Pub Date : 2024-01-17DOI: 10.1038/s41428-023-00869-3
Mineto Uchiyama, Masato Imai, Masami Kamigaito
We report a novel method for synthesizing degradable polymers based on 1,5-shift radical isomerization polymerizations of vinyl ethers with transferable atoms or groups and in-between acid-cleavable ether linkages in the side chains. In particular, vinyl ethers with side chains composed of thiocyano and p-methoxybenzyl ether groups underwent radical isomerization polymerizations via 1,5-shifts, in which a vinyl ether radical abstracted the cyano group intramolecularly to generate a thiyl radical and result in a polymer with a p-methoxybenzyl ether linkage in the main chain. The obtained polymer was easily degraded into low molecular-weight products with HCl solution. Furthermore, the copolymerization with vinyl acetate proceeded via 1,5-shift isomerization to introduce cleavable linkages in the main chains of the copolymers, which were similarly degraded. We developed a novel method for synthesizing degradable polymers based on 1,5-shift radical isomerization polymerizations of vinyl ethers with transferable atoms or groups and in-between acid-cleavable ether linkages in the side chains. In particular, vinyl ethers with side chains composed of thiocyano and p-methoxybenzyl ether groups underwent radical isomerization polymerizations via 1,5-shifts, in which a vinyl ether radical abstracted the cyano group intramolecularly to generate a thiyl radical and result in a polymer with a p-methoxybenzyl ether linkage in the main chain.
{"title":"Synthesis of degradable polymers via 1,5-shift radical isomerization polymerization of vinyl ether derivatives with a cleavable bond","authors":"Mineto Uchiyama, Masato Imai, Masami Kamigaito","doi":"10.1038/s41428-023-00869-3","DOIUrl":"10.1038/s41428-023-00869-3","url":null,"abstract":"We report a novel method for synthesizing degradable polymers based on 1,5-shift radical isomerization polymerizations of vinyl ethers with transferable atoms or groups and in-between acid-cleavable ether linkages in the side chains. In particular, vinyl ethers with side chains composed of thiocyano and p-methoxybenzyl ether groups underwent radical isomerization polymerizations via 1,5-shifts, in which a vinyl ether radical abstracted the cyano group intramolecularly to generate a thiyl radical and result in a polymer with a p-methoxybenzyl ether linkage in the main chain. The obtained polymer was easily degraded into low molecular-weight products with HCl solution. Furthermore, the copolymerization with vinyl acetate proceeded via 1,5-shift isomerization to introduce cleavable linkages in the main chains of the copolymers, which were similarly degraded. We developed a novel method for synthesizing degradable polymers based on 1,5-shift radical isomerization polymerizations of vinyl ethers with transferable atoms or groups and in-between acid-cleavable ether linkages in the side chains. In particular, vinyl ethers with side chains composed of thiocyano and p-methoxybenzyl ether groups underwent radical isomerization polymerizations via 1,5-shifts, in which a vinyl ether radical abstracted the cyano group intramolecularly to generate a thiyl radical and result in a polymer with a p-methoxybenzyl ether linkage in the main chain.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 4","pages":"359-368"},"PeriodicalIF":2.8,"publicationDate":"2024-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-023-00869-3.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139507288","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}
We report the syntheses of novel marine biodegradable poly(ethylene succinate) (PES)- and poly(butylene succinate) (PBS)-based copolymers containing different dicarboxylic acid (DCA) units with various carbon numbers and different feed ratios. Biochemical oxygen demand tests demonstrated that some of the obtained PES- and PBS-based copolymers were biodegradable in seawater. Specifically, polymers with longer-chain DCA units, even at low contents, exhibited marine biodegradability. The thermomechanical properties of the copolymers, such as their thermal stabilities, melting points, glass transition temperatures, tensile moduli, strains at break, and stresses at break, also varied with the DCA contents. These results indicated that the thermomechanical properties and the marine biodegradabilities of the PES- and PBS-based copolymers were regulated by controlling their structures and DCA contents. The polymers obtained in this study may replace general-purpose polymers. Our approach may also be applicable to other polymeric materials. Furthermore, our findings pave the way for the rational design and preparation of polymeric materials that are biodegradable in environments other than oceans and have good thermomechanical properties. We report the syntheses of novel marine biodegradable poly(ethylene succinate) (PES)- and poly(butylene succinate) (PBS)-based copolymers containing different dicarboxylic acid (DCA) units with various carbon numbers and different feed ratios. Specifically, the copolymers with longer-chain DCA units, even at low contents, exhibited marine biodegradability. The thermomechanical properties also varied with the DCA contents. These results indicated that the thermomechanical properties and the marine biodegradability of the PES- and PBS-based copolymers were regulated by controlling their structures and DCA contents.
{"title":"Improving the marine biodegradability of poly(alkylene succinate)-based copolymers","authors":"Sumito Kumagai, Senri Hayashi, Atsushi Katsuragi, Motosuke Imada, Kaoko Sato, Hideki Abe, Noriyuki Asakura, Yasumasa Takenaka","doi":"10.1038/s41428-023-00871-9","DOIUrl":"10.1038/s41428-023-00871-9","url":null,"abstract":"We report the syntheses of novel marine biodegradable poly(ethylene succinate) (PES)- and poly(butylene succinate) (PBS)-based copolymers containing different dicarboxylic acid (DCA) units with various carbon numbers and different feed ratios. Biochemical oxygen demand tests demonstrated that some of the obtained PES- and PBS-based copolymers were biodegradable in seawater. Specifically, polymers with longer-chain DCA units, even at low contents, exhibited marine biodegradability. The thermomechanical properties of the copolymers, such as their thermal stabilities, melting points, glass transition temperatures, tensile moduli, strains at break, and stresses at break, also varied with the DCA contents. These results indicated that the thermomechanical properties and the marine biodegradabilities of the PES- and PBS-based copolymers were regulated by controlling their structures and DCA contents. The polymers obtained in this study may replace general-purpose polymers. Our approach may also be applicable to other polymeric materials. Furthermore, our findings pave the way for the rational design and preparation of polymeric materials that are biodegradable in environments other than oceans and have good thermomechanical properties. We report the syntheses of novel marine biodegradable poly(ethylene succinate) (PES)- and poly(butylene succinate) (PBS)-based copolymers containing different dicarboxylic acid (DCA) units with various carbon numbers and different feed ratios. Specifically, the copolymers with longer-chain DCA units, even at low contents, exhibited marine biodegradability. The thermomechanical properties also varied with the DCA contents. These results indicated that the thermomechanical properties and the marine biodegradability of the PES- and PBS-based copolymers were regulated by controlling their structures and DCA contents.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 4","pages":"419-429"},"PeriodicalIF":2.8,"publicationDate":"2024-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-023-00871-9.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139498608","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}
Hyaluronic acid (HA) has garnered much attention in the development of novel hydrogels. Hydrogels, as drug delivery systems, are very important in tissue engineering applications. In this study, we developed a novel HA nanogel containing a cholesterol and maleimide derivative (HAMICH) and its corresponding crosslinked hydrogel (HAMICH gel) to encapsulate drugs for their subsequent release. HAMICH gels self-assemble into nanoparticles via hydrophobic interactions. Dynamic light scattering analysis of HAMICH revealed that the particle size tended to decrease with increasing degree of cholesterol moiety substitution. The HAMICH gel was prepared through a Michael addition reaction between HAMICH and pentaerythritol tetra(mercaptoethyl)polyoxyethylene. The concentration of HAMICH needed for gelation depends on the degree of cholesterol moiety substitution; the higher the substitution degree is, the greater the concentration of HAMICH needed. The HAMICH gel exhibited less swelling and a smaller volume change than the gel with an unmodified cholesterol moiety in phosphate-buffered saline (pH 7.4). The HAMICH gel displayed enhanced peptide and protein trapping abilities without hydrogel swelling, suggesting its potential as a HA hydrogel for biomedical applications. Hydrogels have attracted considerable attention in the biomedical applications because of their high functionalities, biocompatibility and biodegradability. This study on the novel hyaluronic acid (HA) nanogel-based hydrogel comprising HA modified with cholesterol derivatives and maleimide crosslinking groups. Depending on the degree of cholesterol derivative substitution, the properties such as water uptake, gelation behavior and protein encapsulation was investigated. The results suggested that the hydrogels enhanced peptide and protein trapping abilities have potential as a new hyaluronan hydrogel for biomedical applications.
透明质酸（HA）在新型水凝胶的开发中备受关注。水凝胶作为药物输送系统，在组织工程应用中非常重要。在这项研究中，我们开发了一种含有胆固醇和马来酰亚胺衍生物（HAMICH）的新型 HA 纳米凝胶及其相应的交联水凝胶（HAMICH 凝胶），用于包裹药物并随后释放。HAMICH 凝胶通过疏水相互作用自组装成纳米颗粒。对 HAMICH 的动态光散射分析表明，随着胆固醇分子取代度的增加，粒径呈减小趋势。HAMICH 凝胶是通过 HAMICH 和季戊四醇四（巯基乙基）聚氧乙烯之间的迈克尔加成反应制备的。凝胶化所需的 HAMICH 浓度取决于胆固醇分子的取代程度；取代程度越高，所需的 HAMICH 浓度越大。在磷酸盐缓冲盐水（pH 值为 7.4）中，HAMICH 凝胶比未修饰胆固醇分子的凝胶膨胀更少，体积变化更小。HAMICH 凝胶显示出更强的肽和蛋白质捕获能力，而不会出现水凝胶膨胀，这表明它具有作为 HA 水凝胶用于生物医学应用的潜力。
{"title":"Variable swelling behavior of and drug encapsulation in a maleimide-modified hyaluronic acid nanogel-based hydrogel","authors":"Kohei Yabuuchi, Toru Katsumata, Tsuyoshi Shimoboji, Yoshihide Hashimoto, Tsuyoshi Kimura, Kazunari Akiyoshi, Akio Kishida","doi":"10.1038/s41428-023-00881-7","DOIUrl":"10.1038/s41428-023-00881-7","url":null,"abstract":"Hyaluronic acid (HA) has garnered much attention in the development of novel hydrogels. Hydrogels, as drug delivery systems, are very important in tissue engineering applications. In this study, we developed a novel HA nanogel containing a cholesterol and maleimide derivative (HAMICH) and its corresponding crosslinked hydrogel (HAMICH gel) to encapsulate drugs for their subsequent release. HAMICH gels self-assemble into nanoparticles via hydrophobic interactions. Dynamic light scattering analysis of HAMICH revealed that the particle size tended to decrease with increasing degree of cholesterol moiety substitution. The HAMICH gel was prepared through a Michael addition reaction between HAMICH and pentaerythritol tetra(mercaptoethyl)polyoxyethylene. The concentration of HAMICH needed for gelation depends on the degree of cholesterol moiety substitution; the higher the substitution degree is, the greater the concentration of HAMICH needed. The HAMICH gel exhibited less swelling and a smaller volume change than the gel with an unmodified cholesterol moiety in phosphate-buffered saline (pH 7.4). The HAMICH gel displayed enhanced peptide and protein trapping abilities without hydrogel swelling, suggesting its potential as a HA hydrogel for biomedical applications. Hydrogels have attracted considerable attention in the biomedical applications because of their high functionalities, biocompatibility and biodegradability. This study on the novel hyaluronic acid (HA) nanogel-based hydrogel comprising HA modified with cholesterol derivatives and maleimide crosslinking groups. Depending on the degree of cholesterol derivative substitution, the properties such as water uptake, gelation behavior and protein encapsulation was investigated. The results suggested that the hydrogels enhanced peptide and protein trapping abilities have potential as a new hyaluronan hydrogel for biomedical applications.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 5","pages":"505-515"},"PeriodicalIF":2.8,"publicationDate":"2024-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-023-00881-7.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139498512","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 : 2024-01-16DOI: 10.1038/s41428-023-00875-5
Hiroshi Masai, Tomoki Nakagawa, Jun Terao
Photochemically adaptable polymer materials, which change shape and physical properties under light irradiation, are widely used in the fields of medicine, electronics, and engineering due to their precise and remote processability. This processability is attributed to the photocleavage of chemical bonds introduced into the polymer materials. In particular, the efficient photolytic cleavage of the crosslinking points in the network induces rapid softening and degradation of the materials. Recently, diverse designs of light-responsive units have been developed to fabricate various photocontrollable materials with low-energy, rapid, and reversible photoreactivity. Furthermore, multiple stimuli-responsive materials have been demonstrated to control photodegradation reaction rates and photoreactivity by combining light with another stimulus, leading to advanced photocontrollable capabilities. This paper reviews the recent progress in developing photochemically adaptable polymer network materials by designing photoresponsive units, focusing on the chemical structures of cleavable moieties. Photochemically adaptable polymer materials are widely used in the fields of medicine, electronics, and engineering due to their precise and remote processability. Diverse designs of light-responsive units have been developed to fabricate various photocontrollable materials with low-energy, rapid, and reversible photoreactivity. Recently, multiple stimuli-responsive materials have been demonstrated to further control their photoreactivity by combining light with another stimulus, leading to advanced photocontrollable capabilities. This Focus Review summarizes the recent progress in developing photochemically adaptable polymer network materials by designing photoresponsive units, focusing on the chemical structures of cleavable moieties.
{"title":"Recent progress in photoreactive crosslinkers in polymer network materials toward advanced photocontrollability","authors":"Hiroshi Masai, Tomoki Nakagawa, Jun Terao","doi":"10.1038/s41428-023-00875-5","DOIUrl":"10.1038/s41428-023-00875-5","url":null,"abstract":"Photochemically adaptable polymer materials, which change shape and physical properties under light irradiation, are widely used in the fields of medicine, electronics, and engineering due to their precise and remote processability. This processability is attributed to the photocleavage of chemical bonds introduced into the polymer materials. In particular, the efficient photolytic cleavage of the crosslinking points in the network induces rapid softening and degradation of the materials. Recently, diverse designs of light-responsive units have been developed to fabricate various photocontrollable materials with low-energy, rapid, and reversible photoreactivity. Furthermore, multiple stimuli-responsive materials have been demonstrated to control photodegradation reaction rates and photoreactivity by combining light with another stimulus, leading to advanced photocontrollable capabilities. This paper reviews the recent progress in developing photochemically adaptable polymer network materials by designing photoresponsive units, focusing on the chemical structures of cleavable moieties. Photochemically adaptable polymer materials are widely used in the fields of medicine, electronics, and engineering due to their precise and remote processability. Diverse designs of light-responsive units have been developed to fabricate various photocontrollable materials with low-energy, rapid, and reversible photoreactivity. Recently, multiple stimuli-responsive materials have been demonstrated to further control their photoreactivity by combining light with another stimulus, leading to advanced photocontrollable capabilities. This Focus Review summarizes the recent progress in developing photochemically adaptable polymer network materials by designing photoresponsive units, focusing on the chemical structures of cleavable moieties.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 4","pages":"297-307"},"PeriodicalIF":2.8,"publicationDate":"2024-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-023-00875-5.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139507207","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 : 2024-01-16DOI: 10.1038/s41428-023-00873-7
Keiichi Imato, Naoki Kaneda, Yousuke Ooyama
Photoinduced transitions between the solid, glass, and liquid states based on molecular photoswitches promise a wide variety of applications. Photoswitchable adhesives are representative examples and are expected to contribute to material recycling for a sustainable future in the era of composite materials due to strong bonding and on-demand photo-induced debonding with minimal damage to the adherends. Only a few molecular photoswitches are known to undergo these transitions, but recent progress, mainly with azobenzene, has been remarkable. Here, we review the photoinduced transitions of small molecules and polymers over approximately a decade and systematically discuss the molecular designs, mechanisms, applications, merits and demerits, and future challenges in each photoswitch and the whole field. We hope this review provides useful information, inspiration, and ideas for the development of this field and the expansion of its applications. Photoinduced transitions between the solid, glass, and liquid states based on molecular photoswitches promise an enormous variety of applications, such as photoswitchable adhesives, which contribute to material recycling for a sustainable future in the era of composite materials. In this review, we highlight recent progress in the photoinduced transitions of small molecules and polymers and systematically discuss the molecular designs, mechanisms, applications, merits and demerits, and future challenges in each photoswitch and the whole field.
{"title":"Recent progress in photoinduced transitions between the solid, glass, and liquid states based on molecular photoswitches","authors":"Keiichi Imato, Naoki Kaneda, Yousuke Ooyama","doi":"10.1038/s41428-023-00873-7","DOIUrl":"10.1038/s41428-023-00873-7","url":null,"abstract":"Photoinduced transitions between the solid, glass, and liquid states based on molecular photoswitches promise a wide variety of applications. Photoswitchable adhesives are representative examples and are expected to contribute to material recycling for a sustainable future in the era of composite materials due to strong bonding and on-demand photo-induced debonding with minimal damage to the adherends. Only a few molecular photoswitches are known to undergo these transitions, but recent progress, mainly with azobenzene, has been remarkable. Here, we review the photoinduced transitions of small molecules and polymers over approximately a decade and systematically discuss the molecular designs, mechanisms, applications, merits and demerits, and future challenges in each photoswitch and the whole field. We hope this review provides useful information, inspiration, and ideas for the development of this field and the expansion of its applications. Photoinduced transitions between the solid, glass, and liquid states based on molecular photoswitches promise an enormous variety of applications, such as photoswitchable adhesives, which contribute to material recycling for a sustainable future in the era of composite materials. In this review, we highlight recent progress in the photoinduced transitions of small molecules and polymers and systematically discuss the molecular designs, mechanisms, applications, merits and demerits, and future challenges in each photoswitch and the whole field.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 4","pages":"269-282"},"PeriodicalIF":2.8,"publicationDate":"2024-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-023-00873-7.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139516425","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 : 2024-01-12DOI: 10.1038/s41428-023-00863-9
Simay Aydonat, Adrian H. Hergesell, Claire L. Seitzinger, Regina Lennarz, George Chang, Carsten Sievers, Jan Meisner, Ina Vollmer, Robert Göstl
Over 8 billion tons of plastic have been produced to date, and a 100% reclamation recycling strategy is not foreseeable. This review summarizes how the mechanochemistry of polymers may contribute to a sustainable polymer future by controlling the degradation not only of de novo developed designer polymers but also of plastics in existing waste streams. The historical development of polymer mechanochemistry is presented while highlighting current examples of mechanochemically induced polymer degradation. Additionally, theoretical and computational frameworks are discussed that may lead to the discovery and better understanding of new mechanochemical reactions in the future. This review takes into account technical and engineering perspectives converging the fields of trituration and polymer mechanochemistry with a particular focus on the fate of commodity polymers and potential technologies to monitor mechanochemical reactions while they occur. Therefore, a unique perspective of multiple communities is presented, highlighting the need for future transdisciplinary research to tackle the high-leverage parameters governing an eventually successful mechanochemical degradation approach for a circular economy. Mechanochemistry is a promising technology to tackle current and future polymer waste streams for a sustainable future. With this review, we take into account synthetic, computational, technical, and engineering perspectives to converge trituration and polymer mechanochemistry with a particular focus on the fate of commodity polymers and potential technologies to monitor mechanochemical reactions while they occur. We highlight the need for future transdisciplinary research to tackle the high-leverage parameters governing an eventually successful mechanochemical polymer degradation approach for a circular economy.
{"title":"Leveraging mechanochemistry for sustainable polymer degradation","authors":"Simay Aydonat, Adrian H. Hergesell, Claire L. Seitzinger, Regina Lennarz, George Chang, Carsten Sievers, Jan Meisner, Ina Vollmer, Robert Göstl","doi":"10.1038/s41428-023-00863-9","DOIUrl":"10.1038/s41428-023-00863-9","url":null,"abstract":"Over 8 billion tons of plastic have been produced to date, and a 100% reclamation recycling strategy is not foreseeable. This review summarizes how the mechanochemistry of polymers may contribute to a sustainable polymer future by controlling the degradation not only of de novo developed designer polymers but also of plastics in existing waste streams. The historical development of polymer mechanochemistry is presented while highlighting current examples of mechanochemically induced polymer degradation. Additionally, theoretical and computational frameworks are discussed that may lead to the discovery and better understanding of new mechanochemical reactions in the future. This review takes into account technical and engineering perspectives converging the fields of trituration and polymer mechanochemistry with a particular focus on the fate of commodity polymers and potential technologies to monitor mechanochemical reactions while they occur. Therefore, a unique perspective of multiple communities is presented, highlighting the need for future transdisciplinary research to tackle the high-leverage parameters governing an eventually successful mechanochemical degradation approach for a circular economy. Mechanochemistry is a promising technology to tackle current and future polymer waste streams for a sustainable future. With this review, we take into account synthetic, computational, technical, and engineering perspectives to converge trituration and polymer mechanochemistry with a particular focus on the fate of commodity polymers and potential technologies to monitor mechanochemical reactions while they occur. We highlight the need for future transdisciplinary research to tackle the high-leverage parameters governing an eventually successful mechanochemical polymer degradation approach for a circular economy.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 4","pages":"249-268"},"PeriodicalIF":2.8,"publicationDate":"2024-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-023-00863-9.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139462611","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 development of recyclable polymers has attracted considerable attention for realizing the development of a sustainable society. Polycarbonates (PCs) are engineering plastics with high thermal stability and transparency. We focused on poly(isosorbide carbonate) (PIC), a bio-based PC synthesized from isosorbide (ISB) derived from glucose. PIC is expected to function as an alternative to conventional PCs because of its outstanding transparency and thermal and physical properties. This study prepared PIC copolymers with several types of diol comonomers to clarify the effect of copolymerization on the decomposition reaction with ammonia, i.e., ammonolysis for converting PIC copolymers into monomers and urea. The thermal and physical properties of the resulting copolymers were also investigated. The thermal stability of the PIC copolymers remained stable after copolymerization, and the glass transition temperature was affected mainly by the flexibility of the structure of the introduced comonomer. A drastic change in mechanical properties was observed for the copolymer synthesized with 1,4-butanediol, which provides guidelines for toughening PIC with a small comonomer ratio. Finally, we investigated the decomposition behavior of the copolymers by treatment with aqueous ammonia. The PIC copolymers were decomposed into ISB, comonomers, and urea, and the ammonolysis rate was affected by the introduced structure. This study promotes the effective use of ISB as a biomass resource through ammonolysis, which is an effective chemical recycling process for polycarbonate. To functionalize a poly(isosorbide carbonate) (PIC)-based polymer and evaluate its recyclability, several types of diol comonomers were copolymerized with isosorbide. The thermal and mechanical properties and decomposition behavior of the PIC copolymers were investigated. The thermal stability of PIC was retained, and its glass transition temperature was systematically controlled by copolymerization. The decomposition of the PIC copolymers upon treatment with aqueous ammonia yielded monomers and urea, and the decomposition rate was governed by the structure of the comonomer.
{"title":"Characterization and ammonolysis behavior of poly(isosorbide carbonate)-based copolymers","authors":"Kazuaki Rikiyama, Akari Matsunami, Takayuki Yoshida, Tatsuo Taniguchi, Takashi Karatsu, Shotaro Nishitsuji, Daisuke Aoki","doi":"10.1038/s41428-023-00878-2","DOIUrl":"10.1038/s41428-023-00878-2","url":null,"abstract":"The development of recyclable polymers has attracted considerable attention for realizing the development of a sustainable society. Polycarbonates (PCs) are engineering plastics with high thermal stability and transparency. We focused on poly(isosorbide carbonate) (PIC), a bio-based PC synthesized from isosorbide (ISB) derived from glucose. PIC is expected to function as an alternative to conventional PCs because of its outstanding transparency and thermal and physical properties. This study prepared PIC copolymers with several types of diol comonomers to clarify the effect of copolymerization on the decomposition reaction with ammonia, i.e., ammonolysis for converting PIC copolymers into monomers and urea. The thermal and physical properties of the resulting copolymers were also investigated. The thermal stability of the PIC copolymers remained stable after copolymerization, and the glass transition temperature was affected mainly by the flexibility of the structure of the introduced comonomer. A drastic change in mechanical properties was observed for the copolymer synthesized with 1,4-butanediol, which provides guidelines for toughening PIC with a small comonomer ratio. Finally, we investigated the decomposition behavior of the copolymers by treatment with aqueous ammonia. The PIC copolymers were decomposed into ISB, comonomers, and urea, and the ammonolysis rate was affected by the introduced structure. This study promotes the effective use of ISB as a biomass resource through ammonolysis, which is an effective chemical recycling process for polycarbonate. To functionalize a poly(isosorbide carbonate) (PIC)-based polymer and evaluate its recyclability, several types of diol comonomers were copolymerized with isosorbide. The thermal and mechanical properties and decomposition behavior of the PIC copolymers were investigated. The thermal stability of PIC was retained, and its glass transition temperature was systematically controlled by copolymerization. The decomposition of the PIC copolymers upon treatment with aqueous ammonia yielded monomers and urea, and the decomposition rate was governed by the structure of the comonomer.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 4","pages":"443-453"},"PeriodicalIF":2.8,"publicationDate":"2024-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-023-00878-2.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139462616","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 : 2024-01-12DOI: 10.1038/s41428-023-00874-6
Kazuki Fukushima, Shunta Hakozaki, Rongjian Lang, Yuta Haga, So Nakai, Atsushi Narumi, Masaru Tanaka, Takashi Kato
Investigating polymer degradation mechanisms enables the establishment of controlled degradation techniques for the development of sustainable and recyclable materials. Hydration can play a crucial role in controlling the hydrolysis of polymers. Here, ether-functionalized aliphatic polycarbonates (APCs) susceptible to nonenzymatic hydrolysis were developed for application as biocompatible biomaterials. Among these polymers, those grafted with 2-methoxyethyl and 3-methoxypropyl side chains via an amide group were highly wettable, strongly interacted with water, and experienced almost complete hydrolysis in phosphate-buffered saline over 30 days, which was attributed to the hydrogen bonding between water and the amide/methoxy groups. In an alkaline medium, all amide-linked APCs were completely hydrolyzed within 30 days, regardless of the side-chain structure. In contrast, the nonamide-linked APCs and a representative aliphatic polycarbonate, poly(trimethylene carbonate), were minimally degraded in the buffer and experienced <31% degradation under alkaline conditions. The APC with the 3-methoxypropyl side chain exhibited platelet adhesion properties comparable to those of ether-functionalized APCs previously reported as blood-compatible polymers. Thus, our results demonstrate the effects of an amide linker on the hydration and hydrolytic properties of APCs and can help establish new design concepts for degradable polymers. Aliphatic polycarbonates with ether side groups linked by amide bonds exhibit high hydrolyzability and antiplatelet properties due to enhanced hydration resulting from strong interactions with amide and ether side groups.
{"title":"Hydrolyzable and biocompatible aliphatic polycarbonates with ether-functionalized side chains attached via amide linkers","authors":"Kazuki Fukushima, Shunta Hakozaki, Rongjian Lang, Yuta Haga, So Nakai, Atsushi Narumi, Masaru Tanaka, Takashi Kato","doi":"10.1038/s41428-023-00874-6","DOIUrl":"10.1038/s41428-023-00874-6","url":null,"abstract":"Investigating polymer degradation mechanisms enables the establishment of controlled degradation techniques for the development of sustainable and recyclable materials. Hydration can play a crucial role in controlling the hydrolysis of polymers. Here, ether-functionalized aliphatic polycarbonates (APCs) susceptible to nonenzymatic hydrolysis were developed for application as biocompatible biomaterials. Among these polymers, those grafted with 2-methoxyethyl and 3-methoxypropyl side chains via an amide group were highly wettable, strongly interacted with water, and experienced almost complete hydrolysis in phosphate-buffered saline over 30 days, which was attributed to the hydrogen bonding between water and the amide/methoxy groups. In an alkaline medium, all amide-linked APCs were completely hydrolyzed within 30 days, regardless of the side-chain structure. In contrast, the nonamide-linked APCs and a representative aliphatic polycarbonate, poly(trimethylene carbonate), were minimally degraded in the buffer and experienced <31% degradation under alkaline conditions. The APC with the 3-methoxypropyl side chain exhibited platelet adhesion properties comparable to those of ether-functionalized APCs previously reported as blood-compatible polymers. Thus, our results demonstrate the effects of an amide linker on the hydration and hydrolytic properties of APCs and can help establish new design concepts for degradable polymers. Aliphatic polycarbonates with ether side groups linked by amide bonds exhibit high hydrolyzability and antiplatelet properties due to enhanced hydration resulting from strong interactions with amide and ether side groups.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 4","pages":"431-442"},"PeriodicalIF":2.8,"publicationDate":"2024-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-023-00874-6.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139462937","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}
Controlling adhesion strength during and after the use of bonded materials is crucial. Dismantlable adhesives play important roles in material recycling. However, typical dismantlable adhesives rely on the bulk properties of the adhesive, and specific control of dismantling behavior is challenging. Here, we successfully demonstrated the reusability of a dismantlable adhesion interface system, in which a cleavable molecular layer forms at the adhesion interface through reversible dimerization and cleavage reactions of anthracene. The adhesion peel test was conducted repeatedly by forming a cleavable layer on the substrate surface of the specimens. Strong bonding in the initial state and easy dismantling after stimulation were achieved even in the reused layer. Our strategy for constructing a dismantlable adhesion interface holds promise in material recycling. Overview of the reusable dismantlable adhesion interface system. Heating induces a cleavage reaction of the anthracene photodimer in the molecular layer at the adhesion interface, and the anthracene monomer remains on the substrate surface of the peeled specimen. Photoirradiation to the cleaved molecular layer induces the photodimerization of anthracenes, and the materials exhibit strong adhesion at the adhesion interface.
{"title":"Reusable dismantlable adhesion interfaces induced by photodimerization and thermo/photocleavage reactions","authors":"Miho Aizawa, Haruhisa Akiyama, Yoko Matsuzawa, Atsushi Shishido","doi":"10.1038/s41428-023-00877-3","DOIUrl":"10.1038/s41428-023-00877-3","url":null,"abstract":"Controlling adhesion strength during and after the use of bonded materials is crucial. Dismantlable adhesives play important roles in material recycling. However, typical dismantlable adhesives rely on the bulk properties of the adhesive, and specific control of dismantling behavior is challenging. Here, we successfully demonstrated the reusability of a dismantlable adhesion interface system, in which a cleavable molecular layer forms at the adhesion interface through reversible dimerization and cleavage reactions of anthracene. The adhesion peel test was conducted repeatedly by forming a cleavable layer on the substrate surface of the specimens. Strong bonding in the initial state and easy dismantling after stimulation were achieved even in the reused layer. Our strategy for constructing a dismantlable adhesion interface holds promise in material recycling. Overview of the reusable dismantlable adhesion interface system. Heating induces a cleavage reaction of the anthracene photodimer in the molecular layer at the adhesion interface, and the anthracene monomer remains on the substrate surface of the peeled specimen. Photoirradiation to the cleaved molecular layer induces the photodimerization of anthracenes, and the materials exhibit strong adhesion at the adhesion interface.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 4","pages":"401-408"},"PeriodicalIF":2.8,"publicationDate":"2024-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-023-00877-3.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139462875","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 : 2024-01-12DOI: 10.1038/s41428-023-00879-1
Chung-Yu Kuo, A. V. Emelyanenko, Sheng-Chi Hung, Wei-Chuan Chen, Chun-Yen Liu
In the presence of a strong electric field, helices in a cholesteric liquid crystal (CLC) phase might be unwound, leaving liquid crystal (LC) molecules parallel to the electric field, thereby realizing transparency. Previously, we developed a novel particle-doped CLC cell without alignment layers that exhibited liquid crystal display (LCD) capabilities via electro-optical properties. This ability represents a novel advancement in LCD fabrication, resulting in enhanced electro-optical characteristics. To explore the impact of chirality on LCDs, we synthesized and radially constructed cellulose particles. These were then employed as chiral dopants in the production of LCD cells. The fabricated chiral nanoparticle (CNP)-doped PC05 CLC cell showed a high transparency of 97.4% and a fast response time of 7.6 ms. For the prepared radially constructed PDAT-doped PD2T PSCLC cell, a high transmittance of 93.6% and a fast response time of 13 ms were achieved. Fabrication of LCD cells without an alignment layer on substrates was achieved by indicate adding polymeric chiral nanoparticles into CLC mixtures. Adding 2 wt% chiral CNPs promoted the transmittance of the CLCs from 3.4 to 97%. This novel chiral dopant technique enables the use of a new easy method for the fabrication of LCDs. Fabrication of LCD cell without alignment layer on substrates was achieved via simply adding the chiral polymer nanoparticles into CLC mixtures. The fabricated chiral nanoparticle (CNP) doped CLC cell shows a high contrast 97.4% and a fast response time 7.6 ms.
{"title":"Improving the electro-optical properties of cholesteric liquid crystal devices via cellulose nanoparticle dopants","authors":"Chung-Yu Kuo, A. V. Emelyanenko, Sheng-Chi Hung, Wei-Chuan Chen, Chun-Yen Liu","doi":"10.1038/s41428-023-00879-1","DOIUrl":"10.1038/s41428-023-00879-1","url":null,"abstract":"In the presence of a strong electric field, helices in a cholesteric liquid crystal (CLC) phase might be unwound, leaving liquid crystal (LC) molecules parallel to the electric field, thereby realizing transparency. Previously, we developed a novel particle-doped CLC cell without alignment layers that exhibited liquid crystal display (LCD) capabilities via electro-optical properties. This ability represents a novel advancement in LCD fabrication, resulting in enhanced electro-optical characteristics. To explore the impact of chirality on LCDs, we synthesized and radially constructed cellulose particles. These were then employed as chiral dopants in the production of LCD cells. The fabricated chiral nanoparticle (CNP)-doped PC05 CLC cell showed a high transparency of 97.4% and a fast response time of 7.6 ms. For the prepared radially constructed PDAT-doped PD2T PSCLC cell, a high transmittance of 93.6% and a fast response time of 13 ms were achieved. Fabrication of LCD cells without an alignment layer on substrates was achieved by indicate adding polymeric chiral nanoparticles into CLC mixtures. Adding 2 wt% chiral CNPs promoted the transmittance of the CLCs from 3.4 to 97%. This novel chiral dopant technique enables the use of a new easy method for the fabrication of LCDs. Fabrication of LCD cell without alignment layer on substrates was achieved via simply adding the chiral polymer nanoparticles into CLC mixtures. The fabricated chiral nanoparticle (CNP) doped CLC cell shows a high contrast 97.4% and a fast response time 7.6 ms.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 5","pages":"541-551"},"PeriodicalIF":2.8,"publicationDate":"2024-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-023-00879-1.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139470980","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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