Adsorbed and Spread Layers of Poly(ethylene oxide)−Poly(propylene oxide)−Poly(ethylene oxide) Block Copolymers at the Air−Water Interface Studied by Sum-Frequency Vibrational Spectroscopy and Tensiometry

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Abstract

The surface properties of three water-soluble and amphiphilic PEO−PPO−PEO triblock copolymers of different composition (Pluronic 6100, 6400, and 6800) are investigated by tensiometry and sum-frequency vibrational spectroscopy. We compared the concentration dependence of the structure of surface layers prepared by three different methods:  (i) adsorption from aqueous solution, (ii) dropwise spreading from an organic solution onto a surface of constant area, and (iii) compression of the spread film in a Langmuir trough. The surface density and conformation of the polymers were deduced from the vibrational band intensities of the methyl groups of the central hydrophobic PPO block and from the surface tension isotherms. A transition range related to a conformational change was observed by tensiometry for the adsorbed and the compressed Langmuir films of Pluronics with short PEO blocks, whereas the Pluronic with longest PEO blocks displays a gradual change of surface pressure without the sign of a phase transition. This difference reveals the effect of the relative lengths of the hydrophilic and hydrophobic blocks on the structural changes in the surface layers of block copolymers. A clear indication of the influence of the hydrophilic blocks on the structure of the whole molecule at the interface was also observed in the sum-frequency experiments. Above a given concentration the Pluronic with longest PEO chains exhibited lower sum-frequency intensities and methyl symmetric/asymmetric amplitude ratios than the other Pluronic compounds for all of the layers formed by the various methods. The differences in the surface properties of the dropwise spread layers and of the compressed Langmuir layers exposed the importance of the kinetic aspects of polymer monolayer formation. In the case of the spread films the possible large degree of nonequilibrium chain entanglements might hinder the accomplishment of preferred orientation and conformation of the polymer chains.

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This article has been cited by 5 ACS Journal articles (5 most recent appear below).

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  • Surface Properties of Monolayers of Amphiphilic Poly(ethylene oxide)-Poly(styrene oxide) Block Copolymers

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• 

  Adsorbed and Spread Films of Amphiphilic Triblock Copolymers Based on Poly(2,3-dihydroxypropyl methacrylate) and Poly(propylene oxide) at the Air−Water Interface

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• 

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  Hydrosoluble Cyclodextrin/Poloxamer Polypseudorotaxanes at the Air/Water Interface, in Bulk Solution, and in the Gel State

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  Self-Associative Behavior and Drug-Solubilizing Ability of Poloxamine (Tetronic) Block Copolymers

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  • Self-Associative Behavior and Drug-Solubilizing Ability of Poloxamine (Tetronic) Block Copolymers

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    The incidence of the structural features on the self-assembly of different poloxamines (the conventional sequential Tetronic 304, 901, 904, 908, 1107, 1301, and 1307; a reverse-sequential counterpart Tetronic 150R1; and a chemically modified derivative, N-...

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