Sequence controlled synthesis of soluble oligo(p-benzamide)s [Elektronische Ressource] / Helga Seyler

Helga Mettetal

Informations

• Publié par: johannes_gutenberg-universitat_mainz
• Publié le: 01 janvier 2009
• Nombre de lectures: 45
• Poids de l'ouvrage: 21 Mo

Extrait

Sequence-Controlled Synthesis of
Soluble Oligo(p-benzamide)s

Dissertation zur Erlangung des Grades
„Doktor der Naturwissenschaften“
im Promotionsfach Chemie



am Fachbereich Chemie, Pharmazie und Geowissenschaften der
Johannes Gutenberg-Universität Mainz









Helga Seyler

geboren in Mar del Plata, Argentinien


Mainz 2009 Dekan:

1. Berichterstatter:
2.

Datum der mündlichen Prüfung: 24.Juni 2009



















Hiermit versichere ich gemäß § 10 Abs. 3d der Promotionsordnung vom 24.07.2007,
dass ich die als Dissertation vorgelegte Arbeit selbst angefertigt und alle benutzten
Hilfsmittel (Literatur, Apparaturen, Material) in der Arbeit angegeben habe.


Danksagung









Contents
Contents

Abreviatons 3
1. Introduction 5
1.1. Supramolecular chemistry and polymers 7
1.2 Foldamers 10
1.3. Rod-like macromolecules 11
1.4. Aromatic amide foldamers 14
1.5. Oligo(p-benzamide)s (OPBAs) 18
1.6. Motivation 20
1.7. References20

2. Rod-Coil Coplymers 25
2.1. Rod-coil copolymers from oligo(p-benzamide) foldamers 27
2.1.1. Introduction 28
2.1.2. Results and discussion 28
2.1.3. Conclusions 34
2.1.4. Experimental section 35
2.1.5. References 42
2.1.6. Supporting information 44

3. Comb-and Rod-like Macromolecules 57
3.1. Tuning oligo(p-benzamide) aggregation via heterosequences 59
3.1.1. Introduction 61
3.1.2. Results and discussion 62
3.1.3. Conclusions 70
3.1.4. Experimental section
3.1.5. References 77
3.1.6. Supporting information 79
3.2. Molecular zippers 85
3.2.1. Introduction 86
3.2.2. Results and discussion
3.2.3. Conclusions 92
3.2.4. Experimental section 93
3.2.5. References 94
3.2.6. Supporting information 96
3.3. Comb-like rod-coil copolymers 101
3.3.1. Introduction 102
3.3.2. Results and discussion 103
3.3.3. Conclusions 110
3.3.4. Experimental section 110
3.3.5. References 113
3.3.6. Supporting information 115

1 Contents

4. Hairy Rod-like Macromolecules 117
4.1. Linear soluble poly(p-benzamide) 119
4.1.1. Introduction 120
4.1.2. Results and discussion 120
4.1.3. Conclusions 125
4.1.4. Experimental section 126
4.1.5. References 133
4.1.6. Supporting information 135
4.2. Hairy rod-coil copolymers 143
4.2.1. Introduction 144
4.2.2. Results and discussion 145
4.2.3. Conclusions 155
4.2.4. Experimental section 156
4.2.5. References 158
4.2.6. Supporting information 161

5. Amphiphilic Rod-like Macromolecules 165
5.1. Janus nanorods 167
5.1.1. Introduction 168
5.1.2. Results and discussion 169
5.1.3. Conclusions 177
5.1.4. Experimental section 178
5.1.5. References 180
5.1.6. Supporting information 182
5.2. A facile synthesis of aramide-peptide amphiphiles 185
5.2.1. Introduction 186
5.2.2. Results and discussion 187
5.2.3. Conclusions 191
5.2.4. Experimental section 191
5.2.5. References 194
5.2.6. Supporting information 196

6. Summary and Outlook 203

Appendix 215
A 217
B 218
C 226

Curriculum Vitae 235

List of Publications 236

2 Abbreviations
Abbreviations
4-NBC 4-nitro benzoic acid chloride
A acceptor
BHT butylhydroxytoluene
CHCA -cyano-4-hydroxycinnamic acid
conc. concentrated
COSY Correlation Spectroscopy
D donor
DBU 1,8-diazabicyclo[5.4.0]undec-7-ene,
DCB dichlorobenzene
DCM dichloromethane
DEPT Distortionless Enhanced Polarization Transfer
DLS Dynamic Light Scattering
DMAc dimethylacetamide
DMB dimethoxybenzyl
DSC Differential Scanning Calorimetry
e.g. exempli gratia, for example
Fmoc fluorenylmethoxycarbonyl
Fs (q,t) amplitude correlation function
FT-IR Fourier Transform Infrared Spectroscopy
GAM general activation method
GM general methode
GPC Gel Permeation Chromathography
HABA 2-(4-hydroxyphenylazo) benzoic acid
HFIP 1,1,1,3,3,3-hexafluoro-2-propanol
HOBT 1-hydroxy benzotriazole
HR hairy rod
JNR Janus nanorod
MALDI-TOF Matrix Assisted Laser Desorption Ionization Time of Flight
M number average molecular weight n
mp melting point
M weight average molecular weight w
NMP N-methyl-2-pyrrolidone
NMR Nuclear Magnetic Resonance
NOE Nuclear Overhauser Effect
NOESY Nuclear Overhauser Effect Spectroscopy
NSO N-sulfinylamino
OPBA oligo(p-benzamide)
PAMBA p-aminomethyl benzoic acid
PBA penta(p5
PDI polydispersity index
PEG polyethylene glycol
q scattering vector
R hydrodynamic radius h
RP-HPLC Reverse Phase High Pressure Chromathography
SPS Solid Phase Synthesis
3 Abbreviations
TBTU 2-(1-H-benzotriazole-1-yl)-1,1,3,3-tetramethyluronium tetrafluoroborate
t-Bu tert.-butyl
TCM trichloromethane
T decomposition temperature D
TEG triethylene glycol
TFA trifluoroacetic acid
TGA Thermogravimetric Analysis
THF tetrahydrofurane
TLC Thin Layer Chromathography
TPP triphenylphosphite
VT-NMR Variable Temperature Nuclear Magnetic Resonance spectroscopy


4


Chapter 1

Introduction