Fabrication of controlled supramolecular assembly and establishing the structure-function relationship was of great significance in supramolecular chemistry. Uniform fluorescence supramolecular polymeric vesicles and/or micelles with enhanced photophysical property were elaborately designed and prepared by amphiphilic block polymer hosts bearing pillar[5]arene units, which following the working mechanism of synergistically confined effect of hydrophobic interactions and host-guest interactions. Additionally, transformation from supramolecular polymeric vesicles to supramolecular polymeric micelles was achieved by selecting different length of hydrophilic segments in block polymer hosts. The optical performance was detailed deciphered by the impact factors including guest patterns, density of pillar[5]arene unit, length of hydrophilic segments and solvent environment. By exploiting amphiphilic block polymer hosts, efficient artificial light-harvesting systems with ordered arrangement of donor and acceptor molecules were well constructed to realize tunable emission wavelength, which was used as Morse code for information encryption matrix with high storage capacity capable of simultaneously storing Chinese, English and digits.
{"title":"Assembly-Controlled Supramolecular Aggregation-Induced Emission Systems based on Amphiphilic Block Polymer Hosts","authors":"Yu-Qi Zhu, Zhong-Yuan Chen, Zhi-Wei Zhou, Zhao-Jun Chen, Ming-Xue Wu, Xing-Huo Wang","doi":"10.1039/d4py01009d","DOIUrl":"https://doi.org/10.1039/d4py01009d","url":null,"abstract":"Fabrication of controlled supramolecular assembly and establishing the structure-function relationship was of great significance in supramolecular chemistry. Uniform fluorescence supramolecular polymeric vesicles and/or micelles with enhanced photophysical property were elaborately designed and prepared by amphiphilic block polymer hosts bearing pillar[5]arene units, which following the working mechanism of synergistically confined effect of hydrophobic interactions and host-guest interactions. Additionally, transformation from supramolecular polymeric vesicles to supramolecular polymeric micelles was achieved by selecting different length of hydrophilic segments in block polymer hosts. The optical performance was detailed deciphered by the impact factors including guest patterns, density of pillar[5]arene unit, length of hydrophilic segments and solvent environment. By exploiting amphiphilic block polymer hosts, efficient artificial light-harvesting systems with ordered arrangement of donor and acceptor molecules were well constructed to realize tunable emission wavelength, which was used as Morse code for information encryption matrix with high storage capacity capable of simultaneously storing Chinese, English and digits.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"50 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665545","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}
Izabela Kurowska, Maksym Odnoroh, Oleksandr Ivanchenko, Marc Guerre, Mathias Destarac
The synthesis of PMMA-b-PnBA-b-PMMA triblock copolymers using photoiniferter reversible addition-fragmentation chain transfer (PI-RAFT) polymerisation is reported. By utilising a combination of green and blue LED irradiation, copolymers with high molar masses up to Mn ∼ 800 kg mol−1, low dispersities (Ð < 1.25), and thermoplastic elastomer behaviour were synthesised.
报告采用光增塑剂可逆加成-断裂链转移（PI-RAFT）聚合法合成了 PMMA-b-PnBA-b-PMMA 三嵌段共聚物。通过结合使用绿光和蓝光 LED 照射，合成了摩尔质量高达 Mn ∼ 800 kg mol-1、分散度低（Ð < 1.25）且具有热塑性弹性体特性的共聚物。
{"title":"Synthesis of high molar mass all-(meth)acrylic thermoplastic elastomers by photo-iniferter RAFT polymerisation","authors":"Izabela Kurowska, Maksym Odnoroh, Oleksandr Ivanchenko, Marc Guerre, Mathias Destarac","doi":"10.1039/d4py01123f","DOIUrl":"https://doi.org/10.1039/d4py01123f","url":null,"abstract":"The synthesis of PMMA-<em>b</em>-P<em>n</em>BA-<em>b</em>-PMMA triblock copolymers using photoiniferter reversible addition-fragmentation chain transfer (PI-RAFT) polymerisation is reported. By utilising a combination of green and blue LED irradiation, copolymers with high molar masses up to <em>M<small><sub>n</sub></small></em> ∼ 800 kg mol<small><sup>−1</sup></small>, low dispersities (<em>Ð</em> < 1.25), and thermoplastic elastomer behaviour were synthesised.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"64 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665547","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}
Kseniya A. Bezlepkina, Sergey Milenin, Aziz Muzafarov
To be coPolydimethylsiloxanes (PDMS) occupy a special place among polymers due to their unique properties, including the possibility of their easy functionalization. Click chemistry reactions, in particular, the azide-alkyne cycloaddition reaction, are promising for the production of both functional siloxanes and siloxane copolymers, and for cross-linked materials. This review discusses the emergence and development of the azide-alkyne cycloaddition reaction for the synthesis of polydimethylsiloxane modification and structures based on them, as well as methods for introducing azide and acetylene fragments into the PDMS structure.nfirmed
{"title":"Azide-alkyne cycloaddition for polydimethysiloxane chemistry","authors":"Kseniya A. Bezlepkina, Sergey Milenin, Aziz Muzafarov","doi":"10.1039/d4py01052c","DOIUrl":"https://doi.org/10.1039/d4py01052c","url":null,"abstract":"To be coPolydimethylsiloxanes (PDMS) occupy a special place among polymers due to their unique properties, including the possibility of their easy functionalization. Click chemistry reactions, in particular, the azide-alkyne cycloaddition reaction, are promising for the production of both functional siloxanes and siloxane copolymers, and for cross-linked materials. This review discusses the emergence and development of the azide-alkyne cycloaddition reaction for the synthesis of polydimethylsiloxane modification and structures based on them, as well as methods for introducing azide and acetylene fragments into the PDMS structure.nfirmed","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"29 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637108","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}
Mohammed G. Kotp, Ahmed F. M. El-Mahdy, Shiao-Wei Kuo
Porous organic polymers (POPs) have garnered significant attention across various industries due to their promising physicochemical properties. In this study, we employed the classical Friedel-Crafts alkylation strategy to synthesize two types of porous organic polymers, namely Py-CH POP and TPA-CH POP, utilizing chloranil (CH), pyrene (Py), and triphenylamine (TPA) as building blocks. The Py-CH POP exhibits coaxial-like morphologies, uniform micropores, and a moderate surface area of up to 822 m²/g, along with excellent thermal stability, recording a char output of 69.6 wt%. Notably, these CH POPs contain dynamic hydroxyl groups that can effectively attract Ag⁺ ions from silver nitrate solutions and facilitate their reduction into silver nanoparticles, resulting in the formation of Ag@Py-CH and Ag@TPA-CH POP nanocomposites. These nanocomposites serve as efficient nano-catalysts for the reduction of hazardous p-nitrophenol (p-NP) to the safer p-aminophenol (p-AP) at ambient temperature. Importantly, the Ag@Py-CH and Ag@TPA-CH POP nanocomposites demonstrate comparable normalized reduction rates of p-NP, reaching up to 65.3 mg/s. The quaternary amine sites in the Ag@TPA-CH POP nanocomposites play a crucial role in this catalytic reaction, enhancing interactions with the phenolic hydroxyl groups of p-NP and thereby accelerating the reduction process compared to Ag@Py-CH POP. This strategy presents a dynamic approach for the reduction of p-NP, leading to the clean production of p-AP.
多孔有机聚合物（POPs）因其良好的物理化学特性而在各行各业受到广泛关注。在本研究中，我们采用经典的 Friedel-Crafts 烷基化策略，以氯苯胺 (CH)、芘 (Py) 和三苯胺 (TPA) 为构建基块，合成了两种多孔有机聚合物，即 Py-CH POP 和 TPA-CH POP。Py-CH POP 具有同轴状形态、均匀的微孔和高达 822 m²/g 的适中表面积，同时具有出色的热稳定性，记录的炭产量为 69.6 wt%。值得注意的是，这些 CH 持久性有机污染物含有动态羟基，能有效吸引硝酸银溶液中的银⁺离子，并促进其还原成银纳米粒子，从而形成 Ag@Py-CH 和 Ag@TPA-CH 持久性有机污染物纳米复合材料。这些纳米复合材料可作为高效的纳米催化剂，在常温下将有害的对硝基苯酚（p-NP）还原成更安全的对氨基苯酚（p-AP）。重要的是，Ag@Py-CH 和 Ag@TPA-CH 持久性有机污染物纳米复合材料对对硝基苯酚的归一化还原率相当，高达 65.3 mg/s。与 Ag@Py-CH POP 相比，Ag@TPA-CH POP 纳米复合材料中的季胺位点在这一催化反应中发挥了关键作用，增强了与对-NP 的酚羟基的相互作用，从而加速了还原过程。这种策略为对-NP 的还原提供了一种动态方法，从而实现了对-AP 的清洁生产。
{"title":"Rational Decoration of Porous Organic Polymers with Silver Nanoparticles for Strategic Reduction of Hazardous Nitroaryl Compounds","authors":"Mohammed G. Kotp, Ahmed F. M. El-Mahdy, Shiao-Wei Kuo","doi":"10.1039/d4py01179a","DOIUrl":"https://doi.org/10.1039/d4py01179a","url":null,"abstract":"Porous organic polymers (POPs) have garnered significant attention across various industries due to their promising physicochemical properties. In this study, we employed the classical Friedel-Crafts alkylation strategy to synthesize two types of porous organic polymers, namely Py-CH POP and TPA-CH POP, utilizing chloranil (CH), pyrene (Py), and triphenylamine (TPA) as building blocks. The Py-CH POP exhibits coaxial-like morphologies, uniform micropores, and a moderate surface area of up to 822 m²/g, along with excellent thermal stability, recording a char output of 69.6 wt%. Notably, these CH POPs contain dynamic hydroxyl groups that can effectively attract Ag⁺ ions from silver nitrate solutions and facilitate their reduction into silver nanoparticles, resulting in the formation of Ag@Py-CH and Ag@TPA-CH POP nanocomposites. These nanocomposites serve as efficient nano-catalysts for the reduction of hazardous p-nitrophenol (p-NP) to the safer p-aminophenol (p-AP) at ambient temperature. Importantly, the Ag@Py-CH and Ag@TPA-CH POP nanocomposites demonstrate comparable normalized reduction rates of p-NP, reaching up to 65.3 mg/s. The quaternary amine sites in the Ag@TPA-CH POP nanocomposites play a crucial role in this catalytic reaction, enhancing interactions with the phenolic hydroxyl groups of p-NP and thereby accelerating the reduction process compared to Ag@Py-CH POP. This strategy presents a dynamic approach for the reduction of p-NP, leading to the clean production of p-AP.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"128 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637109","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}
Polyols are versatile molecules present in many polymer materials that are used and often essential in daily life. However, most bio-based polyols are derived from sugar or vegetable oil, and thus, their production directly competes with the food industry. In this case, CNSL is a promising non-edible renewable resource, which is directly extracted from the shell of cashew nuts. The interesting chemical structure of CNSL and its derivatives (cardanol and cardol) has led to the synthesis of original polyols with hydrophobic and internal plasticizing properties. Useful for the development of additives such as surfactants and soft polymers, CNSL polyols are progressively occupying a unique position in the polymer industry. This review focuses on the use of CNSL as a building block for various polyols. Many different chemical pathways leading to CNSL-based polyols are reviewed and evaluated. Furthermore, we focus on the use of these CNSL-based polyols as surfactants and polymer precursors and the contribution of their specific chemical structure (aromatic ring and long unsaturated alkyl chain) to the properties of the resulting polyesters or polyurethanes.
{"title":"Polyols from cashew nut shell liquid (CNSL): corner-stone building blocks for cutting-edge bio-based additives and polymers","authors":"Emilie Rojtman , Maxinne Denis , Camille Sirvent , Vincent Lapinte , Sylvain Caillol , Benoit Briou","doi":"10.1039/d4py00851k","DOIUrl":"10.1039/d4py00851k","url":null,"abstract":"<div><div>Polyols are versatile molecules present in many polymer materials that are used and often essential in daily life. However, most bio-based polyols are derived from sugar or vegetable oil, and thus, their production directly competes with the food industry. In this case, CNSL is a promising non-edible renewable resource, which is directly extracted from the shell of cashew nuts. The interesting chemical structure of CNSL and its derivatives (cardanol and cardol) has led to the synthesis of original polyols with hydrophobic and internal plasticizing properties. Useful for the development of additives such as surfactants and soft polymers, CNSL polyols are progressively occupying a unique position in the polymer industry. This review focuses on the use of CNSL as a building block for various polyols. Many different chemical pathways leading to CNSL-based polyols are reviewed and evaluated. Furthermore, we focus on the use of these CNSL-based polyols as surfactants and polymer precursors and the contribution of their specific chemical structure (aromatic ring and long unsaturated alkyl chain) to the properties of the resulting polyesters or polyurethanes.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 43","pages":"Pages 4375-4415"},"PeriodicalIF":4.1,"publicationDate":"2024-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/py/d4py00851k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142363270","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Gavin Irvine , Stuart Herron , Daniel W. Lester , Efrosyni Themistou
Biocompatible, acid-labile cross-linked star polymer model networks (CSPMNs) have great potential for use in drug delivery. However, a primary complication of this research stems from the prevalence of their synthesis to take place in organic solvents. Herein, to minimize CSPMN potential cytotoxicity, aqueous reversible addition–fragmentation chain transfer polymerization is employed for their synthesis. Initially, “arm-first” star polymers were synthesized in water using a poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA) homopolymer and a non-degradable ethylene glycol dimethacrylate or acid-labile diacetal-based bis[(2-methacryloyloxy)ethoxymethyl] ether cross-linker. Subsequently, OEGMA addition resulted in the preparation of “in–out” star polymers (with higher molecular weights) followed by cross-linker addition to form CSPMNs. Rhodamine B dye encapsulation was performed during CSPMN synthesis and its release was observed under biologically relevant conditions. Having shown the effective breakdown of the diacetal-based CSPMNs, their potential for use in drug delivery in low pH environments (i.e. cancerous tumors) is expected to be high.
{"title":"Acid-labile and non-degradable cross-linked star polymer model networks by aqueous polymerization for in situ encapsulation and release†","authors":"Gavin Irvine , Stuart Herron , Daniel W. Lester , Efrosyni Themistou","doi":"10.1039/d3py00677h","DOIUrl":"10.1039/d3py00677h","url":null,"abstract":"<div><div>Biocompatible, acid-labile cross-linked star polymer model networks (CSPMNs) have great potential for use in drug delivery. However, a primary complication of this research stems from the prevalence of their synthesis to take place in organic solvents. Herein, to minimize CSPMN potential cytotoxicity, aqueous reversible addition–fragmentation chain transfer polymerization is employed for their synthesis. Initially, “arm-first” star polymers were synthesized in water using a poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA) homopolymer and a non-degradable ethylene glycol dimethacrylate or acid-labile diacetal-based bis[(2-methacryloyloxy)ethoxymethyl] ether cross-linker. Subsequently, OEGMA addition resulted in the preparation of “in–out” star polymers (with higher molecular weights) followed by cross-linker addition to form CSPMNs. Rhodamine B dye encapsulation was performed during CSPMN synthesis and its release was observed under biologically relevant conditions. Having shown the effective breakdown of the diacetal-based CSPMNs, their potential for use in drug delivery in low pH environments (<em>i.e.</em> cancerous tumors) is expected to be high.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 43","pages":"Pages 4454-4464"},"PeriodicalIF":4.1,"publicationDate":"2024-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/py/d3py00677h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431620","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
To decrease the adhesion of proteins, bacteria, and cells and increase the usage duration of implants, minimizing biofouling is crucial in medical industries. Traditionally, antifouling coatings are covalently bonded to substrates, a process that can be time-consuming or substrate-dependent. In this study, we synthesized both block and random copolymers using poly(ethylene glycol) methyl ether methacrylate (PEGMA) and methacryloxyethyltrimethyl ammonium chloride (METAC) through reversible addition–fragmentation chain transfer (RAFT) polymerization. These copolymers can be adsorbed onto metal-phenolic network (MPN)-modified substrates based on cation–π interactions, rapidly forming antifouling coatings in about 6 min. Due to the wide surface modification ability of MPNs, the antifouling coatings could form on various substrates. The antifouling coatings can effectively resist the adhesion of proteins, cells, and bacteria. Moreover, block copolymers exhibited superior antifouling abilities compared to random copolymers. Notably, the antifouling performance of copolymers can be promoted by increasing the amount of PEGMA and METAC. The advantage of the reported method is the rapid preparation of antifouling coatings on various substrates. In addition, the study provides an insight into the factors influencing the strength of cation–π interactions.
{"title":"Rapid formation of antifouling coatings via cation–π interactions†","authors":"Zhicheng Huang , Kaijie Zhao , Shaoyin Wei , Yingxin Hao , Qina Yu , Jingcheng Hao , Jiwei Cui , Peiyu Zhang","doi":"10.1039/d4py00859f","DOIUrl":"10.1039/d4py00859f","url":null,"abstract":"<div><div>To decrease the adhesion of proteins, bacteria, and cells and increase the usage duration of implants, minimizing biofouling is crucial in medical industries. Traditionally, antifouling coatings are covalently bonded to substrates, a process that can be time-consuming or substrate-dependent. In this study, we synthesized both block and random copolymers using poly(ethylene glycol) methyl ether methacrylate (PEGMA) and methacryloxyethyltrimethyl ammonium chloride (METAC) through reversible addition–fragmentation chain transfer (RAFT) polymerization. These copolymers can be adsorbed onto metal-phenolic network (MPN)-modified substrates based on cation–π interactions, rapidly forming antifouling coatings in about 6 min. Due to the wide surface modification ability of MPNs, the antifouling coatings could form on various substrates. The antifouling coatings can effectively resist the adhesion of proteins, cells, and bacteria. Moreover, block copolymers exhibited superior antifouling abilities compared to random copolymers. Notably, the antifouling performance of copolymers can be promoted by increasing the amount of PEGMA and METAC. The advantage of the reported method is the rapid preparation of antifouling coatings on various substrates. In addition, the study provides an insight into the factors influencing the strength of cation–π interactions.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 43","pages":"Pages 4465-4473"},"PeriodicalIF":4.1,"publicationDate":"2024-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431621","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}
The aggregation states of polymer chains at solid interfaces are strongly related to their adhesion properties. In this study, we focused on sum-frequency generation (SFG) vibrational spectroscopy, which offers the best depth resolution at the sub-nanometer level among available techniques, and explored its potential as an imaging method. A poly(methyl methacrylate) (PMMA) thin film with a line-and-space pattern was prepared on a quartz substrate. Imaging of the interfacial line-and-space structure in the film was successfully achieved based on SFG signals arising from ester methyl groups as well as carbonyl groups. Once SFG imaging was established, it was applied to blend films of polystyrene (PS) and PMMA with different compositions on the quartz substrate, enabling the direct and non-destructive observation of wetting layers and phase-separated structures buried at the substrate interface for the first time. The interfacial adhesion strength between the blend films and the quartz substrate, evaluated using the surface and interfacial cutting analysis system, showed a clear correlation with the interfacial structure of the blend. This study, which enables the analysis of the relationship between the local orientation of polymer chains at the interface and adhesion strength, is expected to contribute greatly to the design of next-generation adhesives and adhesion technologies.
{"title":"Effect of interfacial local conformation of polymer chains on adhesion strength†","authors":"Tatsuki Abe , Satoru Yamamoto , Keiji Tanaka","doi":"10.1039/d4py00951g","DOIUrl":"10.1039/d4py00951g","url":null,"abstract":"<div><div>The aggregation states of polymer chains at solid interfaces are strongly related to their adhesion properties. In this study, we focused on sum-frequency generation (SFG) vibrational spectroscopy, which offers the best depth resolution at the sub-nanometer level among available techniques, and explored its potential as an imaging method. A poly(methyl methacrylate) (PMMA) thin film with a line-and-space pattern was prepared on a quartz substrate. Imaging of the interfacial line-and-space structure in the film was successfully achieved based on SFG signals arising from ester methyl groups as well as carbonyl groups. Once SFG imaging was established, it was applied to blend films of polystyrene (PS) and PMMA with different compositions on the quartz substrate, enabling the direct and non-destructive observation of wetting layers and phase-separated structures buried at the substrate interface for the first time. The interfacial adhesion strength between the blend films and the quartz substrate, evaluated using the surface and interfacial cutting analysis system, showed a clear correlation with the interfacial structure of the blend. This study, which enables the analysis of the relationship between the local orientation of polymer chains at the interface and adhesion strength, is expected to contribute greatly to the design of next-generation adhesives and adhesion technologies.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 43","pages":"Pages 4425-4432"},"PeriodicalIF":4.1,"publicationDate":"2024-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/py/d4py00951g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142369036","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this manuscript, we report a natural photoinitiation system for polymer synthesis by employing a combination of riboflavin 5′-monophosphate sodium salt (vitamin B2) and hydrogen peroxide, and later a glucose/glucose oxidase system, for conducting reversible addition–fragmentation chain transfer (RAFT) polymerization. Under blue LED irradiation (λ = 451 nm), the bioactive form of riboflavin, flavin mononucleotide (FMN), in the presence of hydrogen peroxide was able to initiate the controlled RAFT polymerization of N,N-dimethylacrylamide. The resulting polymer was found to also possess excellent chain fidelity after chain extension via characterization by GPC. The photopolymerization was found to reach a higher conversion in the presence of hydrogen peroxide than without. This feature was exploited by using a glucose/glucose oxidase mixture to produce hydrogen peroxide in situ during the photopolymerization while additionally introducing oxygen tolerance into the system. These results suggest the excellent potential for this mild and oxygen tolerant bio-photo-Fenton photoinitiation system to be applied.
{"title":"Bio-photo-Fenton-like RAFT polymerization under blue light†","authors":"James L. Grace , Greg G. Qiao","doi":"10.1039/d4py00593g","DOIUrl":"10.1039/d4py00593g","url":null,"abstract":"<div><div>In this manuscript, we report a natural photoinitiation system for polymer synthesis by employing a combination of riboflavin 5′-monophosphate sodium salt (vitamin B2) and hydrogen peroxide, and later a glucose/glucose oxidase system, for conducting reversible addition–fragmentation chain transfer (RAFT) polymerization. Under blue LED irradiation (<em>λ</em> = 451 nm), the bioactive form of riboflavin, flavin mononucleotide (FMN), in the presence of hydrogen peroxide was able to initiate the controlled RAFT polymerization of <em>N</em>,<em>N</em>-dimethylacrylamide. The resulting polymer was found to also possess excellent chain fidelity after chain extension <em>via</em> characterization by GPC. The photopolymerization was found to reach a higher conversion in the presence of hydrogen peroxide than without. This feature was exploited by using a glucose/glucose oxidase mixture to produce hydrogen peroxide <em>in situ</em> during the photopolymerization while additionally introducing oxygen tolerance into the system. These results suggest the excellent potential for this mild and oxygen tolerant bio-photo-Fenton photoinitiation system to be applied.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 43","pages":"Pages 4447-4453"},"PeriodicalIF":4.1,"publicationDate":"2024-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142385179","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}
In recent years, poly(2-oxazoline)s (POx) have become a sought-after biomaterial to replace PEG. However, access to POx based block copolymers is rather limited and their combination with controlled radical polymerization (CRP) techniques is required. Herein, we report the combination of cationic ring opening polymerization (CROP) and nitroxide mediated radical polymerization (NMP) to enable block copolymerization of poly(2-oxazoline)s with styrenics, acrylics, 1,3-dienes, and acrylamides as the second block. A well-defined poly(2-ethyl-2-oxazoline) macroinitiator has been prepared via CROP and in situ termination via the carboxylic acid functional group of BlocBuilder alkoxyamine has been achieved with a functionalization efficiency of 78%. Four different monomers in each class have been copolymerized via NMP and gel permeation chromatography analysis allowed us to identify the suitable set of comonomers to be utilized in block copolymerization with POx in an efficient, facile, metal- and sulfur-free polymerization environment.
{"title":"Expanding the poly(2-oxazoline) block copolymer possibilities through nitroxide mediated polymerisation†","authors":"James Lefley , C. Remzi Becer","doi":"10.1039/d4py00887a","DOIUrl":"10.1039/d4py00887a","url":null,"abstract":"<div><div>In recent years, poly(2-oxazoline)s (POx) have become a sought-after biomaterial to replace PEG. However, access to POx based block copolymers is rather limited and their combination with controlled radical polymerization (CRP) techniques is required. Herein, we report the combination of cationic ring opening polymerization (CROP) and nitroxide mediated radical polymerization (NMP) to enable block copolymerization of poly(2-oxazoline)s with styrenics, acrylics, 1,3-dienes, and acrylamides as the second block. A well-defined poly(2-ethyl-2-oxazoline) macroinitiator has been prepared <em>via</em> CROP and <em>in situ</em> termination <em>via</em> the carboxylic acid functional group of BlocBuilder alkoxyamine has been achieved with a functionalization efficiency of 78%. Four different monomers in each class have been copolymerized <em>via</em> NMP and gel permeation chromatography analysis allowed us to identify the suitable set of comonomers to be utilized in block copolymerization with POx in an efficient, facile, metal- and sulfur-free polymerization environment.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 43","pages":"Pages 4416-4424"},"PeriodicalIF":4.1,"publicationDate":"2024-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/py/d4py00887a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142317640","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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