Translational, orientational and spectral dynamics of individual molecules in nano-structured materials studied with single molecule spectroscopy [Elektronische Ressource] / Christian Hellriegel

Christian Hellriegel

Informations

• Publié par: ludwig-maximilians-universitat_munchen
• Publié le: 01 janvier 2005
• Nombre de lectures: 10
• Langue: English
• Poids de l'ouvrage: 4 Mo

Extrait

Dissertation zur Erlangung des Doktorgrades
der Fakultät für Chemie und Pharmazie
der Ludwig-Maximilians-Universität München





TRANSLATIONAL, ORIENTATIONAL AND SPECTRAL DYNAMICS
OF INDIVIDUAL MOLECULES IN NANO-STRUCTURED MATERIALS
STUDIED WITH SINGLE-MOLECULE-SPECTROSCOPY





Christian Hellriegel

aus

São Paulo, Brasilien




2005



Erklärung

Diese Dissertation wurde im Sinne von §13 Abs. 3 bzw. 4 der Promotionsordung vom 29.
Januar 1998 von Prof. Dr. Christoph Bräuchle betreut

Ehrenwörtliche Versicherung

Diese Dissertation wurde selbstständig, ohne unerlaubte Hilfe erarbeitet.


München, den 30.Juni 2005



(Unterschrift)



Dissertation eingereicht am: 1.7.2005
1. Gutachter: Prof. Dr. Christoph Bräuchle
2. Gutachter:Prof. Dr. Thomas Bein
Mündliche Prüfung am:25.7.2005










Index

1. Introduction 10

2. Theoretical Background 14
2.1. Host-Guest Materials 15
2.2. Fluorescence and SMS 28
2.2.1 Fluorescence 28 2.2.2. Single-Moelcule Spectroscopy 31
2.3. Diffusion 35
2.3.1 Macroscopic 35 2.3.2 Microscopic 7

3. Experimental Section 50
3.1. Microscopy Techniques 51
3.1.1 Confocal Microscopy 53 3.1.2 Widefield Imaging Microscopy 62
3.2. Analysis Programs 66
3.2.1. Evaluation of Diffusion 66 3.2.2. Evaluation of Single Molecule Spectra 79
3.2.3. Evaluation of Orientation Measurements 81 3.2.4. Photostability of Fluorescent Dye Molecules 84

4. Results and Discussion 90
4.1. Characterization of Host-Guest Materials (ensemble) 91
4.2. Photostability of New Dyes for SMS 103
4.3. Orientational Distribution of Oxazine Dyes in AlPO-5 109 4
4.4. Translational Diffusion of TDI in MCM41S Monoliths 114
4.5. Translational Diffusion of 9A1 in Sol-Gel Glass 117
4.6. Translational Diffusion of TDI Molecules in SBA-15 Films 130
4.7. Spectral Behavior of TDI in PMMA 137
4.8. Covalently bound Cy5 in MCM-41 148

5. Summary 158

6. Bibliographical Information 163

7. Appendix 172


1. Introduction

The importance of materials in technology, science and everyday life is self-evident.
Among promising materials for emerging applications (think of smart materials, medical
diagnostics, nanoelectronic devices etc.) are the so-called host-guest materials, where a
molecular species is incorporated as a guest into a solid host. Interesting hosts for the
incorporation of guests (biomolecules, indicators, catalysts, fluorescent dyes, etc.) are, for
example, inorganic micro- and mesoporous materials, which can be thought of as a well-
defined system of nanometer-sized pores.[Davis02], [Wark03]

If such host-guest materials can be seen as a nanometer-sized system of pores in which
the individual guest molecules may move, turn or perform a specific task, then it is of
fundamental importance to observe and to understand the behavior of guest molecules in
such a system.

The characterization of the behavior of fluorescent dye molecules in porous materials is
the central topic of this thesis. The topic is addressed using single-molecule-spectroscopy
(SMS) and microscopy techniques. It will be shown that SMS methods allow for a very
thorough characterization of the behavior of dye molecules in the studied samples.

Since the first observations of individual molecules via fluorescence [Moerner89],
[Orrit90], the SMS technique has developped to become a mature and established
technique that can be used at room-temperature to investigate complex systems, like
polymers, crystals, liquid solutions and biological samples [Basché96], [Nie97], [Xie98],
[Tamarat00], [Rigler01]. Two recent reviews [Moerner02], [Kulzer04] cover the most
recent developments in SMS. Apart from addressing interesting questions in material
science [Gruber97], [Kulzer97], [Deschenes01], [Weston01], [Schuster02], it is clear that
SMS can also be used as a powerful technique to answer biophysical questions
[Rigler90], [Kinosita98], [Weiss99], [Kitamura99], [Seisenberger01].
10