Semicarbazide organogels containing inorganic nanoparticles [Elektronische Ressource] : new supramer particle hybrid systems / vorgelegt von Yvonne Maria Laurentia Noppeney

Semicarbazide Organogels Containing Inorganic Nanoparticles

New Supramer Hybrid Systems





Von der Fakultät für Mathematik, Informatik und Naturwissenschaften der
RWTH Aachen University zur Erlangung des akademischen Grades einer
Doktorin der Naturwissenschaften genehmigte Dissertation



vorgelegt von

Diplom-Gymnasiallehrerin

Yvonne Maria Laurentia Noppeney

aus Aachen



Berichter: Universitätsprofessor Dr. rer. nat. Martin Möller
Universitätsprofessor Dr. rer. nat. Uwe Beginn

Tag der mündlichen Prüfung: 20.05.2009




Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verfügbar.
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Contents


Chapter 1

1. Introduction ........................................................................................................................ 7

Chapter 2 ................................................................................................................................... 9

2. Literature Survey ................................................................................................................ 9
2.1. Supramolecular Organogels ........................................................................................ 9
2.1.1. The Gelation Process .......................................................................................... 12
2.1.2. The Gel State ...................................................................................................... 13
2.1.3. Classification of Gels ......................................................................................... 14
2.1.4. Gel Preparation ................................................................................................... 17
2.1.5. Methods for Gel Investigation ............................................................................ 18
2.1.6. Characterisation of the Organogels .................................................................... 30
2.1.7. Gelation in (Pseudo)-Binary Solutions .............................................................. 32
2.1.8. The Beginning of the Organogel Research and Early Applications .................. 35
2.1.9. Recent and Potential Applications for New Functional Gelling Agents ............ 38
2.2. Metal Nanoparticles ................................................................................................... 41
2.2.1. Fabrication of Nanoparticles .............................................................................. 42
2.2.2. Stabilisation of Gold Nanoparticles ................................................................... 45
2.2.3. The Surface Plasmon Band ................................................................................ 47
2.2.4. Preparing Gold Particles on Templates .............................................................. 48
2.2.5. Application of Gold Nanoparticles Towards Biology, Catalysis and
Nanotechnology ................................................................................................. 49
2.3. Literature ................................................................................................................... 53

Chapter 3 ................................................................................................................................. 67

3. Synthesis ........................................................................................................................... 67
3.1. Introduction ............................................................................................................... 67
3.2. Experimental Section ................................................................................................. 67
3.2.1. Equipment .......................................................................................................... 67
3.2.2. Material .............................................................................................................. 68
3.3. Synthesis of Non-Functional Semicarbazide Organogelators ................................... 69
3.3.1. Synthesis of Bis-[3,4,5-tris(octyloxy)benzoyl]semicarbazide (3) ...................... 69
3.3.2. Synthesis of Bis-[3,4,5-tris(decyloxy)benzoyl]semicarbazide (6) ..................... 71
3.3.3. Synthesis of Bis-[3,4,5-tris(dodeyloxy)benzoyl]semicarbazide (9) ................... 73
3.3.4. Synthesis of 3,4,5-tris(dodecyloxy)benzoylmono-semicarbazide (14) .............. 75
3.3.5. Synthesis of Bis-[3,4,5-tris(octyloxy)benzoyl]diphenylene methylene-4,4’-
diisocyanate (15) ................................................................................................ 76
3.4. Synthesis of Functional Semicarbazide Organogelators ........................................... 77
3.4.1. Synthesis of Bis-[3,4,5-tris(undecenyloxy)benzoyl]semicarbazide (13) ........... 77
3.4.2. Synthesis of Bis-[3,4,5-tris(undecenyloxy)benzoyl]- ........................................ 79
diphenylene methylene-4,4’-diisocyanate (16) .................................................. 79
3.4.3. Synthesis of Bis-[3,4,5-tris(11-mercaptoundeyloxy)benzoyl]-
semicarbazide (19) ............................................................................................. 80

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3.4.4. Synthesis of Bis-[3,4,5-tris(11-hydroxyundecyloxy)benzoyl]-
semicarbizide (22) .............................................................................................. 83
3.4.5. Synthesis of 3,4,5-tris(11-mercaptoundeyloxy)benzoyl-
monosemicarbazide (23) .................................................................................... 85
3.5. Results and Discussion .............................................................................................. 86
3.5.1. Non-Functionalised Semicarbazide Organogelators .......................................... 86
3.5.2. Functionalised Semicarbazide Organogelators .................................................. 97
3.6. Thermal Transitions ................................................................................................. 109

Chapter 4 ............................................................................................................................... 123

4. Supramolecular Organogelators ..................................................................................... 123
4.1. Introduction ............................................................................................................. 123
4.2. Experimental Section ............................................................................................... 124
4.2.1. Equipment ........................................................................................................ 124
4.2.2. Material ............................................................................................................ 125
4.2.3. Techniques ....................................................................................................... 125
4.3. Results and Discussion ............................................................................................ 129
4.3.1. Gelation Tests ................................................................................................... 129
4.3.2. DSC .................................................................................................................. 134
4.3.3. Dropping Ball Method ..................................................................................... 138
4.3.4. Rheological Characterisation of the Organogels .............................................. 142
4.3.5 Gel Morphology ............................................................................................... 152
4.4 Literature ................................................................................................................. 170

Chapter 5 ............................................................................................................................... 171

5. In-Situ Mineralisation of Gold Particles in Organogels ................................................. 171
5.1. Introduction ............................................................................................................. 171
5.2. Experimental Section ............................................................................................... 172
5.2.1. Equipment ........................................................................................................ 172
5.2.2. Material ............................................................................................................ 172
5.2.3. Preparation of Tetraoctylammonium Tetrachloroaurate Solution
+ -
(“Au Precursor Solution”, [N(C H ) ] [AuCl ] ) ............................................ 172 8 17 4 4
5.2.4. Method 1 – In-Situ Mineralisation of Gold Particles in Organogels ............... 173
5.2.5. Method 2 – Direct Gelation of the Au Precursor Solution ............................... 173
5.2.6. Method 3 – Reduction of Au-Loaded Toluene Gel Droplets Dispersed
in Water ........................................................................................................... 173
5.3. Results and Disc