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Yes / Diffusion ordered 1H-NMR spectroscopy (DOSY) is a useful, non-destructive technique for analysing polymer hydrodynamic size and intrinsic/solution viscosity. However, to date there has been no investigation of DOSY under variable temperature conditions that allow trends in polymer conformation to be determined. Poly(2-ethyl-2-oxazoline) (P(EtOx)) is a hydrophilic polymer that has the potential to replace poly(ethylene glycol) (PEG) in biomedical applications. Applying DOSY to a series of narrow-distribution P(EtOx) revealed that the apparent hydrodynamic radii scaled with molecular weight as expected. By altering the temperature of the solution the trends in Flory-type exponents were determined, enabling the determination of the power laws related to the coil-globule conformation of linear polymers directly from NMR data. These measurements were complicated by the onset of convection currents at higher temperatures, which impose a limit to the effective measurement range of ca. 10–35 °C. It was revealed that P(EtOx) had a more expanded random coil conformation than PEG, and it trended towards θ conditions at the lower critical solution temperature. In comparison, PEG was approximately in θ-conditions at room-temperature. This shows the use, and limitations of DOSY in polymer conformation analysis, and applies it to P(EtOx), a polymer which has not been analysed in this manner before. / University of Ghent (Grant Number: RM1602-1695)

In dieser Arbeit wurden auf Substratoberflächen adsorbierte Polymermoleküle mit Rasterkraftmikroskopie (RKM) untersucht. Dabei war die Form der Moleküle (Konformation) von besonderem Interesse. Sie ist von zentralerer Bedeutung in der Polymerphysik und wird üblicherweise in Lösung und mit Streumethoden untersucht. Polymerkonformationen auf Oberflächen sind heutzutage noch wenig untersucht. Üblicherweise wird das Verhalten nach dem so genannten Wormlike-Chain Modell angenommen. Es basiert auf der Annahme, dass die Kettenbiegung nur aus thermischen Fluktuationen resultiert, so dass sich die Kettenform durch statistische Mechanik beschreiben lässt. Es wurden für verschiedene Modellsystem einzelne Moleküle hochaufgelöst abgebildet und die Konformation aus den Bildern bestimmt. Es hat sich gezeigt, dass die idealisierte Vorstellung des Wormlike-Chain Modells tatsächlich nur für wenige der untersuchten Systeme erfüllt ist. Abweichende Konformationen sind oft auffallend regelmäßig: entweder sinusartig mäandrierte oder spiralförmig gedrehte. Beide Charakteristika lassen sich aus dem Prozess der Adsorption erklären, was zeigt, dass die Moleküle auf dem Substrat immobil sind, so dass eine thermische Relaxation der Konformation verhindert ist. Konformtionen lassen sich mit RKM nicht nur beobachten, sondern auch gezielt verändern (Nanomanipulation). Für dendronisierte Polymere konnte so gezeigt werden, dass es einen glasartigen Zustand für das einzelne Molekül gibt. In diesem Zustand verhält sich das Molekül nicht mehr wie eine bewegliche Kette, sondern formstabil, ähnlich einem makroskopischen festen Körper. / In this work single polymer molecules adsorbed onto substrate surfaces were investigated by scanning force microscopy (SFM). The focus was on the shape (conformation) of the molecules, which is of central importance in polymer physics. It is commonly investigated in solutions and with scattering methods. Conformations on surfaces are only little investigated thus far. Often a behavior according to the so-called worm-like chain model is assumed. It is based on the assumption that chain bending results entirely from thermal fluctuations so that the overall chain shape can be described by statistical mechanics. For several model systems single molecules were imaged and the conformation was determined from the images. It was found that the idealistic wormlike chain behavior is only valid for a few systems. Deviations are often remarkable regular: either sine-like undulated or spiral wound. Both characteristics can be explained from the process of adsorption, indicating that molecules are immobile on the substrate so that thermal relaxation is inhibited. Conformations can not only be imaged using the SFM, but also changed in a defined way (nanomanipulation). Manipulation experiments with dendronized polymers the existence of a glassy state for the single polymer. In this state the molecule no longer behaves as a flexible chain but remains its shape, similar to a macroscopic solid body.

The use of polymers as flocculating additives is a common practice in many manufacturing environments. However, exactly how these polymers interact with surfaces is relatively unknown. One specific topic which is thought to be very important to flocculation is an adsorbed polymer's conformation. Substantial amounts of previous work, mainly using simulations, have been performed to elucidate the theory surrounding adsorbed polymer conformations. Yet, there is little experimental work which directly verifies current theory. In order to optimize the use of polymer flocculants in industrial applications, a better understanding of an adsorbed polymer's conformation on a surface beyond theoretical simulations is necessary. This work looks specifically at site blocking, which has a broad impact on flocculation, adsorption, and surface modification, and investigated its effects on the resulting adsorbed polymer conformation. Experimental methods which would allow direct determination of adsorbed polymer conformational details and be comparable with previous experimental results were first determined or developed. Characterization of an adsorbed polymer's conformation was then evaluated using dynamic light scattering, a currently accepted experimental technique to examine this. This commonly used technique was performed to allow the comparison of this works results with past literature. Next, a new technique using atomic force microscopy was developed, building on previous experimental techniques, to allow the direct determination of an adsorbed polymer's loop lengths. This method also was able to quantify changes in the length of adsorbed polymer tails. Finally, mesoscopic simulation was attempted using dissipative particle dynamics. In order to determine more information about an adsorbed polymer's conformation, three different environmental factors were analyzed: an adsorbed polymer on a surface in water, an adsorbed polymer on a surface in aqueous solutions of varying ionic strength, and an adsorbed polymer on a surface functionalized with site blocking additives. This work investigated these scenarios using a low charge density high molecular weight cationic polyacrylamide. Three different substrates, for polymer adsorption were analyzed: mica, anionic latex, and glass. It was determined that, similar to previous studies, the adsorbed polymer layer thickness in water is relatively small even for high molecular weight polymers, on the order of tens of nanometers. The loop length distribution of a single polymer, experimentally verified for the first time, revealed a broad span of loop lengths as high as 1.5 microns. However, the bulk of the distribution was found between 40 and 260 nanometers. For the first time, previous theoretical predictions regarding the salt effect on adsorbed polymer conformation were confirmed experimentally. It was determined that the adsorbed polymer layer thickness expanded with increasing ionic strength of the solvent. Using atomic force microscopy, it was determined that the adsorbed polymer loop lengths and tail lengths increased with increasing ionic strength, supporting the results found using dynamic light scattering. The effect of the addition of site blocking additives on a single polymer's conformation was investigated for the first time. It was determined that the addition of site blocking additives caused strikingly similar results as the addition of salt to the medium. The changes in an adsorbed polymer's loop lengths was found to be inconsistent and minimal. However, the changes in an adsorbed polymer's free tail length was found to increase with increasing site blocking additive levels. These results were obtained using either PDADMAC or cationic nanosilica as site blocking additives.