Pub Date : 2024-07-01DOI: 10.1038/s41428-024-00930-9
Kan Hatakeyama-Sato, Hiroki Ishikawa, Shinya Takaishi, Yasuhiko Igarashi, Yuta Nabae, Teruaki Hayakawa
A semiautomated system for synthesizing polyamic acid particles using a custom liquid-handling device and a robotic arm is proposed in this study. Integration of cameras and a multimodal large language model facilitates continuous monitoring and documentation, enhancing objectivity in synthetic experiments and enabling future advancements in experimental research. This study proposes a semiautomated system for synthesizing polyamic acid particles using a custom liquid-handling device and a robotic arm. Integrating cameras and a multimodal large language model enhances continuous monitoring and documentation, improving objectivity in synthetic experiments and enabling future advancements in research.
{"title":"Semiautomated experiment with a robotic system and data generation by foundation models for synthesis of polyamic acid particles","authors":"Kan Hatakeyama-Sato, Hiroki Ishikawa, Shinya Takaishi, Yasuhiko Igarashi, Yuta Nabae, Teruaki Hayakawa","doi":"10.1038/s41428-024-00930-9","DOIUrl":"10.1038/s41428-024-00930-9","url":null,"abstract":"A semiautomated system for synthesizing polyamic acid particles using a custom liquid-handling device and a robotic arm is proposed in this study. Integration of cameras and a multimodal large language model facilitates continuous monitoring and documentation, enhancing objectivity in synthetic experiments and enabling future advancements in experimental research. This study proposes a semiautomated system for synthesizing polyamic acid particles using a custom liquid-handling device and a robotic arm. Integrating cameras and a multimodal large language model enhances continuous monitoring and documentation, improving objectivity in synthetic experiments and enabling future advancements in research.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 11","pages":"977-986"},"PeriodicalIF":2.3,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00930-9.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141503147","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 : 2024-06-18DOI: 10.1038/s41428-024-00918-5
Kazuki Shibasaki, Yu-I Hsu, Hiroshi Uyama
General-purpose petroleum-derived plastic remains in the environment for long periods and has significant impacts on oceans and land. Biodegradable and biomass plastics are being developed around the world as countermeasures. A poly(lactic acid) (PLA)/thermoplastic starch (TPS) blend is a promising ecofriendly alternative to biodegradable plastic made from plants. However, owing to the hydrophilicity of starch and the hydrophobicity of PLA, phase separation occurs between PLA and starch. Furthermore, PLA/TPS blends have poor water resistance because of the presence of starch, limiting their applications. In this study, to improve the affinity of PLA for starch, oligo(lactic acid)-grafted starch (OLAgSt) was synthesized as a compatibilizer for PLA/TPS blends, and the effect of its addition to PLA/TPS blends was evaluated. OLAgSt with different OLA molecular weights and degrees of substitution (DS) were synthesized, and their effects on PLA/TPS were compared. The results indicated that OLAgSt functioned as a good compatibilizer, improving the dispersibility of TPS in PLA with 4 wt% OLAgSt added to PLA/TPS and improving the water resistance. Moreover, the OLA molecular weight of OLAgSt was greater than that of DS. These results are expected to facilitate the development of PLA/TPS applications in the food packaging and biomedical fields. Blends of poly(lactic acid) (PLA) and thermoplastic starch (TPS) are promising biodegradable plastics, although their poor compatibility results in poor physical properties. In this study, oligo(lactic acid)-grafted starch (OLAgSt) was synthesized and added to PLA/TPS blends as a compatibilizer, and the physical properties of the obtained blends were evaluated. OLAgSt was synthesized by ring-opening polymerization of L-lactide using the hydroxy group of tapioca starch as an initiator. OLAgSt not only enhanced the dispersion of TPS within PLA, but also improved the biodegradability of the blend in a seawater environment.
{"title":"Improvement in the physical properties of poly(lactic acid)/thermoplastic starch blends using oligo(lactic acid)-grafted starch","authors":"Kazuki Shibasaki, Yu-I Hsu, Hiroshi Uyama","doi":"10.1038/s41428-024-00918-5","DOIUrl":"10.1038/s41428-024-00918-5","url":null,"abstract":"General-purpose petroleum-derived plastic remains in the environment for long periods and has significant impacts on oceans and land. Biodegradable and biomass plastics are being developed around the world as countermeasures. A poly(lactic acid) (PLA)/thermoplastic starch (TPS) blend is a promising ecofriendly alternative to biodegradable plastic made from plants. However, owing to the hydrophilicity of starch and the hydrophobicity of PLA, phase separation occurs between PLA and starch. Furthermore, PLA/TPS blends have poor water resistance because of the presence of starch, limiting their applications. In this study, to improve the affinity of PLA for starch, oligo(lactic acid)-grafted starch (OLAgSt) was synthesized as a compatibilizer for PLA/TPS blends, and the effect of its addition to PLA/TPS blends was evaluated. OLAgSt with different OLA molecular weights and degrees of substitution (DS) were synthesized, and their effects on PLA/TPS were compared. The results indicated that OLAgSt functioned as a good compatibilizer, improving the dispersibility of TPS in PLA with 4 wt% OLAgSt added to PLA/TPS and improving the water resistance. Moreover, the OLA molecular weight of OLAgSt was greater than that of DS. These results are expected to facilitate the development of PLA/TPS applications in the food packaging and biomedical fields. Blends of poly(lactic acid) (PLA) and thermoplastic starch (TPS) are promising biodegradable plastics, although their poor compatibility results in poor physical properties. In this study, oligo(lactic acid)-grafted starch (OLAgSt) was synthesized and added to PLA/TPS blends as a compatibilizer, and the physical properties of the obtained blends were evaluated. OLAgSt was synthesized by ring-opening polymerization of L-lactide using the hydroxy group of tapioca starch as an initiator. OLAgSt not only enhanced the dispersion of TPS within PLA, but also improved the biodegradability of the blend in a seawater environment.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 10","pages":"905-913"},"PeriodicalIF":2.3,"publicationDate":"2024-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00918-5.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141528869","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 : 2024-06-18DOI: 10.1038/s41428-024-00929-2
Takuma Kureha, Takuto Hirayama, Taichi Nishi
In this study, gel-phase diagrams of temperature-responsive and biocompatible polymers were obtained, and the characteristic gelation behaviors of the polymers were examined. The polymers are based on three oligoethylene glycol methyl ether methacrylate (OEGMA) monomers with different numbers of ethylene oxide (EO) units, i.e., with side chains that differ in length. The gelation thresholds depend on the OEGMA and crosslinker concentrations as well as the side chain length. Long EO side chains fill the polymerization system and reduce the concentration of polymer overlap, resulting in a high ability to occupy the system. Furthermore, the EO side chains may engage in self-crosslinking, i.e., polymers can branch and grow from the side chains depending on their length, resulting in a high bond probability. Based on these unique behavior patterns, gelation occurs more readily as the length of the side chains increases. We also synthesized ultralow crosslinked pOEGMA gels by tuning the gelation conditions; these gels exhibited improved swelling capacity and temperature responsiveness. These results should facilitate the development of a synthesis strategy to control the physical properties and structures of these materials for advanced applications, such as biofilms, actuators, and carriers. The gel-phase diagrams of temperature-responsive and biocompatible polymers with ethylene oxide (EO) side chains that differ in length were obtained. The gelation thresholds of the polymers depend not only on the monomer and crosslinker concentrations but also on the EO side chain lengths. Long EO side chains reduce the polymer overlap concentration. Furthermore, the EO side chains can engage in self-crosslinking, i.e., polymers can grow from the side chains depending on their length. These unique behaviors indicate that gelation occurs more readily with increasing the side chain length.
本研究获得了具有温度响应性和生物相容性的聚合物的凝胶相图，并研究了这些聚合物的凝胶化特性。这些聚合物基于三种具有不同环氧乙烷（EO）单元数（即侧链长度不同）的低聚乙二醇甲醚甲基丙烯酸酯（OEGMA）单体。凝胶化阈值取决于 OEGMA 和交联剂的浓度以及侧链的长度。长的 EO 侧链可填充聚合体系，降低聚合物重叠的浓度，从而提高占据体系的能力。此外，环氧乙烷侧链可能会发生自交联，即聚合物会根据侧链的长度发生分支和生长，从而产生较高的键合概率。基于这些独特的行为模式，随着侧链长度的增加，凝胶化更容易发生。我们还通过调整凝胶化条件合成了超低交联 pOEGMA 凝胶；这些凝胶显示出更强的溶胀能力和温度响应性。这些结果将有助于开发一种合成策略，以控制这些材料的物理性质和结构，从而应用于生物膜、致动器和载体等先进领域。
{"title":"Phase diagram for the gelation of temperature-responsive and biocompatible poly(oligo ethylene glycol methyl ether methacrylate) polymers in aqueous free-radical polymerization reactions","authors":"Takuma Kureha, Takuto Hirayama, Taichi Nishi","doi":"10.1038/s41428-024-00929-2","DOIUrl":"10.1038/s41428-024-00929-2","url":null,"abstract":"In this study, gel-phase diagrams of temperature-responsive and biocompatible polymers were obtained, and the characteristic gelation behaviors of the polymers were examined. The polymers are based on three oligoethylene glycol methyl ether methacrylate (OEGMA) monomers with different numbers of ethylene oxide (EO) units, i.e., with side chains that differ in length. The gelation thresholds depend on the OEGMA and crosslinker concentrations as well as the side chain length. Long EO side chains fill the polymerization system and reduce the concentration of polymer overlap, resulting in a high ability to occupy the system. Furthermore, the EO side chains may engage in self-crosslinking, i.e., polymers can branch and grow from the side chains depending on their length, resulting in a high bond probability. Based on these unique behavior patterns, gelation occurs more readily as the length of the side chains increases. We also synthesized ultralow crosslinked pOEGMA gels by tuning the gelation conditions; these gels exhibited improved swelling capacity and temperature responsiveness. These results should facilitate the development of a synthesis strategy to control the physical properties and structures of these materials for advanced applications, such as biofilms, actuators, and carriers. The gel-phase diagrams of temperature-responsive and biocompatible polymers with ethylene oxide (EO) side chains that differ in length were obtained. The gelation thresholds of the polymers depend not only on the monomer and crosslinker concentrations but also on the EO side chain lengths. Long EO side chains reduce the polymer overlap concentration. Furthermore, the EO side chains can engage in self-crosslinking, i.e., polymers can grow from the side chains depending on their length. These unique behaviors indicate that gelation occurs more readily with increasing the side chain length.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 11","pages":"1017-1029"},"PeriodicalIF":2.3,"publicationDate":"2024-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00929-2.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141503148","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 : 2024-06-14DOI: 10.1038/s41428-024-00927-4
Simon Sau Yin Law, Mako Kuzumoto, Seiya Fujita, Tsuyohiko Fujigaya, Keiji Numata
Functionalized carbon nanotubes have shown tremendous promise in the field of plant biotechnology for genetic engineering and cargo delivery; recent findings have shown that they can be delivered within specific organelles, such as mitochondria and chloroplasts, in intact plants. 2-Aminoisobutyric acid is an unnatural amino acid that promotes helical conformation and has been demonstrated to increase membrane permeability. Rational substitution of this amino acid into a mitochondrial targeting peptide induced a helical conformation that, when functionalized onto polymer-coated carbon nanotubes, conferred increased membrane permeability compared with that of the native peptide. The secondary structure was maintained on the surface and, when used to deliver pDNA, led to an increase in gene expression, suggesting that this method may be used to enhance the delivery efficiency of existing functional peptides. Induction of helical structures in peptides have been shown to increase their membrane permeability and facilitate cargo delivery applications. Our study has shown that substitution of an unnatural amino acid into a mitochondrial-targeting peptide induces a helical conformation that is maintained even after conjugation onto carbon nanotubes and confers increased membrane permeability. This led to an increase in DNA delivery efficiencies and gene expression into the mitochondria of intact plants when used as a DNA delivery system.
功能化碳纳米管在植物生物技术领域的基因工程和货物运输方面显示出巨大的前景；最近的研究结果表明，功能化碳纳米管可以在完整植物的线粒体和叶绿体等特定细胞器内输送。2-Aminoisobutyric acid 是一种促进螺旋构象的非天然氨基酸，已被证明能增加膜的渗透性。将这种氨基酸合理地置换到线粒体靶向肽中可诱导出一种螺旋构象，当将其功能化到聚合物涂层碳纳米管上时，与原生肽相比，这种肽可增加膜的渗透性。二级结构保持在表面，当用于递送 pDNA 时，可提高基因表达，这表明这种方法可用于提高现有功能肽的递送效率。研究表明，诱导肽的螺旋结构可增加其膜渗透性，促进货物输送应用。我们的研究表明，在线粒体靶向肽中替换一个非天然氨基酸可诱导螺旋构象，这种构象即使在缀合到碳纳米管上后仍能保持，并能增加膜渗透性。因此，在用作 DNA 运送系统时，DNA 运送效率和进入完整植物线粒体的基因表达均有所提高。
{"title":"Carbon nanotubes functionalized with α-aminoisobutyric acid-containing peptide increase gene delivery efficiency in plant mitochondria","authors":"Simon Sau Yin Law, Mako Kuzumoto, Seiya Fujita, Tsuyohiko Fujigaya, Keiji Numata","doi":"10.1038/s41428-024-00927-4","DOIUrl":"10.1038/s41428-024-00927-4","url":null,"abstract":"Functionalized carbon nanotubes have shown tremendous promise in the field of plant biotechnology for genetic engineering and cargo delivery; recent findings have shown that they can be delivered within specific organelles, such as mitochondria and chloroplasts, in intact plants. 2-Aminoisobutyric acid is an unnatural amino acid that promotes helical conformation and has been demonstrated to increase membrane permeability. Rational substitution of this amino acid into a mitochondrial targeting peptide induced a helical conformation that, when functionalized onto polymer-coated carbon nanotubes, conferred increased membrane permeability compared with that of the native peptide. The secondary structure was maintained on the surface and, when used to deliver pDNA, led to an increase in gene expression, suggesting that this method may be used to enhance the delivery efficiency of existing functional peptides. Induction of helical structures in peptides have been shown to increase their membrane permeability and facilitate cargo delivery applications. Our study has shown that substitution of an unnatural amino acid into a mitochondrial-targeting peptide induces a helical conformation that is maintained even after conjugation onto carbon nanotubes and confers increased membrane permeability. This led to an increase in DNA delivery efficiencies and gene expression into the mitochondria of intact plants when used as a DNA delivery system.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 10","pages":"915-924"},"PeriodicalIF":2.3,"publicationDate":"2024-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00927-4.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141339090","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 : 2024-06-12DOI: 10.1038/s41428-024-00925-6
Hiroshi Yamagishi
An optical microresonator is a micrometer-scale object that can confine light inside its body via total internal reflection at the boundary. In addition to well-established applications, including laser oscillators, optical sensors, and quantum memory, optical resonators have attracted renewed attention in chemistry and biology as minute and highly sensitive sensors that work in the environment and inside biological tissues and cells without any connected wires. Optical resonators should be functional for facilitating molecular interactions and biological compatibility, which is, however, challenging with conventional materials and processing techniques. In contrast, the authors have been tackling this issue by using supramolecular chemistry, which enables the assembly of optical resonators from chemically and biologically functional organic materials in solution. This article reviews our recent progress on the methodologies for making organic optical resonators and their emergent optical properties. Optical resonators have attracted renewed attention in chemistry and biology as minute and highly sensitive sensors that work in the environment and inside biological tissues and cells without any connected wires. Optical resonators should be functional for facilitating molecular interactions and biological compatibility, which is, however, challenging with conventional materials and processing techniques. In contrast, the authors have been tackling this issue by using supramolecular chemistry. This article reviews our recent progress on the methodologies for making organic optical resonators and their emergent optical properties.
{"title":"Supramolecular methodologies for the assembly of optical microresonators from functional organic materials","authors":"Hiroshi Yamagishi","doi":"10.1038/s41428-024-00925-6","DOIUrl":"10.1038/s41428-024-00925-6","url":null,"abstract":"An optical microresonator is a micrometer-scale object that can confine light inside its body via total internal reflection at the boundary. In addition to well-established applications, including laser oscillators, optical sensors, and quantum memory, optical resonators have attracted renewed attention in chemistry and biology as minute and highly sensitive sensors that work in the environment and inside biological tissues and cells without any connected wires. Optical resonators should be functional for facilitating molecular interactions and biological compatibility, which is, however, challenging with conventional materials and processing techniques. In contrast, the authors have been tackling this issue by using supramolecular chemistry, which enables the assembly of optical resonators from chemically and biologically functional organic materials in solution. This article reviews our recent progress on the methodologies for making organic optical resonators and their emergent optical properties. Optical resonators have attracted renewed attention in chemistry and biology as minute and highly sensitive sensors that work in the environment and inside biological tissues and cells without any connected wires. Optical resonators should be functional for facilitating molecular interactions and biological compatibility, which is, however, challenging with conventional materials and processing techniques. In contrast, the authors have been tackling this issue by using supramolecular chemistry. This article reviews our recent progress on the methodologies for making organic optical resonators and their emergent optical properties.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 10","pages":"887-894"},"PeriodicalIF":2.3,"publicationDate":"2024-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00925-6.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141353862","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}
Cellulose II exhibits exceptional attributes, including flexibility, high stainability, and gloss. However, its strength is lower than that of cellulose I due to reduced crystallinity during the crystal transition. In this study, we devised a novel method to regulate the proportion and distribution of cellulose I and II crystals. This was achieved by employing a low-concentration alkaline solution and liquid nitrogen, resulting in a high-strength composite material that retained the excellent properties of cellulose II. When cellulose powder was immersed in an 8 wt% NaOH solution and quenched with liquid nitrogen, the crystal transition from cellulose I to II occurred outward from the sample periphery to its center. The percentage of cellulose II increased proportionally with treatment time. This technique was extended to cellulose I-rich cotton fibers, facilitating the creation of a composite fiber with cellulose I at the core and cellulose II on the surface. The tensile strength and Young’s modulus of the composite fiber were greater than those of the mercerized cellulose II fiber. Additionally, the elongation at break and toughness of these fibers surpassed those of conventional cotton fibers. This innovative method allows for the preparation of cellulose I and II composite materials with diverse properties. This study developed a novel method for the control of the cellulose crystal of cellulose I and II. The crystal transition from cellulose I to II was tracked when cellulose I, which is soaked in a low-concentration NaOH aqueous solution, was quenched using liquid nitrogen. The crystal transition progressed from the surface to the center of the sample. This quench treatment has the potential to fabricate new cellulose materials with a cellulose I core and a cellulose II surface.
纤维素 II 具有优异的特性，包括柔韧性、高染色性和光泽度。然而，由于在晶体转变过程中结晶度降低，其强度低于纤维素 I。在这项研究中，我们设计了一种新方法来调节纤维素 I 和纤维素 II 晶体的比例和分布。通过使用低浓度的碱性溶液和液氮，我们得到了一种高强度的复合材料，同时保留了纤维素 II 的优良特性。将纤维素粉末浸入 8 wt% 的 NaOH 溶液中并用液氮淬火后，纤维素 I 向纤维素 II 的晶体转变从样品外围向中心延伸。纤维素 II 的比例随着处理时间的延长而成正比增加。这项技术被推广到富含纤维素 I 的棉纤维上，从而制造出一种核心为纤维素 I、表面为纤维素 II 的复合纤维。复合纤维的拉伸强度和杨氏模量均大于丝光处理后的纤维素 II 纤维。此外，这些纤维的断裂伸长率和韧性也超过了传统棉纤维。这种创新方法可制备出具有不同性能的纤维素 I 和 II 复合材料。这项研究开发了一种控制纤维素 I 和 II 的纤维素晶体的新方法。将浸泡在低浓度 NaOH 水溶液中的纤维素 I 用液氮淬灭后，跟踪了从纤维素 I 到纤维素 II 的晶体转变。晶体转变从样品表面向中心发展。这种淬火处理方法有望制造出具有纤维素 I 核心和纤维素 II 表面的新型纤维素材料。
{"title":"Optimizing crystal transitions in low-temperature, low-concentration NaOH solutions to prepare cellulose I and II composite materials","authors":"Yuki Kugo, Takuya Isono, Masashi Fujiwara, Toshifumi Sato, Hirofumi Tani, Tomoki Erata, Kenji Tajima","doi":"10.1038/s41428-024-00928-3","DOIUrl":"10.1038/s41428-024-00928-3","url":null,"abstract":"Cellulose II exhibits exceptional attributes, including flexibility, high stainability, and gloss. However, its strength is lower than that of cellulose I due to reduced crystallinity during the crystal transition. In this study, we devised a novel method to regulate the proportion and distribution of cellulose I and II crystals. This was achieved by employing a low-concentration alkaline solution and liquid nitrogen, resulting in a high-strength composite material that retained the excellent properties of cellulose II. When cellulose powder was immersed in an 8 wt% NaOH solution and quenched with liquid nitrogen, the crystal transition from cellulose I to II occurred outward from the sample periphery to its center. The percentage of cellulose II increased proportionally with treatment time. This technique was extended to cellulose I-rich cotton fibers, facilitating the creation of a composite fiber with cellulose I at the core and cellulose II on the surface. The tensile strength and Young’s modulus of the composite fiber were greater than those of the mercerized cellulose II fiber. Additionally, the elongation at break and toughness of these fibers surpassed those of conventional cotton fibers. This innovative method allows for the preparation of cellulose I and II composite materials with diverse properties. This study developed a novel method for the control of the cellulose crystal of cellulose I and II. The crystal transition from cellulose I to II was tracked when cellulose I, which is soaked in a low-concentration NaOH aqueous solution, was quenched using liquid nitrogen. The crystal transition progressed from the surface to the center of the sample. This quench treatment has the potential to fabricate new cellulose materials with a cellulose I core and a cellulose II surface.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 10","pages":"939-943"},"PeriodicalIF":2.3,"publicationDate":"2024-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141354671","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}
In this study, a Pd-polymeric porous immobilized catalyst is prepared for the Suzuki–Miyaura coupling reactions by employing a Bayesian optimization method to optimize the catalyst. This research represents the first endeavor to utilize machine learning for the optimization of polymer-immobilized catalysts and provides a novel perspective on utilizing machine learning for the optimization of complex materials. This study presented the workflow of machine learning-guided optimization of Pd-immobilized porous polymer catalysts. Two independent variables (DVB and 1-decanol content) were involved in polymerization to maximize TOF as target variable in Suzuki–Miyaura coupling reaction. Bayesian optimization was applied for predictive modeling, and the optimized conditions were experimentally validated in subsequent iterations. By applying this workflow, the catalytic activity of immobilized polymer porous catalysts was successfully optimized using machine learning.
{"title":"Development of Pd-immobilized porous polymer catalysts via Bayesian optimization","authors":"Xincheng Zhou, Hikaru Matsumoto, Masanori Nagao, Shuji Hironaka, Yoshiko Miura","doi":"10.1038/s41428-024-00923-8","DOIUrl":"10.1038/s41428-024-00923-8","url":null,"abstract":"In this study, a Pd-polymeric porous immobilized catalyst is prepared for the Suzuki–Miyaura coupling reactions by employing a Bayesian optimization method to optimize the catalyst. This research represents the first endeavor to utilize machine learning for the optimization of polymer-immobilized catalysts and provides a novel perspective on utilizing machine learning for the optimization of complex materials. This study presented the workflow of machine learning-guided optimization of Pd-immobilized porous polymer catalysts. Two independent variables (DVB and 1-decanol content) were involved in polymerization to maximize TOF as target variable in Suzuki–Miyaura coupling reaction. Bayesian optimization was applied for predictive modeling, and the optimized conditions were experimentally validated in subsequent iterations. By applying this workflow, the catalytic activity of immobilized polymer porous catalysts was successfully optimized using machine learning.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 9","pages":"865-872"},"PeriodicalIF":2.3,"publicationDate":"2024-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00923-8.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141375975","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}
Termite wings are covered with hair shafts and micrasters, which provide it with dual wettability. Although the surface is superhydrophobic for bulk water and large droplets, it is adhesive for microdroplets of water. We mimicked this rough surface by applying a photoinduced crystal growth phenomenon on a photoreactive crystalline surface consisting of two photochromic diarylethene derivatives. This crystalline surface showed dual wettability, but the photoreactive crystalline system was not applicable under daylight. This lack of applicability was apparent because the rough crystalline structures on the surface melted under visible light irradiation. We used soft lithography and transcribed the rough structure of the crystalline film to a stable polycycloolefin polymer (ZEONEX 480) surface. In this case, ultrasonic treatment was indispensable for molding complex structured surfaces. The transcribed surface showed the same characteristics of dual wettability as the crystalline surface. The crystalline surface using two photochromic diarylethenes was prepared to mimic a termite wing showing dual wettability. The surface is useful to correct small water droplets in the air. However, the crystalline system was not applicable for the use because crystalline structures on the surface melt under daylight. We copied the rough structure of crystalline film to a stable polycycloolefin polymer (Zeonex 480) surface. The copied surface showed the dual wettability as same as that of the crystalline surface.
{"title":"Polymer replica of microcrystalline surface with dual wettability, mimicking a termite wing","authors":"Yuki Hashimoto, Amane Hase, Ayumu Tani, Ryo Nishimura, Yohei Hattori, Hiroyuki Mayama, Satoshi Yokojima, Shinichiro Nakamura, Kingo Uchida","doi":"10.1038/s41428-024-00926-5","DOIUrl":"10.1038/s41428-024-00926-5","url":null,"abstract":"Termite wings are covered with hair shafts and micrasters, which provide it with dual wettability. Although the surface is superhydrophobic for bulk water and large droplets, it is adhesive for microdroplets of water. We mimicked this rough surface by applying a photoinduced crystal growth phenomenon on a photoreactive crystalline surface consisting of two photochromic diarylethene derivatives. This crystalline surface showed dual wettability, but the photoreactive crystalline system was not applicable under daylight. This lack of applicability was apparent because the rough crystalline structures on the surface melted under visible light irradiation. We used soft lithography and transcribed the rough structure of the crystalline film to a stable polycycloolefin polymer (ZEONEX 480) surface. In this case, ultrasonic treatment was indispensable for molding complex structured surfaces. The transcribed surface showed the same characteristics of dual wettability as the crystalline surface. The crystalline surface using two photochromic diarylethenes was prepared to mimic a termite wing showing dual wettability. The surface is useful to correct small water droplets in the air. However, the crystalline system was not applicable for the use because crystalline structures on the surface melt under daylight. We copied the rough structure of crystalline film to a stable polycycloolefin polymer (Zeonex 480) surface. The copied surface showed the dual wettability as same as that of the crystalline surface.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 9","pages":"847-853"},"PeriodicalIF":2.3,"publicationDate":"2024-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141377085","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 : 2024-06-05DOI: 10.1038/s41428-024-00905-w
Keiji Tanaka
{"title":"PJ ZEON Award for outstanding papers in Polymer Journal 2023","authors":"Keiji Tanaka","doi":"10.1038/s41428-024-00905-w","DOIUrl":"10.1038/s41428-024-00905-w","url":null,"abstract":"","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 6","pages":"567-568"},"PeriodicalIF":2.8,"publicationDate":"2024-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00905-w.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141251527","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}
The macroscopic mechanical properties of polyamides depend on their microscopic structural properties, such as the crystalline phase, lamellar thickness, and long period, which change depending on the heat treatment conditions. In this study, the relationships between the macroscopic mechanical properties and lamellar structures of polyamide 11 obtained from different heat treatments were investigated. Heat treatments include quench, isothermal, and quench–annealing conditions. Wide-angle X-ray scattering measurements indicated that different crystalline phases formed depending on the heat treatment conditions. Polarized optical microscopy and differential scanning calorimetry revealed spherulite and crystal morphologies that were not spherulite. Small-angle X-ray scattering revealed that the lamellar thickness and long period increased with the heat treatment temperature. With increasing the long period of lamellae, the number of stress transmitters, which are stress transfer factors (entanglements, loop chains, etc.) between lamellae, increases. The lamellar thickness and long period of polyamide 11 were ~1.5 times greater than that of polyamide 6 under similar heat treatment. In uniaxial tensile tests, polyamide 6 specimens heat-treated at high temperatures fractured and did not elongate. Polyamide 11 elongated without fracture. The thick lamellar and long-period structure of polyamide 11 obtained from heat treatments in this study might explain its excellent elongation until the late stage of deformation. The relationships between the macroscopic mechanical properties and lamellar structures of polyamide 11 obtained from different heat treatments were investigated. From the tensile tests, the maximum stress and strain at necking increase with the heat treatment temperature. WAXS measurements indicated that different crystalline phases formed depending on the heat treatment conditions. SAXS revealed that the lamellar thickness and long period increased with the heat treatment temperature. Based on these results, we elucidated that the macroscopic mechanical properties correlate with the lamellar thickness and long period.
聚酰胺的宏观机械特性取决于其微观结构特性，例如结晶相、薄片厚度和长周期，而这些特性会随着热处理条件的不同而发生变化。本研究探讨了不同热处理条件下聚酰胺 11 的宏观机械性能与薄片结构之间的关系。热处理包括淬火、等温和淬火-退火条件。广角 X 射线散射测量结果表明，不同的热处理条件会形成不同的结晶相。偏光光学显微镜和差示扫描量热法显示了球晶和非球晶的晶体形态。小角 X 射线散射显示，片层厚度和长周期随着热处理温度的升高而增加。随着薄片长周期的增加，薄片之间的应力传递因子（缠结、环链等）数量也随之增加。在类似的热处理条件下，聚酰胺 11 的薄片厚度和长周期是聚酰胺 6 的 1.5 倍。在单轴拉伸试验中，高温热处理的聚酰胺 6 试样会断裂，但不会拉长。聚酰胺 11 则拉长而没有断裂。本研究中通过热处理获得的聚酰胺 11 厚层和长周期结构可能是其直到变形后期都具有出色伸长率的原因。
{"title":"Structure and mechanical properties of biobased polyamide 11 specimens subjected to different heat treatments","authors":"Toyoshi Yoshida, Mei Touji, Hideaki Takagi, Nobutaka Shimizu, Noriyuki Igarashi, Shinichi Sakurai, Makoto Uchida, Yoshihisa Kaneko","doi":"10.1038/s41428-024-00924-7","DOIUrl":"10.1038/s41428-024-00924-7","url":null,"abstract":"The macroscopic mechanical properties of polyamides depend on their microscopic structural properties, such as the crystalline phase, lamellar thickness, and long period, which change depending on the heat treatment conditions. In this study, the relationships between the macroscopic mechanical properties and lamellar structures of polyamide 11 obtained from different heat treatments were investigated. Heat treatments include quench, isothermal, and quench–annealing conditions. Wide-angle X-ray scattering measurements indicated that different crystalline phases formed depending on the heat treatment conditions. Polarized optical microscopy and differential scanning calorimetry revealed spherulite and crystal morphologies that were not spherulite. Small-angle X-ray scattering revealed that the lamellar thickness and long period increased with the heat treatment temperature. With increasing the long period of lamellae, the number of stress transmitters, which are stress transfer factors (entanglements, loop chains, etc.) between lamellae, increases. The lamellar thickness and long period of polyamide 11 were ~1.5 times greater than that of polyamide 6 under similar heat treatment. In uniaxial tensile tests, polyamide 6 specimens heat-treated at high temperatures fractured and did not elongate. Polyamide 11 elongated without fracture. The thick lamellar and long-period structure of polyamide 11 obtained from heat treatments in this study might explain its excellent elongation until the late stage of deformation. The relationships between the macroscopic mechanical properties and lamellar structures of polyamide 11 obtained from different heat treatments were investigated. From the tensile tests, the maximum stress and strain at necking increase with the heat treatment temperature. WAXS measurements indicated that different crystalline phases formed depending on the heat treatment conditions. SAXS revealed that the lamellar thickness and long period increased with the heat treatment temperature. Based on these results, we elucidated that the macroscopic mechanical properties correlate with the lamellar thickness and long period.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 9","pages":"833-845"},"PeriodicalIF":2.3,"publicationDate":"2024-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141251824","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}
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