Inside Block Copolymer Micelles-Tracing Interfacial Influences on Crosslinking Efficiency in Nanoscale Confined Spaces

被引:5
作者
Hoeppener, Christiane [1 ]
Elter, Johanna K. [2 ]
Schacher, Felix H. [2 ,3 ]
Deckert, Volker [1 ,3 ]
机构
[1] Leibniz Inst Photon Technol IPHT, Albert Einstein Str 9, D-07745 Jena, Germany
[2] Friedrich Schiller Univ, Inst Organ Chem & Macromol Chem IOMC, Lessingstr 8, D-07743 Jena, Germany
[3] Friedrich Schiller Univ, Jena Ctr Soft Matter JCSM, Philosophenweg 7, D-07743 Jena, Germany
关键词
block copolymer micelles; Diels-Alder reaction; force-volume atomic force microscopy (AFM); multiparametric imaging; reactions in confined spaces; tip-enhanced Raman spectroscopy (TERS); ATOMIC-FORCE MICROSCOPY; RAMAN-SPECTROSCOPY; LINKED MICELLES; SINGLE-MOLECULE; THIN-FILMS; POLYMERIZATION; RESOLUTION; IDENTIFICATION; SCATTERING; MODULUS;
D O I
10.1002/smll.202206451
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Recently, several studies have demonstrated the excellent capabilities of tip-enhanced Raman spectroscopyfor in-depth investigations of structural properties of matter with unprecedented resolution and chemical specificity. These capabilities are utilized here to study the internal structure of core-crosslinked micelles, which are formed by self-assembly of the diblock terpolymer poly(ethylene oxide)-block-poly(furfuryl glycidylether-co-tert-butylglycidyl ether). Supplementing force-volume atomic force microscopy experiments address additionally the nanomechanical properties. Particularly, TERS enables investigating the underlying principles influencing the homogeneity and efficiency of the Diels-Alder core-crosslinking process in the confined hydrophobic core. While the central core region is homogenously crosslinked, a breakdown of the crosslinking reaction is observed in the core-corona interfacial region. The results corroborate that a strong crosslinking efficiency is directly correlated to the formation of a mixed zone of the glycidyl ether and PEO corona blocks reaching approximate to 5 nm into the core region. Concomitantly a strong exclusion of the encapsulated bismaleimide crosslinker from the interfacial region is observed. It is conceivable that a changed structure, chemical composition and altered nanomechanical properties of this interfacial region may also influence the crosslinking efficiency across the entire core region by a modification of the solubility of the crosslinker in the interfacial core-corona region.
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页数:13
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共 80 条
  • [1] Identification of individual isotopes in a polymer blend using tip enhanced Raman spectroscopy
    Agapov, Rebecca L.
    Scherger, Jacob D.
    Sokolov, Alexei P.
    Foster, Mark D.
    [J]. JOURNAL OF RAMAN SPECTROSCOPY, 2015, 46 (05) : 447 - 450
  • [2] Microstructure Control: An Underestimated Parameter in Recent Polymer Design
    Badi, Nezha
    Chan-Seng, Delphine
    Lutz, Jean-Francois
    [J]. MACROMOLECULAR CHEMISTRY AND PHYSICS, 2013, 214 (02) : 135 - 142
  • [3] Spatial resolution and property contrast in local mechanical mapping of polymer blends using AFM dynamic force spectroscopy
    Bahrami, Amir
    Bailly, Christian
    Nysten, Bernard
    [J]. POLYMER, 2019, 165 : 180 - 190
  • [4] Self-Healing Materials via Reversible Crosslinking of Poly(ethylene oxide)-Block-Poly(furfuryl glycidyl ether) (PEO-b-PFGE) Block Copolymer Films
    Barthel, Markus J.
    Rudolph, Tobias
    Teichler, Anke
    Paulus, Renzo M.
    Vitz, Juergen
    Hoeppener, Stephanie
    Hager, Martin D.
    Schacher, Felix H.
    Schubert, Ulrich S.
    [J]. ADVANCED FUNCTIONAL MATERIALS, 2013, 23 (39) : 4921 - 4932
  • [5] Understanding and tuning the self-assembly of polyether-based triblock terpolymers in aqueous solution
    Barthel, Markus J.
    Mansfeld, Ulrich
    Hoeppener, Stephanie
    Czaplewska, Justyna A.
    Schacher, Felix H.
    Schubert, Ulrich S.
    [J]. SOFT MATTER, 2013, 9 (13) : 3509 - 3520
  • [6] Homo- and Diblock Copolymers of Poly(furfuryl glycidyl ether) by Living Anionic Polymerization: Toward Reversibly Core-Crosslinked Micelles
    Barthel, Markus J.
    Rudolph, Tobias
    Crotty, Sarah
    Schacher, Felix H.
    Schubert, Ulrich S.
    [J]. JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 2012, 50 (23) : 4958 - 4965
  • [7] Tip-Enhanced Raman Spectroscopy to Distinguish Toxic Oligomers from Aβ1-42 Fibrils at the Nanometer Scale
    Bonhommeau, Sebastien
    Talaga, David
    Hunel, Julien
    Cullin, Christophe
    Lecomte, Sophie
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (07) : 1771 - 1774
  • [8] Force measurements with the atomic force microscope: Technique, interpretation and applications
    Butt, HJ
    Cappella, B
    Kappl, M
    [J]. SURFACE SCIENCE REPORTS, 2005, 59 (1-6) : 1 - 152
  • [9] Block Copolymer Micelles in Nanomedicine Applications
    Cabral, Horacio
    Miyata, Kanjiro
    Osada, Kensuke
    Kataoka, Kazunori
    [J]. CHEMICAL REVIEWS, 2018, 118 (14) : 6844 - 6892
  • [10] High-resolution tip-enhanced Raman scattering probes sub-molecular density changes
    Chen, Xing
    Liu, Pengchong
    Hu, Zhongwei
    Jensen, Lasse
    [J]. NATURE COMMUNICATIONS, 2019, 10 (1)