The proposed work, to be a combined experimental and theoretical effort of two groups, aims to provide a foundation for predicting molecular solubilities within """"""""interphases"""""""" of matter, especially the stationary hydrocarbon phases of leversed Phase Liquid Chromatography, (RPLC), and including amphiphilic aggregates such as lipid bilayer membranes, vesicles, and micelles. We have previously developed statistical mechanical theory to predict molecular organization in membranes and micelles. Predictions are in good agreement with results of x-ray diffraction, small angle neutron scattering, 2H, 13C, 19F NMR, and equation of state measurements. The principal conclusion is that chain molecule interphases are not bulk phases of matter, but bear close resemblance to interfacial phases. Bulk phase thermodynamics of colligative properties and of partition coefficients is not applicable to these systems; here we aim to develop more appropriate thermodynamic and statistical mechanical theory for solubilities in interphases. Our experimental efforts have been directed toward both theoretical and applied characterization of chromatographic systems. Here, we aim to test rigorously theoretical models through systematic study of solute size and chemical character, chain length and surface density of the grafted interphase chains, and through the establishment of valid reference states. This work should have direct bearing on: i) Retention mechanisms of RPLC, the most widely used and rapidly growing method of chromatographic separation, and ii) Fundamental physical chemistry of colligative properties of lipid bilayers, vesicle, and biological membranes, and may provide a foundation for understanding molecular mechanisms of anesthetic drug action.

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Research Project (R01)
Project #
1R01GM033382-01A1
Application #
3283054
Study Section
Metallobiochemistry Study Section (BMT)
Project Start
1984-12-01
Project End
1987-11-30
Budget Start
1984-12-01
Budget End
1985-11-30
Support Year
1
Fiscal Year
1985
Total Cost
Indirect Cost
Name
University of Florida
Department
Type
Schools of Arts and Sciences
DUNS #
073130411
City
Gainesville
State
FL
Country
United States
Zip Code
32611
Cole, L A; Dorsey, J G; Dill, K A (1992) Temperature dependence of retention in reversed-phase liquid chromatography. 2. Mobile-phase considerations. Anal Chem 64:1324-7
Cole, L A; Dorsey, J G (1992) Temperature dependence of retention in reversed-phase liquid chromatography. 1. Stationary-phase considerations. Anal Chem 64:1317-23
Cole, L A; Dorsey, J G (1990) Reduction of reequilibration time following gradient elution reversed-phase liquid chromatography. Anal Chem 62:16-21
Michels, J J; Dorsey, J G (1990) Estimation of the reversed-phase liquid chromatographic lipophilicity parameter log k'w using ET-30 solvatochromism. J Chromatogr 499:435-51
Sentell, K B; Dorsey, J G (1989) Retention mechanisms in reversed-phase chromatography. Stationary phase bonding density and solute selectivity. J Chromatogr 461:193-207
Ying, P T; Dorsey, J G; Dill, K A (1989) Retention mechanisms of reversed-phase liquid chromatography: determination of solute-solvent interaction free energies. Anal Chem 61:2540-6
Sentell, K B; Dorsey, J G (1989) Retention mechanisms in reversed-phase liquid chromatography. Stationary-phase bonding density and partitioning. Anal Chem 61:930-4
Sentell, K B; Barnes, K W; Dorsey, J G (1988) Ultrasound driven synthesis of reversed-phase stationary phases for liquid chromatography using 4-dimethyl-aminopyridine as acid-acceptor. J Chromatogr 455:95-104
Michels, J J; Dorsey, J G (1988) Retention in reversed-phase liquid chromatography: solvatochromic investigation of homologous alcohol-water binary mobile phases. J Chromatogr 457:85-98
Johnson, B P; Khaledi, M G; Dorsey, J G (1987) Solvatochromic solvent polarity measurements and selectivity in reversed-phase liquid chromatography. J Chromatogr 384:221-30

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