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Spectroscopic Analysis of Cu(II)-Complexed Thin Films to Characterize Molecular-Level Interactions and Film Behavior

Year: 2021

Journal: Langmuir, Volume 37, APR 27, page 5089–5097

Authors: Capistran, Briana A.; Blanchard, Gary J.

Organizations: NIH [2R01EY016077-08A1, 5R01EY025383-02 R01]

We report on the structure and dynamics of a Cu(2+)complexed arachidic acid (AA) monolayer formed by Langmuir-Blodgett (LB) deposition. Infrared reflection-absorption spectroscopy (IRRAS) was used to characterize aliphatic chain -CH2 symmetric and asymmetric stretching modes and determine the chain tilt angle and order as a function of subphase pH. Monolayer structure is controlled by metal ion-amphiphile interactions. At low subphase pH (<5), film buckling at high surface pressure is observed, while for high subphase pH (>= 5), monolayer buckling is not observed. This finding is correlated to monolayer structural mediation by metal ion-amphiphile interactions. Dynamics and mobility of a fluorophore incorporated into the monolayer were also affected by Cu2+-AA interactions, determined by fluorescence recovery after photobleaching (FRAP) measurements. These data are consistent with the formation of a rigid film due to Cu2+ coordination to AA headgroups, with the extent of headgroup protonation being determined by the pH of the subphase during monolayer deposition.