Gold thiolate and photochemically functionalized microcantilevers using molecular recognition agents

Abstract

Highly sensitive sensor platforms for the detection of specific reagents, such as chromate, gasoline and biological species, using microcantilevers and other microelectromechanical systems (MEMS) whose surfaces have been modified with photochemically attached organic monolayers, such as self-assembled monolayers (SAM), or gold-thiol surface linkage are taught. The microcantilever sensors use photochemical hydrosilylation to modify silicon surfaces and gold-thiol chemistry to modify metallic surfaces thereby enabling individual microcantilevers in multicantilever array chips to be modified separately. Terminal vinyl substituted hydrocarbons with a variety of molecular recognition sites can be attached to the surface of silicon via the photochemical hydrosilylation process. By focusing the activating UV light sequentially on selected silicon or silicon nitride hydrogen terminated surfaces and soaking or spotting selected metallic surfaces with organic thiols, sulfides, or disulfides, the microcantilevers are functionalized. The device and photochemical method are intended to be integrated into systems for detecting specific agents including chromate groundwater contamination, gasoline, and biological species.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims priority to U.S. Provisional Patent Application 60 / 609,610 filed Sep. 14, 2004, and is related to U.S. patent application Ser. No. 11 / 059,170, filed Feb. 16, 2005, both herein incorporated by reference.STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH [0002] This invention was made with United States Government support under Contract No. DE-AC05-00OR22725 between the United States Department of Energy and U. T. Battelle, LLC. The United States Government has certain rights in this invention.FIELD OF THE INVENTION [0003] This invention relates to highly sensitive sensor platforms for the detection of specific reagents, such as chromate, gasoline and biological species, using microcantilevers and other microelectromechanical systems (MEMS) whose surfaces have been modified with photochemically attached organic monolayers, such as self-assembled monolayers (SAM), or gold-thiol surface linkage. The microcantilever sen...

AI Technical Summary

Benefits of technology

[0009] Photochemical hydrosilylation of 11-undecenyltriethylammonium bromide with hydrogen-terminated silicon microcantilever surfaces yielded a robust quaternary ammonium terminated organic monolayer that is suitable for chromate detection. Terminal vinyl substituted hydrocarbons with a variety of molecular recognition sites can be attached to the surface of silicon via the photochemical hydrosilylation process. Since the chemicals only react at the surface of Si when irradiated it allows an array of cantilevers to be sequentially modified by exposing an array to the derivatization agent but only activating one or a select group of cantilevers before changing the solution and activating a different cantilever of group of cantilevers. Another embodiment of this invention enables the detection of hexavalent chromium, Cr(VI), in ground water using at least one microcantilever coated with a self-assembled monolayer of 4-mercaptopyridine. The microcantilever sensors use gold-thiol attachment approach for 4-mercaptopyridine (4-MPy) and photochemical hydrosilylation for grafting 11-undecenyltriethylammonium bromide or vinyl pyridine to modify the microcantilever surface for chromate sensing.

Problems solved by technology

Microcantilever-based sensors have been shown to be extremely sensitive; however silicon or silicon nitride microcantilevers coated on one surface with gold do not have any particular chemical selectivity.

They have a high surface-to-volume ratio, and therefore changes in the Gibbs surface free energy induced by surface-analyte interactions lead to large surface forces.

When such interactions are restricted to one surface, then the resulting differential stress leads to bending of the cantilever.

A problem exists with the formation of SAM coatings on gold coated cantilevers if an array of cantilevers is used.

It is difficult to apply a coating, especially if a long period of time is required for a tightly packed layer to form, to a single cantilever in an array without contaminating other cantilevers in the array.

Other approaches to modifying a single surface of a silicon cantilever involve reaction of silane reagents with the Si—OH groups on the surface, but again it is problematic to modify only a single cantilever in an array.

Most of the methods used to determine CrO42− (such as ion exchange, chromatography, and atomic absorption spectroscopy) are generally time-consuming, have less than desired accuracy, or are expensive.

Various techniques have been tested for the direct determination of Cr(VI) in water, but most techniques are not suitable due to insufficient detection limits and / or matrix interferences.

However, this method is not viable for remote monitoring, and also would not be applicable if federal / local regulated levels are tightened.

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