A COMPARATIVE STUDY OF CHAIN DYNAMICS OF DI-AND TRI-BLOCK COPOLYMERS IN SEMIDILUTE SOLUTION IN A NON-SELECTIVE SOLVENT

The chain dynamics of a pair of diblock poly(styrene-b-butadiene) (PS210-b-PB960) and triblock poly(styrene-b-butadiene-b-styrene) (PS200-b-PB1815-b-PS200) copolymers in both dilute and semidilute toluene solutions has been comparatively studied by dynamic laser light scattering. As expected, the mutual diffusion of individual chain changes into a fast cooperative diffusion of the chain segments ('blobs') between two neighboring entanglement points for both the copolymers as the solution changes from dilute to semidilute. Further increases of the concentration lead to a second slow relaxation mode. For the triblock chains, there exists an additional middle relaxation between the fast and the slow modes. The concentration (c) dependent study of the average characteristic decay time of the fast mode ((tau(f))) reveals that 1/(tau(f)) - c(-a) with 0.33 < alpha < 0.44, much smaller than 0.75 predicted or 0.72 observed for linear homopolymer chains in good solvent. It implies that the solvent quality of toluene for PB might not be as good as that for PS. Due to such a difference in solubility, it is reasonable to speculate that the PB and PS blocks are transiently segregated in semidilute solution. The relaxation of these transient PB and PS richer domains leads to the observed slow relaxation. Such a speculation is supported by the appearance of an additional slow relaxation mode in the study of polyisoprene-b-polystyrene-b-polyisoprene in semidilute solution in cyclohexane, a non-selective solvent, in which we alternated the solubility difference by a variation of the solution temperature.

THE ADSORPTION OF LINEAR POLY(N-ISOPROPYLACRYLAMIDE)CHAINS ON SURFACTANT-FREE POLYSTYRENE NANOPARTICLES

The adsorption of linear poly(N-isopropylacrylamide) (PNIPAM) chains on surfactant-free polystyrene (PS) nanoparticles was used as a model system to study the hydrophobic adsorption of polymer on the surface, because the hydrophobility of PNIPAM can be continuously varied by a small temperature change. The adsorption was investigated by a combination of static and dynamic laser light scattering (LLS) measurements. In static LLS, the absolute excess scattered light intensity led to the amount of PNIPAM adsorbed on the surface. In dynamic LLS, the hydrodynamic thickness of the adsorbed PNIPAM layer was accurately measured. For a given particle concentration, the adsorption increases as the PNIPAM concentration and the incubation temperature increase. The average density of the adsorbed PNIPAM layer is reciprocally proportional to the number of the PNIPAM chains on the surface, revealing a simple scaling of the chain density distribution. The adsorption follows the Langmuir's isotherm. The enthalpy change estimated from the adsorption at 25 degrees C and 30 degrees C is slightly positive, indicating that the adsorption involves the coil-to-globule transition of the chains on the surface.

How Does a Polymer Brush Repel Proteins?

The captioned question has been addressed by the steric effect; namely, the adsorption of proteins on a surface grafted with linear polymer chains decreases monotonically as the grafting density increases. However, there is no quantitative and satisfactory explanation why the adsorption starts to increase when the grafting density is sufficiently high and why polyethylene glycol（PEG） still remains as one of the best polymers to repel proteins. After considering each grafted chain as a molecular spring confined inside a ＂tube＂ made of its surrounding grafted chains, we estimated how its free energy depends on the grafting density and chain length, and calculated its thermal energy-agitated chain conformation fluctuation, enabling us to predict an adsorption minimum at a proper grafting density, which agrees well with previous experimental results. We propose that it is such a chain fluctuation that slows down the adsorption kinetically.