleotide cargo or the cationic carrier polymer. Here, we report a modified strategy for PCM formation in which the ends of target DNAs (tDNAs) are hybridized with poly(ethylene glycol)-conjugated DNA (DNA-PEG) helper molecules to generate diblock and triblock pseudoblock copolymers (pseudo-BCPs). These pseudo-BCPs are subsequently complexed with branched polyethylenimine (BPEI) to form PCMs. Pseudo-BCPs bearing PEG chains of 5 kg/mol (pseudo-BCP(5k)) or greater yield PCMs with well-defined core-shell morphologies and exhibit excellent temporal stability and salt resistance. In vitro analyses using cultured cells demonstrate that all PCM systems show enhanced cellular uptake relative to free tDNA, with pseudo-BCP(5k)-derived PCMs exhibiting the highest efficiency. These results establish pseudo-BCP-based PCM assembly as a feasible new route to prepare nanocarriers for oligonucleotide delivery.
{"title":"PEGylated DNA Helper Molecule-Assisted Self-Assembly of Polyelectrolyte Complex Micelles.","authors":"Kwanghee Lee,Jin Sol Shin,Weijia Tang,Jeehae Shin,Sheng Li","doi":"10.1021/acsmacrolett.5c00779","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00779","url":null,"abstract":"Polyelectrolyte complex micelles (PCMs) offer a promising platform for oligonucleotide delivery; however, conventional preparation methods based on block copolymers require chemical modification of either the oligonucleotide cargo or the cationic carrier polymer. Here, we report a modified strategy for PCM formation in which the ends of target DNAs (tDNAs) are hybridized with poly(ethylene glycol)-conjugated DNA (DNA-PEG) helper molecules to generate diblock and triblock pseudoblock copolymers (pseudo-BCPs). These pseudo-BCPs are subsequently complexed with branched polyethylenimine (BPEI) to form PCMs. Pseudo-BCPs bearing PEG chains of 5 kg/mol (pseudo-BCP(5k)) or greater yield PCMs with well-defined core-shell morphologies and exhibit excellent temporal stability and salt resistance. In vitro analyses using cultured cells demonstrate that all PCM systems show enhanced cellular uptake relative to free tDNA, with pseudo-BCP(5k)-derived PCMs exhibiting the highest efficiency. These results establish pseudo-BCP-based PCM assembly as a feasible new route to prepare nanocarriers for oligonucleotide delivery.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"397 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056739","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}
Catching-by-polymerization (CBP) is a recently developed DNA purification strategy that works by covalently anchoring target sequences within a hydrogel. In this study, we evaluated CBP for purifying non-biological poly(phosphodiester)s. These polymers were produced via automated solid-phase synthesis using 2-cyanoethyl (3-dimethoxytrityloxy-propyl) diisopropylphosphoramidite as a model monomer. At the final step of the iterative synthesis, a specially designed CBP linker was attached to the polymer chains. This linker includes (i) a reactive phosphoramidite group, (ii) a preloaded monomer unit, (iii) a cleavable trityl moiety, (iv) a spacer, and (v) a polymerizable methacrylamide terminus. Following cleavage from the solid support, the polymers were incorporated into a hydrogel network through aqueous radical copolymerization with N,N-dimethylacrylamide and bis-acrylamide. Subsequent washing removed defective chains, which had been capped during synthesis and, therefore, lacked the covalent linkage required for hydrogel attachment. The correctly synthesized sequences were then released from the gel by detritylation and analyzed by HPLC and Mass Spectrometry. These analyses demonstrate that CBP provides an effective and straightforward method for purifying polymers across a range of lengths. Notably, it enabled the isolation of long chains that had not previously been obtained from this monomer, including 150-mer and 170-mer for the first time.
{"title":"Applying Catching-by-Polymerization for the Preparation of Long Sequence-Defined Polymers.","authors":"Zhaozheng Yang,Ala Covas,Quentin Combe,Cyril Antheaume,Laurence Charles,Maria Nerantzaki,Jean-François Lutz","doi":"10.1021/acsmacrolett.5c00833","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00833","url":null,"abstract":"Catching-by-polymerization (CBP) is a recently developed DNA purification strategy that works by covalently anchoring target sequences within a hydrogel. In this study, we evaluated CBP for purifying non-biological poly(phosphodiester)s. These polymers were produced via automated solid-phase synthesis using 2-cyanoethyl (3-dimethoxytrityloxy-propyl) diisopropylphosphoramidite as a model monomer. At the final step of the iterative synthesis, a specially designed CBP linker was attached to the polymer chains. This linker includes (i) a reactive phosphoramidite group, (ii) a preloaded monomer unit, (iii) a cleavable trityl moiety, (iv) a spacer, and (v) a polymerizable methacrylamide terminus. Following cleavage from the solid support, the polymers were incorporated into a hydrogel network through aqueous radical copolymerization with N,N-dimethylacrylamide and bis-acrylamide. Subsequent washing removed defective chains, which had been capped during synthesis and, therefore, lacked the covalent linkage required for hydrogel attachment. The correctly synthesized sequences were then released from the gel by detritylation and analyzed by HPLC and Mass Spectrometry. These analyses demonstrate that CBP provides an effective and straightforward method for purifying polymers across a range of lengths. Notably, it enabled the isolation of long chains that had not previously been obtained from this monomer, including 150-mer and 170-mer for the first time.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"28 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056743","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}
Pub Date : 2026-01-27DOI: 10.1021/acsmacrolett.5c00731
Zilong Chen,Xi Zhang,Jinghang Li,Congshu Feng,Yuyue Xiong,Lesan Yan
Polymer nanocarriers offer significant advantages in antitumor drug delivery; however, achieving a balance between minimizing nonspecific drug release in blood circulation and maximizing specific intracellular drug release remains a critical challenge. To address this, this study developed a cross-linked poly(amino acid) nanocarrier sensitive to intracellular reactive oxygen species (ROS). A novel thioketal-functionalized, ROS-sensitive bicyclic amino acid N-carboxyanhydride (NCA) monomer was designed and synthesized, and ROS-responsive poly(amino acid)s were prepared via ring-opening polymerization. Polymeric nanomicelles loaded with doxorubicin (DOX) were successfully fabricated using a microemulsion method, and their ROS-responsive properties were systematically evaluated. In vitro release experiments demonstrated that the nanocarrier exhibited H2O2 concentration-dependent, ROS-triggered drug release characteristics. The oxidative response behavior of the drug-loaded nanomicelles was further validated in cellular and animal models by introducing the ROS scavenger N-acetylcysteine (NAC). In a 4T1 tumor-bearing mouse model, these drug-loaded nanomicelles showed enhanced tumor retention and superior tumor suppression compared to free DOX. This study demonstrates that thioketal-functionalized poly(amino acid) nanocarriers hold promise in balancing blood circulation stability and intracellular specific drug release, providing a novel design strategy for developing efficient and safe poly(amino acid)-based anticancer nanomedicines.
{"title":"Facile Synthesis of Thioketal-Functionalized Poly(amino acid) Nanocarriers for ROS-Triggered Drug Release in Cancer Therapy.","authors":"Zilong Chen,Xi Zhang,Jinghang Li,Congshu Feng,Yuyue Xiong,Lesan Yan","doi":"10.1021/acsmacrolett.5c00731","DOIUrl":"https://doi.org/10.1021/acsmacrolett.5c00731","url":null,"abstract":"Polymer nanocarriers offer significant advantages in antitumor drug delivery; however, achieving a balance between minimizing nonspecific drug release in blood circulation and maximizing specific intracellular drug release remains a critical challenge. To address this, this study developed a cross-linked poly(amino acid) nanocarrier sensitive to intracellular reactive oxygen species (ROS). A novel thioketal-functionalized, ROS-sensitive bicyclic amino acid N-carboxyanhydride (NCA) monomer was designed and synthesized, and ROS-responsive poly(amino acid)s were prepared via ring-opening polymerization. Polymeric nanomicelles loaded with doxorubicin (DOX) were successfully fabricated using a microemulsion method, and their ROS-responsive properties were systematically evaluated. In vitro release experiments demonstrated that the nanocarrier exhibited H2O2 concentration-dependent, ROS-triggered drug release characteristics. The oxidative response behavior of the drug-loaded nanomicelles was further validated in cellular and animal models by introducing the ROS scavenger N-acetylcysteine (NAC). In a 4T1 tumor-bearing mouse model, these drug-loaded nanomicelles showed enhanced tumor retention and superior tumor suppression compared to free DOX. This study demonstrates that thioketal-functionalized poly(amino acid) nanocarriers hold promise in balancing blood circulation stability and intracellular specific drug release, providing a novel design strategy for developing efficient and safe poly(amino acid)-based anticancer nanomedicines.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"63 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056738","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}
Pub Date : 2026-01-26DOI: 10.1021/acsmacrolett.6c00018
Zhezhe Li, Suzhen Wang, Lili Zhao, Jian Gu, Hailong Che
It has come to our attention that in the Acknowledgments section in the original article (ACS Macro Lett. 2024, 13, 87–93), the funding number is incorrect. The funding number of the National Natural Science Foundation of China should be corrected from “5220317” to “52203175”. This article has not yet been cited by other publications.
我们注意到，在原始文章的致谢部分（ACS Macro Lett. 2024, 13, 87-93），资助编号不正确。国家自然科学基金资助号由“5220317”修改为“52203175”。这篇文章尚未被其他出版物引用。
{"title":"Correction to “Nitric Oxide-Releasing Tubular Polymersomes toward Advanced Gas Therapeutic Carriers”","authors":"Zhezhe Li, Suzhen Wang, Lili Zhao, Jian Gu, Hailong Che","doi":"10.1021/acsmacrolett.6c00018","DOIUrl":"https://doi.org/10.1021/acsmacrolett.6c00018","url":null,"abstract":"It has come to our attention that in the Acknowledgments section in the original article (<i>ACS Macro Lett.</i> 2024, <i>13</i>, 87–93), the funding number is incorrect. The funding number of the National Natural Science Foundation of China should be corrected from “5220317” to “52203175”. This article has not yet been cited by other publications.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"44 1","pages":""},"PeriodicalIF":5.8,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044771","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}
Pub Date : 2026-01-25DOI: 10.1021/acsmacrolett.5c00701
Supriya Bandyopadhyay,Swadesh Paul,Chinmayee Mandar Mhaskar,Ayan Roy Chaudhuri,Anuja Datta,Suhrit Ghosh
This study reveals biomimetic folding and hierarchical self-assembly of a segmented polyurethane by employing multiple noncovalent interactions, operating in orthogonal manner. The polymer contains a pendant donor (D)-acceptor (A) dyad in each repeating unit and urethane groups in its backbone. Intrachain D-A charge-transfer (CT) interaction in the pendant chains and intrachain hydrogen bonding in the polymer backbone work simultaneously (but independently), enabling a multistage folding in a nonpolar solvent, leading to the formation of a remarkably stable secondary structure. This folded structure further self-assembles into a hierarchical fibrillar network through interchain extended H-bonding among the terminal urethane groups and van der Waals interactions, forming a stable organogel with an entangled fibrillar network. Such hierarchical self-assembly of folded chains results in a remarkably stable supramolecular structure with an embedded CT-complex, which was confirmed by variable-temperature UV-vis and circular dichroism spectroscopy. Furthermore, the self-assembled material exhibits prominent piezoelectric properties, with a robust d33 coefficient of 9 ± 3 pm/V, even in the "off-state". This work highlights a promising strategy for creating functional, biomimetic polymers with potential applications in organic micropower energy harvesting.
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