Molecular-Level Structure and Packing in Phase-Separated Arachidic Acid–Perfluorotetradecanoic Acid Monolayer Films

Sowah-Kuma, David; Fransishyn, Kyle M.; Cayabyab, Chelsea; Martynowycz, Michael W.; Kuzmenko, Ivan; Paige, Matthew F.

doi:10.1021/acs.langmuir.8b02291

Title: Molecular-Level Structure and Packing in Phase-Separated Arachidic Acid–Perfluorotetradecanoic Acid Monolayer Films

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Abstract

Synchrotron-based X-ray scattering measurements of phase-separated surfactant monolayers at the air–water interface provide molecular-level structural information about the packing and ordering of film components. In this work, grazing incidence X-ray diffraction (GIXD) and X-ray reflectivity (XR) measurements were used to collect crystallographic structural information for binary mixed monolayers of arachidic acid (AA, C₁₉H₃₉COOH) with perfluorotetradecanoic acid (PA, C₁₃F₂₇COOH), a system that has previously been investigated using a variety of thermodynamic and micron-scale structural characterization methods. GIXD measurements at surface pressures of π = 5, 15, and 30 mN/m indicated that AA in pure and mixed films forms a rectangular lattice at π = 5 and 15 mN/m but a hexagonal lattice at π = 30 mN/m. PA formed hexagonal lattices under all conditions, with films being highly ordered and crystalline (as determined by Bragg peak width) at even the lowest surface pressures investigated. Phase separation occurred for all mixed monolayer film compositions and surface pressures, manifesting as diffraction peaks characteristic of the individual components appearing at different in-plane scattering vector q_xy. For both pure and mixed films, the molecular tilt angle of the AA hydrocarbon chain toward the nearest-neighbor was substantial at low pressures but decreased with increasing pressure. Themore »« less

Authors:

Sowah-Kuma, David ^[1]; Fransishyn, Kyle M. ^[1]; Cayabyab, Chelsea ^[1]; Martynowycz, Michael W. ^[2]; Kuzmenko, Ivan ^[2];

^[1]

Univ. of Saskatchewan, Saskatoon, SK (Canada)
Argonne National Lab. (ANL), Lemont, IL (United States)

Publication Date:: Mon Aug 13 00:00:00 EDT 2018

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC)

OSTI Identifier:: 1483647

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Langmuir

Additional Journal Information:: Journal Volume: 34; Journal Issue: 36; Journal ID: ISSN 0743-7463

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; X-ray reflectivity; grazing incidence X-ray diffraction; orientation; phase-separation; perfluorotetradecanoic acid; arachidic acid

Citation Formats


                    Sowah-Kuma, David, Fransishyn, Kyle M., Cayabyab, Chelsea, Martynowycz, Michael W., Kuzmenko, Ivan, and Paige, Matthew F. Molecular-Level Structure and Packing in Phase-Separated Arachidic Acid–Perfluorotetradecanoic Acid Monolayer Films.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.langmuir.8b02291.

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                    Sowah-Kuma, David, Fransishyn, Kyle M., Cayabyab, Chelsea, Martynowycz, Michael W., Kuzmenko, Ivan, & Paige, Matthew F. Molecular-Level Structure and Packing in Phase-Separated Arachidic Acid–Perfluorotetradecanoic Acid Monolayer Films.  United States.  https://doi.org/10.1021/acs.langmuir.8b02291

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                    Sowah-Kuma, David, Fransishyn, Kyle M., Cayabyab, Chelsea, Martynowycz, Michael W., Kuzmenko, Ivan, and Paige, Matthew F. Mon .  
"Molecular-Level Structure and Packing in Phase-Separated Arachidic Acid–Perfluorotetradecanoic Acid Monolayer Films".  United States.  https://doi.org/10.1021/acs.langmuir.8b02291.  https://www.osti.gov/servlets/purl/1483647.

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@article{osti_1483647,

  title        = {Molecular-Level Structure and Packing in Phase-Separated Arachidic Acid–Perfluorotetradecanoic Acid Monolayer Films},

  author       = {Sowah-Kuma, David and Fransishyn, Kyle M. and Cayabyab, Chelsea and Martynowycz, Michael W. and Kuzmenko, Ivan and Paige, Matthew F.},

  abstractNote = {Synchrotron-based X-ray scattering measurements of phase-separated surfactant monolayers at the air–water interface provide molecular-level structural information about the packing and ordering of film components. In this work, grazing incidence X-ray diffraction (GIXD) and X-ray reflectivity (XR) measurements were used to collect crystallographic structural information for binary mixed monolayers of arachidic acid (AA, C19H39COOH) with perfluorotetradecanoic acid (PA, C13F27COOH), a system that has previously been investigated using a variety of thermodynamic and micron-scale structural characterization methods. GIXD measurements at surface pressures of π = 5, 15, and 30 mN/m indicated that AA in pure and mixed films forms a rectangular lattice at π = 5 and 15 mN/m but a hexagonal lattice at π = 30 mN/m. PA formed hexagonal lattices under all conditions, with films being highly ordered and crystalline (as determined by Bragg peak width) at even the lowest surface pressures investigated. Phase separation occurred for all mixed monolayer film compositions and surface pressures, manifesting as diffraction peaks characteristic of the individual components appearing at different in-plane scattering vector qxy. For both pure and mixed films, the molecular tilt angle of the AA hydrocarbon chain toward the nearest-neighbor was substantial at low pressures but decreased with increasing pressure. The PA fluorocarbon chain showed negligible molecular tilt under all conditions, and was oriented normal to the subphase surface regardless of surface pressure or the presence of AA in the films. In all cases, the two components in the mixed film behaved entirely independently of film composition, which is exactly the expected result for a fully phase-separated, immiscible system. XR measurements of film thickness at the air–water interface supported these results; overall film thickness approached the calculated ideal surfactant tail lengths with increasing surface pressure, indicating nearly normal oriented surfactants. Furthermore, the overall surfactant packing and crystallographic features of the mixed monolayers are discussed in terms of the lipophobic nature of the perfluorinated surfactant as well as in context of thermodynamic miscibility and domain structure formation reported elsewhere in the literature for these mixed monolayer systems.},

  doi          = {10.1021/acs.langmuir.8b02291},

  journal      = {Langmuir},

  number       = 36,

  volume       = 34,

  place        = {United States},

  year         = {Mon Aug 13 00:00:00 EDT 2018},

  month        = {Mon Aug 13 00:00:00 EDT 2018}

}

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