title: Silane coupling agent bearing a photoremovable succinimidyl carbonate for patterning amines on glass and silicon surfaces with controlled surface densities.
abstract: Patterned immobilization of synthetic and biological ligands on material surfaces with controlled surface densities is important for various bioanalytical and cell biological purposes. This paper describes the synthesis, characterization, and application of a novel silane coupling agent bearing a photoremovable succinimidyl carbonate, which enables the photopatterning of various primary amines on glass and silicon surfaces. The silane coupling agent is 1-[5-methoxy-2-nitro-4-(3-trimethoxysilylpropyloxy)phenyl]ethyl N-succinimidyl carbonate. The distinct feature of this molecule is that it has a photocleavable 2-nitrobenzyl switch between a trimethoxysilyl group and a succinimidyl carbonate, each reactive to the hydroxy groups of inorganic oxides and primary amines. Based on this molecular design, the compound allows for the one-step introduction of succinimidyl carbonates onto the surface of glass and silicon, immobilization of primary amines, and region-selective and dose-dependent release of the amines by near-UV irradiation. Therefore, we were able to pattern amine ligands on the substrates in given surface densities and arbitrary geometries by controlling the doses and regions of photoirradiation. These features were verified by UV-vis spectroscopy, contact angle measurements, infrared (IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), ellipsometry, and atomic force microscopy (AFM). The compound was applied to form a chemical density gradient of amino-biotin on a silicon substrate in a range of 0.87-0.12 chains/nm(2) by controlling photoirradiation under a standard fluorescence microscope. Furthermore, we also succeeded in forming a chemical density gradient at a lower surface density range (0.15-0.011 chains/nm(2)) on the substrate by diluting the feed amino-biotin with an inert control amine.
authors.affiliation: World Premier International (WPI) Research Center Initiative, International Center for Materials Nanoarchitectonics (MANA) and National Institute for Materials Science (NIMS), Namiki, Tsukuba, Japan.
authors.forename: Hidekazu
authors.initials: H
authors.lastname: Nakayama
authors.forename: Jun
authors.initials: J
authors.lastname: Nakanishi
authors.forename: Takahiro
authors.initials: T
authors.lastname: Shimizu
authors.forename: Yutaro
authors.initials: Y
authors.lastname: Yoshino
authors.forename: Hideo
authors.initials: H
authors.lastname: Iwai
authors.forename: Shingo
authors.initials: S
authors.lastname: Kaneko
authors.forename: Yasuhiro
authors.initials: Y
authors.lastname: Horiike
authors.forename: Kazuo
authors.initials: K
authors.lastname: Yamaguchi
mesh_terms: D000588:Amines / Q000737:chemistry*; D002254:Carbonates / Q000737:chemistry*; D003432:Cross-Linking Reagents / Q000138:chemical synthesis / Q000737:chemistry*; D005898:Glass / Q000737:chemistry*; D018625:Microscopy, Atomic Force; D015394:Molecular Structure; D010777:Photochemistry; D012821:Silanes / Q000138:chemical synthesis / Q000737:chemistry*; D012825:Silicon / Q000737:chemistry*; D013388:Succinimides / Q000737:chemistry*; D013499:Surface Properties
chemical_list: D000588:Amines; D002254:Carbonates; D003432:Cross-Linking Reagents; D012821:Silanes; D013388:Succinimides; C085786:succinimidyl carbonate; D012825:Silicon