TY - JOUR
T1 - In situ single particle characterization of the themoresponsive and co-nonsolvent behavior of PNIPAM microgels and silica@PNIPAM core-shell colloids
AU - Grau-Carbonell, Albert
AU - Hagemans, Fabian
AU - Bransen, Maarten
AU - Elbers, Nina A.
AU - Dijk-Moes, Relinde J.A. van
AU - Sadighikia, Sina
AU - Welling, Tom A.J.
AU - Blaaderen, Alfons van
AU - Huis, Marijn A. van
N1 - Funding Information:
This project received funding from the European Research Council (ERC) via the ERC Consolidator Grant NANO-INSITU (Grant No. 683076). F. Hagemans was funded by the Netherlands Organisation for Scientific Research (NWO). N. Elbers was supported by the Industrial Partnership Programme (IPP) Innovatie Physics for Oil and Gas (iPOG) of the ’Stichting voor Fundamenteel Onderzoek der Materie’ (FOM), which was supported financially by Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO). The IPP iPOG is cofinanced by Stichting Shell Research.. The authors also acknowledge funding from the NWO-TTW Perspectief Program ”Understanding Processes Using Operando Nanoscopy,” project UPON-B3 (No. 14206). M.B. acknowledge funding from the Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC), an NWO Gravitation programme funded by the Ministry of Education, Culture, and Science of the government of the Netherlands.
Funding Information:
This project received funding from the European Research Council (ERC) via the ERC Consolidator Grant NANO-INSITU (Grant No. 683076). F. Hagemans was funded by the Netherlands Organisation for Scientific Research (NWO). N. Elbers was supported by the Industrial Partnership Programme (IPP) Innovatie Physics for Oil and Gas (iPOG) of the ’Stichting voor Fundamenteel Onderzoek der Materie’ (FOM), which was supported financially by Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO). The IPP iPOG is cofinanced by Stichting Shell Research. The authors also acknowledge funding from the NWO-TTW Perspectief Program ”Understanding Processes Using Operando Nanoscopy,” project UPON-B3 (No. 14206). M.B. acknowledge funding from the Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC), an NWO Gravitation programme funded by the Ministry of Education, Culture, and Science of the government of the Netherlands.
Publisher Copyright:
© 2022 The Authors
PY - 2023/4
Y1 - 2023/4
N2 - Poly(N-isopropylacrylamide) (PNIPAM) microgels and PNIPAM colloidal shells attract continuous strong interest due to their thermoresponsive behavior, as their size and properties can be tuned by temperature. The direct single particle observation and characterization of pure, unlabeled PNIPAM microgels in their native aqueous environment relies on imaging techniques that operate either at interfaces or in cryogenic conditions, thus limiting the observation of their dynamic nature. Liquid Cell (Scanning) Transmission Electron Microscopy (LC-(S) TEM) imaging allows the characterization of materials and dynamic processes such as nanoparticle growth, etching, and diffusion, at nanometric resolution in liquids. Here we show that via a facile post-synthetic in situ polymer labelling step with high-contrast marker core–shell Au@SiO2 nanoparticles (NPs) it is possible to determine the full volume of PNIPAM microgels in water. The labelling allowed for the successful characterization of the thermoresponsive behavior of PNIPAM microgels and core shell silica@PNIPAM hybrid microgels, as well as the co-nonsolvency of PNIPAM in aqueous alcoholic solutions. The interplay between electron beam irradiation and PNIPAM systems in water resulted in irreversible shrinkage due to beam induced water radiolysis products, which in turn also affected the thermoresponsive behavior of PNIPAM. The addition of 2-propanol as radical scavenger improved PNIPAM stability in water under electron beam irradiation.
AB - Poly(N-isopropylacrylamide) (PNIPAM) microgels and PNIPAM colloidal shells attract continuous strong interest due to their thermoresponsive behavior, as their size and properties can be tuned by temperature. The direct single particle observation and characterization of pure, unlabeled PNIPAM microgels in their native aqueous environment relies on imaging techniques that operate either at interfaces or in cryogenic conditions, thus limiting the observation of their dynamic nature. Liquid Cell (Scanning) Transmission Electron Microscopy (LC-(S) TEM) imaging allows the characterization of materials and dynamic processes such as nanoparticle growth, etching, and diffusion, at nanometric resolution in liquids. Here we show that via a facile post-synthetic in situ polymer labelling step with high-contrast marker core–shell Au@SiO2 nanoparticles (NPs) it is possible to determine the full volume of PNIPAM microgels in water. The labelling allowed for the successful characterization of the thermoresponsive behavior of PNIPAM microgels and core shell silica@PNIPAM hybrid microgels, as well as the co-nonsolvency of PNIPAM in aqueous alcoholic solutions. The interplay between electron beam irradiation and PNIPAM systems in water resulted in irreversible shrinkage due to beam induced water radiolysis products, which in turn also affected the thermoresponsive behavior of PNIPAM. The addition of 2-propanol as radical scavenger improved PNIPAM stability in water under electron beam irradiation.
KW - Liquid Cell STEM
KW - PNIPAM
KW - Thermoresponsive behavior
KW - Co-nonsolvent behavior
UR - http://www.scopus.com/inward/record.url?scp=85145781458&partnerID=8YFLogxK
U2 - 10.1016/j.jcis.2022.12.116
DO - 10.1016/j.jcis.2022.12.116
M3 - Article
SN - 0021-9797
VL - 635
SP - 552
EP - 561
JO - Journal of Colloid and Interface Science
JF - Journal of Colloid and Interface Science
ER -