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Nonequilibrium 2-hydroxyoctadecanoic acid monolayers: effect of electrolytes.

Conrad D Lendrum1, Bridget Ingham, Binhua Lin

  • 1MacDiarmid Institute for Advanced Materials and Nanotechnology, School of Chemical and Physical Sciences, Victoria University of Wellington, Wellington, New Zealand.

Langmuir : the ACS Journal of Surfaces and Colloids
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The study reveals how 2-hydroxyoctadecanoic acid monolayers change behavior on different water surfaces. Hydrogen bonding and ion interactions significantly influence their complex phase behavior, crucial for biomineralization.

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Area of Science:

  • Surface chemistry
  • Biomineralization
  • Materials science

Background:

  • 2-Hydroxyacids exhibit complex monolayer phase behavior due to dual hydrogen bonding capabilities.
  • The alpha-hydroxy group enables chelation, important for crystallization and biomineralization processes.
  • Biomineralization is a nonequilibrium process, necessitating the study of dynamic interfacial phenomena.

Purpose of the Study:

  • To investigate the nonequilibrium monolayer phase behavior of 2-hydroxyoctadecanoic acid.
  • To examine the influence of various aqueous subphases (pure water, CaCl2, NaHCO3, CaCO3, NaCl) on monolayer structure.
  • To understand the role of bicarbonate ions and calcium ions in modulating interfacial properties relevant to biomineralization.

Main Methods:

  • Surface pressure/area isotherms
  • Surface potential measurements
  • Brewster angle microscopy
  • Synchrotron-based grazing incidence X-ray diffraction (GIXD) and X-ray reflectivity (XRR)

Main Results:

  • Complex phase behavior was observed on pure water, CaCl2, NaHCO3, and CaCO3 subphases, but not on NaCl.
  • Hydrogen bonding dominated on pure water, leading to three coexisting phases at low pressures.
  • Calcium ions induced strong cation binding via chelation, while bicarbonate ions destabilized monolayers through hydrogen bonding and enhanced solubility.
  • Monolayer symmetry was dictated by hydrogen bonding, electrostatic, and steric effects.

Conclusions:

  • The study elucidates the intricate monolayer phase behavior of 2-hydroxyoctadecanoic acid under varying ionic conditions.
  • Interactions involving hydrogen bonding, chelation, and electrostatic forces critically control interfacial structure.
  • Findings provide insights into precursor phenomena for calcium carbonate biomineralization systems.