Gold nanoparticles decorated with oligo(ethylene glycol) thiols:enhanced Hofmeister effects in colloid−protein mixtures

Oligo(ethylene glycol) (OEG) thiol self-assembled monolayer (SAM) decorated gold nanoparticles (AuNPs) have potential applications in bionanotechnology due to their unique property of preventing the nonspecific absorption of protein on the colloidal surface. For colloid-protein mixtures, a previous study (Zhang et al. J. Phys. Chem. A 2007, 111, 12229) has shown that the OEG SAM-coated AuNPs become unstable upon addition of proteins (BSA) above a critical concentration, c*. This has been explained as a depletion effect in the two-component system. Adding salt (NaCl) can reduce the value of c*; that is, reduce the stability of the mixture. In the present work, we study the influence of the nature of the added salt on the stability of this two-component colloid-protein system. It is shown that the addition of various salts does not change the stability of either protein or colloid in solution in the experimental conditions of this work, except that sodium sulfate can destabilize the colloidal solutions. In the binary mixtures, however, the stability of colloid-protein mixtures shows significant dependence on the nature of the salt: chaotropic salts (NaSCN, NaClO4, NaNO3, MgCl2) stabilize the system with increasing salt concentration, while kosmotropic salts (NaCl, Na2SO4, NH4Cl) lead to the aggregation of colloids with increasing salt concentration. These observations indicate that the Hofmeister effect can be enhanced in two-component systems; that is, the modification of the colloidal interface by ions changes significantly the effective depletive interaction via proteins. Real time SAXS measurements confirm in all cases that the aggregates are in an amorphous state.

Mass transfer characteristics of two-aqueous-phase liquid-liquid mixtures

Mass transfer rates were studied using the falling drop method. Cibacron Blue 3 GA dye was the transferring solute from the salt phase to the PEG phase. Measurements were undertaken for several concentrations of the dye and the phase-forming solutes and with a range of different drop sizes, e.g. 2.8, 3.0 and 3.7 mm. The dye was observed to be present in the salt phase as finely dispersed solids but a model confirmed that the mass transfer process could still be described by an equation based upon the Whitman two-film model. The overall mass transfer coefficient increased with increasing concentration of the dye. The apparent mass transfer coefficient ranged from 1 x 10-5 to 2 x 10 -4 m/s. Further experiments suggested that mass transfer was enhanced at high concentration by several mechanisms. The dye was found to change the equilibrium composition of the two phases, leading to transfer of salt between the drop and continuous phases. It also lowered the interfacial tension (i.e. from 1.43 x 10-4 N/m for 0.01% w/w dye concentration to 1.07 x 10-4 N/m for 0.2% w/w dye concentration) between the two phases, which could have caused interfacial instabilities (Marangoni effects). The largest drops were deformable, which resulted in a significant increase in the mass transfer rate. Drop size distribution and Sauter mean drop diameter were studied on-line in a 1 litre agitated vessel using a laser diffraction technique. The effects of phase concentration, dispersed phase hold-up and impeller speed were investigated for the salt-PEG system. An increase in agitation speed in the range 300 rpm to 1000 rpm caused a decrease in mean drop diameter, e.g. from 50 m to 15 m. A characteristic bimodal drop size distribution was established within a very short time. An increase in agitation rate caused a shift of the larger drop size peak to a smaller size.