Pub Date : 2024-11-15DOI: 10.1016/j.reactfunctpolym.2024.106104
Di Zhang , Yingke Zhu , Weihong Cao , Jinquan Chen , Zhenghong Guo , Zhengping Fang , Juan Li
The flammability of poly (methyl methacrylate) (PMMA) poses a fire safety hazard to its applications. A hybrid of piperazine pyrophosphates (PAPP) and aluminum diethylhypophosphate (ADP) were used to modify the flame retardancy of PMMA, and a phosphorus-containing vitrimer (V) was incorporated to toughen the PMMA blends. The PMMA containing 20 wt% PAPP/ADP achieves the UL-94 V0 rating with an increased limiting oxygen index (LOI) value of 24.3 vol%. After incorporating 2.0 wt% V into flame retardant PMMA, both the UL-94 V0 rating and an increase of 56 % for the impact strength of PMMA blends are obtained. The gas-condensed hybrid effects of ADP/PAPP modify the flame retardancy of PMMA and the transesterification between vitrimer and PMMA enhances its mechanical properties. This provides a feasible method to prepare PMMA blends with good comprehensive performances.
{"title":"Flame retardant polymethyl methacrylate toughened by a phosphorus-containing vitrimer","authors":"Di Zhang , Yingke Zhu , Weihong Cao , Jinquan Chen , Zhenghong Guo , Zhengping Fang , Juan Li","doi":"10.1016/j.reactfunctpolym.2024.106104","DOIUrl":"10.1016/j.reactfunctpolym.2024.106104","url":null,"abstract":"<div><div>The flammability of poly (methyl methacrylate) (PMMA) poses a fire safety hazard to its applications. A hybrid of piperazine pyrophosphates (PAPP) and aluminum diethylhypophosphate (ADP) were used to modify the flame retardancy of PMMA, and a phosphorus-containing vitrimer (<em>V</em>) was incorporated to toughen the PMMA blends. The PMMA containing 20 wt% PAPP/ADP achieves the UL-94 <em>V</em>0 rating with an increased limiting oxygen index (LOI) value of 24.3 vol%. After incorporating 2.0 wt% V into flame retardant PMMA, both the UL-94 V0 rating and an increase of 56 % for the impact strength of PMMA blends are obtained. The gas-condensed hybrid effects of ADP/PAPP modify the flame retardancy of PMMA and the transesterification between vitrimer and PMMA enhances its mechanical properties. This provides a feasible method to prepare PMMA blends with good comprehensive performances.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"206 ","pages":"Article 106104"},"PeriodicalIF":4.5,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142660588","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bifidobacterium bifidum (B. bifidum) is considered as one of the most important intestinal probiotics for its health benefits. However, the survival of B. bifidum is typically hindered by a number of factors, including pH and heating, which constrains the potential applications of B. bifidum in food products and the realization of its beneficial effects. In this study, B. bifidum was encapsulated in emulsions prepared from whey protein isolate (WPI) and pectin. The microscopic morphology of the emulsions was observed by Cryo-scanning electron microscopy (Cryo-SEM) and transmission electron microscopy (TEM) as well as ultra-high resolution microscopy (URM). The pH, ionic strength, and thermal stability of the emulsions are recorded best on 2 % pectin concentration as compared to 1 % or 3 %. The viability of B. bifidum is enhanced by encapsulation in emulsion after in vitro digestion compared to free B. bifidum. The findings indicate that emulsion encapsulation can be an effective method for maintaining the activity of probiotics, which could be a valuable approach for developing orally consumed probiotic foods.
{"title":"Improving the stability and digestive property of Bifidobacterium bifidum encapsulated in whey protein isolate/pectin emulsions","authors":"Yuhang Cao, Lingyu Yin, Meihui Wang, Fei Li, Baohua Kong, Qian Liu, Fangda Sun, Hui Wang","doi":"10.1016/j.reactfunctpolym.2024.106100","DOIUrl":"10.1016/j.reactfunctpolym.2024.106100","url":null,"abstract":"<div><div><em>Bifidobacterium bifidum</em> (<em>B. bifidum</em>) is considered as one of the most important intestinal probiotics for its health benefits. However, the survival of <em>B. bifidum</em> is typically hindered by a number of factors, including pH and heating, which constrains the potential applications of <em>B. bifidum</em> in food products and the realization of its beneficial effects. In this study, <em>B. bifidum</em> was encapsulated in emulsions prepared from whey protein isolate (WPI) and pectin. The microscopic morphology of the emulsions was observed by Cryo-scanning electron microscopy (Cryo-SEM) and transmission electron microscopy (TEM) as well as ultra-high resolution microscopy (URM). The pH, ionic strength, and thermal stability of the emulsions are recorded best on 2 % pectin concentration as compared to 1 % or 3 %. The viability of <em>B. bifidum</em> is enhanced by encapsulation in emulsion after <em>in vitro</em> digestion compared to free <em>B. bifidum</em>. The findings indicate that emulsion encapsulation can be an effective method for maintaining the activity of probiotics, which could be a valuable approach for developing orally consumed probiotic foods.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"206 ","pages":"Article 106100"},"PeriodicalIF":4.5,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142660587","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-09DOI: 10.1016/j.reactfunctpolym.2024.106096
Quinten Thijssen , Antonio Jaén Ortega , Roniérik Pioli Vieira , Sandra Van Vlierberghe
The introduction of tomographic volumetric 3D printing is revolutionizing the manufacturing and bioprinting landscape by enabling the rapid creation of complex three-dimensional (biological) structures with high precision down to 20 μm. Despite the recognized role of radical inhibition in volumetric 3D printing, a study of inhibition has remained elusive. Here, A comprehensive framework is presented to study the role of the widely reported radical inhibitor TEMPO in the volumetric 3D printability of a thiol-ene photocrosslinkable photoresist composed of triallyl isocyanurate (TTT) and pentaerythritol tetrakis(3-mercaptopropionate) (PETMP). Through photorheological measurements, kinetic modeling, FTIR spectroscopy, and validation via volumetric 3D printing, the relationship between inhibitor concentrations, the evolution of the shear moduli as well as the conversion as a function of light dose, and volumetric 3D printing is elucidated. The findings in this study provide a robust methodology for predicting optimal printing conditions of photoresists for tomographic volumetric 3D printing, obviating the need for extensive trial-and-error.
断层体积三维打印技术的引入，使复杂的三维（生物）结构以低至 20 μm 的高精度被快速创建出来，从而彻底改变了制造和生物打印领域。尽管自由基抑制在体积三维打印中的作用已得到公认，但对抑制作用的研究却一直没有进展。本文提出了一个综合框架，以研究广泛报道的自由基抑制剂 TEMPO 在由异氰脲酸三烯丙酯（TTT）和季戊四醇四巯基丙酸酯（PETMP）组成的硫醇烯光交联光刻胶的体积三维打印性中的作用。通过光流变学测量、动力学建模、傅立叶变换红外光谱以及体积三维打印验证，阐明了抑制剂浓度、剪切模量的演变、光剂量与体积三维打印之间的关系。本研究的发现为预测断层体积三维打印光刻胶的最佳打印条件提供了可靠的方法，从而避免了大量的试验和错误。
{"title":"Radical inhibition in tomographic volumetric 3D printing for thiol-Ene photoresists: From Photorheology to printability","authors":"Quinten Thijssen , Antonio Jaén Ortega , Roniérik Pioli Vieira , Sandra Van Vlierberghe","doi":"10.1016/j.reactfunctpolym.2024.106096","DOIUrl":"10.1016/j.reactfunctpolym.2024.106096","url":null,"abstract":"<div><div>The introduction of tomographic volumetric 3D printing is revolutionizing the manufacturing and bioprinting landscape by enabling the rapid creation of complex three-dimensional (biological) structures with high precision down to 20 μm. Despite the recognized role of radical inhibition in volumetric 3D printing, a study of inhibition has remained elusive. Here, A comprehensive framework is presented to study the role of the widely reported radical inhibitor TEMPO in the volumetric 3D printability of a thiol-ene photocrosslinkable photoresist composed of triallyl isocyanurate (TTT) and pentaerythritol tetrakis(3-mercaptopropionate) (PETMP). Through photorheological measurements, kinetic modeling, FTIR spectroscopy, and validation via volumetric 3D printing, the relationship between inhibitor concentrations, the evolution of the shear moduli as well as the conversion as a function of light dose, and volumetric 3D printing is elucidated. The findings in this study provide a robust methodology for predicting optimal printing conditions of photoresists for tomographic volumetric 3D printing, obviating the need for extensive trial-and-error.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"205 ","pages":"Article 106096"},"PeriodicalIF":4.5,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142653546","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Organic dyes were integrated into networks of polyurethane (PU) in the form of croconaine segments, in order to bestow photothermal properties on the materials. In addition, the PU networks were crosslinked with polysilsesquioxane (PSSQ) so that the materials can be reprocessed (or self-healing) via the metathesis of silyl ether bonds under catalysis. Toward this end, we synthesized a novel diol bearing croconaine moiety, which was used as one of chain extenders and a series of linear PU telechelics with dihydroxyl termini were synthesized. The α,ω-dihydroxyl PU telechelics were then allowed to react with 3-isocyanatopropyltriethoxysilane to gain α,ω-ditriethoxysilane PU telechelics. Through sol-gel process, α,ω-ditriethoxysilane PU telechelics readily underwent crosslinking with PSSQ as the crosslinkages. The crosslinking of PU was in marked contrast to traditional crosslinking of PU with multifunctional ols (or amines) as the crosslinkers. Owing to the crosslinking, shape memory properties were bestowed on the organic-inorganic PU networks. Thanks to the metathesis of silyl ether bonds under catalysis, the organic-inorganic PU networks were reprocessable (or recyclable). Benefiting from the built-in of dye segments, the PU networks significantly displayed excellent photothermal conversion properties. By leveraging the photothermal properties, the shape shifting of the PU networks can be triggered via the irradiation under infrared laser and in a non-contact fashion. In addition, the PU networks were capable of displaying the light-triggered self-healing properties. Thanks to these excellent properties, we demonstrated a successful application of the PU networks a soft robot.
{"title":"Shape memory, reprocessable and photothermal networks of polyurethane with silyl ether bonds and croconaine segments","authors":"Jiawei Hu, Guohua Hang, Jianglu Teng, Xibin Shen, Yuan Gao, Lei Li, Sixun Zheng","doi":"10.1016/j.reactfunctpolym.2024.106098","DOIUrl":"10.1016/j.reactfunctpolym.2024.106098","url":null,"abstract":"<div><div>Organic dyes were integrated into networks of polyurethane (PU) in the form of croconaine segments, in order to bestow photothermal properties on the materials. In addition, the PU networks were crosslinked with polysilsesquioxane (PSSQ) so that the materials can be reprocessed (or self-healing) <em>via</em> the metathesis of silyl ether bonds under catalysis. Toward this end, we synthesized a novel diol bearing croconaine moiety, which was used as one of chain extenders and a series of linear PU telechelics with dihydroxyl termini were synthesized. The α,ω-dihydroxyl PU telechelics were then allowed to react with 3-isocyanatopropyltriethoxysilane to gain α,ω-ditriethoxysilane PU telechelics. Through sol-gel process, α,ω-ditriethoxysilane PU telechelics readily underwent crosslinking with PSSQ as the crosslinkages. The crosslinking of PU was in marked contrast to traditional crosslinking of PU with multifunctional ols (or amines) as the crosslinkers. Owing to the crosslinking, shape memory properties were bestowed on the organic-inorganic PU networks. Thanks to the metathesis of silyl ether bonds under catalysis, the organic-inorganic PU networks were reprocessable (or recyclable). Benefiting from the built-in of dye segments, the PU networks significantly displayed excellent photothermal conversion properties. By leveraging the photothermal properties, the shape shifting of the PU networks can be triggered <em>via</em> the irradiation under infrared laser and in a non-contact fashion. In addition, the PU networks were capable of displaying the light-triggered self-healing properties. Thanks to these excellent properties, we demonstrated a successful application of the PU networks a soft robot.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"205 ","pages":"Article 106098"},"PeriodicalIF":4.5,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142653550","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-08DOI: 10.1016/j.reactfunctpolym.2024.106094
Elizaveta A. Manokhina , Rinat S. Tukhvatshin , Dmitriy A. Khanin , Inga V. Frank , Viktor G. Vasil'ev , Anton A. Anisimov
The structure of organosilicon vinyl-containing boroxine was confirmed by 1H nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy and matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. Its thermal properties were studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) methods. The ability of boroxine to undergo hydrosilylation using the Karstedt's catalyst was investigated on various organosilicon substrates. Boroxine was shown to be involved in these reactions as a cross-linking agent. The formation of dynamic boroxine cross-links allowed the analysis of the reaction products by NMR spectroscopy, including the use of polyfunctional hydride-containing reagents. In all cases the addition proceeds selectively to the β-position and with complete conversion. The structure of the resulting polyborosiloxane containing 1.4 mol% of modified units was also confirmed by 1H NMR spectroscopy, and its thermal and rheological properties were studied.
{"title":"Use of a hydrosilylation reaction for the preparation of structure-controlled boroxine-based polyborosiloxanes","authors":"Elizaveta A. Manokhina , Rinat S. Tukhvatshin , Dmitriy A. Khanin , Inga V. Frank , Viktor G. Vasil'ev , Anton A. Anisimov","doi":"10.1016/j.reactfunctpolym.2024.106094","DOIUrl":"10.1016/j.reactfunctpolym.2024.106094","url":null,"abstract":"<div><div>The structure of organosilicon vinyl-containing boroxine was confirmed by <sup>1</sup>H nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy and matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. Its thermal properties were studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) methods. The ability of boroxine to undergo hydrosilylation using the Karstedt's catalyst was investigated on various organosilicon substrates. Boroxine was shown to be involved in these reactions as a cross-linking agent. The formation of dynamic boroxine cross-links allowed the analysis of the reaction products by NMR spectroscopy, including the use of polyfunctional hydride-containing reagents. In all cases the addition proceeds selectively to the β-position and with complete conversion. The structure of the resulting polyborosiloxane containing 1.4 mol% of modified units was also confirmed by <sup>1</sup>H NMR spectroscopy, and its thermal and rheological properties were studied.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"205 ","pages":"Article 106094"},"PeriodicalIF":4.5,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142653551","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-07DOI: 10.1016/j.reactfunctpolym.2024.106097
Yonghua Xue , Kui Tang , Xiaoyuan Liao
In recent years, PBAT, i.e., Poly(butylene adipate-co-terephthalate) stands out as a potential material for packaging due to its favorable characteristics. However, its high manufacturing costs, poor crystallization, and inadequate barrier properties have impeded its broader acceptance in the industry. To tackle these issues, our study introduces a novel approach by incorporating octadecylamine (ODA)-modified cellulose (OMCC) as an eco-friendly additive. OMCC not only enhances the dispersion of cellulose within the PBAT matrix but also prevents its re-agglomeration. The integration of OMCC into PBAT has led to its significant improvements in mechanical strength, UV resistance, compatibility, hydrophobicity, and effectively enhances gas barrier properties. This work provides a new and biodegradable composite film for food packaging.
{"title":"Preparation of modified cellulose/PBAT films and its application in food preservation","authors":"Yonghua Xue , Kui Tang , Xiaoyuan Liao","doi":"10.1016/j.reactfunctpolym.2024.106097","DOIUrl":"10.1016/j.reactfunctpolym.2024.106097","url":null,"abstract":"<div><div>In recent years, PBAT, i.e., Poly(butylene adipate-<em>co</em>-terephthalate) stands out as a potential material for packaging due to its favorable characteristics. However, its high manufacturing costs, poor crystallization, and inadequate barrier properties have impeded its broader acceptance in the industry. To tackle these issues, our study introduces a novel approach by incorporating octadecylamine (ODA)-modified cellulose (OMCC) as an eco-friendly additive. OMCC not only enhances the dispersion of cellulose within the PBAT matrix but also prevents its re-agglomeration. The integration of OMCC into PBAT has led to its significant improvements in mechanical strength, UV resistance, compatibility, hydrophobicity, and effectively enhances gas barrier properties. This work provides a new and biodegradable composite film for food packaging.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"205 ","pages":"Article 106097"},"PeriodicalIF":4.5,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142653544","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-07DOI: 10.1016/j.reactfunctpolym.2024.106095
Yiyuan Sun , Zenghui Yang , Liming Tao , Qihua Wang , Xinrui Zhang , Yaoming Zhang , Tingmei Wang
High performance shape memory polymer (HPSMP) has a wide range of application such as smart device, smart mold. In this study, we designed a rigid-flexible shape memory epoxy with flexible chain segment as the main chain and rigid benzene ring as the side group. Meanwhile, carboxyl-terminated nitrile butadiene rubber (CTBN) was accessed into the epoxy main chain as a fatigue-resistant functional filler. The results showed that the flexible backbone plays a major role in improving the ductility. The superior fatigue-resistant shape memory cycling performance was synergistically achieved by modulating the epoxy topological network through altering the disulfide cross-linker prompted by CTBN, and the materials exhibited good high and low-temperature resistant mechanical properties. Comparatively, it is found that disulfide bonding can significantly improve the tensile property and thermal stability for epoxy. The synergistic effect between the elastic chain segments in CTBN and the flexible backbone achieves excellent shape recovery ratio. Therefore, the rational structural design provides an effective way to develop HPSMP, which can expand the application areas for HPSMP.
{"title":"Rubber-assisted and modulated epoxy topological network for developing fatigue-resistant, high-strain-cycle high performance shape memory polymer composites","authors":"Yiyuan Sun , Zenghui Yang , Liming Tao , Qihua Wang , Xinrui Zhang , Yaoming Zhang , Tingmei Wang","doi":"10.1016/j.reactfunctpolym.2024.106095","DOIUrl":"10.1016/j.reactfunctpolym.2024.106095","url":null,"abstract":"<div><div>High performance shape memory polymer (HPSMP) has a wide range of application such as smart device, smart mold. In this study, we designed a rigid-flexible shape memory epoxy with flexible chain segment as the main chain and rigid benzene ring as the side group. Meanwhile, carboxyl-terminated nitrile butadiene rubber (CTBN) was accessed into the epoxy main chain as a fatigue-resistant functional filler. The results showed that the flexible backbone plays a major role in improving the ductility. The superior fatigue-resistant shape memory cycling performance was synergistically achieved by modulating the epoxy topological network through altering the disulfide cross-linker prompted by CTBN, and the materials exhibited good high and low-temperature resistant mechanical properties. Comparatively, it is found that disulfide bonding can significantly improve the tensile property and thermal stability for epoxy. The synergistic effect between the elastic chain segments in CTBN and the flexible backbone achieves excellent shape recovery ratio. Therefore, the rational structural design provides an effective way to develop HPSMP, which can expand the application areas for HPSMP.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"205 ","pages":"Article 106095"},"PeriodicalIF":4.5,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142653552","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
For the first time, a pronounced biocidal activity of modified polymers with a porphyrin content of 21.4 μM (0.002 wt%) against Staphylococcus aureus was demonstrated. In order to develop new biocidal polymer coatings, a study was carried out on diglycidyl ether of bisphenol A (DGEBA) and porphyrin-modified oligomeric diamine systems. The study investigated the solubility of porphyrins in oligomers through experimental and theoretical means, using Van Krevelen's approach of additive group contributions. Fully cured epoxy-amine polymer materials modified with varied free-base tetraarylporphyrins were obtained. The materials were studied by means of thermogravimetry, differential scanning calorimetry, UV–Vis and fluorescence spectroscopy. The proposed approach to the formation of modified epoxy-amine materials allows preservation of the photophysical properties of porphyrins, including their photostability. The addition of modifiers in 4.28–21.4 μM range of concentrations makes it possible to keep the thermophysical and thermochemical properties of the polymer matrix.
研究首次证明，卟啉含量为 21.4 μM（0.002 wt%）的改性聚合物对金黄色葡萄球菌具有明显的杀菌活性。为了开发新型杀菌聚合物涂层，研究人员对双酚 A 二缩水甘油醚（DGEBA）和卟啉改性低聚二胺体系进行了研究。研究采用 Van Krevelen 的添加剂基团贡献法，通过实验和理论方法研究了卟啉在低聚物中的溶解度。研究获得了用不同游离基四芳基卟啉改性的完全固化环氧胺聚合物材料。通过热重法、差示扫描量热法、紫外-可见光谱法和荧光光谱法对这些材料进行了研究。所提出的形成改性环氧胺材料的方法可以保持卟啉的光物理特性，包括其光稳定性。在 4.28-21.4 μM 的浓度范围内添加改性剂可以保持聚合物基体的热物理和热化学特性。
{"title":"Biocidal polymer coatings based on porphyrin-modified epoxy-amine networks","authors":"A.M. Tsyklinskaya , D.A. Polivanovskaia , N.E. Grammatikova , E.S. Zhavoronok , K.P. Birin , I.N. Senchikhin","doi":"10.1016/j.reactfunctpolym.2024.106099","DOIUrl":"10.1016/j.reactfunctpolym.2024.106099","url":null,"abstract":"<div><div>For the first time, a pronounced biocidal activity of modified polymers with a porphyrin content of 21.4 μM (0.002 wt%) against <em>Staphylococcus aureus</em> was demonstrated. In order to develop new biocidal polymer coatings, a study was carried out on diglycidyl ether of bisphenol A (DGEBA) and porphyrin-modified oligomeric diamine systems. The study investigated the solubility of porphyrins in oligomers through experimental and theoretical means, using Van Krevelen's approach of additive group contributions. Fully cured epoxy-amine polymer materials modified with varied free-base tetraarylporphyrins were obtained. The materials were studied by means of thermogravimetry, differential scanning calorimetry, UV–Vis and fluorescence spectroscopy. The proposed approach to the formation of modified epoxy-amine materials allows preservation of the photophysical properties of porphyrins, including their photostability. The addition of modifiers in 4.28–21.4 μM range of concentrations makes it possible to keep the thermophysical and thermochemical properties of the polymer matrix.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"205 ","pages":"Article 106099"},"PeriodicalIF":4.5,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142653545","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-04DOI: 10.1016/j.reactfunctpolym.2024.106080
Isaac Isarn , Ignacio Collado , Alberto Jiménez-Suárez , Silvia G. Prolongo
Epoxidized resveratrol (RES) has been cured with different amines in order to compare their possibilities to obtain high-temperature resistance of bio-based epoxy resins. Materials obtained from the bio-based monomer present glass transition temperatures (Tg) among the highest ever reported for an epoxy-amine curing system, with extremely high char residue, making them excellent candidates for extremely high-temperature applications. Particularly, epoxidized RES stoichiometrically cured with 4,4′-sulfonyldianiline (DDS) reached 297 °C, measured as the tan δ peak by DMTA, and two other materials, using 4,4′-methylenedianiline (DDM) and 4,4′-diaminodicyclohexylmethane (CAA) as curing agents, exceeded 300 °C. In fact, the material begins to degrade before the chains are fully relaxed, so they are thermosetting that never go completely into the rubbery state. Additionally, this resin improves the direct current (DC) insulating character (∼1015 Ωcm) while decreasing the optical band gap (∼2 eV) when compared to other epoxy resins available, which is of great interest for photovoltaic applications. Moreover, some of the materials presented a very high char residue proportion when heated (>40 wt% at 800 °C under nitrogen atmosphere), presenting good fire-retardant properties.
为了比较不同胺类在获得生物基环氧树脂耐高温性方面的可能性，我们用不同的胺类固化了环氧化白藜芦醇（RES）。从这种生物基单体中获得的材料的玻璃化转变温度（Tg）是迄今所报道的环氧胺固化体系中最高的，而且具有极高的炭残留量，是极高温应用的理想候选材料。特别是用 4,4′-磺酰基二苯胺（DDS）按一定比例固化的环氧化 RES 达到了 297 ℃（用 DMTA 测量的 tan δ 峰值），而用 4,4′-亚甲基二苯胺（DDM）和 4,4′-二氨基二环己基甲烷（CAA）作为固化剂的另外两种材料则超过了 300 ℃。事实上，这种材料在链完全松弛之前就开始降解，因此它们属于热固性，永远不会完全进入橡胶状态。此外，与现有的其他环氧树脂相比，这种树脂提高了直流（DC）绝缘性（∼1015 Ωcm），同时降低了光带隙（∼2 eV），这对光伏应用具有重大意义。此外，其中一些材料在加热时的残炭比例非常高（氮气环境下 800 °C 时为 40 wt%），具有良好的阻燃性能。
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Pub Date : 2024-11-04DOI: 10.1016/j.reactfunctpolym.2024.106084
Olga García, Isabel Quijada-Garrido
In this study, we expand the scope of polymerization-induced self-assembly (PISA) by modifying one of the most prototypical copolymers derived from RAFT-mediated PISA, poly(glycerol methacrylate)-b-poly(hydroxypropyl methacrylate) (pGMA-b-pHPMA), by incorporating a comonomer with a protected thiol group-2-(acetylthio)ethyl methacrylate (AcSEMA) into the hydrophobic block. The photoinitiated synthesis of pGMA-b-p(HPMA-co-AcSEMA) was conducted in a water/ethanol mixture (60/40 v/v) to increase the solubility of AcSEMA. Thus, this modification enabled the formation of diverse polymeric nano-morphologies such as spheres, worms, and vesicles, dictated by the balance between hydrophilic and hydrophobic block ratios and the AcSEMA content. Besides, the strong metal affinity of thiol groups makes the incorporation of AcSEMA into self-assembled nanostructures a versatile platform for generating advanced hybrid materials with potential applications in biomedicine, sensing, catalysis, or water purification. As evidenced in this work, the post-hydrolysis of the thioacetate group into thiol allowed the use of polymeric nano-objects as templates to power on the luminescenece of functionalized copper nanoclusters (CuNCs). These polymeric CuNCs, composed of several to hundreds of copper atoms, exhibit remarkable red emission, positioning the synthesized hybrids as promising luminescent probes for the development of highly selective “switch-off” luminescent sensors for Hg2+ detection. This work paves the way for the design of multifunctional hybrid nanomaterials with advanced applications.
{"title":"Thiolated RAFT-PISA nano-templates power on luminescent copper nanoclusters (CuNCs) for selective mercury (II) detection","authors":"Olga García, Isabel Quijada-Garrido","doi":"10.1016/j.reactfunctpolym.2024.106084","DOIUrl":"10.1016/j.reactfunctpolym.2024.106084","url":null,"abstract":"<div><div>In this study, we expand the scope of polymerization-induced self-assembly (PISA) by modifying one of the most prototypical copolymers derived from RAFT-mediated PISA, poly(glycerol methacrylate)-<em>b</em>-poly(hydroxypropyl methacrylate) (pGMA-<em>b</em>-pHPMA), by incorporating a comonomer with a protected thiol group-2-(acetylthio)ethyl methacrylate (AcSEMA) into the hydrophobic block. The photoinitiated synthesis of pGMA-<em>b</em>-p(HPMA-<em>co</em>-AcSEMA) was conducted in a water/ethanol mixture (60/40 <em>v</em>/v) to increase the solubility of AcSEMA. Thus, this modification enabled the formation of diverse polymeric nano-morphologies such as spheres, worms, and vesicles, dictated by the balance between hydrophilic and hydrophobic block ratios and the AcSEMA content. Besides, the strong metal affinity of thiol groups makes the incorporation of AcSEMA into self-assembled nanostructures a versatile platform for generating advanced hybrid materials with potential applications in biomedicine, sensing, catalysis, or water purification. As evidenced in this work, the post-hydrolysis of the thioacetate group into thiol allowed the use of polymeric nano-objects as templates to power on the luminescenece of functionalized copper nanoclusters (CuNCs). These polymeric CuNCs, composed of several to hundreds of copper atoms, exhibit remarkable red emission, positioning the synthesized hybrids as promising luminescent probes for the development of highly selective “switch-off” luminescent sensors for Hg<sup>2+</sup> detection. This work paves the way for the design of multifunctional hybrid nanomaterials with advanced applications.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"205 ","pages":"Article 106084"},"PeriodicalIF":4.5,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142653542","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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