Surface treatment of polymeric solids without impairing their bulk properties is a crucial functionalization strategy for the promotion of their wider application. We here propose a facile method using a nonsolvent which can subtly alter or swell the polymer surface to be modified. A thin film of poly(methyl methacrylate) (PMMA) was immersed in a methanol solution of poly(2methoxyethyl acrylate) (PMEA). Electron spectroscopy for chemical analysis and neutron reflectometry revealed that a PMEA layer formed on the PMMA film with a diffused interface. The PMEA layer was very swollen in water and exhibited the ability to suppress serum protein adsorption and platelet adhesion on it. The functionalization technique using a nonsolvent was also applicable to the surface of other polymeric solids such as polyurethane.
The polymer dynamics at the water interface play a crucial role in the manifestation of biorelated functions. One of the strategies for this is to form inclusion complexes of polymer chains with cyclic compounds. However, such an idea has been limited to bulk materials so far. Here we propose a preparation pathway for a polyrotaxane structure composed of poly(ethylene oxide) (PEO) and α-cyclodextrin (CD) at the outermost surface of a glassy poly(methyl methacrylate) film on the basis of the combination of a click reaction and the Langmuir-Blodgett method. The chain motion of PEO at the water interface could be regulated by threading of CD molecules on PEO and thereby the biological responses such as protein adsorption and platelet adhesion altered depending on the extent of complexation.
Surface modification without changing the physical properties in the bulk is of pivotal importance for the development of polymers as devices. We recently proposed a simple surface functionalization method for polymer films by partial swelling using a nonsolvent and demonstrated the incorporation of poly(2-methoxyethyl acrylate) (PMEA), which has an excellent antibiofouling ability, only into the outermost region of a poly(methyl methacrylate) (PMMA) film. We here extend this technology to another versatile polymer, polystyrene (PS). In this case, PS and PMEA have different solubility parameters making it difficult to select a suitable solvent, which is a nonsolvent for PS and a good solvent for PMEA, unlike the combination of PMMA with PMEA. Thus, such a solvent was first sought by examining the swelling behavior of PS films in contact with various alcohols. Once a mixed solvent of methanol/1-butanol (50/50 (v/v)) was chosen, PMEA chains could be successfully incorporated at the outermost region of the PS film. Atomic force microscopy in conjunction with neutron reflectivity revealed that chains of PMEA incorporated in the PS surface region were well swollen in water. This leads to an excellent ability to suppress the adhesion of platelets on the PS film.
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