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Engineering Adhesion to Thermoresponsive Substrates: Effect of Polymer Composition on Liquid-Liquid-Solid Wetting

  • Adhesion control in liquidliquidsolid systems represents a challenge for applications ranging from self-cleaning to biocompatibility of engineered materials. By using responsive polymer chemistry and molecular self-assembly, adhesion at solid/liquid interfaces can be achieved and modulated by external stimuli. Here, we utilize thermosensitive polymeric materials based on random copolymers of di(ethylene glycol) methyl ether methacrylate (x = MEO(2)MA) and oligo(ethylene glycol) methyl ether methacrylate (y = OEGMA), that is, P(MEO(2)MA(x)-co-OEGMA(y)), to investigate the role of hydrophobicity on the phenomenon of adhesion. The copolymer ratio (x/y) dictates macromolecular changes enabling control of the hydrophilic-to-lipophilic balance (HBL) of the polymer brushes through external triggers such as ionic strength and temperature. We discuss the HBL of the thermobrushes in terms of the surface energy of the substrate by measuring the contact angle at waterdecaneP(MEO(2)MA(x)-co-OEGMA(y)) brush contact line as a function of polymerAdhesion control in liquidliquidsolid systems represents a challenge for applications ranging from self-cleaning to biocompatibility of engineered materials. By using responsive polymer chemistry and molecular self-assembly, adhesion at solid/liquid interfaces can be achieved and modulated by external stimuli. Here, we utilize thermosensitive polymeric materials based on random copolymers of di(ethylene glycol) methyl ether methacrylate (x = MEO(2)MA) and oligo(ethylene glycol) methyl ether methacrylate (y = OEGMA), that is, P(MEO(2)MA(x)-co-OEGMA(y)), to investigate the role of hydrophobicity on the phenomenon of adhesion. The copolymer ratio (x/y) dictates macromolecular changes enabling control of the hydrophilic-to-lipophilic balance (HBL) of the polymer brushes through external triggers such as ionic strength and temperature. We discuss the HBL of the thermobrushes in terms of the surface energy of the substrate by measuring the contact angle at waterdecaneP(MEO(2)MA(x)-co-OEGMA(y)) brush contact line as a function of polymer composition and temperature. Solid supported polyelectrolyte layers grafted with P(MEO(2)MA(x)-co-OEGMA(y)) display a transition in the wettability that is related to the lower critical solution temperature of the polymer brushes. Using experimental observation of the hydrophilic to hydrophobic transition by the contact angle, we extract the underlying energetics associated with liquidliquidsolid adhesion as a function of the copolymer ratio. The change in cellular attachment on P(MEO(2)MA(x)-co-OEGMA(y)) substrates of variable (x/y) composition demonstrates the subtle role of compositional tuning on the ability to control liquidliquidsolid adhesion in biological applications.show moreshow less

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Metadaten
Author:Filippo Gambinossi, Lauren S. Sefcik, Erik Wischerhoff, André LaschewskyORCiDGND, James K. Ferri
DOI:https://doi.org/10.1021/am507418m
ISSN:1944-8244 (print)
Pubmed Id:http://www.ncbi.nlm.nih.gov/pubmed?term=25569588
Parent Title (English):ACS applied materials & interfaces
Publisher:American Chemical Society
Place of publication:Washington
Document Type:Article
Language:English
Year of first Publication:2015
Year of Completion:2015
Release Date:2017/03/27
Tag:di(ethylene glycol) methy ether methacrylate; hydrophilic-to-lipophilic balance; oligo(ethylene glycol) methyl ether methacrylate; programmable adhesion; thermoresponsive substrates; water/decane contact angle
Volume:7
Issue:4
Pagenumber:11
First Page:2518
Last Page:2528
Funder:National Aeronautics and Space Administration (NASA)/Glenn Research Center (Particle Stabilized Emulsions and Foams) [NNX10AV26G]; European Space Administration (ESA) through Opportunity [AO-2009-0813]; Camille and Henry Dreyfus Foundation
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie
Peer Review:Referiert