Using the Intrinsic Chirality of a Molecule as a Label-Free Probe to Detect Molecular Adsorption to a Surface by Second Harmonic Generation

Authors: Kriech, Matthew A.1; Conboy, John C.1

Source: Applied Spectroscopy, Volume 59, Issue 6, Pages 120A-138A and 707-851 (June 2005) , pp. 746-753(8)

Publisher: Society for Applied Spectroscopy

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Abstract:

Chiral second harmonic generation (C-SHG) has been used for the label-free detection of (R)-(+)-1,1′-bi-2-naphthol (RBN) and (S)-(+)-1,1′-bi-2-naphthol (SBN) binding to planar-supported lipid bilayers of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphotidylcholine (POPC) based on the intrinsic chirality of the molecules. C-SHG adsorption isotherms of RBN and SBN reveal Langmuir adsorption behavior with binding constants of 2.7 ± 0.2 × 105 M−1 and 3.0 ± 0.1 × 105 M−1, respectively. The kinetics of RBN binding to a POPC bilayer was also measured. It was determined that the adsorption rate for RBN was 5.7 ± 0.4 × 103 s−1M−1 and the desorption rate was 2.1 ± 0.8 × 10−2 s−1. From the kinetic data a binding constant of 2.7 ± 1.0 × 105 M−1 was calculated, which agrees well with the thermodynamic measurement. The C-SHG technique was correlat- ed with surface tension measurements in order to determine the RBN surface excess within the POPC membrane. The maximum surface excess of RBN in a monolayer of POPC was 4.3 ± 0.5 × 10−11 mol cm2. Using the maximum surface excess in conjunction with the C-SHG binding data a lower limit of detection of 1.5 ± 0.1 × 10−13 mols cm−2was calculated. The results of these studies show that C-SHG is a powerful tool for the study of chiral molecular interactions at surfaces.

Keywords: SECOND HARMONIC GENERATION; RBN; SBN; SURFACE ADSORPTION; CHIRAL; NONLINEAR OPTICS; PLANAR SUPPORTED LIPID BILAYER

Document Type: Research article

DOI: 10.1366/0003702054280711

Affiliations: 1: Department of Chemistry, University of Utah, 315 S. 1400 E. RM 2020, Salt Lake City, Utah 84112

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