Während eines Forschungsprojektes tauchen oft Fragen auf, deren Beantwortung den Rahmen der jeweiligen Fragestellung übersteigen würde. Einige werden im Rahmen dieses Ausblicks diskutiert.
In dieser Arbeit wurde die Diffusion von Farbstoffsonden während der radikalischen Polymerisation von Styrol und MMA untersucht. Beide Monomere sind oft verwendete Modellsysteme, nicht zuletzt auf Grund ihrer großen wirtschaftlichen Bedeutung. Es wäre interessant zu untersuchen, in wie weit die beobachteten Heterogenitäten auch in anderen Polymerisationssystemen auftreten. Dafür bieten sich besonders Systeme an, die bekannter Maßen eine starke Selbstbeschleunigung bei der radikalischen Polymerisation zeigen, z.B. Acrylate wie Methylacrylat oder Methacrylate oder auch Vinylacetat. Dabei sollte auch genauer untersucht werden, welchen Einfluss mögliche Kettenverschlaufungen und Löslichkeitsunterschiede auf die Bildung von Heterogenitäten haben.
Bei den eingesetzten Farbstoffen handelte es sich um Perylendiimid-Derivate, welche mit Dendrimer-Seitengruppen der Generation G0 und G3 modifiziert waren. Bei der MMA-Polymerisation wurde aber nur für PDI-G0 eine heterogene Verteilung des Diffusionskoeffizienten beobachtet. Wenn die Diffusion von weiteren Farbstoffderivaten während der MMA-Polymerisation untersucht wird, könnte eventuell geklärt werden in wie weit diese Beobachtung mit der Größe des Farbstoffs zusammenhängt. Dabei ist auch die Diffusion kleinerer Farbstoffe interessant. So
zeigten Fluoreszenzlebenszeit-Untersuchungen während MMA-Polymerisation schon bei einem Umsatz von 10% zwei Komponenten mit unterschiedlich langer Lebenszeit, was als Hinweis auf Bildung von Heterogenitäten gewertet wurde.[228]
Das in Kapitel 5.9.2 beschriebene Nanokomposit-Hydrogel befindet sich nach DLS-Studien an der Konzentrationsgrenze zwischen Sol und Gel. Weitere temperaturabhängige Untersuchungen an Systemen die eindeutig als Sol bzw. Gel einzuordnen sind, könnten klären ob und wie sich das Diffusionsverhalten während des Volumenphasenübergangs in Sol und Gel unterscheidet. Die Konzentration der Proben muss dabei so gewählt werden, dass sich die Diffusion der markierten Tonpartikel in einem für die Einzelmolekülfluoreszenz-Weitfeldmikroskopie geeigneten Bereich befindet. Wird zusätzlich die makroskopische Viskosität, z.B. mit DLS und Scherrheologie analysiert, könnten die Ergebnisse auch im Kontext bereits dazu veröffentlichter Studien beurteilt werden.
Das Diffusionsverhalten einer freien Sonde im Nanokomposit-Hydrogel ist im Hinblick auf einen Vergleich mit chemisch vernetzten, herkömmlichen Polymernetzwerken.
ebenfalls von Interesse. Wie von Wöll et al.[17] bereits gezeigt wurde, ist die Diffusion in solchen Systemen sehr heterogen. In Nanokomposit-Hydrogelen lässt sich die Vernetzerdichte und der Abstand der Verknüpfungspunkte dagegen gezielt steuern.[177]
Die Einzelmolekülfluoreszenz-Weitfeldmikroskopie könnte dazu eingesetzt werden, die Struktur dieses Netzwerks genauer aufzuklären. Denkbar ist z.B. ein Zweifarben-Experiment mit markierten Tonpartikel einerseits und einer freien Farbstoffsonde andererseits. So könnten beide Spezies direkt verglichen werden.
10 Abkürzungsverzeichnis
Chemische Verbindungen
AIBN Azoisobutyronitril
APES Aminopropyldimethylethoxysilan
MMA Methylmethacrylat
PDI Perylendiimid
PE Polyethylen
PMMA Polymethylmethacrylat PNIPAM Poly(N-isopropylacrylamid)
PS Polystyrol
PVA Polyvinylalkohol
Rh6G Rhodamin 6G
SDS Natriumdodecylsulfat
Geräte und Methoden
AFM Rasterkraftmikroskopie (engl.: Atomic Force Microscopy) CCD Charge-coupled device
DSC Dynamische Differenzkalorimetrie (engl.: Differential Scanning Calorimetry)
EM-CCD Electron multiplying CCD
EMWFM Einzelmolekül-Weitfeldmikroskopie ESR Elektronenspinresonanz
FCS Fluoreszenzkorrelationsspektroskopie (engl.: Fluorescence Correlation Spectroscopy)
GPC Größenausschlusschromatographie (engl.: Gel Permeation Chromatography)
NMR Kernspinresonanz (engl.: Nuclear Magnetic Resonance)
TIRF Interne Totalreflexionsfluoreszenz (engl.: Total Internal Reflection Fluorescence)
Sonstige
c Konzentration
c* Überlappkonzentration
D Diffusionskoeffizient
Gew% Gewichtsprozent
I Intensität
kb Boltzmann-Konstante
ki Geschwindigkeitskonstante der Initiierung kp Geschwindigkeitskonstante der Polymerisation kt Geschwindigkeitskonstante der Terminierung Kα Allgemeiner Diffusionskoeffizient
λ Wellenlänge
LCST Untere kritische Lösungstemperatur (engl.: Lower Critical Solution Temperature)
MSD Mittleres Verschiebungsquadrat (engl.: Mean Squared Displacement) Mw Gewichtsmittleres Molekulargewicht
n Brechungsindex
NA Avogadrozahl
NA Numerische Apertur
PSF Optische Transferfunktion (engl.: Point Spread Function) Rel. D Relativer Diffusionskoeffizient
Rg Gyrationsradius
rh Hydrodynamischer Radius
RT Trajektorienradius
SRV Signal-zu-Rausch-Verhältnis
t Zeit
T Temperatur
VPÜ Volumenphasenübergang
α Anomalieparameter
ν Wellenzahl
ξb Segmentgröße
τ Korrelationszeit
Φ Azimutwinkel
χli Anteil langsamer Moleküle
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