Physical Properties of Chromophore Functionalized Gold Nanoparticles [Elektronische Ressource] / Christian Müller. Betreuer: Christoph Lambert

Christian Berner

Informations

• Publié par: julius-maximilians-universitat_wurzburg
• Publié le: 01 janvier 2011
• Nombre de lectures: 24
• Langue: Deutsch
• Poids de l'ouvrage: 4 Mo

Extrait

Physical Properties of Chromophore
Functionalized Gold Nanoparticles



Dissertation zur Erlangung des
naturwissenschaftlichen Doktorgrades
der Bayerischen Julius-Maximilians-Universität Würzburg



vorgelegt von
Christian Müller
aus Kreuztal-Kredenbach
Würzburg 2011

Eingereicht bei der Fakultät für Chemie und Pharmazie am







Gutachter der schriftlichen Arbeit

1. Gutachter:

2. Gutachter:






Prüfer des öffentlichen Promotionskolloquiums

1. Prüfer:

2. Prüfer:

3. Prüfer:






Datum des öffentlichen Promotionskolloquiums








Doktorurkunde ausgehändigt am


Die vorliegende Arbeit wurde in der Zeit von November 2005 bis März 2011 am Institut für
Organische Chemie der Universität Würzburg angefertigt.














































Mein besonderer Dank gilt
Herrn Prof. Dr. Christoph Lambert
für die Vergabe des vielseitigen Themas, die intensive Betreuung und Förderung und das mit
vielen Anregungen und Diskussionen verbundene Interesse an dieser Arbeit.
Contents
Inhalt
1 Introduction ....................................................................................................................... 1
1.1 Structure of Spherically Shaped Gold Nanoparticles .................. 4
1.2 Gold Core Structure ..................................................................................................... 5
1.3 Structure of Thiol-Functionalized Gold Nanoparticles ................ 6
1.3.1 Au (SR) ................................................................................................................... 6 102 44
1.3.2 [NR' ][Au25(SR)18] .................................................................................................... 7 4
1.3.3 Au (SR) .................................................................................................................... 8 38 24
1.3.4 The Superatom Concept ............................... 9
1.4 Absorption Properties of Metal Nanoparticles ........................................................... 10
1.5 Electrochemical Properties of Redox-Center-Functionalized Metal Nanoparticles .. 12
1.6 General Aspects for the Synthesis of Thiol Protected Spherically Shaped
Nanoparticles ............................................................................................................. 15
1.7 Analytical Methods .... 17
2 Optical and Electrochemical Properties of Triarylamine and Perchlorinated
Triarylmethyl Functionalized Gold Nanoparticles ...................................................... 18
2.1 Optical and Electrochemical Properties of Triarylamines-Gold-Nanoparticle
Conjugates: Short π-Conjugated Bridging Unit ......................... 20
2.1.1 Synthesis .................................................................................................................... 20
2.1.2 Analysis ...................... 23
2.1.3 Electrochemical Measurements ................................................................................. 27
2.1.4 UV/vis/NIR Absorption Spectroscopy and Fluorescence-Anisotropy Measurements ..
.................................................................................................................................... 28
2.1.5 Spectroelectrochemistry ............................. 30
2.1.6 Conclusion ................................................................................................................. 33
2.2 Optical and Electrochemical Properties of Triarylamines-Gold-Nanoparticle
Conjugates: Varying the Bridging Unit ............ 34
2.2.1 Synthesis .................................................................................................................... 35
2.2.2 Analysis ...................... 39
2.2.3 Electrochemistry ...................................................................................................... 44
2.2.4 UV/vis/NIR Absorption Spectroscopy ....... 51
2.2.5 Spectroelectrochemistry ............................................................................................. 55
2.2.6 Conclusions ................................................ 58
2.3 Optical and Electrochemical Properties of Perchlorinated Triarylmethyl Radical-
Functionalized Gold Nanoparticle Systems ............................................................... 60
2.3.1 Introduction ................................................................................................................ 60
2.3.2 Synthesis .................... 61
2.3.3 Analysis ...................................................................................................................... 62
2.3.4 Electrochemistry ........................................................................................................ 64
2.3.5 UV/vis/NIR Absorption Spectroscopy ....... 65
2.3.6 Spectroelectrochemistry ............................................................................................. 66
2.3.7 Conclusion ................................................. 67
2.4 Synthesis of Au-Tara Systems with Short Bridging Units......................................... 68
2.4.1 Synthesis of Au-Tara5................................................................ 68
2.4.2 Synthesis of Au-Tara6................................ 69
2.4.3 Concluding Remarks .................................................................. 70
3 Raman-Reporter Molecules for SERS Application ..................... 71
3.1 Introduction ................................................................................................................ 71
3.1.1 Drug Delivery Systems .............................. 71
3.1.2 Tuning the Absorption Properties .............. 72
3.1.3 Light Emitting and Scattering Probes ........................................................................ 72
3.1.4 Fluorescent Probes ..................................... 74
3.1.5 Surface Enhanced Raman Spectroscopy (SERS) Probes ........................................... 75
3.2 Synthesis .................................................................................... 78
3.3 SERS-Measurements ................................................................. 83
3.4 Immuno-SERS Microscopy ....................... 84
3.5 Conclusion ................................................................................................................. 86
4 Summary .......................... 87
5 Experimental Section ...................................................................................................... 90
5.1 Analytical Methods .... 90
5.1.1 General Analytical Methods ...................................................................................... 90
5.1.2 NMR Spectroscopy .................................................................................................... 90
5.1.3 Mass Spectroscopy ..................................................................................................... 91
5.1.4 Osteryoung Square Wave Voltammetry and Cyclic Voltammetry ............................ 91
5.1.5 UV/vis/NIR Spectroscopy .......................................................................................... 92
5.1.6 Spectroelectrochemistry ............................. 92
5.1.7 Polarised Steady-State Fluorescence Spectroscopy ................................................... 92
5.1.8 Scanning Transmission Electron Microscopy (STEM) ............. 93
5.1.9 X-ray Photoelectron Spectroscopy (XPS) .................................................................. 93
5.1.10 Thermogravimetric Analysis (TGA) .......... 94
5.1.11 Recycling-GPC .......................................................................................................... 94
5.1.12 IR-Spectroscopy ......... 94
5.2 Synthesis .................................................................................................................... 95
6 Literature ....................... 128
7 Table of Formulas ......... 137
8 Zusammenfassung ......................................................................................................... 140














Abbreviations


APTMS 3-amino-n-propyltrimethoxysilane
CV cyclic voltammetry
DMTCC dimethylthiocarbamoyl chloride
DOSY diffusion ordered NMR Spectroscopy
EDC ethyldimethyl-aminopropylcarbodiimide
GPC gel permeation chromatography
IVCT intervalence charge transfer
LSPR localized surface plasmon resonance
AuNP thiol protected gold nanoparticle
NHS N-hydroxy-succinimide
OSWV Osteryoung square wave voltammetry
PCTM perchlorinated triarylmethyl
PDT photodynamic therapy
QDL quantized double layer
SAH succini