Abstract
Different models and statistical mechanical approximations for titrating polyelectrolytes are studied and the results compared with Monte Carlo simulations and experimental data. Three types of models have been used in the simulations: i) rigid structures and freely jointed chains with ii) rigid bonds and iii) flexible, harmonic bonds. Sampling is facilitated for the latter two by the use of pivot algorithms, which allow simulations of literally thousands of monomers. Electrostatic interactions are treated within the primitive model. There are no interactions between macromolecules; only single chain properties are investigated.
The main part of the thesis is devoted to the study of flexible polyelectrolytes, which represent systems like polyacrylic acid and polyglutamic acid. The apparent dissociation constant and the endtoend separation are calculated for varying degree of dissociation, bond length/bond strength, number of monomers and salt concentration. Simple scaling relations obtained by a Flory type approach are investigated as well as the results of more elaborate variational calculations using a Gaussian Ansatz where all interactions are modelled by harmonic springs. Various rigid models that have appeared in the literature are also examined.
The last part of the thesis deals with integral equation theory in the form of RISMMSA for proteins and other more or less rigid polyelectrolytes. The theory is applied to the calcium binding and titrational behaviour of the protein calbindin D9k.
The main part of the thesis is devoted to the study of flexible polyelectrolytes, which represent systems like polyacrylic acid and polyglutamic acid. The apparent dissociation constant and the endtoend separation are calculated for varying degree of dissociation, bond length/bond strength, number of monomers and salt concentration. Simple scaling relations obtained by a Flory type approach are investigated as well as the results of more elaborate variational calculations using a Gaussian Ansatz where all interactions are modelled by harmonic springs. Various rigid models that have appeared in the literature are also examined.
The last part of the thesis deals with integral equation theory in the form of RISMMSA for proteins and other more or less rigid polyelectrolytes. The theory is applied to the calcium binding and titrational behaviour of the protein calbindin D9k.
Original language  English 

Qualification  Doctor 
Awarding Institution 

Supervisors/Advisors 

Award date  1996 Mar 8 
Publisher  
ISBN (Print)  9162819348 
Publication status  Published  1996 
Bibliographical note
Defence detailsDate: 19960308
Time: 14:15
Place: Lecture hall F, Chemical Center
External reviewer(s)
Name: Joanny, JeanFrancois
Title: Prof.
Affiliation: Institut Charles Sadron, Strasbourg, France

Subject classification (UKÄ)
 Physical Chemistry
Keywords
 integral equation theory
 variational calculations
 Monte Carlo simulations
 endtoend separation
 apparent dissociation constant
 titrating polyelectrolytes
 electrostatic interactions
 Physical chemistry
 Fysikalisk kemi