Polymer science has enhanced human life for more than 100 years, and numerous scientific papers have been published in this field. Although reviewing overall trends is valuable, manually processing such a large volume of information is difficult. In this study, we captured trends in polymer science by performing an automated analysis of papers using topic-modeling techniques grounded in natural language processing (NLP). We analyzed the titles and abstracts of papers that contained the keyword “polymer” in their titles and were published from 1991–2023, applying latent Dirichlet allocation (LDA), singular value decomposition (SVD), and nonnegative matrix factorization (NMF) as topic models. This research showed that LDA, SVD, and NMF can capture trends across multiple fields over the past three decades. Accordingly, NLP-based topic models are promising tools for automatically extracting useful information from papers and other textual data in polymer science. Polymer science has enhanced human life for more than 100 years, and numerous scientific papers have been published in this field. In this study, we captured trends in polymer science by performing an automated analysis of the titles and abstracts of papers that contained the keyword “polymer” using topic-modeling techniques grounded in natural language processing (NLP). NLP-based topic models are promising tools for automatically extracting useful information from papers and other textual data in polymer science.
{"title":"Natural language processing-based topic models for analyzing trends in polymer science","authors":"Yoshifumi Amamoto, Yoh-ichi Mototake, Takaaki Ohnishi","doi":"10.1038/s41428-025-01060-6","DOIUrl":"10.1038/s41428-025-01060-6","url":null,"abstract":"Polymer science has enhanced human life for more than 100 years, and numerous scientific papers have been published in this field. Although reviewing overall trends is valuable, manually processing such a large volume of information is difficult. In this study, we captured trends in polymer science by performing an automated analysis of papers using topic-modeling techniques grounded in natural language processing (NLP). We analyzed the titles and abstracts of papers that contained the keyword “polymer” in their titles and were published from 1991–2023, applying latent Dirichlet allocation (LDA), singular value decomposition (SVD), and nonnegative matrix factorization (NMF) as topic models. This research showed that LDA, SVD, and NMF can capture trends across multiple fields over the past three decades. Accordingly, NLP-based topic models are promising tools for automatically extracting useful information from papers and other textual data in polymer science. Polymer science has enhanced human life for more than 100 years, and numerous scientific papers have been published in this field. In this study, we captured trends in polymer science by performing an automated analysis of the titles and abstracts of papers that contained the keyword “polymer” using topic-modeling techniques grounded in natural language processing (NLP). NLP-based topic models are promising tools for automatically extracting useful information from papers and other textual data in polymer science.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 9","pages":"1033-1041"},"PeriodicalIF":2.7,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01060-6.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144990814","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-26DOI: 10.1038/s41428-025-01054-4
Shigehito Osawa
A water-soluble polymer with dipicolylamide (DPAm) groups as the metal ligand was designed through the condensation reaction of a poly(maleic anhydride) derivative with dipicolylamine. The obtained polymer forms complexes with copper ions and accelerates the copper-catalyzed redox reaction at a mixing molar ratio of 1 or little less than 1, owing to the locally concentrated state of copper. In contrast, the Cu-catalyzed reaction was prohibited at mixing molar ratios above 2, verifying the properties of the polymer as a metal ligand to control the redox reaction.
{"title":"A water-soluble polymer having blue color and metal–ligand property derived from dipicolylamide structures","authors":"Shigehito Osawa","doi":"10.1038/s41428-025-01054-4","DOIUrl":"10.1038/s41428-025-01054-4","url":null,"abstract":"A water-soluble polymer with dipicolylamide (DPAm) groups as the metal ligand was designed through the condensation reaction of a poly(maleic anhydride) derivative with dipicolylamine. The obtained polymer forms complexes with copper ions and accelerates the copper-catalyzed redox reaction at a mixing molar ratio of 1 or little less than 1, owing to the locally concentrated state of copper. In contrast, the Cu-catalyzed reaction was prohibited at mixing molar ratios above 2, verifying the properties of the polymer as a metal ligand to control the redox reaction.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 11","pages":"1275-1278"},"PeriodicalIF":2.7,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41428-025-01054-4.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145436556","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-21DOI: 10.1038/s41428-025-01053-5
Hsuan-Hung Liu
The self-assembly of ABC amphiphilic multiblock terpolymers into multicompartment micelles in dilute solutions has gained significant attention. In this study, we employed the three-dimensional (3D) self-consistent field theory (SCFT) method to explore the micellization behavior of amphiphilic linear A-b-(B-alt-C)₂-b-A multiblock terpolymers in a solvent selective for the terminal A block. A variety of intriguing micellar structures were identified, including B- and C-disk segmented vesicles, B- and C-toroidal packing within a tubular structure, BC-segmented toroidal micelles, infinite BC-segmented cylindrical micelles, and BC-mixed toroidal micelles. Owing to the connection of blocks B and C with block A, the segmented arrangement of layers B and C follows the axial direction of the structures. As the volume fraction of the A block (fA) decreases, a structural transition from vesicles to micelles occurs in the linear A-b-(B-alt-C)₂-b-A system, in contrast with the behavior of A(BC)n multiblock terpolymers, which transition from micelles to vesicles. The SCFT method has proven to be an effective tool for identifying molecular architectures with the potential to self-assemble into complex, technologically valuable hierarchical structures. This study systematically explored the micellization of A-b-(B-alt-C)₂-b-A multiblock terpolymers using SCFT, revealing how block composition, interaction strength, and solvent selectivity govern diverse morphologies—including segmented vesicles, toroids, and cylinders. Symmetric and asymmetric solvent conditions yielded distinct BC-segmented structures, while poor solvent conditions led to hierarchical transitions. These insights offer design principles for functional materials like drug carriers by enabling precise control over self-assembled nanostructures.
{"title":"Discovering the micellization of linear A-b-(B-alt-C)2-b-A multiblock terpolymers in selective solvents","authors":"Hsuan-Hung Liu","doi":"10.1038/s41428-025-01053-5","DOIUrl":"10.1038/s41428-025-01053-5","url":null,"abstract":"The self-assembly of ABC amphiphilic multiblock terpolymers into multicompartment micelles in dilute solutions has gained significant attention. In this study, we employed the three-dimensional (3D) self-consistent field theory (SCFT) method to explore the micellization behavior of amphiphilic linear A-b-(B-alt-C)₂-b-A multiblock terpolymers in a solvent selective for the terminal A block. A variety of intriguing micellar structures were identified, including B- and C-disk segmented vesicles, B- and C-toroidal packing within a tubular structure, BC-segmented toroidal micelles, infinite BC-segmented cylindrical micelles, and BC-mixed toroidal micelles. Owing to the connection of blocks B and C with block A, the segmented arrangement of layers B and C follows the axial direction of the structures. As the volume fraction of the A block (fA) decreases, a structural transition from vesicles to micelles occurs in the linear A-b-(B-alt-C)₂-b-A system, in contrast with the behavior of A(BC)n multiblock terpolymers, which transition from micelles to vesicles. The SCFT method has proven to be an effective tool for identifying molecular architectures with the potential to self-assemble into complex, technologically valuable hierarchical structures. This study systematically explored the micellization of A-b-(B-alt-C)₂-b-A multiblock terpolymers using SCFT, revealing how block composition, interaction strength, and solvent selectivity govern diverse morphologies—including segmented vesicles, toroids, and cylinders. Symmetric and asymmetric solvent conditions yielded distinct BC-segmented structures, while poor solvent conditions led to hierarchical transitions. These insights offer design principles for functional materials like drug carriers by enabling precise control over self-assembled nanostructures.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 9","pages":"959-973"},"PeriodicalIF":2.7,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144990858","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-12DOI: 10.1038/s41428-025-01050-8
Hirotake Udono, Tomoya Maruyama, Nathan N. Evangelista, Naoki Yoshida, Yuta Aizaki, Kei Goraku, Kanta Takagi, Ryoya Hasegawa, Masahiro Takinoue
Research on biomolecular liquid-state condensates (droplets) in cells has sparked burgeoning interest among synthetic biologists in programmable droplets assembled from synthetic nucleic acids––information-encoding biomolecules amenable to facile synthesis, versatile sequence design, and molecular decoration. Analogous to biological condensates, well-engineered nanostructures consisting of DNA or RNA strands, which are negatively charged, phase-separate into membrane-free droplets via weak multivalent specific interactions or via electrostatic attraction with positively charged peptides. The membraneless compartments of these droplets allow stimuli responsiveness to molecular cues (DNA/RNA, enzymes, etc.). Nucleic acid droplets thus offer a powerful platform for programming their various features, including hierarchical structuring, molecular recognition capabilities, droplet interactions, and physical properties. Specifically, we describe a DNA linker that serves as a programmable surfactant bridging immiscible DNA phases, which, upon molecular inputs, alters their separation level from mixed to divided states. Furthermore, a rational combination of these features can create intelligent liquid-state architectures capable of naturally unachievable functions and dynamics, such as Boolean operations and directional motion. To predict how molecular-level encoding leads to macroscopic characteristics, coarse-grained models, which treat nucleic acids as strings of interacting rigid beads, are widely utilized. This emerging field represents a cross-disciplinary integration of various fields, from biophysics to information science. This Focus Review highlights recent advances in synthetic nucleic-acid droplets and their far-reaching potential, concluding with perspectives on their future directions and challenges. Emerging from DNA/RNA nanoengineering, synthetic nucleic-acid liquid condensates, forming via phase separation of nanostructures, have attracted increasing attention as a powerful platform for synthetic biology and molecular computing. Base-sequence specificity allows for molecular encoding for their organization, functions, and droplet interactions. Authors overview key topics of these programmable droplets, from dynamics programmability to numerical modeling. Additionally, this review highlights cross-linker modules, which enable dynamic compartmentalization and division of droplets triggered by specific molecular input. These modules allow the condensate phase behavior to represent Boolean logic operation.
{"title":"Synthetic nucleic-acid droplets: a bioprogramming platform for designer microliquids","authors":"Hirotake Udono, Tomoya Maruyama, Nathan N. Evangelista, Naoki Yoshida, Yuta Aizaki, Kei Goraku, Kanta Takagi, Ryoya Hasegawa, Masahiro Takinoue","doi":"10.1038/s41428-025-01050-8","DOIUrl":"10.1038/s41428-025-01050-8","url":null,"abstract":"Research on biomolecular liquid-state condensates (droplets) in cells has sparked burgeoning interest among synthetic biologists in programmable droplets assembled from synthetic nucleic acids––information-encoding biomolecules amenable to facile synthesis, versatile sequence design, and molecular decoration. Analogous to biological condensates, well-engineered nanostructures consisting of DNA or RNA strands, which are negatively charged, phase-separate into membrane-free droplets via weak multivalent specific interactions or via electrostatic attraction with positively charged peptides. The membraneless compartments of these droplets allow stimuli responsiveness to molecular cues (DNA/RNA, enzymes, etc.). Nucleic acid droplets thus offer a powerful platform for programming their various features, including hierarchical structuring, molecular recognition capabilities, droplet interactions, and physical properties. Specifically, we describe a DNA linker that serves as a programmable surfactant bridging immiscible DNA phases, which, upon molecular inputs, alters their separation level from mixed to divided states. Furthermore, a rational combination of these features can create intelligent liquid-state architectures capable of naturally unachievable functions and dynamics, such as Boolean operations and directional motion. To predict how molecular-level encoding leads to macroscopic characteristics, coarse-grained models, which treat nucleic acids as strings of interacting rigid beads, are widely utilized. This emerging field represents a cross-disciplinary integration of various fields, from biophysics to information science. This Focus Review highlights recent advances in synthetic nucleic-acid droplets and their far-reaching potential, concluding with perspectives on their future directions and challenges. Emerging from DNA/RNA nanoengineering, synthetic nucleic-acid liquid condensates, forming via phase separation of nanostructures, have attracted increasing attention as a powerful platform for synthetic biology and molecular computing. Base-sequence specificity allows for molecular encoding for their organization, functions, and droplet interactions. Authors overview key topics of these programmable droplets, from dynamics programmability to numerical modeling. Additionally, this review highlights cross-linker modules, which enable dynamic compartmentalization and division of droplets triggered by specific molecular input. These modules allow the condensate phase behavior to represent Boolean logic operation.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 8","pages":"845-862"},"PeriodicalIF":2.7,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-025-01050-8.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144774174","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A theoretical-computational scheme for analyzing the effect of an added cosolvent on the aggregation equilibrium of a biomolecule is presented. The scheme is based on the relation that the derivative of the excess chemical potential with respect to the cosolvent concentration is determined by the corresponding derivative of the solvation free energy averaged over the solute configurations. The role of solvation is highlighted in the cosolvent-induced shift in the aggregation equilibrium of a biomolecule, and an illustrative analysis with all-atom models is provided for an amyloid peptide by employing the energy-representation method to compute the solvation free energy. Adenosine triphosphate (ATP) and urea are adopted as a cosolvent added to water, and the former is seen to inhibit aggregation more effectively than the latter. The solvation free energy is decomposed into the contributions from intermolecular-interaction components such as electrostatic, van der Waals, and excluded-volume, and it is found that the cosolvent effects are governed by the van der Waals interaction for both of ATP and urea. A theoretical-computational scheme is formulated to analyze the shift in the aggregation equilibrium of a biomolecule upon addition of a cosolvent. The cosolvent-induced change in the solvation free energy plays the central role in the formulation, and it is shown for a model peptide that the ATP and urea cosolvents make the solvent environment more favorable for dissociated monomers than for aggregates. The effect of ATP to inhibit aggregation is brought by van der Waals interactions due to cancellation of the electrostatic effects between ATP and water.
{"title":"Free-energy analysis of cosolvent effects on biomolecular aggregation","authors":"Nobuyuki Matubayasi, Tuan Minh Do, Dominik Horinek","doi":"10.1038/s41428-025-01041-9","DOIUrl":"10.1038/s41428-025-01041-9","url":null,"abstract":"A theoretical-computational scheme for analyzing the effect of an added cosolvent on the aggregation equilibrium of a biomolecule is presented. The scheme is based on the relation that the derivative of the excess chemical potential with respect to the cosolvent concentration is determined by the corresponding derivative of the solvation free energy averaged over the solute configurations. The role of solvation is highlighted in the cosolvent-induced shift in the aggregation equilibrium of a biomolecule, and an illustrative analysis with all-atom models is provided for an amyloid peptide by employing the energy-representation method to compute the solvation free energy. Adenosine triphosphate (ATP) and urea are adopted as a cosolvent added to water, and the former is seen to inhibit aggregation more effectively than the latter. The solvation free energy is decomposed into the contributions from intermolecular-interaction components such as electrostatic, van der Waals, and excluded-volume, and it is found that the cosolvent effects are governed by the van der Waals interaction for both of ATP and urea. A theoretical-computational scheme is formulated to analyze the shift in the aggregation equilibrium of a biomolecule upon addition of a cosolvent. The cosolvent-induced change in the solvation free energy plays the central role in the formulation, and it is shown for a model peptide that the ATP and urea cosolvents make the solvent environment more favorable for dissociated monomers than for aggregates. The effect of ATP to inhibit aggregation is brought by van der Waals interactions due to cancellation of the electrostatic effects between ATP and water.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 8","pages":"773-784"},"PeriodicalIF":2.7,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-025-01041-9.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144774173","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-09DOI: 10.1038/s41428-025-01043-7
Bing Jhang Li, Biplab K C, Teruki Nii, Takeshi Mori, Yoshiki Katayama, Akihiro Kishimura
Biomolecular condensates offer a versatile platform for the accumulation of biomacromolecules, particularly proteins. This study investigated synthetic complex coacervates as a model of biomolecular condensates and developed a novel tool for the intracellular delivery of proteins to overcome the issues of cytotoxicity and poor cellular uptake. By optimizing preparation conditions and chemical structures and developing a simple pre-coating method, we achieved an improvement in the interaction and internalization of coacervates for HeLa and Jurkat cells and the reduction of cytotoxicity. Furthermore, the use of charge-density reduced polymers enabled the effective encapsulation and intracellular delivery of various proteins. The mechanism of cellular internalization was also investigated, and macropinocytosis was concluded to be a primary internalization pathway. These findings provide a foundation for future advancements in biomaterials. Complex coacervates (CCs) are a promising platform for protein encapsulation obtained via simple mixing of some components. Using the novel precoating treatment of living cells, the cellular internalization of CCs was greatly enhanced. Besides, upon using the side-chain modified aniomers for CC fabrication, a wide variety of proteins were successfully encapsulated, which can expand the future biomedical application of CCs.
{"title":"Designable synthetic complex coacervates enabling protein delivery to cells","authors":"Bing Jhang Li, Biplab K C, Teruki Nii, Takeshi Mori, Yoshiki Katayama, Akihiro Kishimura","doi":"10.1038/s41428-025-01043-7","DOIUrl":"10.1038/s41428-025-01043-7","url":null,"abstract":"Biomolecular condensates offer a versatile platform for the accumulation of biomacromolecules, particularly proteins. This study investigated synthetic complex coacervates as a model of biomolecular condensates and developed a novel tool for the intracellular delivery of proteins to overcome the issues of cytotoxicity and poor cellular uptake. By optimizing preparation conditions and chemical structures and developing a simple pre-coating method, we achieved an improvement in the interaction and internalization of coacervates for HeLa and Jurkat cells and the reduction of cytotoxicity. Furthermore, the use of charge-density reduced polymers enabled the effective encapsulation and intracellular delivery of various proteins. The mechanism of cellular internalization was also investigated, and macropinocytosis was concluded to be a primary internalization pathway. These findings provide a foundation for future advancements in biomaterials. Complex coacervates (CCs) are a promising platform for protein encapsulation obtained via simple mixing of some components. Using the novel precoating treatment of living cells, the cellular internalization of CCs was greatly enhanced. Besides, upon using the side-chain modified aniomers for CC fabrication, a wide variety of proteins were successfully encapsulated, which can expand the future biomedical application of CCs.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 8","pages":"911-922"},"PeriodicalIF":2.7,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-025-01043-7.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144774167","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-08DOI: 10.1038/s41428-025-01037-5
Ryou Kubota
Coacervates are condensed, liquid-like assemblies formed through liquid–liquid phase separation via associative interactions among molecular components. Owing to their membraneless nature, coacervates exhibit unique dynamic features, such as coalescence and molecular sequestration, thus serving as promising platforms for drug delivery and the regulation of biological events. In this Focus Review, representative examples of simple coacervates composed of phase-separating low-molecular-weight molecules (LMWMs) are highlighted. This review provides a minimalist design strategy for LMWM-based simple coacervates based on surfactants and peptides and summarizes their unique functions, including stimulus-responsive structural transformations. The sophisticated design of these droplets is expected to enable a wide range of applications, including studies on the origins of life, the development of artificial cells, intracellular and in vivo protein delivery, biosensing, and molecular computing. Simple coacervates formed from low-molecular-weight molecules offer unique dynamic features, including stimulus-responsive phase transitions and reversible assembly/disassembly. This Focus Review highlights molecular design strategies, from historical perspectives to recent advancements. The sophisticated design of coacervates provides new opportunities in protocell models, biosensing, and drug delivery systems.
{"title":"A minimalist design approach to simple coacervates from low-molecular-weight components","authors":"Ryou Kubota","doi":"10.1038/s41428-025-01037-5","DOIUrl":"10.1038/s41428-025-01037-5","url":null,"abstract":"Coacervates are condensed, liquid-like assemblies formed through liquid–liquid phase separation via associative interactions among molecular components. Owing to their membraneless nature, coacervates exhibit unique dynamic features, such as coalescence and molecular sequestration, thus serving as promising platforms for drug delivery and the regulation of biological events. In this Focus Review, representative examples of simple coacervates composed of phase-separating low-molecular-weight molecules (LMWMs) are highlighted. This review provides a minimalist design strategy for LMWM-based simple coacervates based on surfactants and peptides and summarizes their unique functions, including stimulus-responsive structural transformations. The sophisticated design of these droplets is expected to enable a wide range of applications, including studies on the origins of life, the development of artificial cells, intracellular and in vivo protein delivery, biosensing, and molecular computing. Simple coacervates formed from low-molecular-weight molecules offer unique dynamic features, including stimulus-responsive phase transitions and reversible assembly/disassembly. This Focus Review highlights molecular design strategies, from historical perspectives to recent advancements. The sophisticated design of coacervates provides new opportunities in protocell models, biosensing, and drug delivery systems.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 8","pages":"815-829"},"PeriodicalIF":2.7,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-025-01037-5.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144774176","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-02DOI: 10.1038/s41428-025-01044-6
Haruto Tanaka, Tomoyuki Toda, Katsuhiko Takenaka
The control of the microstructure of polymers derived from conjugated dienes was investigated using coordination polymerization. In this work, we conducted coordination polymerization of (Z)-1-phenyl[3]dendralene (1Z-P3D) as a diene monomer. The polymerization of 1Z-P3D using a homogeneous neodymium catalyst yielded poly(1Z-P3D) with predominantly 4,6-structures (~100%). Coordination polymerization of (Z)-1-phenyl[3]dendralene(1Z-P3D) was investigated using by homogeneous neodymium catalyst. The polymer was obtained under the appropriate polymerization condition and the most part of polymer became insoluble in the progress of isolation. The microstructure of poly(1Z-P3D) prepared by neodymium catalyst was only 4,6-structure whereas poly(1Z-P3D) prepared by anionic initiator contained a predominant amount of 1,4-structure.
{"title":"Coordination polymerization of (Z)-1-phenyl[3]dendralene by a neodymium catalyst","authors":"Haruto Tanaka, Tomoyuki Toda, Katsuhiko Takenaka","doi":"10.1038/s41428-025-01044-6","DOIUrl":"10.1038/s41428-025-01044-6","url":null,"abstract":"The control of the microstructure of polymers derived from conjugated dienes was investigated using coordination polymerization. In this work, we conducted coordination polymerization of (Z)-1-phenyl[3]dendralene (1Z-P3D) as a diene monomer. The polymerization of 1Z-P3D using a homogeneous neodymium catalyst yielded poly(1Z-P3D) with predominantly 4,6-structures (~100%). Coordination polymerization of (Z)-1-phenyl[3]dendralene(1Z-P3D) was investigated using by homogeneous neodymium catalyst. The polymer was obtained under the appropriate polymerization condition and the most part of polymer became insoluble in the progress of isolation. The microstructure of poly(1Z-P3D) prepared by neodymium catalyst was only 4,6-structure whereas poly(1Z-P3D) prepared by anionic initiator contained a predominant amount of 1,4-structure.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 9","pages":"1043-1048"},"PeriodicalIF":2.7,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144990859","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Alpha hydroxy acids (AHAs) play various roles in modern biology such as in metabolism, but could have played different roles as “non-biomolecules” at the origins of life. Specifically, lactic acid (LA) and other AHAs can polymerize into polyesters and subsequently assemble into membraneless microdroplets (MMDs) upon dehydration-rehydration cycles, suggesting that polyester MMDs could have been relevant protocell models on early Earth. However, in particular, how the harsh conditions of early Earth, namely salinity and decreased reactant volume/concentration, could have affected primitive LA polymerization and subsequent MMD assembly is unclear. In this study, we found that while monovalent salts such as NaCl and KCl did not inhibit LA polymerization and MMD assembly even at high concentrations (up to 1 M), divalent salts such as MgCl2 and CaCl2 were inhibitory at much lower concentrations. Additionally, we found that lower reaction volumes and concentrations, potentially simulating confined microenvironments on early Earth, still supported LA polymerization and MMD assembly to some extent, albeit with decreased efficiency. These results suggest that early Earth’s environmental conditions could have still supported the polymerization of LA and the formation of MMD-based protocells in a variety of settings despite being quite harsh and variable. Lactic acid (LA), likely abundant on early Earth, can polymerize into polyesters and assemble into membraneless microdroplets (MMDs). However, how the harsh conditions of early Earth could have affected primitive LA polymerization and subsequent MMD assembly is unclear. In this study, we probed the effect of salinity, reaction volume, and reaction concentration on primitive LA polymerization and subsequent MMD assembly, and find that early Earth’s harsh environmental conditions could have still supported the formation of LA-based MMD protocells in a variety of settings.
{"title":"A deeper dive into primitive polylactate polymerization and microdroplet assembly under restrictive early Earth conditions","authors":"Mahendran Sithamparam, Ming-Jing He, Navaniswaran Tharumen, Rehana Afrin, Niannian Ding, Chen Chen, Ruiqin Yi, Po-Hsiang Wang, Tony Z. Jia, Kuhan Chandru","doi":"10.1038/s41428-025-01048-2","DOIUrl":"10.1038/s41428-025-01048-2","url":null,"abstract":"Alpha hydroxy acids (AHAs) play various roles in modern biology such as in metabolism, but could have played different roles as “non-biomolecules” at the origins of life. Specifically, lactic acid (LA) and other AHAs can polymerize into polyesters and subsequently assemble into membraneless microdroplets (MMDs) upon dehydration-rehydration cycles, suggesting that polyester MMDs could have been relevant protocell models on early Earth. However, in particular, how the harsh conditions of early Earth, namely salinity and decreased reactant volume/concentration, could have affected primitive LA polymerization and subsequent MMD assembly is unclear. In this study, we found that while monovalent salts such as NaCl and KCl did not inhibit LA polymerization and MMD assembly even at high concentrations (up to 1 M), divalent salts such as MgCl2 and CaCl2 were inhibitory at much lower concentrations. Additionally, we found that lower reaction volumes and concentrations, potentially simulating confined microenvironments on early Earth, still supported LA polymerization and MMD assembly to some extent, albeit with decreased efficiency. These results suggest that early Earth’s environmental conditions could have still supported the polymerization of LA and the formation of MMD-based protocells in a variety of settings despite being quite harsh and variable. Lactic acid (LA), likely abundant on early Earth, can polymerize into polyesters and assemble into membraneless microdroplets (MMDs). However, how the harsh conditions of early Earth could have affected primitive LA polymerization and subsequent MMD assembly is unclear. In this study, we probed the effect of salinity, reaction volume, and reaction concentration on primitive LA polymerization and subsequent MMD assembly, and find that early Earth’s harsh environmental conditions could have still supported the formation of LA-based MMD protocells in a variety of settings.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 8","pages":"897-910"},"PeriodicalIF":2.7,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-025-01048-2.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144774178","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Cytosine-rich sequences can fold into a four-stranded structure called the i-motif. These i-motif-forming DNA sequences are enriched in the promoter regions of cancer-related genes and telomeres, indicating their biological importance. Interestingly, an i-motif-forming DNA oligonucleotide derived from telomeres was reported to undergo liquid‒liquid phase separation (LLPS), suggesting that i-motifs regulate cellular processes involving gene expression via LLPS. However, it is still unclear whether i-motifs are able to undergo LLPS under physiological conditions because i-motif structures are thermodynamically stable only under acidic conditions. In this study, we systematically studied the thermodynamics of a series of i-motif-forming oligonucleotides and their ability to undergo LLPS under molecular crowding conditions that mimic the conditions inside cells at various pH values. The thermodynamic analyses revealed that crowding reagents with higher molecular weights stabilize the i-motif structure and increase its pKa. Moreover, we demonstrated that i-motif structures stabilized by molecular crowding undergo LLPS under neutral and even basic conditions. On the other hand, mutated oligonucleotides that do not form stable i-motif structures did not undergo LLPS. These results indicate that i-motif-forming DNAs can robustly and widely undergo LLPS depending on cellular environmental factors such as the solution pH, composition of crowding reagents and degree of molecular crowding in living cells. We showed that various i-motif-forming DNAs undergo LLPS with cationic peptide in acidic conditions. Considering cellular condition, we further investigated LLPS of DNAs in the molecular crowding conditions at physiological pH. LLPS is promoted by molecular crowding conditions at even in basic pH through stabilization of i-motif structure by molecular crowding condition.
{"title":"Liquid‒liquid phase separation induced by i-motif DNA under molecular crowding conditions","authors":"Ryosuke Suzuki, Mitsuki Tsuruta, Sumit Shil, Kosei Morohashi, Keiko Kawauchi, Daisuke Miyoshi","doi":"10.1038/s41428-025-01047-3","DOIUrl":"10.1038/s41428-025-01047-3","url":null,"abstract":"Cytosine-rich sequences can fold into a four-stranded structure called the i-motif. These i-motif-forming DNA sequences are enriched in the promoter regions of cancer-related genes and telomeres, indicating their biological importance. Interestingly, an i-motif-forming DNA oligonucleotide derived from telomeres was reported to undergo liquid‒liquid phase separation (LLPS), suggesting that i-motifs regulate cellular processes involving gene expression via LLPS. However, it is still unclear whether i-motifs are able to undergo LLPS under physiological conditions because i-motif structures are thermodynamically stable only under acidic conditions. In this study, we systematically studied the thermodynamics of a series of i-motif-forming oligonucleotides and their ability to undergo LLPS under molecular crowding conditions that mimic the conditions inside cells at various pH values. The thermodynamic analyses revealed that crowding reagents with higher molecular weights stabilize the i-motif structure and increase its pKa. Moreover, we demonstrated that i-motif structures stabilized by molecular crowding undergo LLPS under neutral and even basic conditions. On the other hand, mutated oligonucleotides that do not form stable i-motif structures did not undergo LLPS. These results indicate that i-motif-forming DNAs can robustly and widely undergo LLPS depending on cellular environmental factors such as the solution pH, composition of crowding reagents and degree of molecular crowding in living cells. We showed that various i-motif-forming DNAs undergo LLPS with cationic peptide in acidic conditions. Considering cellular condition, we further investigated LLPS of DNAs in the molecular crowding conditions at physiological pH. LLPS is promoted by molecular crowding conditions at even in basic pH through stabilization of i-motif structure by molecular crowding condition.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 8","pages":"931-940"},"PeriodicalIF":2.7,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-025-01047-3.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144774177","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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