Ternary Nanoswitches Realized with Multiresponsive PMMA‐<i>b</i>‐PNIPMAM Films in Mixed Water/Acetone Vapor Atmospheres

Geiger, Christina; Reitenbach, Julija; Henschel, Cristiane; Kreuzer, Lucas P.; Widmann, Tobias; Wang, Peixi; Mangiapia, Gaetano; Moulin, Jean‐François; Papadakis, Christine M.; Laschewsky, André; Müller‐Buschbaum, Peter

doi:10.1002/adem.202100191

Cited by 4 publications

(14 citation statements)

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“…For comparison, we recently investigated a PMMA-b-PNIPMAM DBC film in mixed water/ acetone vapors, which showed three different film thickness regimes, in dependence on the vapor composition. 57 By replacing the permanently hydrophobic PMMA block with the responsive PSPE block, an additional thickness regime is accessible, in which the film is in a metastable state. By reducing the methanol content in the vapor, the thin film might equilibrate in this distinct thin-film regime, where only the PSPE block is in a collapsed state.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…26 In a related study about co-solvent-induced thin-film swelling and contraction, we recently investigated thin films of a DBC consisting of a short hydrophobic poly(methyl methacrylate) (PMMA) block and a long PNIPMAM block. 57 This DBC can be used for realizing ternary nanoswitches when being exposed to nitrogen, pure water vapor, and mixed water/acetone vapor.…”

Section: ■ Introductionmentioning

confidence: 99%

“…While most of these studies address the co-nonsolvency behavior of polymers in dilute solution, experiments that investigate a co-solvent induced collapse of polymers in an intermediate concentration regime, e.g., tethered polymer brushes, , or in a highly concentrated regime, e.g., thin polymer films, are rare. ,− In our previous work, we exposed a poly(sulfobetaine) and a PNIPMAM thin homopolymer film first to pure water vapor, before a part of the water vapor was exchanged by methanol (ratio water/methanol 70/30 vol %). For both thin films, a co-nonsolvency-type behavior in mixed water/methanol vapor was found .…”

Section: Introductionmentioning

confidence: 99%

“…It was found that at 22 °C in the poly(sulfobetaine) thin film, interactions with water are favored over interactions with methanol, while the opposite is the case in the PNIPMAM thin film . In a related study about co-solvent-induced thin-film swelling and contraction, we recently investigated thin films of a DBC consisting of a short hydrophobic poly(methyl methacrylate) (PMMA) block and a long PNIPMAM block . This DBC can be used for realizing ternary nanoswitches when being exposed to nitrogen, pure water vapor, and mixed water/acetone vapor.…”

Section: Introductionmentioning

confidence: 99%

“…Alternatively, steric hindrance or repulsive interactions between the polymer blocks may alter the co-nonsolvency-type behavior of the DBC thin film. In addition, we aim to develop a versatile thin-film system that can achieve multiple distinct thin-film regimes, regarding the film thickness and solvent contents, analogously to the recently reported PMMA -b- PNIPMAM thin films . With the hydrophobic and nonresponsive PMMA block being replaced by the responsive PSPE block, complex nanoswitches with multiple thin-film regimes, featuring an “ON” and “OFF” setting, as well as intermediate settings, might be enabled.…”

Section: Introductionmentioning

confidence: 99%

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Solvation Behavior of Poly(sulfobetaine)-Based Diblock Copolymer Thin Films in Mixed Water/Methanol Vapors

et al. 2021

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The swelling of thin diblock copolymer (DBC) films is investigated in situ at 22 °C in pure water vapor as well as in mixed water/methanol vapor. The DBC consists of a zwitterionic poly(sulfobetaine) block, poly[3–((2-(methacryloyloxy)ethyl)dimethylammonio) propane-1-sulfonate] (PSPE), and a nonionic poly(N-isopropylmethacrylamide) (PNIPMAM) block. The swelling in water vapor (either H2O or D2O) and the thin-film response to methanol vapor exchange (i.e., a part of the H2O vapor is exchanged by CD3OH vapor and a part of the D2O vapor is exchanged by CH3OH vapor) are followed with simultaneous time-of-flight neutron reflectometry (ToF-NR) and spectral reflectance (SR) measurements. In situ Fourier transform infrared (FTIR) spectroscopy complements these data. Exposure to H2O vapor leads to a slightly higher degree of swelling and amount of absorbed H2O compared to D2O. Upon methanol exchange, the PSPE-b-PNIPMAM thin film undergoes two contractions, which are assigned to the specific responses of the individual polymer blocks of the DBC. Due to its isotope sensitivity, FTIR confirms these two separate contraction processes of the blocks on a molecular level and reveals the role of each polymer block during swelling in water vapor and upon the methanol exchange. Thus, four distinct film regimes with different thicknesses dependencies on the vapor composition can be established, thereby enabling a quarternary nanoswitch.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Solvation Behavior of Poly(sulfobetaine)-Based Diblock Copolymer Thin Films in Mixed Water/Methanol Vapors

et al. 2021

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Thermoresponsive and co-nonsolvency behavior of poly(N-vinyl isobutyramide) and poly(N-isopropyl methacrylamide) as poly(N-isopropyl acrylamide) analogs in aqueous media

et al. 2023

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Sets of the nonionic polymers poly(N-vinyl isobutyramide) (pNVIBAm) and poly(N-isopropyl methacrylamide) (pNIPMAm) are synthesized by radical polymerization covering the molar mass range from about 20,000 to 150,000 kg mol−1, and their thermoresponsive and solvent-responsive behaviors in aqueous solution are studied. Both polymers feature a lower critical solution temperature (LCST) apparently of the rare so-called type II, as characteristic for their well-studied analogue poly(N-isopropyl acrylamide) (pNIPAm). Moreover, in analogy to pNIPAm, both polymers exhibit co-nonsolvency behavior in mixtures of water with several co-solvents, including short-chain alcohols as well as a range of polar aprotic solvents. While the cloud points of the aqueous solutions are a few degrees higher than those for pNIPAm and increase in the order pNIPAm < pNVIBAm < pNIPMAm, the co-nonsolvency behavior becomes less pronounced in the order pNIPAm > pNVIBAm > pNIPMAm. Exceptionally, pNIPMAm does not show co-nonsolvency in mixtures of water and N,N-dimethylformamide. Graphical Abstract

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Poly(sulfobetaine)-Based Diblock Copolymer Thin Films in Water/Acetone Atmosphere: Modulation of Water Hydration and Co-nonsolvency-Triggered Film Contraction

et al. 2022

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The water swelling and subsequent solvent exchange including co-nonsolvency behavior of thin films of a doubly thermo-responsive diblock copolymer (DBC) are studied via spectral reflectance, time-of-flight neutron reflectometry, and Fourier transform infrared spectroscopy. The DBC consists of a thermo-responsive zwitterionic (poly(4-((3-methacrylamidopropyl) dimethylammonio) butane-1-sulfonate)) (PSBP) block, featuring an upper critical solution temperature transition in aqueous media but being insoluble in acetone, and a nonionic poly(Nisopropylmethacrylamide) (PNIPMAM) block, featuring a lower critical solution temperature transition in water, while being soluble in acetone. Homogeneous DBC films of 50−100 nm thickness are first swollen in saturated water vapor (H 2 O or D 2 O), before they are subjected to a contraction process by exposure to mixed saturated water/acetone vapor (H 2 O or D 2 O/acetone-d6 = 9:1 v/v). The affinity of the DBC film toward H 2 O is stronger than for D 2 O, as inferred from the higher film thickness in the swollen state and the higher absorbed water content, thus revealing a pronounced isotope sensitivity. During the co-solvent-induced switching by mixed water/acetone vapor, a two-step film contraction is observed, which is attributed to the delayed expulsion of water molecules and uptake of acetone molecules. The swelling kinetics are compared for both mixed vapors (H 2 O/acetone-d6 and D 2 O/acetone-d6) and with those of the related homopolymer films. Moreover, the concomitant variations of the local environment around the hydrophilic groups located in the PSBP and PNIPMAM blocks are followed. The first contraction step turns out to be dominated by the behavior of the PSBP block, whereas the second one is dominated by the PNIPMAM block. The unusual swelling and contraction behavior of the latter block is attributed to its co-nonsolvency behavior. Furthermore, we observe cooperative hydration effects in the DBC films, that is, both polymer blocks influence each other's solvation behavior.

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Ternary Nanoswitches Realized with Multiresponsive PMMA‐b‐PNIPMAM Films in Mixed Water/Acetone Vapor Atmospheres

Cited by 4 publications

References 70 publications

Solvation Behavior of Poly(sulfobetaine)-Based Diblock Copolymer Thin Films in Mixed Water/Methanol Vapors

Solvation Behavior of Poly(sulfobetaine)-Based Diblock Copolymer Thin Films in Mixed Water/Methanol Vapors

Thermoresponsive and co-nonsolvency behavior of poly(N-vinyl isobutyramide) and poly(N-isopropyl methacrylamide) as poly(N-isopropyl acrylamide) analogs in aqueous media

Poly(sulfobetaine)-Based Diblock Copolymer Thin Films in Water/Acetone Atmosphere: Modulation of Water Hydration and Co-nonsolvency-Triggered Film Contraction

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