Search results for "Light"

Composition-dependent Flory-Huggins parameters: molecular weight influences at high concentrations

1995

Flory-Huggins interaction parameters X were determined by means of equilibrium vapor pressures (measured via a combination of a head-space sampler with a gas chromatograph) and light scattering as a function of composition and temperature for the systems cyclohexanone/polystyrene [CHO/PS] and cyclohexanone/poly(butyl methacrylate) [CHO/PBMA]. The investigation of molecular weight influences on X with the system CHO/PBMA demonstrates that they persist almost up to the pure polymer. In order to rationalize this result, it is postulated (in accord with experimental findings and theoretical predictions) that the dimensions of polymer chains may vary upon the addition of solvent even in highly c…

Kinetics of Complex Formation between DNA and Cationically Charged Cylindrical Brush Polymers Observed by Stopped Flow Light Scattering

2009

The complex formation of pUC19 DNA and a cylindrical brush polymer with quaternized poly(vinyl pyridinium) side chains is investigated by stopped flow light scattering (LS). In highly dilute solutions up to two kinetic processes are observable, depending on the mole fraction of anionic charges, x(anion) . For x(anion)  0.4-0.5 only one kinetic process was identified leading to the largest complexes at x(anion)  = 0.4 well below charge stoichiometry. For 0.2 < x(anion)  < 0.4 two kinetic growth processes were identified: The initially formed complexes on the time scale of a few hundred milliseconds keep growing by an unusual fractal growth process until after several minutes they become stab…

Ion-Induced Stretching of Low Generation Dendronized Polymers with Crown Ether Branching Units

2009

Synthesis of the first (G1) and second generation (G2) dendronized macromonomers MG1 and MG2 with the dibenzo-24-crown-8 moiety as branching unit is reported. The corresponding dendronized polymers, the polymethacrylates PG1 and PG2, were synthesized by free radical polymerization using AIBN as initiator at 60−80 °C. Static and dynamic light scattering revealed a significant chain expansion upon complexation of these polymers’ crown ether side chains with K+ ions. It is concluded that electrostatic repulsion does not significantly contribute to the chain expansion because of excessive counterion binding even well below the Manning limit, as evidenced by 19F NMR and 1H−19F NOE experiments. R…

1982

The molecular weight distribution (MWD) of a high polymer is calculated from a weakly perturbed Zimm-plot of the classical light scattering on dilute solutions of Gaussian polymer coils (theta state). A typical Zimm-plot is simulated corresponding to the measurements of high accuracy as would be obtained by using the laser photometer described by Hack and Meyerhoff. The accuracy as published by these authors for small dissymmetries is used. Two inversion procedures are described in detail and tested, both of them avoiding the use of an empirical formula for the Laplace image of the calculated MWD. A complete numerical analysis of the results is given. The results are compared with those of …

A Unified Theory of Liquid-Liquid Demixing and Polymer Formation Kinetics

2009

Sickle hemoglobin is a natural hemoglobin mutation with a hydrophobic replacement of a charged aminoacid on the molecular surface. This leads to aggregation into rigid helical structures (“polymerization”), the underlying cause of sickle cell disease. It has also been shown that polymerization occurs in close correspondence with the phase transition of liquid-liquid demixing , or with the critically diverging fluctuations of local concentration occurring in its proximity. Due to this correspondence, polymerization kinetics remarkably appear to exhibit, with respect to demixing temperature, the same universal scaling features shown by amplitudes and lifetimes of fluctuations occurring in pro…

Development of core-shell colloids to study self-diffusion in highly concentrated dispersions

2007

To study single particle motion in highly concentrated colloidal dispersions, a host-tracer colloid system was developed, consisting of crosslinked polymer micronetwork spheres placed in a good solvent. The host colloid is made invisible to the experimental probe by matching its refractive index to that of the solvent. For the tracer particles a core-shell structure was chosen to ensure the interaction potential to be identical to that of the host particles. Therefore the shell was made of the same polymer as the host. The core differs in refractive index from the solvent and is therefore visible due to scattered light.

Influence of gamma-irradiation on thermally-induced mesoscopic gelation of degalactosylated xyloglucans

2014

Thermoresponsive degalactosylated xyloglucans have been already proposed as in situ gelling scaffolds for tissue engineering, due to their reversible macroscopic thermal gelation at body temperature and biodegradability. The highly branched, hydroxyl group-rich molecular structure renders xyloglucans interesting raw materials also in the form of micro/nanoparticles for application as nanoscalar drug delivery devices in cosmetic and pharmaceutical formulations. Owing to their natural source, xyloglucans show high average molecular weight, broad molecular weight distribution and poor water solubility, as large and compact aggregates usually form via inter-molecular hydrogen bonding. Co-60 gam…

Applications of “Forced Rayleigh Scattering” and “Photon Correlation Spectroscopy” for the examination of transport properties in polymer melts

2007

The importance of optical techniques for the characterization of the dynamics in polymers has increased in the last 10 years. This was caused by the rapid development in optics and microelectronics which has made these techniques easily available and extremely precise. However, in case of the examination of transport properties in bulk polymers, new difficulties arise due to the comparably slow dynamics underlying these phenomena. The topic of this paper is a small survey of two optical techniques which can be applied to solve the arising problems and a presentation of some results of our working group concerning slow translational transport processes in polymers. In a first part, the techn…

A friction factor analysis of the coupling between polymer/solvent self- and mutual-diffusion: polystyrene/toluene

1996

The Bearman statistical mechanical theory, which couples the mutual-diffusion and self-diffusion coefficients via friction factors, has been applied to polystyrene/toluene solutions with polystyrene molecular weights of 18 kDa and 900 kDa. Toluene and polystyrene self-diffusion coefficients, obtained from the literature and measured here, along with polystyrene/toluene binary mutual-diffusion coefficients and thermodynamic data, were employed to independently calculate the three friction coefficients (ξ 12 , ξ 11 , and ξ 22 ) required to describe transport within binary solutions. Results reveal that the frequently used geometric mean approximation (GMA) for relating the friction coefficien…

Polymer-induced phase separation in suspensions of bacteria

2010

We study phase separation in suspensions of two unrelated species of rod-like bacteria, Escherichia coli and Sinorhizobium meliloti, induced by the addition of two different anionic polyelectrolytes, sodium polystyrene sulfonate or succinoglycan, the former being synthetic and the latter of natural origin. Comparison with the known behaviour of synthetic colloid-polymer mixtures and with simulations show that "depletion" (or, equivalently, "macromolecular crowding") is the dominant mechanism: exclusion of the non-adsorbing polymer from the region between two neighbouring bacteria creates an unbalanced osmotic force pushing them together. The implications of our results for understanding phe…