Bruno Espuche, Krishan Kumar, Paolo Moretti, Maria Grazia Ortore, Olena Ivashchenko, Emerson Coy, Heinz Amenitsch, Sergio E. Moya* and Marcelo Calderón*,
{"title":"Core–Shell Nanogels With Raspberry Architecture and Amine Loading in the Core via Precipitation Polymerization: A Mechanistic Study","authors":"Bruno Espuche, Krishan Kumar, Paolo Moretti, Maria Grazia Ortore, Olena Ivashchenko, Emerson Coy, Heinz Amenitsch, Sergio E. Moya* and Marcelo Calderón*, ","doi":"10.1021/acs.macromol.4c00350","DOIUrl":null,"url":null,"abstract":"<p >Nanogels (NGs) are synthesized by precipitation polymerization of dendritic polyglycerol (dPG), <i>N</i>-isopropylacrylamide (NIPAM), and <i>N</i>-isopropyl methacrylamide (NIPMAM). The stabilization and agglomeration of subunits during the NG growth result in raspberry-like structures, as shown by transmission electron microscopy, atomic force microscopy, and small-angle X-ray scattering measurements. Positive charges are introduced into dPG-NIPAM-NIPMAM NGs by (1) the copolymerization of dimethylaminoethyl methacrylate (DMAEMA) and (2) the copolymerization of glycidyl methacrylate (GMA), followed by its functionalization with ethylenediamine (ED) through the epoxy group. Homogeneous structures are obtained by the copolymerization in batch of DMAEMA with the other monomers, whereas core–shell NGs are reached by semibatch copolymerization of GMA. After amination, the charges are restricted to the core of the NGs.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":null,"pages":null},"PeriodicalIF":5.1000,"publicationDate":"2024-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.macromol.4c00350","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecules","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.macromol.4c00350","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
引用次数: 0
Abstract
Nanogels (NGs) are synthesized by precipitation polymerization of dendritic polyglycerol (dPG), N-isopropylacrylamide (NIPAM), and N-isopropyl methacrylamide (NIPMAM). The stabilization and agglomeration of subunits during the NG growth result in raspberry-like structures, as shown by transmission electron microscopy, atomic force microscopy, and small-angle X-ray scattering measurements. Positive charges are introduced into dPG-NIPAM-NIPMAM NGs by (1) the copolymerization of dimethylaminoethyl methacrylate (DMAEMA) and (2) the copolymerization of glycidyl methacrylate (GMA), followed by its functionalization with ethylenediamine (ED) through the epoxy group. Homogeneous structures are obtained by the copolymerization in batch of DMAEMA with the other monomers, whereas core–shell NGs are reached by semibatch copolymerization of GMA. After amination, the charges are restricted to the core of the NGs.
纳米凝胶(NGs)是通过树枝状聚甘油(dPG)、N-异丙基丙烯酰胺(NIPAM)和 N-异丙基甲基丙烯酰胺(NIPMAM)的沉淀聚合合成的。透射电子显微镜、原子力显微镜和小角 X 射线散射测量结果表明,在 NG 生长过程中,亚基的稳定和聚集形成了树莓状结构。通过(1)甲基丙烯酸二甲胺基乙酯(DMAEMA)共聚和(2)甲基丙烯酸缩水甘油酯(GMA)共聚,然后通过环氧基团与乙二胺(ED)官能化,将正电荷引入 dPG-NIPAM-NIPMAM NG。DMAEMA 与其他单体的批量共聚可获得均质结构,而 GMA 的半批量共聚则可获得核壳 NG。胺化后,电荷被限制在 NG 的核心部分。
期刊介绍:
Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.