The chemical composition of the functional surfaces of substrates used for microarrays is one of the important parameters that determine the quality of a microarray experiment. In addition to the commonly used contact angle measurements to determine the wettability of functionalized supports, X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) are more specific methods to elucidate details about the chemical surface constitution. XPS yields information about the atomic composition of the surface, whereas from ToF-SIMS, information on the molecular species on the surface can be concluded. Applied on printed DNA microarrays, both techniques provide impressive chemical images down to the micrometer scale and can be utilized for label-free spot detection and characterization. Detailed information about the chemical constitution of single spots of microarrays can be obtained by high-resolution XPS imaging.
Self-assembled monolayers of aromatic omega-aminothiols on gold: surface chemistry and reactivity
(2010)
Amino-terminated self-assembled monolayers on gold substrates were studied by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS) measurements, and atomic force microscopy (AFM). Two different ω-amino-4,4'-terphenyl substituted alkanethiols of the general structure H2N-(C6H4)3-(CH2)n-SH (ATPn) were used: 2-(4''-amino-1,1':4',1''-terphenyl-4-yl)ethane-1-thiol (n = 2, ATP2) and 3-(4''-amino-1,1':4',1''-terphenyl-4-yl)propane-1-thiol (n = 3, ATP3). Moreover, the addressability of amino groups within the films was investigated by chemical derivatization of ATPn SAMs with 3,5-bis(trifluoromethyl)phenyl isothiocyanate (ITC) forming fluorinated thiourea ATPn-F films. Evaluation of high-resolution C 1s and N 1s XPS data revealed successful derivatization of at least 50% of surface amino species. Furthermore, it could be demonstrated by angle-resolved NEXAFS spectroscopy that chemical derivatization with ITC has no noticeable influence on the preferential upright orientation of the molecules in the SAMs.
Functionalised surfaces are of interest in many fields, e.g. in biomedicine, materials science and molecular electronics. In this study a series of self-assembled aliphatic and aromatic monolayers on gold substrates with terminal amino groups was investigated. Four different thiol molecules were used: aliphatic 11-aminoundecane-1-thiol (AUDT), aromatic 4-aminobenzenethiol (ABT) and aromatic ω-amino thiols with an alkyl spacer as 4-aminophenylbutane-1-thiol (APBT) and 3-(4''-amino-1,1':4',1''-terphenyl-4-yl)propane-1-thiol (ATPT). Evaluation of N 1s XPS data revealed that on the aromatic self-assembled monolayers (SAMs) amino groups exist preferentially as primary amines, whereas on the aliphatic SAM protonated and/or hydrogen-bonded amines are the major species. This result is crosschecked by N K edge near edge X-ray absorption fine structure (NEXAFS) spectroscopy and can be rationalised by the different basicity of aliphatic and aromatic amines.