Scanning force microscopic studies of surface structure and protein adsorption behavior of organosilane monolayers

Abstract

Alkyltrichlorosilanes, [2-(perfluorooctyl)ethyl]trichlorosilane (FOETS) and their mixed monolayers were polymerized on the water subphase and were subsequently immobilized onto the silicon wafer surface by covalent bonding. Atomic force microscopic (AFM) observation of the [n-octadecyltrichlorosilane(OTS)/FOETS] mixed monolayer revealed that the crystalline OTS formed circular domains of ∼1–2 μm in diameter that were surrounded by an amorphous FOETS matrix. Lateral force microscopic (LFM) and scanning viscoelasticity microscopic (SVM) observations of the (OTS/FOETS) mixed monolayer could also distinguish the difference in the physical and mechanical properties between domain and matrix. The (alkylsilane/FOETS) mixed monolayers with a shorter alkyl chain such as n-dodecyltrichlorosilane (DDTS) did not show the phase-separated structure maybe due to the lack in crystallinity of DDTS component. AFM observation of the [crystalline fatty acid (nonreactive)/FOETS (reactive)] mixed monolayer also revealed the phase-separated structure. The crystalline fatty acid domains in the mixed monolayer were extracted by solvent and then, the monolayer of FOETS with the holes of ∼1–2 μm in diameter, that is, the (Si/FOETS) monolayer was finally obtained. The Si phase of (Si/FOETS) was backfilled with the another organosilane by chemisorption. Then, the [(3-mercaptopropyl) trimethoxysilane (MTS)/FOETS] mixed monolayer was newly obtained by the chemisorption of MTS. The absorption of bovine serum albumin (BSA) onto mixed monolayers was studied by exposure of the mixed monolayers to a BSA solution. BSA was preferentially adsorbed onto the MTS part due to a specific reaction between disulfide bond (–S–S–) in BSA and SH groups in MTS. On the other hand, in the case of (OTS/FOETS) mixed monolayer, BSA adsorbed preferentially onto the FOETS matrix in order to minimize the interfacial free energy in the aqueous environment.