Ion specific 2D to 3D structural modification of Langmuir monolayer at lower surface pressure

Abstract

2D to 3D structural transformation of stearic acid Langmuir monolayer in presence of Ca2+ and Zn2+ ions at lower surface pressure (≈25 mN/m) has been studied at lower (pH ≈ 6.8) and higher (pH ≈ 9.5) subphase pH. Generally, 2D to 3D structural transformation of monolayer occurs at higher surface pressure (>50 mN/m) after collapse point which can be identified from surface pressure (π) vs. specific molecular area (A) isotherms. In presence of Ca2+ ions and for both lower and higher subphase pH, stearic acid monolayer remains as 2D monolayer at that lower surface pressure as confirmed from the Atomic Force Microscopy (AFM) studies on the films deposited at π ≈ 25mN/m. However, in presence of Zn2+ at higher subphase pH, stearic acid monolayer shows 2D to 3D structural transformation where less covered bilayer-like structure forms on top of the monolayer as obtained from the AFM studies. Fourier transform infrared (FTIR) spectroscopy results reveal that formation of relatively more amount of bidentate bridging coordination of metal carboxylate headgroup may be the key reason of such 2D to 3D structural transformation for Zn2+.