Affinity capillary electrophoresis and density functional theory applied to binding constant determination and structure elucidation of hexaarylbenzene-based receptor complex with ammonium cation

• Published in: Journal of Chromatography A 2011-07, Vol.1218 (30), p.4982-4987
• Main Authors: Ehala, Sille, Toman, Petr, Makrlík, Emanuel, Rathore, Rajendra, Kašička, Václav
• Format: Article
• Language: English
• Subjects: Affinity capillary electrophoresis; ammonium compounds; Binding constant; capillary electrophoresis; chromatography; Density functional theory calculations; electrolytes; Hexaarylbenzene derivatives; methanol; Non-covalent interactions; regression analysis; temperature
• ISSN: 0021-9673
• DOI: 10.1016/j.chroma.2011.01.073

Affinity capillary electrophoresis (ACE) and quantum mechanical density functional theory (DFT) calculations have been employed for the investigation of noncovalent interactions between hexaarylbenzene-based receptor ( R) and ammonium cation NH 4 +. Firstly, by means of ACE, the binding constant of the NH 4R + complex in methanol was estimated from the dependence of the effective electrophoretic mobility of the receptor R (in advance corrected by our earlier developed procedure to a reference temperature of 25 °C) on the concentration of ammonium ion in the background electrolyte using non-linear regression analysis. The logarithmic form of the apparent binding (stability) constant of NH 4 R + complex in the methanolic background electrolyte (25 mM Tris, 50 mM chloroacetate, pH MeOH 7.8) was evaluated as log K N H 4 R = 4.03 ± 0.15 . Secondly, the structural characteristics of NH 4 R + complex were determined by DFT calculations.