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Determination of the ionization state of 11-thioundecyl-1-phosphonic acid in self-assembled monolayers by chemical force microscopy

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UNSPECIFIED (2000) Determination of the ionization state of 11-thioundecyl-1-phosphonic acid in self-assembled monolayers by chemical force microscopy. ANALYTICAL CHEMISTRY, 72 (9). pp. 1973-1978. ISSN 0003-2700

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Abstract

The present article describes the preparation and preliminary characterization of a novel phosphate-functionalized self-assembled monolayer (SAM) and the determination of the surface ionization states of the phosphate headgroup in aqueous solutions by chemical force microscopy (CFM). The phosphate headgroup used was PO-(OH)(2), a diprotic acid. The adhesion force between an AFM probe and a flat substrate, both of which were chemically modified with the same phosphate SAM, was also measured as a function of pH and ionic strength. At low ionic strength (10(-4) M), two peaks were observed in the force titration curve (adhesion force versus pH) at pH 4.5 and 8.4. The two peaks are positioned 2.4 and 1.2 pH units higher, respectively, than the acid dissociation constants obtained for the phosphate group free in aqueous solution. At high ionic strength (10(-1) M), the adhesion forces were reduced by 1 order of magnitude and the peaks were replaced by shoulders similar to those previously reported for acid force titrations. On the basis of JKR theory, the surface pK(a) values of the phosphate group in high ionic strength solutions were found to be 4.5 and 7.7, respectively. However, in light of the effects of ionic strength on the force titration curves, we discuss the applicability of JKR theory to nanoscopic measurements of adhesion force and surface pK(a).

Item Type: Journal Article
Subjects: Q Science > QD Chemistry
Journal or Publication Title: ANALYTICAL CHEMISTRY
Publisher: AMER CHEMICAL SOC
ISSN: 0003-2700
Date: 1 May 2000
Volume: 72
Number: 9
Number of Pages: 6
Page Range: pp. 1973-1978
Publication Status: Published
URI: http://wrap.warwick.ac.uk/id/eprint/13411

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