Hongcai Wang, Xiuqiong Chen, Yanan Bu, Ting Wu, Huiqiong Yan, Qiang Lin
In recent years, Stimulus-responsive hydrogels have been extensively researched in the field of actuators due to their capacity to undergo significant deformation in response to various external stimuli. However, it is difficult for the existing hydrogel actuators to meet the requirements of simple preparation, fast response speed and shape memory function, which greatly limits their further application. In the present study, a multi-functional Fe3+-sodium alginate/poly (N-isopropyl acrylamide) interpenetrating network (IPN) hydrogel with ultrafast thermal response, shape memory function and solvent drive was prepared via a simple method. The creation of Fe3+-carboxylate coordination within the hydrogel network, coupled with ultraviolet (UV) photodissociation, was employed to achieve shape memory properties. Moreover, the local gradient of the hydrogel could be precisely programmed by manipulating the UV irradiation time and position. As a result, the obtained gradient hydrogels possessed excellent temperature driving and solvent driving properties, which could not only carry out 4 s fast grasp of objects in 70 ℃ water, but also achieve 2D to 3D complex deformation in methanol aqueous solution. This work provided a new manufacturing method and application prospect for the development of novel intelligent hydrogel actuators
{"title":"Ultrafast thermal responsive, shape memory and solvent-driven Fe3+-alginate/poly (N-isopropyl acrylamide) based hydrogel actuator","authors":"Hongcai Wang, Xiuqiong Chen, Yanan Bu, Ting Wu, Huiqiong Yan, Qiang Lin","doi":"10.1039/d4py01047g","DOIUrl":"https://doi.org/10.1039/d4py01047g","url":null,"abstract":"In recent years, Stimulus-responsive hydrogels have been extensively researched in the field of actuators due to their capacity to undergo significant deformation in response to various external stimuli. However, it is difficult for the existing hydrogel actuators to meet the requirements of simple preparation, fast response speed and shape memory function, which greatly limits their further application. In the present study, a multi-functional Fe3+-sodium alginate/poly (N-isopropyl acrylamide) interpenetrating network (IPN) hydrogel with ultrafast thermal response, shape memory function and solvent drive was prepared via a simple method. The creation of Fe3+-carboxylate coordination within the hydrogel network, coupled with ultraviolet (UV) photodissociation, was employed to achieve shape memory properties. Moreover, the local gradient of the hydrogel could be precisely programmed by manipulating the UV irradiation time and position. As a result, the obtained gradient hydrogels possessed excellent temperature driving and solvent driving properties, which could not only carry out 4 s fast grasp of objects in 70 ℃ water, but also achieve 2D to 3D complex deformation in methanol aqueous solution. This work provided a new manufacturing method and application prospect for the development of novel intelligent hydrogel actuators","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"116 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142924906","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Geonwoo Lee, Jinhoon Lee, Geonho Lee, Chihyun Seo, Myung Jin Baek, Dong Woog Lee
Pressure-sensitive adhesives (PSAs) are used in a wide range of applications, including electronics, automobiles, healthcare, and packaging, due to their excellent bonding affinity with minimal applied pressure without the need for solvents, heat, or additional processing. Although they exhibit excellent usability with high adhesion strength, PSAs must overcome the limitation of delamination caused by poor strain recovery to be applied to flexible electronics. In this study, we achieved rapid strain recovery in PSAs by utilizing polyurethane diacrylate (PUDA) as a crosslinker. The fabricated PSA demonstrated a significantly faster strain recovery time (~2.5 sec) compared to the conventional crosslinked 1,6-hexanediol diacrylate (HDDA) PSA (~61.0 sec). Notably, the PUDA PSA also exhibited outstanding 180º peel strength (~22.0 N/25mm), surpassing that of a commercial PSA. (~12.3 N/25mm). The fabricated PSAs showed promise for applications under harsh straining conditions, confirmed through 100 strain-recovery cycles at 20 % tensile strain. This study directs the way to improve PSA’s poor strain recovery properties and paves the way for future advancements direction in adhesive technology.
{"title":"Polyurethane diacrylate incorporated pressure-sensitive adhesives with enhanced strain recovery","authors":"Geonwoo Lee, Jinhoon Lee, Geonho Lee, Chihyun Seo, Myung Jin Baek, Dong Woog Lee","doi":"10.1039/d4py01084a","DOIUrl":"https://doi.org/10.1039/d4py01084a","url":null,"abstract":"Pressure-sensitive adhesives (PSAs) are used in a wide range of applications, including electronics, automobiles, healthcare, and packaging, due to their excellent bonding affinity with minimal applied pressure without the need for solvents, heat, or additional processing. Although they exhibit excellent usability with high adhesion strength, PSAs must overcome the limitation of delamination caused by poor strain recovery to be applied to flexible electronics. In this study, we achieved rapid strain recovery in PSAs by utilizing polyurethane diacrylate (PUDA) as a crosslinker. The fabricated PSA demonstrated a significantly faster strain recovery time (~2.5 sec) compared to the conventional crosslinked 1,6-hexanediol diacrylate (HDDA) PSA (~61.0 sec). Notably, the PUDA PSA also exhibited outstanding 180º peel strength (~22.0 N/25mm), surpassing that of a commercial PSA. (~12.3 N/25mm). The fabricated PSAs showed promise for applications under harsh straining conditions, confirmed through 100 strain-recovery cycles at 20 % tensile strain. This study directs the way to improve PSA’s poor strain recovery properties and paves the way for future advancements direction in adhesive technology.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"27 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917590","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Anahita Keer, Arielle Mann, Chengyuan Wang, Marcus Weck
The discovery of living, chain-growth polymerizations of poly(p-phenylenevinylene)s (PPVs) allows for low dispersed, controlled, and architecturally complex PPV-based polymers. This contribution presents the synthesis of PPVs functionalized with crown-ethers on each repeat unit that assemble with chain-end functionalized monotelechelic poly(styrene)s (PS) containing a terminal amine salt to form pseudorotaxane-based bottlebrush copolymers. The PPVs are synthesized by living ring-opening metathesis polymerization (ROMP) and the PS through atom-transfer radical polymerization (ATRP). The bottlebrush copolymer formation was confirmed by nuclear magnetic resonance spectroscopy, gel-permeation chromatography, isothermal titration calorimetry, dynamic light-scattering, wide-angle X-ray scattering, and optical spectroscopy. This work depicts the first example of a backbone modified PPV synthesized through ROMP and introduces a versatile strategy towards supramolecular bottlebrush copolymers containing conducting polymers. Our methodology lends itself to supramolecular materials for applications in chemical sensing, optoelectronics, and fluorescent imaging.
{"title":"Supramolecular bottlebrush copolymers from crown-ether functionalized poly(p-phenylenevinylene)s","authors":"Anahita Keer, Arielle Mann, Chengyuan Wang, Marcus Weck","doi":"10.1039/d4py01225a","DOIUrl":"https://doi.org/10.1039/d4py01225a","url":null,"abstract":"The discovery of living, chain-growth polymerizations of poly(<em>p</em>-phenylenevinylene)s (PPVs) allows for low dispersed, controlled, and architecturally complex PPV-based polymers. This contribution presents the synthesis of PPVs functionalized with crown-ethers on each repeat unit that assemble with chain-end functionalized monotelechelic poly(styrene)s (PS) containing a terminal amine salt to form pseudorotaxane-based bottlebrush copolymers. The PPVs are synthesized by living ring-opening metathesis polymerization (ROMP) and the PS through atom-transfer radical polymerization (ATRP). The bottlebrush copolymer formation was confirmed by nuclear magnetic resonance spectroscopy, gel-permeation chromatography, isothermal titration calorimetry, dynamic light-scattering, wide-angle X-ray scattering, and optical spectroscopy. This work depicts the first example of a backbone modified PPV synthesized through ROMP and introduces a versatile strategy towards supramolecular bottlebrush copolymers containing conducting polymers. Our methodology lends itself to supramolecular materials for applications in chemical sensing, optoelectronics, and fluorescent imaging.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917537","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Polymers of higher cyclic formals (polyacetals) containing alternating oxymethylene (OM) units and a few oxyethylene (EO) units can be considered as intermediates between poly(ethylene oxide) and poly(1,3-dioxolane), both of which are used as components in solid polymer electrolytes. In this work, polyacetals from di-, tri-, and tetraethylene glycol cyclic formals (POMEO2, POMEO3, and POMEO4) were obtained with high efficiency (>95%) by cationic polymerization conducted at 20 °C in CH2Cl2, using triethyloxonium hexafluorophosphate as a catalyst. Analogously, polyacetals (POMEOx) of higher cyclic formals of commercially available poly(ethylene oxide) diols (Mn ∼ 200 g mol−1) were prepared under these conditions. The obtained polymers were carefully characterised using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) to determine their glass transition temperature (Tg), melting temperature (Tm) and thermal stability. Subsequently, solid-state electrolytes were prepared by applying lithium trifluoromethane sulfonate (lithium triflate –LiOTf). The complexation of the lithium cation was studied by classical 7Li NMR and DOSY techniques. Ionic conductivity measurements of the polyacetal electrolytes were performed using electrochemical impedance spectroscopy (EIS) in the temperature range from 20 to 100 °C. The results show that disrupting the regular structure of polymers obtained by polymerizing cyclic formals of individual diols, by introducing ethylene oxide units of different lengths within a macromolecule, may benefit ionic transport.
含有氧亚甲基（OM）单元和少量氧亚乙基（EO）单元交替出现的高环醛聚合物（聚缩醛）可被视为聚环氧乙烷和聚（1,3-二氧戊环）之间的中间体，这两种聚合物都可用作固体聚合物电解质的成分。在这项研究中，以六氟磷酸三乙氧基铵为催化剂，在 20 °C 的 CH2Cl2 溶液中进行阳离子聚合反应，以高效率（95%）获得了由二、三和四乙二醇环醛（POMEO2、POMEO3 和 POMEO4）组成的聚缩醛。同样，在这些条件下还制备了市售聚环氧乙烷二元醇（Mn ∼ 200 g mol-1）的高环形式的聚醋酸酯（POMEOx）。使用差示扫描量热法（DSC）和热重分析法（TGA）对获得的聚合物进行了仔细的表征，以确定其玻璃化转变温度（Tg）、熔化温度（Tm）和热稳定性。随后，利用三氟甲烷磺酸锂（三氟甲基磺酸锂-LiOTf）制备了固态电解质。通过经典的 7Li NMR 和 DOSY 技术研究了锂阳离子的络合。使用电化学阻抗谱（EIS）测量了聚缩醛电解质在 20 至 100 °C 温度范围内的离子电导率。结果表明，通过在大分子中引入不同长度的环氧乙烷单元，破坏通过聚合单个二元醇的环状形式获得的聚合物的规则结构，可能有利于离子传输。
{"title":"Polyacetals of higher cyclic formals: synthesis, properties and application as polymer electrolytes","authors":"Bartłomiej Kost, Malgorzata Basko, Sławomir Kaźmierski, Ewa Zygadło-Monikowska, Magdalena Słojewska, Przemysław Kubisa","doi":"10.1039/d4py01194e","DOIUrl":"https://doi.org/10.1039/d4py01194e","url":null,"abstract":"Polymers of higher cyclic formals (polyacetals) containing alternating oxymethylene (OM) units and a few oxyethylene (EO) units can be considered as intermediates between poly(ethylene oxide) and poly(1,3-dioxolane), both of which are used as components in solid polymer electrolytes. In this work, polyacetals from di-, tri-, and tetraethylene glycol cyclic formals (POMEO2, POMEO3, and POMEO4) were obtained with high efficiency (>95%) by cationic polymerization conducted at 20 °C in CH<small><sub>2</sub></small>Cl<small><sub>2</sub></small>, using triethyloxonium hexafluorophosphate as a catalyst. Analogously, polyacetals (POMEO<em>x</em>) of higher cyclic formals of commercially available poly(ethylene oxide) diols (<em>M</em><small><sub>n</sub></small> ∼ 200 g mol<small><sup>−1</sup></small>) were prepared under these conditions. The obtained polymers were carefully characterised using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) to determine their glass transition temperature (<em>T</em><small><sub>g</sub></small>), melting temperature (<em>T</em><small><sub>m</sub></small>) and thermal stability. Subsequently, solid-state electrolytes were prepared by applying lithium trifluoromethane sulfonate (lithium triflate –LiOTf). The complexation of the lithium cation was studied by classical <small><sup>7</sup></small>Li NMR and DOSY techniques. Ionic conductivity measurements of the polyacetal electrolytes were performed using electrochemical impedance spectroscopy (EIS) in the temperature range from 20 to 100 °C. The results show that disrupting the regular structure of polymers obtained by polymerizing cyclic formals of individual diols, by introducing ethylene oxide units of different lengths within a macromolecule, may benefit ionic transport.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917538","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Enhancing both the protective and mechanical properties of chemical-resistant coatings is a challenging task. In this study, ultraviolet (UV) cured polyurethane–urea acrylate (PUUA) containing hindered urea groups were prepared to function as a transitional coating during periods of non-use. This transitional coating offers both flexibility and impact resistance. Upon heat treatment, the PUUA network shifts from the transitional state to a defensive state, forming a polyurethane–urea (PUU) network with improved resistance to 2-chloroethyl sulfide (CEES), a mustard gas simulant. The effects of different heat curing agents (diamines) on the PUUs were investigated in terms of physical and chemical structures, curing mechanism, mechanical properties, coating properties, and chemical resistance. Compared to their PUUA counterparts, the PUUs with a higher glass transition temperature (Tg), lower crosslinking density and reduced surface N–H proportion showed increase resistance to CEES. Among the PUUs, PUU-PEA prepared from polyether-amine (PEA) exhibited superior chemical resistance and mechanical properties. These findings provide valuable insights for the development of UV-curable chemoprotective coatings.
{"title":"Polyurethane–urea coatings derived from UV-cured polyurethane–urea acrylate transition coatings for enhanced resistance to chemical warfare agent simulants","authors":"Xucong Chen, Linjing Xiao, Guiyou Wang, Hong Li","doi":"10.1039/d4py01060d","DOIUrl":"https://doi.org/10.1039/d4py01060d","url":null,"abstract":"Enhancing both the protective and mechanical properties of chemical-resistant coatings is a challenging task. In this study, ultraviolet (UV) cured polyurethane–urea acrylate (PUUA) containing hindered urea groups were prepared to function as a transitional coating during periods of non-use. This transitional coating offers both flexibility and impact resistance. Upon heat treatment, the PUUA network shifts from the transitional state to a defensive state, forming a polyurethane–urea (PUU) network with improved resistance to 2-chloroethyl sulfide (CEES), a mustard gas simulant. The effects of different heat curing agents (diamines) on the PUUs were investigated in terms of physical and chemical structures, curing mechanism, mechanical properties, coating properties, and chemical resistance. Compared to their PUUA counterparts, the PUUs with a higher glass transition temperature (<em>T</em><small><sub>g</sub></small>), lower crosslinking density and reduced surface N–H proportion showed increase resistance to CEES. Among the PUUs, PUU-PEA prepared from polyether-amine (PEA) exhibited superior chemical resistance and mechanical properties. These findings provide valuable insights for the development of UV-curable chemoprotective coatings.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"20 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912282","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shiori Matsuo, Sho Nonaka, Aki Mihata, Kazuhiro Shikinaka, Yoshiro Kaneko
Aiming to enhance the high-temperature stability of nanoaggregates of amphiphilic polymers in water, an amphiphilic ladder-like (double-chain) polymer (PGE–PAMS) was successfully prepared via the thiol–ene reaction between 3-mercaptopropyldimethoxymethylsilane and poly(allyl glycidyl ether), followed by intramolecular polycondensation (template polymerization) of the dimethoxysilyl groups in the side chains of the resulting polymer. Solubility tests, FT-IR spectroscopy, 1H NMR spectroscopy, 29Si NMR spectroscopy and transmission electron microscopy confirmed that PGE–PAMS possesses a ladder-like structure, where the hydrophilic poly(glycidyl ether) chain and the hydrophobic polyalkylmethylsiloxane chain are linked in parallel by sulfide bonds. PGE–PAMS formed nanoaggregates with a diameter of ca. 60–70 nm in water, which were stable even at high temperatures (80°C–90°C). Additionally, in water containing a small amount of N,N-dimethylformamide, the PGE–PAMS nanoaggregates could solubilize tetraphenylporphyrin, a hydrophobic dye, and stably retain it even at a high temperature of 90°C.
{"title":"Preparation and nanoaggregate formation ability in water of amphiphilic ladder-like polymers with parallelly linked hydrophilic polyether and hydrophobic polysiloxane chains","authors":"Shiori Matsuo, Sho Nonaka, Aki Mihata, Kazuhiro Shikinaka, Yoshiro Kaneko","doi":"10.1039/d4py01316f","DOIUrl":"https://doi.org/10.1039/d4py01316f","url":null,"abstract":"Aiming to enhance the high-temperature stability of nanoaggregates of amphiphilic polymers in water, an amphiphilic ladder-like (double-chain) polymer (PGE–PAMS) was successfully prepared via the thiol–ene reaction between 3-mercaptopropyldimethoxymethylsilane and poly(allyl glycidyl ether), followed by intramolecular polycondensation (template polymerization) of the dimethoxysilyl groups in the side chains of the resulting polymer. Solubility tests, FT-IR spectroscopy, <small><sup>1</sup></small>H NMR spectroscopy, <small><sup>29</sup></small>Si NMR spectroscopy and transmission electron microscopy confirmed that PGE–PAMS possesses a ladder-like structure, where the hydrophilic poly(glycidyl ether) chain and the hydrophobic polyalkylmethylsiloxane chain are linked in parallel by sulfide bonds. PGE–PAMS formed nanoaggregates with a diameter of <em>ca</em>. 60–70 nm in water, which were stable even at high temperatures (80°C–90°C). Additionally, in water containing a small amount of <em>N</em>,<em>N</em>-dimethylformamide, the PGE–PAMS nanoaggregates could solubilize tetraphenylporphyrin, a hydrophobic dye, and stably retain it even at a high temperature of 90°C.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"9 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912279","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Photoacid generators (PAGs) play an important role in chemically amplified resists (CARs), but small molecule PAGs have low solubility and limited compatibility with resins, which may lead to various problems. One of the important solutions is to bound PAG to polymer chains but differences in monomer reactivity can lead to an uneven distribution of molecular chain sequences between different polymer chains during polymerization, potentially impacting the lithographic performance. In this work, PAG units were incorporated into the photoresist resin polymer backbone via reversible addition-fragmentation chain transfer (RAFT) polymerization to synthesize methyl methacrylate polymer with different PAG loadings. The lithographic properties of the PAG bound polymer resist and the PAG blend polymer resist were studied and compared. The direct incorporation of PAG functionality into the polymer showed lower sensitivity, shorter acid diffusion length, and better compatibility. By observing the lithography results through AFM and SEM, the lithography lines of the PAG bound polymer photoresist synthesized via RAFT polymerization exhibited improved morphology and narrower line edge roughness (LER).
{"title":"Enhanced Lithographic Performance of Polymer-Bound PAG Photoresists Synthesized via RAFT Polymerization","authors":"Nan Qin, Na Li, Xiang Gao","doi":"10.1039/d4py01271b","DOIUrl":"https://doi.org/10.1039/d4py01271b","url":null,"abstract":"Photoacid generators (PAGs) play an important role in chemically amplified resists (CARs), but small molecule PAGs have low solubility and limited compatibility with resins, which may lead to various problems. One of the important solutions is to bound PAG to polymer chains but differences in monomer reactivity can lead to an uneven distribution of molecular chain sequences between different polymer chains during polymerization, potentially impacting the lithographic performance. In this work, PAG units were incorporated into the photoresist resin polymer backbone via reversible addition-fragmentation chain transfer (RAFT) polymerization to synthesize methyl methacrylate polymer with different PAG loadings. The lithographic properties of the PAG bound polymer resist and the PAG blend polymer resist were studied and compared. The direct incorporation of PAG functionality into the polymer showed lower sensitivity, shorter acid diffusion length, and better compatibility. By observing the lithography results through AFM and SEM, the lithography lines of the PAG bound polymer photoresist synthesized via RAFT polymerization exhibited improved morphology and narrower line edge roughness (LER).","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"48 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912277","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ethan C Quinn, Celine Parker, Sophie M Guillaume, Eugene Y.-X. Chen
Biodegradable plastics, especially those that can biodegrade in uncontrolled enviroments, are of importance to help curb the global plastics crisis. Poly(3-hydroxyalkanoate)s (PHAs), which can be either microbially or chemically synthesized, are one of the rare classes of plastics that can biodegrade under both managed and unmanaged conditions. Besides this exceptional upside, PHAs can also be tuned to exhibit thermal, mechanical, and optical properties of commodity polymers including polyolefins, and they can be designed to be chemically recyclable towards a circular PHA economy or functionalized to acquire additional, diverse and/or improved properties. To enable for such modularity in the chemocatalytic PHAs, the development of stereoselective and controlled molecular catalysts as well as the design of monomer structures and polymerization processes, are of primary importance. In this context, this Perspective article focuses on the three recent advancements, including PHA stereomicrostructural engineering, melt-processability and chemical recyclability, and chemical functionalization.
{"title":"Regulating Stereomicrostructure, Circularity and Functionality of Synthetic PHAs","authors":"Ethan C Quinn, Celine Parker, Sophie M Guillaume, Eugene Y.-X. Chen","doi":"10.1039/d4py01313a","DOIUrl":"https://doi.org/10.1039/d4py01313a","url":null,"abstract":"Biodegradable plastics, especially those that can biodegrade in uncontrolled enviroments, are of importance to help curb the global plastics crisis. Poly(3-hydroxyalkanoate)s (PHAs), which can be either microbially or chemically synthesized, are one of the rare classes of plastics that can biodegrade under both managed and unmanaged conditions. Besides this exceptional upside, PHAs can also be tuned to exhibit thermal, mechanical, and optical properties of commodity polymers including polyolefins, and they can be designed to be chemically recyclable towards a circular PHA economy or functionalized to acquire additional, diverse and/or improved properties. To enable for such modularity in the chemocatalytic PHAs, the development of stereoselective and controlled molecular catalysts as well as the design of monomer structures and polymerization processes, are of primary importance. In this context, this Perspective article focuses on the three recent advancements, including PHA stereomicrostructural engineering, melt-processability and chemical recyclability, and chemical functionalization.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"35 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142905428","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Cyclic peptide-based [2]rotaxanes were synthesized from cyclo(PG)4 and monocationic ammonium threads via copper-catalyzed azide–alkyne cycloaddition (CuAAC), achieving relatively high yields of up to 36%. Cyclic peptides that do not contain bulky side chains or amino acids that induce the formation of cis-amide bonds were found to be unsuitable for rotaxane synthesis. This innovative synthetic approach advances the development of multifunctional rotaxanes and opens new avenues for their applications in various fields.
{"title":"Synthesis of cyclic peptide-based [2]rotaxanes via copper-catalyzed azide–alkyne cycloaddition†","authors":"Taichi Kurita and Keiji Numata","doi":"10.1039/D4PY01169D","DOIUrl":"10.1039/D4PY01169D","url":null,"abstract":"<p >Cyclic peptide-based [2]rotaxanes were synthesized from cyclo(PG)<small><sub>4</sub></small> and monocationic ammonium threads <em>via</em> copper-catalyzed azide–alkyne cycloaddition (CuAAC), achieving relatively high yields of up to 36%. Cyclic peptides that do not contain bulky side chains or amino acids that induce the formation of <em>cis</em>-amide bonds were found to be unsuitable for rotaxane synthesis. This innovative synthetic approach advances the development of multifunctional rotaxanes and opens new avenues for their applications in various fields.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 4","pages":" 409-414"},"PeriodicalIF":4.1,"publicationDate":"2024-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888698","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Francesc Borrull, Peter A. G. Cormack, Alan Corrigan, Calum Craig, Núria Fontanals, Rosa Maria Marcé, Alberto Moral, Greg Smith
Mixed-mode ion-exchange sorbents with amphoteric character are intriguing materials because not only can anions and cations be extracted from liquid samples using one single sorbent rather than two (anion extraction under one set of conditions, cation extraction under a second set of conditions), but it may be feasible to establish extraction conditions where anionic and cationic analytes can be extracted simultaneously. In the present study, an unusual but versatile synthetic route was used to install amphoteric character into polydivinylbenzene microspheres produced through precipitation polymerisation. The key synthetic step used for the chemical functionalisation of the polydivinylbenzenes exploited Diels-Alder cycloaddition chemistry to target the pendent styryl groups that are present in polydivinylbenzenes. With maleic anhydride as a dienophile, Diels-Alder cycloaddition yielded polydivinylbenzenes decorated with anhydride moieties. Whilst such materials are interesting in their own right as reactive resins, ring-opening of the polymer-bound anhydride units with ethylenediamine yielded an amphoteric material with both weak anion-exchange (WAX) and weak cation-exchange (WCX) character. This polymer was evaluated as a pH-tuneable sorbent for the solid-phase extraction (SPE) of acidic and basic pharmaceuticals from water samples. Following optimisation of the analytical method and the SPE, the method was subjected to validation and then applied to the extraction and determination of acidic and basic pharmaceuticals present at low concentrations in river water, effluent wastewater and influent wastewater samples. Simultaneous extraction and determination of acidic and basic compounds was found to be achievable, with method quantification limits down to 1 ng/L.
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