No abstract

A focused library of methacrylate terpolymers was synthesized to explore the effects of varying surface chemistry and adhesive peptide ligands on cell function. The chemical diversity of methacrylate monomers enabled construction of a library of polymers in which one can systematically vary the chemical composition to achieve a wide range of contact angle, Young's modulus, and Tg values. Furthermore, the materials were designed to allow surface immobilization of bioactive peptides. We then examined the effects of these material compositions on protein adsorption and cell attachment, proliferation, and differentiation. We observed that chemical composition of the polymers was an important determinant for NIH 3T3 cell attachment and proliferation, as well as human mesenchymal stem cell differentiation, and correlated directly with the ability of the polymers to adsorb proteins that mediate cell adhesion. Importantly, functionalization of the methacrylate terpolymer library with an adhesive GRGDS peptide normalized cellular responses. RGD-functionalized polymers uniformly exhibited robust attachment, proliferation, and differentiation irrespective of the underlying substrate chemistry. These studies provide a library-based approach to rapidly explore the biological functionality of biomaterials with a wide range of compositions, and highlights the importance of cell and protein cell adhesion in predicting their performance.

The surface properties and biocompatibility of a class of thermoplastic polyurethanes (TPUs) with applications in blood-contacting medical devices have been studied. Thin films of commercial TPUs and novel polyisobutylene (PIB)-poly(tetramethylene oxide) (PTMO) TPUs were characterized by contact angle measurements, X-ray photoelectron spectroscopy, and atomic force microscopy (AFM) imaging. PIB-PTMO TPU surfaces have significantly higher C/N ratios and lower amounts of oxygen than the theoretical bulk composition, which is attributed to surface enrichment of PIB. Greater differences in the C/N ratios were observed with the softer compositions due to their higher relative amounts of PIB. The contact angles were higher on PIB-PTMO TPUs than on commercial polyether TPUs, indicating lower surface energy. AFM imaging showed phase separation and increasing domain sizes with increasing hard segment content. The biocompatibility was investigated by quantifying the adsorption of fouling and passivating proteins, fibrinogen (Fg) and human serum albumin (HSA) respectively, onto thin TPU films spin coated onto the electrode of a quartz crystal microbalance with dissipation monitoring (QCM-D). Competitive adsorption experiments were performed with a mixture of Fg and albumin in physiological ratio followed by binding of GPIIb-IIIa, the platelet receptor ligand that selectively binds to Fg. The QCM-D results indicate similar adsorbed amounts of both Fg and HSA on PIB-PTMO TPUs and commercial TPUs. The strength of the protein interactions with the various TPU surfaces measured with AFM (colloidal probe) was similar among the various TPUs. These results suggest excellent biocompatibility of these novel PIB-PTMO TPUs, similar to that of polyether TPUs.

No abstract

It has often been observed anecdotally and implied through experimentation that acrylic emulsion paintings accumulate and entrain soils over time due to the inherent mechanical softness in artist's acrylic paint films, through the presence of hydrophilic film components, and by virtue of the ubiquitous presence of surfactant moieties on these film surfaces once they dry. In the present study, it has been this last effect that we have sought to describe more fully in terms of surfactant responsiveness to both temperature and relative humidity (RH). Surfactant hydration and dehydration under varying temperature and RH conditions affects the ultimate partitioning of the surfactant at the paint-air interface, as well as the inherent size, aggregation tendencies, and solubility of surfactant in the bulk paint materials which contain components that are highly responsive to changes in temperature and RH (e.g. polyacrylic or polymaleic anhydride-type dispersal materials). In this work, analytical techniques including three-dimensional microscopy and quartz crystal microbalance with dissipation were used to add to and reinforce current understanding of the physical and mechanical changes to acrylic paint films with temperature and RH. The migration of surfactant at the film surface was studied using desorption electrospray ionization-mass spectrometry and attenuated total reflectance Fourier transform infrared microscopy.