2026-09-23T02:09:42Z https://www.ideals.illinois.edu/oai-pmh

oai:www.ideals.illinois.edu:2142/77257 2023-07-11 col_2142_5131 col_2142_14789 com_2142_5130 com_2142_14788 com_2142_8903

Ogawa, Mark Kenneth 2015-05-13T15:37:25Z 2015-05-13T15:37:25Z 10000-01-01 1987 1987 The mechanism by which certain surfactants change the ultraviolet-visible (UV-vis) spectroscopic properties of certain metal-dye complexes has been largely ignored in the chemical literature. In this manuscript a model is developed to describe this mechanism. Intramolecular forces among surfactant molecules and host molecules are described to emphasize the importance of specific interactions to the mechanism. A review of the theoretical basis of UV-vis spectroscopic changes in dyes (chromatotropism) is given followed by application to the dyes of interest in this study. UV-vis spectra of the dyes, metal-dye complexes, and metal-dye-surfactant systems are analysed and a relationship between the symmetry of the chromophore and the UV-vis spectroscopic properties is described. This is the basis of the mechanistic model which postulates that the metal ion of the complex migrates from an asymmetric binding site to a symmetric binding site of the dye upon interaction with surfactant. Evidence in support of the molecular structures of the metal-dye complexes and metal-dye-surfactant systems proposed by the model is given in the analysis of infrared (IR) and Raman (R) spectra of these species. Structures of two metal-dye surfactant systems are proposed on the basis of the vibrational data. Thermodynamics of the rearrangements proposed by the model are investigated using ab-initio Hartree-Fock molecular orbital calculations. Made available in DSpace on 2015-05-13T15:37:25Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 8803159.PDF: 10397516 bytes, checksum: ad39b5fef7ecb222e4234624864ffe7e (MD5) Previous issue date: 1987 Embargo set by: Seth Robbins for item 78468 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs U of I Only 335 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1987. http://hdl.handle.net/2142/77257 (UMI)AAI8803159 eng Chemistry, Analytical Multi-Method Investigation of the Mechanism of Surfactant-Induced Chromatotropism of Metal-Chelometric Dye Complexes text Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.