Advanced NMR analysis of polymers and biomolecules [Elektronische Ressource] / vorgelegt von Claudiu Melian-Flamand

Cmelian

Sujets

• Naturwissenschaften

Informations

• Publié par: rheinisch-westfalischen_technischen_hochschule_-rwth-_aachen
• Publié le: 01 janvier 2009
• Nombre de lectures: 74
• Langue: Deutsch
• Poids de l'ouvrage: 4 Mo

Extrait

Advanced NMR Analysis of Polymers
and Biomolecules







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


vorgelegt von

Master of Science

Claudiu Melian-Flamand

aus Bistrita, Romania



Berichter: Prof. Dr. Dr. h.c. Bernhard Blümich
Prof. Dr. Dan Eugen Demco


Tag der mündlichen Prüfung: 21. August 2009

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

Contents


Introduction .............................................................................................................................. 1
References .............................................................................................................................. 4


1 Characterization of local dynamics of lecithin by multi-nuclear NMR ..................... 5
1.1 Introduction................................................................................................................5
1.2 Experimental..............................................................................................................6
1.3 Results and discussion..............................................................................................12
131.3.1 C CP-MAS of bulk lecithin .......................................................................... 12
13 11.3.2 C - H WISE of bulk lecithin......................................................................... 13
13 11.3.3 C - H REDOR of bulk lecithin..................................................................... 14
131.3.4 C T in bulk lecithin .................................................................................... 16 1 ρ
311.3.5 P spectra of bulk lecithin ............................................................................... 18
1291.3.6 Thermally polarized and hyperpolarized Xe ...............................................19
1.4 Conclusions..............................................................................................................21
1.5 References................................................................................................................21


2 Morphology and motional heterogeneity in styrene - methyl methacrylate diblock
1 13copolymer by H and C solid-state NMR ................................................................. 23
2.1 Introduction23
2.2 Experimental............................................................................................................25
2.3 Results and discussion..............................................................................................27
2.3.1 Second van Vleck moments by DQ build-up curves. ......................................
12.3.2 Domain sizes by H spin-diffusion with a DQ dipolar filter............................ 28
132.3.3 C longitudinal magnetization relaxation in the rotating frame...................... 34
2.4 Conclusions..............................................................................................................37
2.5 References................................................................................................................38


3 Site-selective segmental dynamics by stimulated echo decay under rotor-
synchronized MAS. Application to elastomers........................................................... 41
3.1 Introduction41
3.2 Experimental............................................................................................................42
3.3 Theory...................................................................................................................... 43
3.3.1 Spin-system model...........................................................................................43
3.3.2 Spin-pair residual dipolar Hamiltonian............................................................ 44
3.3.3 Total spin Hamiltonian..................................................................................... 46
3.4 Results and discussion..............................................................................................47
3.4.1 Proton MAS spectra .........................................................................................
3.4.2 Proton NOESY spectra 48
3.4.3 ROSY-SED......................................................................................................49
3.5 Conclusions..............................................................................................................53
3.6 References................................................................................................................54
II
4 Morphology and properties of injection molded isotactic polypropylene / silica
nanocomposites prepared via in situ sol-gel technology ............................................ 57
4.1 Introduction..............................................................................................................57
4.2 Experimental............................................................................................................59
4.2.1 Samples
4.2.2 Characterization methods.................................................................................61
4.3 Results and discussion..............................................................................................63
4.3.1 Characterization of “one-pot” synthesized PEOS............................................
4.3.2 Polypropylene / silica nanocomposites ............................................................ 68
In-situ sol-gel conversion of liquid PAOS to solid silica ........................... 68
1Phase composition and chain dynamics by H NMR ................................. 71
Double-quantum dipolar filter ................................................................... 72
Proton residual second van Vleck moments............................................... 74
Proton spin-diffusivities ............................................................................. 75
The effect of silica particles on the domain thickness of iPP/SiO 2
composites. ................................................................................................. 77
Dynamic heterogeneity of iPP/SiO composite at interface....................... 79 2
Small-angle X-ray scattering (SAXS) measurements................................. 80
Differential scanning calorimetry measurements ...................................... 81
Thermogravimetric analysis (TGA) ........................................................... 83
Mechanical tests......................................................................................... 83
4.4 Conclusions..............................................................................................................84
4.5 References................................................................................................................85


1 13 1295 Morphology and chain dynamics of UHMWPE by H, C and Xe NMR
spectroscopy and relaxometry...................................................................................... 89
5.1 Introduction89
5.2 Experimental............................................................................................................91
5.3 Results and discussion..............................................................................................95
15.3.1 Phase composition and chain dynamics by H NMR.......................................
5.3.2 Chain ordering and packing by van Vleck moments ..................................... 103
® 15.3.3 Domain sizes of drawn Dyneema fibers by H spin-diffusion NMR........... 104
15.3.4 Chain orientation by H solid-state NMR ...................................................... 109
135.3.5 CP-MAS C NMR spectra............................................................................. 112
13 15.3.6 Mobility characterization by C- H WISE NMR.......................................... 116
13 ®5.3.7 C T filtered spectra of partially oriented Dyneema fibres ..................... 117 1,C
135.3.8 Mobility Characterization by C Chemical Shift Anisotropy....................... 120
1295.3.9 Voids size by thermally polarized Xe NMR ............................................ 123
5.4 Conclusions............................................................................................................127
5.5 References..............................................................................................................129


1 1296 Ultrafast H and hyperpolarized Xe multidimensional NMR spectroscopy...... 133
6.1 Introduction133
6.2 Experimental..........................................................................................................136
6.3 Ultrafast 2D proton NMR spectroscopy................................................................. 140
1296.4 Hyperpolarized Xe 2D NMR spectroscopy of porous polymers ....................... 149
6.5 Conclusions154
6.6 References..........................................................................................