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Statistical Mechanical Studies of Aqueous solutions and Biomolecular Systems

Da Silva, Fernando Luis Barroso LU (1999)
Abstract
This thesis is concerned with theoretical studies of aqueous solutions and biomolecular systems. Part of the present work is to understand equilibrium solvent and solute properties, while the other part is to study processes that occur in these solutions. Three points were focused: (a) the study of structure and dynamics of 1M aqueous NaCl electrolyte solution at a molecular level, which revealed particular features of these solutions such as the formation of large clusters; (b) the development of a new simulation algorithm for the Reverse Monte Carlo technique aimed to study aqueous solutions and disordered systems. Results for spherical molecules and liquid water are presented; (c) the study of binding small ions to macromolecules... (More)
This thesis is concerned with theoretical studies of aqueous solutions and biomolecular systems. Part of the present work is to understand equilibrium solvent and solute properties, while the other part is to study processes that occur in these solutions. Three points were focused: (a) the study of structure and dynamics of 1M aqueous NaCl electrolyte solution at a molecular level, which revealed particular features of these solutions such as the formation of large clusters; (b) the development of a new simulation algorithm for the Reverse Monte Carlo technique aimed to study aqueous solutions and disordered systems. Results for spherical molecules and liquid water are presented; (c) the study of binding small ions to macromolecules (proteins and micelles). The Tanford-Kirkwood model is critically analysed for models of biomolecules by means of Monte Carlo calculations. Anomalous behaviour found for the binding of ions to macromolecules in the presence of highly charged macroparticles is also reported. And, a titration study is performed to characterize interfacial properties of a prototropic molecule in self-assembled surfactant aggregates.



The core of our discussion is based on electrostatic interactions and statistical mechanics. The studied systems were modeled by effective Hamiltonians within the Born-Oppenheimer and McMillan-Mayer model levels. These Hamiltonians were solved by computer simulations (Monte Carlo and Molecular Dynamics), and, in some cases, also by solving the Poisson-Boltzmann equation. Dielectric continuum models are largely used, and a discussion of uniform and non-uniform cases for studies with biomolecules and micellar systems is also included. (Less)
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author
supervisor
opponent
  • Prof Berendsen, Herman J. C.
organization
publishing date
type
Thesis
publication status
published
subject
keywords
highly charged macromolecules, dielectric discontinuity, dissociation constant, Tanford-Kirkwood model, protein mutation, electrostatic interactions, chemical potential, titration, biomolecules, computer simulations, radial distribution function, electrolyte solutions, continuum model., Theoretical chemistry, quantum chemistry, Teoretisk kemi, kvantkemi
pages
264 pages
publisher
Department of Theoretical Chemistry, Lund University
defense location
room G, Chemical Center, Sölvegatan 39, Lund, Sweden
defense date
2000-01-14 10:15:00
external identifiers
  • other:ISRN: LUNKDL/NKTC--99/1011--SE
ISBN
91-628-3903-9
language
English
LU publication?
yes
additional info
Article: A new algorithm for Reverse Monte Carlo simulationsF. L. B. da Silva, B. Svensson, T. Åkesson and B. JönssonThe Journal of Chemical Physics 109, 2624-2629, 1998 Article: Application of a new Reverse Monte Carlo method to polyatomic molecules. 1. Liquid water caseF. L. B. da Silva, L. Degrève, W. Olivares-Rivas and T. ÅkessonSubmitted for publication. Article: Structure of concentrated aqueous NaCl solution: a Monte Carlo studyL. Degrève and F. L. B. da SilvaThe Journal of Chemical Physics 110, 3070-3078, 1999. Article: Large ionic clusters in concentrated aqueous NaCl solutionL. Degrève and F. L. B. da SilvaThe Journal of Chemical Physics 111, 5150-5156, 1999. Article: A critical investigation of the Tanford-Kirkwood scheme by means of Monte Carlo simulationsF. L. B. da Silva, B. Jönsson and R. PenfoldSubmitted for publication. Article: Titration of fatty acids solubilized in cationic, nonionic and anionic micelles. Theory and experimentF. L. B. da Silva, D. Bogren, O. Söderman and B. JönssonSubmitted for publication. Article: The binding of charged ligands to macromolecules. Anomalous salt dependenceF. L. B. da Silva, S. Linse and B. JönssonSubmitted for publication. The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
id
5a555836-0988-437c-a54b-c9ca0e4b7bda (old id 40175)
date added to LUP
2016-04-04 10:49:57
date last changed
2018-11-21 21:01:01
@phdthesis{5a555836-0988-437c-a54b-c9ca0e4b7bda,
  abstract     = {This thesis is concerned with theoretical studies of aqueous solutions and biomolecular systems. Part of the present work is to understand equilibrium solvent and solute properties, while the other part is to study processes that occur in these solutions. Three points were focused: (a) the study of structure and dynamics of 1M aqueous NaCl electrolyte solution at a molecular level, which revealed particular features of these solutions such as the formation of large clusters; (b) the development of a new simulation algorithm for the Reverse Monte Carlo technique aimed to study aqueous solutions and disordered systems. Results for spherical molecules and liquid water are presented; (c) the study of binding small ions to macromolecules (proteins and micelles). The Tanford-Kirkwood model is critically analysed for models of biomolecules by means of Monte Carlo calculations. Anomalous behaviour found for the binding of ions to macromolecules in the presence of highly charged macroparticles is also reported. And, a titration study is performed to characterize interfacial properties of a prototropic molecule in self-assembled surfactant aggregates.<br/><br>
<br/><br>
The core of our discussion is based on electrostatic interactions and statistical mechanics. The studied systems were modeled by effective Hamiltonians within the Born-Oppenheimer and McMillan-Mayer model levels. These Hamiltonians were solved by computer simulations (Monte Carlo and Molecular Dynamics), and, in some cases, also by solving the Poisson-Boltzmann equation. Dielectric continuum models are largely used, and a discussion of uniform and non-uniform cases for studies with biomolecules and micellar systems is also included.},
  author       = {Da Silva, Fernando Luis Barroso},
  isbn         = {91-628-3903-9},
  language     = {eng},
  publisher    = {Department of Theoretical Chemistry, Lund University},
  school       = {Lund University},
  title        = {Statistical Mechanical Studies of Aqueous solutions and Biomolecular Systems},
  year         = {1999},
}