دورية أكاديمية
أعرض في EDS

Unraveling an Alternative Mechanism in Polymer Self-Assemblies: An Order-Order Transition with Unusual Molecular Interactions between Hydrophilic and Hydrophobic Polymer Blocks.

التفاصيل البيبلوغرافية
العنوان: Unraveling an Alternative Mechanism in Polymer Self-Assemblies: An Order-Order Transition with Unusual Molecular Interactions between Hydrophilic and Hydrophobic Polymer Blocks.
المؤلفون: Hahn L; Institute for Functional Materials and Biofabrication, Department of Chemistry and Pharmacy, Julius-Maximilians-University Würzburg, Röntgenring 11, 97070 Würzburg, Germany.; Institute of Pharmacy and Food Chemistry, Department of Chemistry and Pharmacy, Julius-Maximilians-University Würzburg, Am Hubland, 97074 Würzburg, Germany., Zorn T; Center for Nanosystems Chemistry & Institute of Organic Chemistry, Department of Chemistry and Pharmacy, Julius-Maximilians-University Würzburg, Am Hubland, 97074 Würzburg, Germany., Kehrein J; Institute of Pharmacy and Food Chemistry, Department of Chemistry and Pharmacy, Julius-Maximilians-University Würzburg, Am Hubland, 97074 Würzburg, Germany., Kielholz T; Institute of Pharmaceutical Technology and Buchmann Institute for Molecular Life Sciences, Goethe University Frankfurt, Max-von-Laue-Str. 9, 60438 Frankfurt am Main, Germany., Ziegler AL; Institute for Functional Materials and Biofabrication, Department of Chemistry and Pharmacy, Julius-Maximilians-University Würzburg, Röntgenring 11, 97070 Würzburg, Germany., Forster S; Institute for Functional Materials and Biofabrication, Department of Chemistry and Pharmacy, Julius-Maximilians-University Würzburg, Röntgenring 11, 97070 Würzburg, Germany., Sochor B; Chair for X-Ray Microscopy, Julius-Maximilians-University Würzburg, Josef-Martin-Weg 63, 97074 Würzburg, Germany., Lisitsyna ES; Faculty of Engineering and Natural Science, Tampere University, Korkeakoulunkatu 8, 33720 Tampere, Finland., Durandin NA; Faculty of Engineering and Natural Science, Tampere University, Korkeakoulunkatu 8, 33720 Tampere, Finland., Laaksonen T; Faculty of Engineering and Natural Science, Tampere University, Korkeakoulunkatu 8, 33720 Tampere, Finland.; Division of Pharmaceutical Biosciences, Faculty of Pharmacy, University of Helsinki, Viikinkaari 5 E, 00014 Helsinki, Finland., Aseyev V; Soft Matter Chemistry, Department of Chemistry, Helsinki Institute of Sustainability Science, Faculty of Science, University of Helsinki, 00014 Helsinki, Finland., Sotriffer C; Institute of Pharmacy and Food Chemistry, Department of Chemistry and Pharmacy, Julius-Maximilians-University Würzburg, Am Hubland, 97074 Würzburg, Germany., Saalwächter K; Institute of Physics-NMR, Martin-Luther-Universität Halle-Wittenberg, Betty-Heimann-Str. 7, 06120 Halle, Germany., Windbergs M; Institute of Pharmaceutical Technology and Buchmann Institute for Molecular Life Sciences, Goethe University Frankfurt, Max-von-Laue-Str. 9, 60438 Frankfurt am Main, Germany., Pöppler AC; Center for Nanosystems Chemistry & Institute of Organic Chemistry, Department of Chemistry and Pharmacy, Julius-Maximilians-University Würzburg, Am Hubland, 97074 Würzburg, Germany., Luxenhofer R; Institute for Functional Materials and Biofabrication, Department of Chemistry and Pharmacy, Julius-Maximilians-University Würzburg, Röntgenring 11, 97070 Würzburg, Germany.; Soft Matter Chemistry, Department of Chemistry, Helsinki Institute of Sustainability Science, Faculty of Science, University of Helsinki, 00014 Helsinki, Finland.
المصدر: ACS nano [ACS Nano] 2023 Apr 11; Vol. 17 (7), pp. 6932-6942. Date of Electronic Publication: 2023 Mar 27.
نوع المنشور: Journal Article
اللغة: English
بيانات الدورية: Publisher: American Chemical Society Country of Publication: United States NLM ID: 101313589 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1936-086X (Electronic) Linking ISSN: 19360851 NLM ISO Abbreviation: ACS Nano Subsets: PubMed not MEDLINE; MEDLINE
أسماء مطبوعة: Original Publication: Washington D.C. : American Chemical Society
مستخلص: Polymer self-assembly leading to cooling-induced hydrogel formation is relatively rare for synthetic polymers and typically relies on H-bonding between repeat units. Here, we describe a non-H-bonding mechanism for a cooling-induced reversible order-order (sphere-to-worm) transition and related thermogelation of solutions of polymer self-assemblies. A multitude of complementary analytical tools allowed us to reveal that a significant fraction of the hydrophobic and hydrophilic repeat units of the underlying block copolymer is in close proximity in the gel state. This unusual interaction between hydrophilic and hydrophobic blocks reduces the mobility of the hydrophilic block significantly by condensing the hydrophilic block onto the hydrophobic micelle core, thereby affecting the micelle packing parameter. This triggers the order-order transition from well-defined spherical micelles to long worm-like micelles, which ultimately results in the inverse thermogelation. Molecular dynamics modeling indicates that this unexpected condensation of the hydrophilic corona onto the hydrophobic core is due to particular interactions between amide groups in the hydrophilic repeat units and phenyl rings in the hydrophobic ones. Consequently, changes in the structure of the hydrophilic blocks affecting the strength of the interaction could be used to control macromolecular self-assembly, thus allowing for the tuning of gel characteristics such as strength, persistence, and gelation kinetics. We believe that this mechanism might be a relevant interaction pattern for other polymeric materials as well as their interaction in and with biological environments. For example, controlling the gel characteristics could be considered important for applications in drug delivery or biofabrication.
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فهرسة مساهمة: Keywords: NMR spectroscopy; inverse thermogelation; molecular dynamics simulation; poly(2-oxazine); poly(2-oxazoline)
تواريخ الأحداث: Date Created: 20230327 Date Completed: 20230411 Latest Revision: 20230415
رمز التحديث: 20230415
مُعرف محوري في PubMed: PMC10100562
DOI: 10.1021/acsnano.3c00722
PMID: 36972400
قاعدة البيانات: MEDLINE
الوصف
تدمد:1936-086X
DOI:10.1021/acsnano.3c00722