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Investigations in molecular recognition: statistical tools and experimental studies


Barrans, Richard E., Jr. (1993) Investigations in molecular recognition: statistical tools and experimental studies. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/42WC-0V58.


The free energies of formation of intermolecular complexes in solution are often estimated by fitting a nonlinear model to an NMR titration experiment. A regression procedure that assigns weights to each observation on the basis of expected measurement errors has been developed, and yields better parameter estimates than other methods in common use. Procedures for critically evaluating the fit of the model to the experimental data and for assigning confidence limits to the fitted parameters have also been developed. These employ Monte Carlo simulations of the NMR titration experiment to obtain probability distributions that are not available by theoretical means.

Aspects of the complexation behavior of a family of water-soluble macrocyclic cyclophanes are also described. Significant heat capacity effects, which are interpreted in terms of hydrophobic hydration, are seen in variable-temperature studies. The alkylation reactions of pyridine-based compounds are accelerated by complexation with these cyclophanes; an interpretation based on the dynamic properties of the alkylation reaction, the solvent, and the cyclophane is offered. In addition, accounts of efforts to make axially-substituted cyclophanes, to synthesize cyclophanes incorporating a diphosphine ligand, to append additional water-solubilizing groups to the cyclophanes, and to employ small cyclophanes as complexants for alkali metal cations are given.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:cyclophane, molecular recognition, complexation, nonlinear regression, monte carlo simulation
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Dougherty, Dennis A.
Thesis Committee:
  • Myers, Andrew G. (chair)
  • Dougherty, Dennis A.
  • Imperiali, Barbara
  • Baldeschwieler, John D.
Defense Date:16 June 1992
Non-Caltech Author Email:rbarrans (AT)
Record Number:CaltechTHESIS:12062012-140020355
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:7310
Deposited By: Benjamin Perez
Deposited On:06 Dec 2012 22:54
Last Modified:21 Dec 2019 04:26

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