Characterization of short polypropylene glycol monoalkylethers and design of enzymatic reaction media [Elektronische Ressource] / Pierre Bauduin
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Characterization of short polypropylene glycol monoalkylethers and design of enzymatic reaction media [Elektronische Ressource] / Pierre Bauduin

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DissertationCharacterization of shortpolypropylene glycol monoalkylethersand design of enzymatic reactionmediaPierre BauduinUniversity of RegensburgAt the Natural Sciences Faculty IVChemistry & PharmacyMai 2005Ph.D. Supervisor: Prof. Dr. Werner KunzAdjudicators: Prof. Dr. Werner KunzProf. Dr. Barry W. NinhamProf. Dr. Claudia SteinemChair: Prof. Dr. Georg SchmeerPrefaceThisthesisaimsatthecharacterizationofpropyleneglycolmonoalkylethers. Itcom-prises different studies ranging from phase diagram determination to enzymatic ac-tivity. For this reason this thesis was written so that each chapter can be readindependently. Separate bibliographies are given at the end of each chapter. Eachchapter layout follows the usual convention: Abstract, Introduction, Results andDiscussion and Conclusion. The different studies led to publications which arealready published, accepted or submitted, summarized in the following Table. Co-authors on the Ph.D. work in Regensburg are listed. A complete list of publicationsand a list of poster presentations, which were presented at international congresses,are also given at the end.iPrefaceChapter PublicationBauduin, P.; Wattebled, L.; Schroedle, S.; Touraud, D.; Kunz, W. Tem-2 peraturedependenceofindustrialpropyleneglycolalkylether/watermix-tures. Journal of Molecular Liquids 2004 115(1), 23-28.Bauduin, P.; Wattebled, L.; Touraud, D.; Kunz, W.

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Dissertation
Characterization of short
polypropylene glycol monoalkylethers
and design of enzymatic reaction
media
Pierre Bauduin
University of Regensburg
At the Natural Sciences Faculty IV
Chemistry & Pharmacy
Mai 2005
Ph.D. Supervisor: Prof. Dr. Werner Kunz
Adjudicators: Prof. Dr. Werner Kunz
Prof. Dr. Barry W. Ninham
Prof. Dr. Claudia Steinem
Chair: Prof. Dr. Georg SchmeerPreface
Thisthesisaimsatthecharacterizationofpropyleneglycolmonoalkylethers. Itcom-
prises different studies ranging from phase diagram determination to enzymatic ac-
tivity. For this reason this thesis was written so that each chapter can be read
independently. Separate bibliographies are given at the end of each chapter. Each
chapter layout follows the usual convention: Abstract, Introduction, Results and
Discussion and Conclusion. The different studies led to publications which are
already published, accepted or submitted, summarized in the following Table. Co-
authors on the Ph.D. work in Regensburg are listed. A complete list of publications
and a list of poster presentations, which were presented at international congresses,
are also given at the end.
iPreface
Chapter Publication
Bauduin, P.; Wattebled, L.; Schroedle, S.; Touraud, D.; Kunz, W. Tem-
2 peraturedependenceofindustrialpropyleneglycolalkylether/watermix-
tures. Journal of Molecular Liquids 2004 115(1), 23-28.
Bauduin, P.; Wattebled, L.; Touraud, D.; Kunz, W. Hofmeister
ion effects on the phase diagrams of water-propylene glycol propyl
3
ethers. Zeitschrift fuer Physikalische Chemie (Muenchen, Germany)
2004 218(6), 631-641.
Bauduin, P.; Renoncourt, A.; Kopf, A.; Touraud, D.; Kunz, W. Uni-
4 fied concept of solubilization in water by hydrotropes and co-solvents.
Langmuir (Submitted) 2005.
Bauduin, P.; Basse, A.; Touraud, D.; Kunz, W. Effect of short non-ionic
5 amphiphiles derived from ethylene and propylene glycol alkyl ethers on
the CMC of SDS. Colloids and Surfaces A (Accepted) 2004.
Bauduin, P.; Touraud, D., Kunz, W. Design of low-toxic anionic temper-
6 ature sensitive microemulsions using short propyleneglycol alkylethers as
co-surfactants. Langmuir (Submitted) 2005.
Bauduin, P.; Nohmie, F.; Touraud, D.; Neueder, R.; Kunz, W.; Ninham,
B.W. Hofmeister Specific-Ion Effects on Enzyme Activity and buffer pH:
7
Horseradish Peroxidase in citrate buffer. Journal of Molecular Liquids
(Accepted) 2005.
Bauduin, P.; Renoncourt, A.; Touraud, D.; Kunz, W.; Ninham, B. W.
7 Hofmeistereffectonenzymaticcatalysisandcolloidalstructures. Current
Opinion in Colloid and Interface Science 2004 9(1,2), 43-47.
Bauduin, P.; Touraud, D.; Kunz, W.; Ninham, B.W. The influence of
8 structure and composition of a reverse SDS microemulsion on enzymatic
activities. Journal of Colloid Interface Science (Submitted) 2005.
iiAcknowledgements
ThepresentworktookplacebetweenOctober2002andMay2005attheDepartment
of Physical Chemistry for Natural Sciences at the University of Regensburg under
the leadership of Prof. Dr. Werner Kunz.
First and foremost, I would like to thank Prof. Dr. Werner Kunz not only for
giving me the opportunity to do my Ph.D. in his lab but also for his unstinting
support in countless ways both privately and professionnally.
I would also like to thank Prof. Dr. Barry W. Ninham with whom I had the
privilege to work during his stay in Regensburg. His kindness and his innovative
way of seeing Science were of great help for me.
Thanks to Prof. Dr. Jean-Marie Aubry for accepting me in his lab in May
2004, within the framework of an exchange between his laboratory in Lille and the
laboratory of Regensburg, and for the always fruitful scientific discussions we had
during this time and before that.
I would like to thank all my research group-colleagues, for whom a single page
of thanks would not suffice, for their kindness and technical support down these
years. Special thanks to Didier Touraud for his constant support and his unique
and unconventional way of approaching the Science.
Morepersonally, Iwouldliketothank: AndreasG.whobecameatruefrienddur-
ing these last three years and tried to teach me the nice bavarian dialect (I´m afraid
he did not succeed well but anyway...), Sigrid whose friendship and constant cheer-
1fulness contributed to my well-being in the lab , Alina, Astrid, Cristina, Andreas
K., Chamsoudine, Nicolas and John for their friendship.
Of course I would like to thank my family not only for putting me on earth, but
also for coming to my assistance whenever I needed it. Without them I would never
have become what I am today.
Last but not least I want to particularly offer my heartfelt thanks to Audrey
Renoncourt for her unvaluable support in the lab and in the every-day life.
1Sigrid: thank you so much for importing these delicious Dutch honey waffles in Bavaria and for
bringing them into our lives!
iiiAcknowledgements
ivContents
Preface i
Acknowledgements iii
Introduction 7
1 Overview of “glycol ethers” and of their industrial applications 9
1.1 Glycol ethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.2 Health effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.3 Structures and properties of propylene glycol alkyl ethers (C PO ) . 14n m
1.3.1 Structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.3.2 Synthesis and isomer compositions . . . . . . . . . . . . . . . 14
1.3.3 Physical properties and comparisons to other solvents . . . . . 15
1.4 Propylene glycol alkyl ethers (C PO ): efficient and low toxic indus-n m
trial solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1.4.1 Deinking of cables . . . . . . . . . . . . . . . . . . . . . . . . 17
1.4.2 Degreasing of metal plates . . . . . . . . . . . . . . . . . . . . 21
Bibliography 29
I Properties and characterization of C PO /water mixtures 31n m
2 Temperaturedependenceofpropyleneglycolalkylether/watermixtures 33
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.2 Materials and Methods . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.2.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.2.2 Phase diagram determination . . . . . . . . . . . . . . . . . . 35
2.2.3 Surface tension measurements . . . . . . . . . . . . . . . . . . 36
2.3 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.3.1 Phase diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.3.2 C PO /water system . . . . . . . . . . . . . . . . . . . . . . . 383 1
2.3.3 n-propyl C PO / water phase diagrams . . . . . . . . . . . . 39n m
2.3.4 C PO /water phase diagrams . . . . . . . . . . . . . . . . . . 403 m
2.3.5 C PO /water phase diagrams . . . . . . . . . . . . . . . . . . 404 m
1Contents
2.3.6 ComparisonoftheLCSTvaluesbetweentheC EO sandthen m
C PO s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41n m
2.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
Bibliography 43
3 Hofmeister effects on propylene glycol propyl ethers 47
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
3.2.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
3.2.2 Cloud point determination . . . . . . . . . . . . . . . . . . . . 50
3.3 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.4 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
3.5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
Bibliography 59
4 Unifiedconceptofsolubilizationinwaterbyhydrotropesandco-solvents 63
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
4.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4.2.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4.2.2 Solubilization experiments . . . . . . . . . . . . . . . . . . . . 66
4.3 Modelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
4.4 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . 66
4.4.1 Solubilization curves: comparison between hydrotrope, co-
solvent and surfactant . . . . . . . . . . . . . . . . . . . . . . 66
4.4.2 Aqueous solubilization in the water rich part: the hydrotropic
behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
4.4.3 The ordering of the hydrotropes . . . . . . . . . . . . . . . . . 71
4.4.4 The extent of the hydrophobic part in hydrotrope molecules:
a determining factor in the hydrotropic efficiency . . . . . . . 72
4.5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
Bibliography 77
II Co-surfactant properties of C PO s 81n m
5 Effect of propyleneglycol monoalkylether on the CMC of SDS 83
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
5.2 Materials and Methods . . . . . . . . . . . . . . . . . . . . . . . . . . 84
5.3 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . 86
5.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
Bibliography 95
2Contents
6 Propyleneglycol monoalkylethers as co-surfactants in the design of mi-
croemulsions 97
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
6.2 Experimental Section . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
6.2.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
6.2.2 Phase diagrams determination . . . . . . . . . . . . . . . . . . 99
6.2.3 Phase transitionion by increasing temperature . . 100
6.3 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . 101
6.3.1 C PO as co-surfactant in the formation of microemulsions . 101n m
6.3.2 Temperature dependence of C PO /SDS based systems . . . 103n m
6.3.3 Design of an anionic monophasic temperature sensitive mi-
croemulsion using C PO as co-surfactant . . . . . . . . . . . 1084 3
6.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
Bibliography 113
III Enzymatic activity 119
7 Hofmeister Specific-Ion Effects on Enzyme Activity and Buffer pH 121
7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
7.2 Materials and Methods . . . . . . . . . . . . . . . . . . . . . . . . . . 122
7.2.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
7.2.2 Determination of the ABTS kinetic constants . . . . . . . . . 123
7.3 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
7.3.1 pH variation of a 0.025M citrate buffer with salt concentration 123
7.3.2 K and V as a function of pH . . . . . . . . . . . 125mABTS maxABTS
7.3.3 K and V as a of salt concentration . . 125mABTSTS
7.4 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
7.4.1 Can we trust our pH values? . . . . . . . . . . . . . . . . . . . 126
7.4.2 The catalytic constants K and V . . . . . . . . 128mABTS maxABTS
7.4.3 The catalytic efficiency (V / K ) . . . . . . . . . 128maxABTS mABTS
7.5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
7.6 Appendix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
Bibliography 135
8 Enzymatic activity in reverse SDS microemulsions 137
8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
8.2 Materials and Methods . . . . . . . . . . . . . . . . . . . . . . . . . . 140
8.2.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
8.2.2 Conductivity Experiments . . . . . . . . . . . . . . . . . . . . 140
8.2.3 Preparation of the Reaction Mixtures . . . . . . . . . . . . . . 140
8.2.4 Determination of Enzyme Activity . . . . . . . . . . . . . . . 140
3Contents
8.3 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
8.3.1 Phase diagrams of microemulsions . . . . . . . . . . . . . . . . 142
8.3.2 Conductivity Measurements . . . . . . . . . . . . . . . . . . . 142
8.3.3 Preliminary Enzymatic Tests . . . . . . . . . . . . . . . . . . 146
8.3.4 Dependence of the enzymatic activity on the alcohol carbon
number for various buffer contents. . . . . . . . . . . . . . . . 147
8.4 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
8.4.1 Phase Diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . 148
8.4.2 Conductivity measurements . . . . . . . . . . . . . . . . . . . 150
8.4.3 Preliminary Enzymatic Tests . . . . . . . . . . . . . . . . . . 151
8.4.4 Microemulsions: the dependence of the enzymatic activity on
the number of carbon atoms in the alcohols at different water
contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
8.5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
Bibliography 161
Conclusion 171
List of Figures 173
List of Tables 179
List of Publications 181
List of Poster Presentations in Congress 183
4