Combinatorial approach for development of optical gas sensors [Elektronische Ressource] : concept and application of high-throughput experimentation / vorgelegt von Athanasios Apostolidis

Combinatorial Approach for Development
of Optical Gas Sensors
Concept and Application of High-Throughput
Experimentation


DISSERTATION ZUR ERLANGUNG DES
DOKTORGRADES DER NATURWISSENSCHAFTEN
(DR. RER. NAT.)

DER FAKULTÄT FÜR CHEMIE UND PHARMAZIE
DER UNIVERSITÄT REGENSBURG







vorgelegt von
Athanasios Apostolidis
aus Regensburg
im Juni 2004
Combinatorial Approach for Development
of Optical Gas Sensors
Concept and Application of High-Throughput
Experimentation







Doctoral Thesis
by
Athanasios Apostolidis












Für meine Familie

Diese Doktorarbeit entstand in der Zeit von April 2000 bis Mai 2004 am Institut für
Analytische Chemie, Chemo- und Biosensorik an der Universität Regensburg.

Die Arbeit wurde angeleitet von Prof. Dr. Otto S. Wolfbeis


















Promotionsgesuch eingereicht am: 27.05.2004


Kolloquiumstermin: 21.06.2004

Prüfungsausschuss: Vorsitzender: Prof. Dr. Manfred Liefländer
Erstgutachter: Prof. Dr. Otto S. Wolfbeis
Zweitgutachter: Prof. Dr. Ingo Klimant
Drittprüfer: Prof. Dr. Werner Kunz



Acknowledgements

Above all, I would like to thank Prof. Dr. Otto S. Wolfbeis for providing the fascinating
subject and for the active support during this thesis.

I also gratefully acknowledge the extensive assistance of Prof. Dr. Ingo Klimant, his helpful
ideas, largely contributing to the completion of this thesis, and his open-minded personality
during many discussions on or off matters of chemistry.

I gratefully appreciate financial support of the Robert Bosch GmbH and the German Federal
Ministry of Education and Research within the “KombiSens” project 03C0305A making this
thesis possible.


Furthermore, I would like to thank Gisela Hierlmeier for her technical assistance during our
collaboration and the wonderful personal assistance in any adverseness of everyday life.
I gratefully appreciate the extensive help and friendship of Dr. Damian Andrzejewski
providing the LabView tools making the accomplishment of this thesis possible.
I want to thank Edeltraud Schmid for her friendly assistance in any official or personal
business.

I appreciate the support of Sarina Arain, Claudia Schröder, Bernhard Weidgans, and all other
colleagues of our institute.

I would not like to miss the friendship of Dr. Torsten Mayr and Dr. Gregor Liebsch.

Finally, very special thanks to my wife Patricia and my daughter Sophia for their emotional
support, and to my parents, Thomai and Georgios Apostolidis, for their emotional and
financial support during my whole studies.


Table of Contents

Table of Contents

Chapter 1. Introduction...................................................................... 1
1.1. Combinatorial Chemistry............................................................................1
1.1.1. Concept of Combinatorial Chemistry in Drug Discovery........................................3
1.1.1.1. Combinatorial Synthesis of Organic Libraries .................................................3
1.1.1.2. High-Throughput Characterisation of Organic Combinatorial Libraries........4
1.1.2. Data Handling and Analysis.....................................................................................5
1.1.3. Combinatorial Chemistry in Material Science .........................................................6
1.2. Optical Chemical Gas Sensors....................................................................9
1.2.1. Sensing Schemes of Optical Gas Sensors...............................................................10
1.2.2. Composition of Polymer-Based Optical Chemical Gas Sensors............................11
1.3. Aim of the Thesis ......................................................................................12
1.4. References .................................................................................................12
Chapter 2. Combinatorial Approach to the Development of
Optical Chemical Gas Sensor Materials......................................... 21
2.1. Background ...............................................................................................21
2.2. Concept......................................................................................................22
2.2.1. Library Design........................................................................................................22
2.2.2. Combinatorial Blending .........................................................................................24
2.2.3. High-Throughput Characterisation.........................................................................25
2.2.4. Data Handling.........................................................................................................25
2.3. Experimental Setup for Sensor Preparation and Characterisation............26
2.3.1. Instrumentation for Library Preparation.................................................................27
2.3.2. Setup for Library Characterisation .........................................................................29
2.3.2.1. Measurement Setup .........................................................................................29
2.3.2.2. Gas Mixing Device ..........................................................................................30
I Table of Contents
2.3.2.3. Measurement Control......................................................................................31
2.4. Results and Discussion..............................................................................34
®2.4.1. Validation of the MicroLab S...............................................................................34
2.4.2. Validation of the purpose-built Measurement Setup..............................................39
2.4.2.1. Design of Measurement Cell and Performance of Gas Exchange ..................39
2.4.2.2. Performance of the Optical Measurement Setup.............................................41
2.5. Conclusion.................................................................................................43
2.6. References .................................................................................................44
Chapter 3. Application of High-Throughput Screening in a Study
on Optical Oxygen Sensors .............................................................. 45
3.1. Introduction ...............................................................................................45
3.2. Theoretical Background – Luminescence Quenching-Based Sensing .....46
3.2. Materials and Methods..............................................................................47
3.2.1. Chemicals ...............................................................................................................47
3.2.1.1. Indicator Dyes .................................................................................................47
3.2.1.2. Solvents............................................................................................................49
3.2.1.3. Polymers ..........................................................................................................49
3.2.1.4. Plasticizers ......................................................................................................51
3.2.1.5. Gases ...............................................................................................................51
3.2.2. Preparation of Sensor Materials .............................................................................51
3.2.3. Instrumentation and Measurement .........................................................................52
3.2.3.1. Instrumentation for Blending ..........................................................................52
3.2.3.2. Luminescence Decay Time Measurements......................................................52
3.3. Results and Discussion..............................................................................53
3.3.1. Choice of Materials ................................................................................................53
3.3.2. Library Design........................................................................................................54
3.3.3. Characterisation of the Sensor Materials................................................................55
3.3.3.1. Effect of Polymer on Sensitivity of Oxygen Probes .........................................55
3.3.3.2. Effect of Plasticizer on the Sensor Properties.................................................63
3.4. Conclusion.................................................................................................74
II Table of Contents
3.5. References .................................................................................................75
Chapter 4. Combinatorial Approach to the Development of
Optical CO Gas Sensors.........................................