Interfacial phenomena often play a key role in the research and development of biomaterials, biomedical devices, pharmaceutical formulations and separation. In that frame, the interaction between proteins and polymer surfaces constitutes an important phenomenon in colloid and materials science, [1][2][3][4][5] where protein sorption is, on the one hand, desired for bioactive applications (e.g., uptake of collagenized implants) and, on the other, should be prevented for bioinert purposes (e.g., clotting on medical devices, membrane fouling) in order to block or delay further bioadhesion cascades.Recently, much theoretical and experimental research, as well as industrial development work, has been focused on electrostatic forces between proteins and charged surfaces. Experimentally, those charged surfaces can be provided by single-polyelectrolyte or polyelectrolyte-brush layers, [6,7] selfassembled monolayers (SAMs) [8,9] with charged end groups and polyelectrolyte multilayers (PEMs). [10,11] This contribution focuses on PEMs and their interactions with a model protein, which has also been extensively studied by Voegel, Schaaf and co-workers, [12][13][14][15][16] Salloum and Schlenoff, [17] Brynda at al., [18] Sukhishvili at al. [19] and Mü ller and co-workers. [20][21][22] Meanwhile it is commonly accepted, that PEM assemblies are well-defined platforms for studying protein sorption due to fundamental aspects, and for generating protein-inert or binding surfaces for several applications like ophthalmic [23] or bone implant related ones. [24] Some concerning questions are still open. One of these questions is dedicated to the location of the protein after its interaction with the PEM system. In that context, certain reports claim migration into the PEM phase [17] and evidence diffusion and embedding to a certain extent in the PEM phase, [13] while other authors claim the interaction of proteins to PEMs to be restricted to the surface. [25] Herein, we would like to give a further contribution to that issue. While in our former work this was already addressed based on PEM systems that were composed of synthetic polyelectrolytes (PELs), [20,22,25,26] herein we report PEM systems that consisted of linear PEL components of natural origin, claimed to be biocompatible. We chose two PEM systems: poly(ethyleneimine)/alginate (PEI/ALG) and chitosan/alginate (CHT/ALG). In situ attenuated-total-reflection Fourier transform infrared (ATR-FTIR) spectroscopy was selected to address both the deposition and the protein interactions related to these PEM systems. An ATR-FTIR-spectroscopy attachment and measurement concept that was introduced by Fringeli [27] was used, which we have applied since the nineties on the characterization of PEM deposition, [20] composition [21] and internal structure, [28] and of the interactions of model polymers and especially PEM films with proteins, peptides and drugs. [20,25,[29][30][31] Experimental
Chemicals and SolutionsSodium alginate (ALG) (460 000 g mol À1 ) was purchased from Kelco (San Diego, ...