ABSTRACT
The electrostatic charge density of particles is of paramount importance for the control of the dispersion stability. Conventional methods use potentiometric, conductometric or turbidity titration but require large amount of samples. Here we report a simple and cost-effective method called polyelectrolyte assisted charge titration spectrometry or PACTS. The technique takes advantage of the propensity of oppositely charged polymers and particles to assemble upon mixing, leading to aggregation or phase separation. The mixed dispersions exhibit a maximum in light scattering as a function of the volumetric ratio X, and the peak position XMax is linked to the particle charge density according to σâ¼D0XMax where D0 is the particle diameter. The PACTS is successfully applied to organic latex, aluminum and silicon oxide particles of positive or negative charge using poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate). The protocol is also optimized with respect to important parameters such as pH and concentration, and to the polyelectrolyte molecular weight. The advantages of the PACTS technique are that it requires minute amounts of sample and that it is suitable to a broad variety of charged nano-objects.
ABSTRACT
Recent studies have pointed out the importance of polyelectrolyte assembly in the elaboration of innovative nanomaterials. Beyond their structures, many important questions on the thermodynamics of association remain unanswered. Here, we investigate the complexation between poly(diallyldimethylammonium chloride) (PDADMAC) and poly(sodium acrylate) (PANa) chains using a combination of three techniques: isothermal titration calorimetry (ITC), static and dynamic light scattering and electrophoresis. Upon addition of PDADMAC to PANa or vice-versa, the results obtained by the different techniques agree well with each other, and reveal a two-step process. The primary process is the formation of highly charged polyelectrolyte complexes of size 100 nm. The secondary process is the transition towards a coacervate phase made of rich and poor polymer droplets. The binding isotherms measured are accounted for using a phenomenological model that provides the thermodynamic parameters for each reaction. Small positive enthalpies and large positive entropies consistent with a counterion release scenario are found throughout this study. Furthermore, this work stresses the importance of the underestimated formulation pathway or mixing order in polyelectrolyte complexation.
ABSTRACT
When dispersed in biological fluids, engineered nanoparticles are selectively coated with proteins, resulting in the formation of a protein corona. It is suggested that the protein corona is critical in regulating the conditions of entry into the cytoplasm of living cells. Recent reports describe this phenomenon as ubiquitous and independent of the nature of the particle. For nanomedicine applications, however, there is a need to design advanced and cost-effective coatings that are resistant to protein adsorption and that increase the biodistribution in vivo. In this study, phosphonic acid poly(ethylene glycol) copolymers were synthesized and used to coat iron oxide particles. The copolymer composition was optimized to provide simple and scalable protocols as well as long-term stability in culture media. It is shown that polymers with multiple phosphonic acid functionalities and PEG chains outperform other types of coating, including ligands, polyelectrolytes, and carboxylic acid functionalized PEG. PEGylated particles exhibit moreover exceptional low cellular uptake, of the order of 100 femtograms of iron per cell. The present approach demonstrates that the surface chemistry of engineered particles is a key parameter in the interactions with cells. It also opens up new avenues for the efficient functionalization of inorganic surfaces.
