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Controlling Growth of Poly (Triethylene Glycol Acrylate-Co-Spiropyran Acrylate) Copolymer Liquid Films on a Hydrophilic Surface by Light and Temperature

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Controlling Growth of Poly (Triethylene Glycol Acrylate-Co-Spiropyran Acrylate) Copolymer Liquid Films on a Hydrophilic Surface by Light and Temperature polymers Article Controlling Growth of Poly (Triethylene Glycol Acrylate-Co-Spiropyran Acrylate) Copolymer Liquid Films on a Hydrophilic Surface by Light and Temperature Aziz Ben-Miled 1 , Afshin Nabiyan 2 , Katrin Wondraczek 3, Felix H. Schacher 2,4 and Lothar Wondraczek 1,* 1 Otto Schott Institute of Materials Research (OSIM), Friedrich Schiller University Jena, D-07743 Jena, Germany; [email protected] 2 Institute of Organic Chemistry and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena, D-07743 Jena, Germany; [email protected] (A.N.); [email protected] (F.H.S.) 3 Leibniz Institute of Photonic Technology (Leibniz IPHT), D-07745 Jena, Germany; [email protected] 4 Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena, D-07743 Jena, Germany * Correspondence: [email protected]; Tel.: +49-3641-9-48500 Abstract: A quartz crystal microbalance with dissipation monitoring (QCM-D) was employed for in situ investigations of the effect of temperature and light on the conformational changes of a poly (triethylene glycol acrylate-co-spiropyran acrylate) (P (TEGA-co-SPA)) copolymer containing 12–14% of spiropyran at the silica–water interface. By monitoring shifts in resonance frequency and in acoustic dissipation as a function of temperature and illumination conditions, we investigated the evolution of viscoelastic properties of the P (TEGA-co-SPA)-rich wetting layer growing on the sensor, Citation: Ben-Miled, A.; Nabiyan, A.; from which we deduced the characteristic coil-to-globule transition temperature, corresponding to Wondraczek, K.; Schacher, F.H.; the lower critical solution temperature (LCST) of the PTEGA part. We show that the coil-to-globule Wondraczek, L. Controlling Growth of Poly (Triethylene Glycol transition of the adsorbed copolymer being exposed to visible or UV light shifts to lower LCST as Acrylate-Co-Spiropyran Acrylate) compared to the bulk solution: the transition temperature determined acoustically on the surface is 4 Copolymer Liquid Films on a to 8 K lower than the cloud point temperature reported by UV/VIS spectroscopy in aqueous solution. Hydrophilic Surface by Light and We attribute our findings to non-equilibrium effects caused by confinement of the copolymer chains Temperature. Polymers 2021, 13, 1633. on the surface. Thermal stimuli and light can be used to manipulate the film formation process and https://doi.org/10.3390/ the film’s conformational state, which affects its subsequent response behavior. polym13101633 Keywords: dual-stimuli-responsive materials; thin films; out-of-equilibrium Academic Editor: Mattia Sponchioni Received: 14 April 2021 Accepted: 12 May 2021 1. Introduction Published: 18 May 2021 Controlling and understanding polymer adsorption at solid–liquid interfaces is of key Publisher’s Note: MDPI stays neutral importance in, e.g., coating [1], lubrication [2], surface adhesion [3], or colloid stabiliza- with regard to jurisdictional claims in tion [4]. Polymer adsorption on a surface may occur in two general ways: by chemisorption published maps and institutional affil- or by physisorption. Chemisorption happens when polymers attach to a solid surface iations. through a covalent bond. This type of adsorption is irreversible, and it is employed in many applications, such as repellant surface layers [5] or other types of functional coat- ings [6]. Alternatively, physisorption takes place as a result of physical attractive forces between polymer segments and the surface [7]. Physisorbed chains may consist of loops, tails and trains [8]. In general, physisorption of polymers from a bulk liquid on a solid Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. surface can be either irreversible or reversible [9]. Irreversibility is usually achieved using This article is an open access article hydrogen bonding or other dipolar forces, dispersive forces, or attractions between charged distributed under the terms and groups along the polymer backbone and the surface [10]. It typically occurs on metals, conditions of the Creative Commons semiconductors, inorganic glasses, or sol-gel layers such as polydimethylsiloxane (PDMS), Attribution (CC BY) license (https:// for example, when surface oxygens of the substrate form strong hydrogen bonds with the creativecommons.org/licenses/by/ polymer [11]. Similarly, various macromolecules (polymers, proteins, DNA, etc.) are prone 4.0/). to adsorb strongly on oxide glass surfaces through hydrogen bonds or other physical forces Polymers 2021, 13, 1633. https://doi.org/10.3390/polym13101633 https://www.mdpi.com/journal/polymers Polymers 2021, 13, x FOR PEER REVIEW 2 of 17 (PDMS), for example, when surface oxygens of the substrate form strong hydrogen bonds with the polymer [11]. Similarly, various macromolecules (polymers, proteins, DNA, etc.) Polymers 2021, 13, 1633 are prone to adsorb strongly on oxide glass surfaces through hydrogen bonds2 of 16 or other physical forces (electrostatic attractions, hydrophobic interactions in the solvent) [1,12,13]. On the other hand, physisorption from a solution is reversible when the polymer binds (electrostaticweakly to the attractions, surface hydrophobicand has only interactions few conformational in the solvent) restrictions. [1,12,13]. On the other hand, physisorptionIn order to tailor from surface a solution adhesion, is reversible stimuli when responsive the polymer polymers binds weakly have toattracted the great surfaceattention and hasin the only last few decades conformational due to their restrictions. ability to respond to external triggers, including In order to tailor surface adhesion, stimuli responsive polymers have attracted great temperature [14], light [15], pH [16], ionic strength [17], or combinations of thereof [18,19]. attention in the last decades due to their ability to respond to external triggers, including temperatureLayers formed [14], lightfrom [15 such], pH polymers [16], ionic are strength expected [17], to or enable combinations switchable of thereof surfaces [18,19 which]. may Layerschange formed their fromproperties such polymers in controllable are expected and programmable to enable switchable ways surfaces [20]. Sometimes, which such mayswitching change theircan be properties through in combinations controllable and of multiple programmable stimuli ways (e.g., [20 light]. Sometimes, and temperature, such[21]), switching what enables can be throughlogic gate combinations operations. of Th multipleermo-responsive stimuli (e.g., polymers light and are tempera- the most stud- ture,ied [21stimulus]), what responsive enables logic materi gate operations.als. In aqueous Thermo-responsive solution, they polymers usually are display the most a fully re- studiedversible stimulus hydrophilic–hydrophobic responsive materials. Intransition aqueous (F solution,igure 1), they characterized usually display by aa fullylower critical reversiblesolution hydrophilic–hydrophobic temperature (LCST) [22]. transition Below the (Figure LCST,1), characterized the polymer by swells a lower with critical a random coil solution temperature (LCST) [22]. Below the LCST, the polymer swells with a random conformation, while above LCST, the polymer collapses into a globular state and under- coil conformation, while above LCST, the polymer collapses into a globular state and undergoesgoes a liquid–liquid a liquid–liquid phase phase separation. separation. This This tr transformationansformation from from coil to globuleglobule is based ison based hydrogen on hydrogen bonds bonds that thatare present are present between between the the polymer polymer chains chains and and the sur-surrounding roundingwater molecules water molecules at temperatures at temperatures below below the LC theST LCST [23]. [ 23At]. higher At higher temperatures, temperatures, the hydro- thegen hydrogen bonds become bonds become weaker, weaker, leading leading to the todehyd the dehydrationration of the of polymer the polymer chains. chains. Some prom- Someinent prominent examples examples for this for behavior this behavior are aremicrogels microgels [24,25], [24,25], poly poly ((NN-isopropyl-isopropyl acry- acrylamide, lamide,PNIPAM PNIPAM [23,26], [23 ,acrylamides26], acrylamides [27,28], [27,28 poly], poly (2-oxazolines) (2-oxazolines) [[29,30],29,30], polypoly (propylene (propylene glycol) glycol)[31,32], [31 and,32], poly and poly (oligo (oligo (ethylene (ethylene glycol) glycol) acrylates acrylates [33–35]. [33–35]. FigureFigure 1. Coil1. Coil to globuleto globule transition transition at different at different temperatures temperatures shown by shown way of by example way of for example the dual for the lightdual and light temperature and temperature responsive responsive P (TEGA-co-SP/MC) P (TEGA-co-SP/MC) copolymer copolymer during in situ during observation in situ observation of adsorptionof adsorption and film and formation film formation on a silica on surface a silica by surface QCM-D. by QCM-D. PolymersPolymers 20212021, ,1313, ,x 1633 FOR PEER REVIEW 3 3of of 17 16 IncorporationIncorporation of of photochromic photochromic moieties moieties into into thermosensitive thermosensitive polymer polymer backbones backbones is is aa practical practical way way to to control control their their solubility solubility in in aqueous aqueous solutions solutions by by changing changing the the tempera- temper- tureature at which at which thethe phase phase transition transition happens happens through through an optical an optical stimulus
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