Choline applied as counterion [Elektronische Ressource] : a strategy for the design of biocompatible surfactants and green ionic liquids / vorgelegt von Regina Klein
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Choline applied as counterion [Elektronische Ressource] : a strategy for the design of biocompatible surfactants and green ionic liquids / vorgelegt von Regina Klein

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Choline Applied as Counterion – A Strategy for the Design of Biocompatible Surfactants and Green Ionic Liquids Dissertation zur Erlangung des Grades Doktor der Naturwissenschaften (Dr. rer. nat.) der Naturwissenschaftlichen Fakultät IV Chemie und Pharmazie Universität Regensburg vorgelegt von Regina Klein Regensburg 2011 Promotionsgesuch eingereicht am: 15.03.2011 Promotionskolloquium am: 01.04.2011 Die Arbeit wurde angeleitet von Prof. Dr. Werner Kunz Gutachter: Prof. Dr. Werner Kunz Prof. Dr. Hubert Motschmann Prof. Dr. Jörg Heilmann Vorsitzender: Prof. Dr. Dominik Horinek „So eine Arbeit wird eigentlich nie fertig, man muss sie für fertig erklären, wenn man nach Zeit und Umständen das Möglichste getan hat.“ - Johann Wolfgang von Goethe - Preface This dissertation is based on research carried out between February 2006 and March 2011 at the Institute of Physical and Theoretical Chemistry (Faculty of Natural Sciences IV) of the University of Regensburg.

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Published 01 January 2011
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Choline Applied as Counterion –
A Strategy for the Design of Biocompatible
Surfactants and Green Ionic Liquids
Dissertation
zur Erlangung des Grades
Doktor der Naturwissenschaften (Dr. rer. nat.)
der Naturwissenschaftlichen Fakultät IV
Chemie und Pharmazie
Universität Regensburg

vorgelegt von
Regina Klein
Regensburg 2011

















Promotionsgesuch eingereicht am: 15.03.2011
Promotionskolloquium am: 01.04.2011
Die Arbeit wurde angeleitet von Prof. Dr. Werner Kunz
Gutachter: Prof. Dr. Werner Kunz
Prof. Dr. Hubert Motschmann
Prof. Dr. Jörg Heilmann
Vorsitzender: Prof. Dr. Dominik Horinek

















„So eine Arbeit wird eigentlich nie fertig,
man muss sie für fertig erklären,
wenn man nach Zeit und Umständen
das Möglichste getan hat.“
- Johann Wolfgang von Goethe -




















Preface
This dissertation is based on research carried out between February 2006 and March
2011 at the Institute of Physical and Theoretical Chemistry (Faculty of Natural Sciences
IV) of the University of Regensburg. The many experiments performed required a
number of cooperations with experts of various fields and involved several stays of the
author at departments of different collaborating groups, including the Laboratoire
Interdisciplinaire sur l’Organisation Nanométrique et Supramoléculaire (CEA/IRAMIS,
CEA Saclay, France), the Institute for Advanced Chemistry of Catalonia (CSIC,
Barcelona, Spain), the Department of Chemical Engineering at the University of
Manchester, and the Institut de Chemie Séparative de Marcoule (CEA/CNRS, UM2,
ENSCM, France).
This work would not have been possible without the help and support of many people to
whom I am happy to express my honest gratitude.
First of all, I am sincerely indebted to my supervisor Prof. Dr. Werner Kunz for
bestowing me the confidence to work independently, for allocating this fascinating
topic, his interest in outcome of the experiments, and the financial support over the
years.
Furthermore, I owe a great debt of gratitude to Prof. Dr. Gordon J. T. Tiddy, who gave
me the opportunity to work in his laboratory in Manchester and let me benefit from his
great expert knowledge in the broad field of surfactants. In particular, I thank him for
his excellent support in light microscopy issues and NMR experiments. Moreover, I am
grateful to his co-worker Dr. Helen Dutton for performing the NMR relaxation
measurements of choline soaps.
In addition, I thank Dr. Jordi Esquena and Prof. Dr. Conxita Solans for their hospitality
during my one-week stay at the CSIC Barcelona, for allowing me to use their equipment
for X-ray measurements, and for valuable discussions. Likewise, I would like to
acknowledge Dr. Olivier Spalla and Olivier Tache (CEA Saclay) for granting me access
to their SAXS instrument as well as for their kindness and assistance during my visit.
Cordial thanks go to Dr. Olivier Diat (CEA/CNRS Marcoule) for giving me the
opportunity to use the X-ray setup at the Institut de Chemie Séparative, and for his
genial support during and after my stay at Marcoule. Further, I am grateful to Gabriele Wienskohl (Max-Planck-Institute Golm) for
completing the X-ray experiments. In this context, I would also like to express my
sincere thanks to Prof. Dr. Hubert Motschmann for bringing me into contact with the
MPI Golm and, apart from that, for his open ears at any time, his permanent assuasive
influence on me and his willingness to be examiner of this thesis.
In particular, I appreciate the help of the people who collaborated in the
interdisciplinary field of biodegradation and cytotoxicity of soaps. These are Dr. Boris
Estrine (Agroindustrie Recherche et Dévelopment, Pomacle, France) as well as Gabi
Brunner, Marcel Flemming, Dr. Birgit Krauss and Prof. Dr. Jörg Heilmann (Institute of
Pharmaceutical Biology, University of Regensburg). I am especially grateful to Dr.
Birgit Krauss and Prof. Dr. Jörg Heilmann for our fruitful discussions and their valuable
contributions in the interpretation of the data and development of ideas.
Beyond that, I am pleased to acknowledge Dr. Markus Drechsler (Institute of
Macromolecular Chemistry, University of Bayreuth) for performing cryo-transmission
electron microscopy studies on distinct series of samples.
Further thanks go to all staff members of the Institute of Physical and Theoretical
Chemistry, particularly to Dr. Didier Touraud for his innovative ideas and his
continuous interest in the progress of this work, to Dr. Oliver Zech for the fruitful
discussions in the field of ionic liquids and his help with conductivity measurements, to
Dr. Alexander Stoppa and Dr. Rainer Müller for their support in the handling of
technical equipment, to Eva Maurer for carrying out cytotoxicity analyses, and to my
lab colleague Doris Rengstl for the great time we had and her patience with me.
This work was partially funded by the Bavarian program “Förderung der
Chancengleichheit für Frauen in Forschung und Lehre”, and I acknowledge the granting
of a one-year fellowship.
Of course, I wish to thank my whole family for understanding and encouraging me in
any respect. Last but not least, I want to offer my heartfelt thanks to my boyfriend
Matthias for his permanent mental and practical support, which was essential for the
success of this dissertation.
Regina Klein
Table of Contents

Chapter I Introduction and Strategy .................................................. 1
I.1. Motivation .......................................................................................................... 1
I.2. How to Decrease a Surfactant’s Krafft Point? ............................................... 2
I.3. Choline Soaps ..................................................................................................... 3
I.4. Biocompatibility................................................................................................. 4
I.5. Aqueous Self-Assembly Behavior .................................................................... 5
I.6. Temperature-Dependent Self-Assembly Behavior of Neat Choline
Soaps ............................................................................................................... 9
I.7. Specific Ion Effects and their Consequences ................................................ 10
I.8. Choline Alkyl Sulfates ..................................................................................... 14
I.9. Oligoether Carboxylates – Task-Specific Room-Temperature Ionic
Liquids ............................................................................................................. 15
I.10. References ........................................................................................................ 17


Chapter II Choline Carboxylate Surfactants: Biocompatible and
Highly Soluble in Water ................................................... 21
II.1. Introduction ..................................................................................................... 22
II.2. Results and Discussion .................................................................................... 24
II.2.1. Critical Micellization Concentration (cmc)..................................................... 24
II.2.2. Krafft Point ..................................................................................................... 25
II.3. Conclusion ........................................................................................................ 27
II.4. Experimental .................................................................................................... 27
II.4.1. Soap Synthesis ................................................................................................ 27
II.4.2. Methods ........................................................................................................... 29
II.5. References ........................................................................................................ 31


Chapter III Biodegradability and Cytotoxicity on Human Cell
Lines of Choline Soaps ..................................................... 33
III.1. Introduction ..................................................................................................... 34
III.2. Results and Discussion .................................................................................... 36
III.2.1. Biodegradability .............................................................................................. 36
III.2.2. Cytotoxicity ..................................................................................................... 38
III.2.3. Monitoring of Cellular Uptake and Intracellular Distribution by
Fluorescence Microscopy ............................................................................... 42
III.3. Conclusion ........................................................................................................ 43
III.4. Experimental .................................................................................................... 44
III.4.1. Chemicals and Sample Preparation................................................................. 44
III.4.2. Biodegradability 45
III.4.3. Cytotoxicity Tests ........................................................................................... 46
III.4.4. Fluorescence Microscopy ............................................................................... 47
III.4.5. Statistics .......................................................................................................... 47
III.5. References ........................................................................................................ 48


Chapter IV Aqueous Phase Behavior of Choline Carboxylate
Surfactants ......................................................................... 53
IV.1. Introduction ..................................................................................................... 54
IV.2. Results and Discussion .................................................................................... 55
IV.2.1. Penetration Scans ............................................................................................ 55
IV.2.2. Binary Phase Diagrams ................................................................................... 57
IV.2.3. SAXS Data and Analysis ................................................................................ 60
IV.3. Conclusions ...................................................................................................... 70
IV.4. Experimental .................................................................................................... 71
IV.4.1. Materials and Sample Preparation .................................................................. 71
IV.4.2. Methods ........................................................................................................... 72
IV.5. References ........................................................................................................ 75